KR20220119599A - Adhesive composition, laminated body, manufacturing method of laminated body, and manufacturing method of electronic component - Google Patents

Abstract

An adhesive composition used to form an adhesive layer for temporarily adhering a semiconductor substrate or electronic device and a support that transmits light, wherein (a) a light absorber, a polyisocyanate, and a polyol, or (b) a light absorber, a polymerizable carbon- An adhesive composition comprising a urethane resin containing a carbon unsaturated bond, and a polymerization initiator.

Description

Adhesive composition, laminated body, manufacturing method of laminated body, and manufacturing method of electronic component

The present invention relates to an adhesive composition, a laminate, a method for manufacturing a laminate, and a method for manufacturing an electronic component.

This application claims priority based on Japanese Patent Application No. 2019-238291 for which it applied to Japan on December 27, 2019, and Japanese Patent Application No. 2020-110426 for which it applied to Japan on June 26, 2020, and the The content is cited here.

BACKGROUND ART A semiconductor package (electronic component) including a semiconductor element has various forms depending on a corresponding size, and includes, for example, a Wafer Level Package (WLP), a Panel Level Package (PLP), and the like.

As a technology of a semiconductor package, a fan-in type technology and a fan-out type technology are mentioned. As a semiconductor package by a fan-type technology, the fan-in-type WLP (Fan-in Wafer Level Package) etc. which rearrange the terminal at the end of a bare chip in a chip area are known. As a semiconductor package by a fan-out type technology, the fan-out type WLP (Fan-out Wafer Level Package) etc. which rearrange the terminal outside a chip area are known.

In recent years, in particular, the fan-out type technology has been applied to a fan-out type PLP (Fan-out Panel Level Package) in which a semiconductor element is arranged and packaged on a panel, and further higher integration, thickness and miniaturization in the semiconductor package. It is attracting attention as a method that can realize such things.

In order to achieve size reduction of a semiconductor package, it becomes important to make the thickness of the board|substrate in the element mounted|mounted thin. However, when the thickness of the substrate is reduced, the strength thereof is lowered and the substrate is easily damaged during semiconductor package manufacturing. On the other hand, there is known a technique of temporarily adhering a substrate to a support using an adhesive, processing the substrate, and then separating the substrate and the support.

As the adhesive used for temporary bonding of the substrate and the support, a thermoplastic adhesive is often used in view of easy removal of the adhesive layer with a solvent or the like. For example, Patent Document 1 discloses an adhesive composition containing a thermoplastic elastomer, a high boiling point solvent, and a low boiling point solvent.

International Publication No. 2016/052315

By the way, in semiconductor package manufacture, high-temperature processing, such as thin film formation, baking, and die bonding, may be performed. When the heat resistance of the adhesive is low, the elastic modulus of the adhesive layer is lowered at the time of high-temperature treatment, and there is a possibility that the position of the substrate, sinking of the substrate, or the like may occur. On the other hand, when the heat resistance of the adhesive is increased, the applicability to the substrate or support tends to decrease.

When a thermosetting adhesive is used for bonding the support and the substrate, problems such as misalignment and sinking do not occur during high-temperature treatment. However, it is difficult to remove the adhesive layer with a solvent or the like, and even when a separation layer is formed, it is difficult to remove the adhesive layer attached to the substrate after separating the support and the substrate due to deterioration of the separation layer.

Moreover, in the conventional adhesive agent, in order to isolate|separate a support body and a board|substrate after processing of a board|substrate, a separation layer is normally required. Therefore, it is necessary to separately perform the formation of the separation layer and the formation of the adhesive layer, and the operation is complicated.

The present invention has been made in view of the above circumstances, and an adhesive composition that does not require a separation layer, has high heat resistance and is easy to remove the adhesive layer, a laminate manufactured using the adhesive composition, a method for producing the laminate, And it makes it a subject to provide the manufacturing method of the electronic component using the said adhesive agent composition.

In order to solve the said subject, this invention employ|adopted the following structure.

That is, the first aspect of the present invention is an adhesive composition used for forming an adhesive layer for temporarily adhering a semiconductor substrate or electronic device and a support that transmits light, (a) a light absorber, polyisocyanate, and polyol, or (b) an adhesive composition containing a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.

A second aspect of the present invention is a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or an electronic device are laminated in this order, wherein the adhesive layer is a cured product of the adhesive composition according to the first aspect, the laminate to be.

A third aspect of the present invention is a method for producing a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are laminated in this order, wherein the adhesive composition according to the first aspect is applied to the support or semiconductor substrate. Production of a laminate comprising a step of forming a composition layer, a step of placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween, and a step of curing the adhesive composition layer to form the adhesive layer way.

A fourth aspect of the present invention is a composite of a member made of a metal or semiconductor and a resin for sealing or insulating the member after obtaining a layered product by the method for manufacturing a layered product according to the third aspect, the former It is a manufacturing method of the laminated body in which the support body which transmits light, an adhesive layer, and an electronic device are laminated|stacked in this order, further having an electronic device forming process which forms a device.

In a fifth aspect of the present invention, after obtaining a laminate by the method for manufacturing a laminate according to the fourth aspect, the electronic device and , a step of separating the support, and a step of removing the adhesive layer adhering to the electronic device by decomposing the urethane bond in the adhesive layer with an acid or alkali.

According to the present invention, an adhesive composition that does not require a separation layer, has high heat resistance and is easy to remove the adhesive layer, a laminate manufactured using the adhesive composition, a method for manufacturing the laminate, and an electron using the adhesive composition A method of manufacturing a component is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied.
It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied.
It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied.
It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied.
5A to 5B are schematic process diagrams for explaining one embodiment of a method for manufacturing a laminate 100' in which a support, an adhesive composition layer, and a semiconductor substrate are laminated in this order. It is a figure explaining the adhesive composition layer formation process.
It is a figure explaining a semiconductor substrate mounting process.
6 : is a figure explaining a contact bonding layer formation process.
7A-7C are schematic process diagrams explaining one Embodiment of the method of manufacturing the laminated body 120. As shown in FIG. It is a figure explaining a sealing process.
It is a figure explaining a grinding process.
7C is a view for explaining a wiring layer forming process.
8A to 8C are schematic process diagrams for explaining one embodiment of a method for manufacturing a semiconductor package (electronic component) from the stacked body 120 . 8A is a diagram illustrating the laminate 200 .
It is a figure explaining a separation process.
8C is a view for explaining a step of removing an adhesive layer.

In the present specification and claims, "aliphatic" is a concept relative to aromatic, and is defined as meaning a group, compound, or the like having no aromaticity.

Unless otherwise specified, "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.

The "alkylene group" shall include divalent saturated hydrocarbon groups of linear, branched and cyclic, unless otherwise specified.

A "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

A "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atoms of an alkyl group or an alkylene group are substituted with fluorine atoms.

A "structural unit" means a monomer unit (monomer unit) constituting a high molecular compound (resin, polymer, copolymer).

When describing "may have a substituent" or "may have a substituent", a case where a hydrogen atom (-H) is substituted with a monovalent group, and a case where a methylene group (-CH ₂ -) is substituted with a divalent group includes both sides of

"Exposure" is a concept including the overall irradiation of radiation.

The "structural unit derived from hydroxystyrene" means a structural unit constituted by cleavage of the ethylenic double bond of hydroxystyrene. The "structural unit derived from a hydroxystyrene derivative" means a structural unit constituted by cleavage of the ethylenic double bond of the hydroxystyrene derivative.

The "hydroxystyrene derivative" is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As those derivatives, the hydrogen atom of the hydroxyl group of the hydroxystyrene by which the hydrogen atom of the (alpha)-position may be substituted by the substituent is substituted by the organic group; The thing in which the substituent other than the hydroxyl group couple|bonded with the benzene ring of hydroxystyrene which the hydrogen atom at the alpha-position may be substituted with the substituent, etc. are mentioned. Incidentally, the α-position (a carbon atom at the α-position) refers to a carbon atom to which the benzene ring is bonded, unless otherwise specified.

Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.

Specific examples of the halogenated alkyl group as the substituent at the α-position include a group in which a part or all of the hydrogen atoms of the above “alkyl group as a substituent at the α-position” are substituted with halogen atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as this halogen atom, A fluorine atom is especially preferable.

Further, specific examples of the hydroxyalkyl group as the substituent at the α-position include a group in which a part or all of the hydrogen atoms of the above “alkyl group as a substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

In the present specification and claims, depending on the structure represented by the chemical formula, an asymmetric carbon may exist and enantiomers and diastereomers may exist, but in that case represents their isomers in one formula. These isomers may be used independently and may be used as a mixture.

(Adhesive composition)

The adhesive composition according to the first aspect of the present invention is an adhesive composition used to form an adhesive layer for temporarily adhering a semiconductor substrate or electronic device and a support that transmits light, (a) a light absorber, polyisocyanate, and polyol , or (b) a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.

<target of temporary adhesion>

The adhesive composition which concerns on this embodiment is used in order to form the adhesive layer which temporarily adheres a semiconductor substrate or an electronic device, and a support body. In this specification, "temporary adhesion" means that the adhesion object is temporarily adhere|attached (for example, between arbitrary operation processes). More specifically, a semiconductor substrate or electronic device is temporarily adhered to and fixed on a support (temporary adhesion) to a support for device thinning, transport of a semiconductor substrate, mounting on a semiconductor substrate, etc., after completion of the process , separated from the support.

≪Semiconductor substrate≫

The semiconductor substrate to which the adhesive composition which concerns on this embodiment is applied is not specifically limited, What is generally used as a semiconductor substrate may be sufficient. A semiconductor substrate (bare chip) is provided to processes, such as thinning and mounting, in the state supported by a support body. Structures, such as an integrated circuit and a metal bump, may be mounted on the semiconductor substrate, for example.

As a semiconductor substrate, although a silicon wafer substrate is mentioned typically, it is not limited to this, A ceramic substrate, a thin film substrate, a flexible substrate, etc. may be sufficient.

≪Electronic device≫

In this specification, an "electronic device" means the member which comprises at least one part of an electronic component. The electronic device is not particularly limited, and various mechanical structures and circuits may be formed on the surface of the semiconductor substrate. The electronic device may be a composite of a member preferably made of a metal or a semiconductor, and a resin that seals or insulates the member. The electronic device may have a single-layered or multi-layered structure in which a redistribution layer and/or a semiconductor element or other element described later may be sealed or insulated with an encapsulant or an insulating material.

«Support»

A support body is a member which supports a semiconductor substrate or an electronic device. A support body is comprised from the member which has the characteristic which transmits light and supports a semiconductor substrate so that it may mention later.

The adhesive composition of this embodiment contains any component of following (a) or (b).

(a) light absorbers, polyisocyanates, and polyols.

(b) a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator.

Hereinafter, for convenience, the adhesive composition containing the component of (a) is referred to as "adhesive composition (a)", and the adhesive composition containing the component of (b) is also referred to as "adhesive composition (b)".

The adhesive composition (a) and the adhesive composition (b) are both curable adhesive compositions, and form and harden|cure a crosslinked structure by heating etc. Therefore, by forming an adhesive composition layer between a semiconductor substrate or an electronic device (hereinafter collectively referred to as "semiconductor substrate, etc.") and a support and curing it, an adhesive layer for temporarily adhering a semiconductor substrate or the like to a support can be formed.

On the other hand, the adhesive layer formed by the adhesive composition (a) or adhesive composition (b) contains a light absorber. Therefore, when light is irradiated to the adhesive layer through a support that transmits light, the light absorber in the adhesive layer absorbs light and the adhesive layer is altered. Thereby, the semiconductor substrate or device temporarily bonded through the adhesive layer and the light-transmitting support can be separated.

In addition, since the adhesive layer formed by the adhesive composition (a) or adhesive composition (b) contains a urethane resin, an adhesive layer can be decomposed|disassembled by decomposing|disassembling a urethane bond with an acid or alkali. Thereby, after separation from the light-transmitting support, the residue of the adhesive layer attached to the semiconductor substrate or device can be removed.

<Adhesive composition (a)>

The adhesive composition (a) contains a light absorber, a polyisocyanate, and a polyol. The adhesive composition (a) is crosslinked by urethane bonding between polyisocyanate and polyol by heating. Thereby, the adhesive composition layer is hardened|cured, and the adhesive layer which temporarily adheres a support body, a semiconductor substrate, etc. is formed. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light and the adhesive layer is altered. Thereby, the support body and the semiconductor substrate and the like can be separated. In addition, the residue of the adhesive layer adhering to a semiconductor substrate etc. can be removed by decomposing|disassembling a urethane bond with an acid or alkali.

≪Light Absorber: (B) Component≫

The adhesive composition (a) contains a light absorber (hereinafter, also referred to as "component (B)"). When adhesive composition (a) contains (B) component, it can irradiate light and can change a contact bonding layer in quality.

(B) The component will not be specifically limited if it is a substance which has light absorption ability. As component (B), according to the wavelength of the light irradiated at the time of separation|separation of a support body, a semiconductor substrate, etc., what can absorb the light of the said wavelength can be used. For example, as component (B), what can absorb light in the wavelength range of 300-800 nm can be used. It is preferable that component (B) can absorb light in the wavelength range of 400-700 nm, It is more preferable that it can absorb light in the wavelength range of 450-600 nm, It absorbs light in the wavelength range of 500-550 nm It is more preferable that it is possible.

(B) As a component, a pigment and dye are mentioned, for example.

・Pigment

An organic pigment may be sufficient as a pigment, and an inorganic pigment may be sufficient as it. Any of a black pigment and a color coloring pigment may be sufficient as a pigment.

As a black organic pigment, perylene black (perylene type black pigment), cyanine black, aniline black, lactam black etc. are mentioned, for example. Examples of the black inorganic pigment include carbon black (lamp black, acetylene black, thermal black, channel black, furnace black, etc.), chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, strontium titanate, chromium oxide. , and ceria.

As a color coloring pigment, for example, the compound classified as a pigment in the color index (C.I.; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I.) number and those to which are given.

C. I. Pigment Yellow 1 (hereinafter, “C. I. Pigment Yellow” is the same and only numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185 ;

C. I. Pigment Orange 1 (hereinafter, “C. I. Pigment Orange” is the same and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, 73;

C. I. Pigment Violet 1 (hereinafter, “C. I. Pigment Violet” is the same and only numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

C. I. Pigment Red 1 (hereinafter, “C. I. Pigment Red” is the same and only the numbers are described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49 : 2, 50 : 1, 52 : 1, 53 : 1, 57, 57 : 1, 57 : 2, 58 : 2, 58 : 4, 60 : 1, 63 : 1, 63 : 2, 64 : 1, 81 : 1, 83, 88, 90 : 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 , 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C. I. Pigment Blue 1 (hereinafter, “C. I. Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

C. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 37 ;

C. I. Pigment Brown 23, C. I. Pigment Brown 25, C. I. Pigment Brown 26, C. I. Pigment Brown 28;

C. I. Pigment Black 1, Pigment Black 7.

Although the particle diameter of a pigment can be set suitably, For example, as a volume average particle diameter, they are 10 nm or more and 1000 nm or less, Preferably they are 10 nm or more and 500 nm or less, More preferably, they are 10 nm or more and 300 nm or less. The volume average particle diameter can be calculated|required by the dynamic light scattering method.

A pigment may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use combining the some pigment which absorbs the light of a different wavelength range, for example, can use combining a black pigment and 1 or more types of color coloring pigments.

·dyes

Dyes include, for example, azo dyes (monoazo and polyazo dyes, metal complex salt azo dyes, pyrazoloneazo dyes, stilbenazo dyes, thiazolazo dyes), anthraquinone dyes (anthraquinone derivatives, anthrone derivatives) ), indigoid dyes (indigoid derivatives, thioindigoid derivatives), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes), quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes), methine dyes (cyanine dyes, azomethine dyes), quinoline dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, and perinone dyes. .

As the dye, a commercially available dye may be used. As a commercially available dye, PC-5857 (made by Orient Industrial Co., Ltd.) etc. is mentioned, for example.

Dye may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use combining the some dye which absorbs the light of a different wavelength range.

(B) A component may be used individually by 1 type, and may use 2 or more types together.

1-20 mass % is preferable with respect to the total mass (100 mass %) of adhesive composition (a), and, as for content of (B) component in adhesive composition (a), 2-15 mass % is more preferable, , 3-15 mass % is more preferable. (B) The light absorption efficiency in a contact bonding layer improves that content of a component is more than the said lower limit, and the quality change of a contact bonding layer becomes favorable. (B) When content of a component is below the said upper limit, it will become easy to balance with another component.

Moreover, 5 mass % or more may be sufficient as content of (B) component in adhesive composition (a), and 10 mass % or more may be sufficient as it with respect to the gross mass (100 mass %) of adhesive composition (a).

«Polyisocyanate compound: (I) component»

The adhesive composition (a) contains a polyisocyanate compound (hereinafter also referred to as "component (I)"). In this specification, "polyisocyanate compound" means a compound (polyisocyanate) having two or more isocyanate groups (-N=C=O) or a compound having two or more blocked isocyanate groups (blocked polyisocyanate) . It does not specifically limit as polyisocyanate, What is generally used for manufacture of a urethane resin can be used without particular restriction|limiting.

Blocked polyisocyanate is a compound in which the isocyanate group of polyisocyanate is blocked by reaction with a blocking agent, and was deactivated. It is preferable that the blocked polyisocyanate used as component (I) is what blocked the isocyanate group with the thermally dissociable blocking agent. Examples of the thermally dissociable blocking agent include blocking agents such as oximes, diketones, phenols, and caprolactams. In the blocked polyisocyanate by the thermally dissociable blocking agent, the isocyanate group is inactive at normal temperature, and when heated, the thermally dissociable blocking agent dissociates and regenerates the isocyanate group.

As a specific example of polyisocyanate, For example, Aliphatic diisocyanate, such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, and lysine diisocyanate; Alicyclics such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate diisocyanate; and tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, naphthylene diisocyanate Aromatic diisocyanate, such as; And these biuret forms, isocyanurate forms, adduct forms of trimethylolpropane, etc. are mentioned. Polyisocyanate may be used individually by 1 type, and may use 2 or more types together.

As the polyisocyanate, commercially available ones may be used. Commercially available polyisocyanates include, for example, Duranate (registered trademark) 24A-100, Duranate 22A-75 P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21 S. -75E, Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, Duranate TLA-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Dura Nate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (above, a brand name, the Asahi Kasei Chemicals make) etc. are mentioned. These products may be used individually by 1 type, and may use 2 or more types together.

As block isocyanate, the compound in which the isocyanate group of the above polyisocyanates was protected by reaction with a blocking agent is mentioned. The blocking agent is not particularly limited as long as it is a thermally dissociable blocking agent, i.e., a compound that is stable at room temperature in addition to an isocyanate group, but is advantageous when heated above the dissociation temperature and generates an isocyanate group, and known compounds can be used without particular limitation.

As a specific example of a blocking agent, For example, Lactam compounds, such as (gamma)-butyrolactam, (epsilon)-caprolactam, (gamma)-valerolactam, and propiolactam; oxime compounds such as methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, formamide oxime, acetamide oxime, acetoxime, diacetyl monooxime, benzophenone oxime, and cyclohexanone oxime; monocyclic phenol compounds such as phenol, cresol, catechol, and nitrophenol; polycyclic phenol compounds such as 1-naphthol; alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, trimethylolpropane, and 2-ethylhexyl alcohol; Ether compounds, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; Active methylene compounds, such as malonic acid alkyl ester, malonic acid dialkyl ester, acetoacetic acid alkyl ester, and acetylacetone; and the like. A blocking agent may be used individually by 1 type, and may use 2 or more types together.

Blocked polyisocyanate can be manufactured by making polyisocyanate and a blocking agent react. Reaction of polyisocyanate and blocking agent is carried out, for example, in a solvent having no active hydrogen (1.4 dioxane, cellosolve acetate, etc.) under heating at about 50 to 100° C., and optionally in the presence of a blocking catalyst. . Although the ratio in particular of polyisocyanate and blocking agent is not restrict|limited, Preferably, as an equivalent ratio of isocyanate group in polyisocyanate and blocking agent, it is 0.95:1.0-1.1:1.0, More preferably, it is 1:1.05-1.15. A well-known thing can be used as a blocking catalyst, For example, Metal alcoholates, such as sodium methylate, sodium ethylate, sodium phenolate, potassium methylate; Hydroxide of tetraalkylammonium, such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium; Organic weak acid salts, such as these acetate, octylic acid salt, myristic acid salt, and a benzoate; and alkali metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octylic acid, and myristic acid; and the like. A blocking catalyst may be used individually by 1 type, and may use 2 or more types together.

As block polyisocyanate, you may use a commercially available thing. Commercially available blocked polyisocyanates include, for example, Duranate MF-K60B, Duranate SBB-70P, Duranate SBN-70D, Duranate MF-B60B, Duranate 17B-60P, Duranate TPA-B80E, and Dura Nate E402-B80B (above, a brand name, the Asahi Chemical Co., Ltd. make) etc. are mentioned.

As component (I), the blocked polyisocyanate in which the isocyanate group was blocked by the thermally dissociable blocking agent is preferable.

(I) A component may be used individually by 1 type, and may use 2 or more types together.

5-50 mass % is preferable with respect to the total mass (100 mass %) of adhesive composition (a), and, as for content of (I) component in adhesive composition (a), 10-40 mass % is more preferable, , 20-40 mass % is more preferable. (I) Sclerosis|hardenability of an adhesive composition (a) becomes favorable as content of a component is more than the said lower limit. (I) It becomes it easy to balance with another component that content of a component is below the said upper limit.

≪Polyol: (O) component≫

The adhesive composition (a) contains a polyol (hereinafter also referred to as "component (O)"). A polyol is a compound which has two or more hydroxyl groups (-OH). The polyol is not particularly limited, and those generally used in the production of urethane resins may be used without particular limitation. (O) The component may be an aliphatic polyol or an aromatic polyol may be sufficient as it. The component (O) may be a low molecular polyol (eg, molecular weight less than 500) or a high molecular polyol (eg, molecular weight 500 or more).

Specific examples of the low molecular weight polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1 ,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkanediol having 7 to 22 carbon atoms, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, 2- Ethyl-2-butyl-1,3-propanediol, alkane-1,2-diol having 17 to 20 carbon atoms, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexane dihydric alcohols such as diol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, and bisphenol A; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; pentahydric alcohols such as xylitol; Hexahydric alcohols, such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; Heptahydric alcohols, such as perceitol; and octahydric alcohols such as sucrose; and the like.

Examples of the polymer polyol include a phenol resin, a resin containing a hydroxystyrene skeleton, a polyester polyol, a polyether polyol, a polyether ester polyol, a polyester amide polyol, an acrylic polyol, a polycarbonate polyol, a polyhydroxyalkane , polyurethane polyols, and vegetable oil-based polyols. It is preferable that the number average molecular weights of a polymeric polyol are 500-100,000.

[Phenolic resin]

A novolak-type phenol resin may be sufficient as a phenol resin, and a resol-type phenol resin may be sufficient as it. A novolak-type phenol resin can be obtained by addition-condensing the aromatic compound (henceforth "phenols") and aldehydes which have a phenolic hydroxyl group in the presence of an acid catalyst. A resol-type phenol resin can be obtained by carrying out addition condensation of phenols and aldehydes under an alkali catalyst.

As said phenols, For example, phenol; Cresols, such as m-cresol, p-cresol, and o-cresol; xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkylphenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis Polyhydroxyphenols, such as (4-hydroxy-3-methylphenyl) fluorene and 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane, etc. are mentioned.

The aldehydes include, for example, formaldehyde, paraformaldehyde, trioxane, furfural, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenz Aldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenz Aldehyde, cinnamon aldehyde, 4-isopropylbenzaldehyde, 4-isobutylbenzaldehyde, 4-phenylbenzaldehyde, etc. are mentioned.

The acid catalyst at the time of addition condensation reaction is not specifically limited, For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. are used. The alkali catalyst at the time of addition condensation reaction is not specifically limited, Sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, sodium carbonate, hexamethylenetetramine, etc. are used.

[Resin Containing Hydroxystyrene Skeleton]

The resin containing a hydroxystyrene skeleton is not particularly limited as long as it has a structural unit derived from hydroxystyrene or a hydroxystyrene derivative. Specific examples of the structural unit derived from hydroxystyrene or a hydroxystyrene derivative include a structural unit represented by the following general formula (a10-1).

[Formula 1]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group. n _ax1 is an integer of 1 to 3.]

In said formula (a10-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.

The C1-C5 alkyl group of R is preferably a C1-C5 linear or branched alkyl group, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and the like. The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as this halogen atom, A fluorine atom is especially preferable.

As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferable.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.

Preferable examples of the divalent linking group for Ya ^x1 include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

· A divalent hydrocarbon group which may have a substituent:

When Ya ^{x 1} is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

... aliphatic hydrocarbon group for Ya ^x1

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and it is usually preferable that it is saturated.

Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in its structure.

... linear or branched aliphatic hydrocarbon group

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH ₂ -], an ethylene group [-(CH ₂ ) ₂ -], a trimethylene group [-( CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -], pentamethylene group [-(CH ₂ ) ₅ -], and the like.

The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

The branched chain aliphatic hydrocarbon group is preferably a branched chain alkylene group, specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, Alkyl methylene groups, such as -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) alkylethylene groups such as ₂ -CH ₂ -; Alkyltrimethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; Alkylalkylene groups, such as alkyltetramethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, etc. are mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

... an aliphatic hydrocarbon group containing a ring in its structure

Examples of the aliphatic hydrocarbon group having a ring in its structure include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) which may contain a substituent containing a hetero atom in the ring structure, and the cyclic aliphatic group described above. and a group in which a hydrocarbon group is bonded to a terminal of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.

The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

The cyclic aliphatic hydrocarbon group may be either polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and a methoxy group time, the ethoxy group is most preferred.

A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom as said substituent, A fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.

In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As a substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O- are preferable. .

··Aromatic hydrocarbon group for Ya ^x1

The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is still more preferable, C6-C12 is especially preferable. However, carbon number in a substituent shall not be included in the carbon number. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (eg, biphenyl, fluorene, etc.); A group in which one hydrogen atom of the group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (eg, benzyl group, phenethyl group, 1-naph group in which one hydrogen atom is further removed from the aryl group in an arylalkyl group such as a tylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group). It is preferable that carbon number of the alkylene group couple|bonded with the said aryl group or heteroaryl group is 1-4, It is more preferable that it is C1-C2, It is especially preferable that it is C1.

As for the said aromatic hydrocarbon group, the hydrogen atom which the said aromatic hydrocarbon group has may be substituted by the substituent. For example, the hydrogen atom couple|bonded with the aromatic ring in the said aromatic hydrocarbon group may be substituted by the substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as substituents for substituting a hydrogen atom in the cyclic aliphatic hydrocarbon group.

· A divalent linking group containing a hetero atom:

When Ya ^x1 is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O- , -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group.), -S-, -S (= O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(= O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) a group represented by ₂ -OY ²² - [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, m" is an integer of 0 to 3], etc. can be heard

The divalent linking group containing the hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- In this case, H may be substituted with a substituent such as an alkyl group or acyl. It is preferable that carbon number is 1-10, as for the substituent (an alkyl group, an acyl group, etc.), it is more preferable that it is 1-8, It is especially preferable that it is 1-5.

Formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, wherein Y ²¹ and Y ²² are each independently , is a divalent hydrocarbon group which may have a substituent.The divalent hydrocarbon group includes the same as (divalent hydrocarbon group which may have a substituent) mentioned in the description of the divalent linking group.

As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is still more preferable, and a methylene group or an ethylene group is particularly preferable.

As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, or an alkylmethylene group is more preferable. A C1-C5 linear alkyl group is preferable, as for the alkyl group in this alkylmethylene group, a C1-C3 linear alkyl group is more preferable, A methyl group is the most preferable.

In the group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1 and 1 is particularly preferable. That is, the group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² - is particularly preferably a group represented by the formula -Y ²¹ -C(=O)-OY ²² -. Among these, the group represented by the formula -Y 21 -C(=O)-OY 22 - , a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable, wherein a' is an integer of 1 to 10, and 1 to 8 An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is still more preferable, and most preferably 1. b' is an integer of 1-10, preferably an integer of 1-8, 1 The integer of -5 is more preferable, 1 or 2 is still more preferable, and 1 is the most preferable.

As Ya ^x1 , a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), -C(=O)-NH-, a linear or branched alkylene group; Or it is preferable that it is a combination thereof, and a single bond is especially more preferable especially.

In the formula (a10-1), Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group for Wa ^x1 include a group in which (n _ax1 +1) hydrogen atoms have been removed from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is still more preferable, C6-C12 is especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

In said formula (a10-1), n _ax1 is an integer of 1-3, 1 or 2 is preferable and 1 is more preferable.

Specific examples of the structural unit represented by the general formula (a10-1) are shown below.

In the following formula, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 2]

It is preferable that it is a polymer of hydroxystyrene or a hydroxystyrene derivative, and, as for resin containing a hydroxystyrene skeleton, it is more preferable that it is a polymer (polyhydroxystyrene) of hydroxystyrene.

[Polycarbonate Polyol]

Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9 -nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, or hydrogenated bisphenol A The polycarbonate polyol obtained by making 1 type, or 2 or more types of glycol react with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.

Among them, the polycarbonate polyol is preferably a polycarbonate diol represented by the following general formula (PC-1).

[Formula 3]

[In the formula, Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. np is an integer of 2 or more.]

In the general formula (PC-1), Rp ¹ and Rp ² are each independently a divalent hydrocarbon group. An aromatic hydrocarbon group may be sufficient as the said divalent hydrocarbon group, and an aliphatic hydrocarbon group may be sufficient as it. Examples of the divalent hydrocarbon group include the same as those mentioned for Ya ^x1 in the general formula (a10-1). As the divalent hydrocarbon group for Rp ¹ and Rp ² , an aliphatic hydrocarbon group is preferable, and a linear or branched alkylene group is more preferable. C1-C10 is preferable, as for the said divalent hydrocarbon group, C3-C8 is more preferable, and, as for the said divalent hydrocarbon group, C4-C6 is still more preferable. Specific examples of Rp ¹ and Rp ² include -(CH ₂ ) ₆ - or -(CH ₂ ) ₅ -.

500-5000 are preferable, as for the weight average molecular weight (Mw) of polycarbonate polyol, 500-3000 are more preferable, 500-2000 are still more preferable, 500-1000 are especially preferable.

[Other polyols]

Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, dialkyl esters thereof, or mixtures thereof, and, for example, ethylene glycol, propylene glycol, diethylene Glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene Polyester polyol obtained by reacting glycols such as ether glycol or a mixture thereof, or polyester obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone) polyols.

As polyether polyol, for example, oxirane compounds, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, are low, such as water, ethylene glycol, propylene glycol, trimethylol propane, glycerol, for example. Polyether polyol obtained by superposing|polymerizing molecular weight polyol as an initiator is mentioned.

The polyether ester polyol includes, for example, a polyether obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid or a dialkyl ester thereof or a mixture thereof with the polyether polyol. and ester polyols.

Examples of the polyesteramide polyol include polyesteramide polyols obtained by using as a raw material an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, or hexamethylenediamine in the esterification reaction.

As acrylic polyol, acrylic acid hydroxyethyl, acrylic acid hydroxypropol, acrylic hydroxybutyl, etc. which contain one or more hydroxyl groups in 1 molecule, or these corresponding methacrylic acid derivatives, etc., for example, acrylic acid, methacrylic acid Polyesteramide polyol obtained by copolymerizing an acid or its ester is mentioned.

Examples of the polyhydroxyalkane include liquid rubber obtained by copolymerizing butadiene or butadiene with acrylamide or the like.

The polyurethane polyol is a polyol having one or more urethane bonds in one molecule, for example, polyether polyol, polyester polyol, polyether ester polyol, etc. having a number average molecular weight of 200 to 20,000, and polyisocyanate, preferably NCO/OH is less than 1, More preferably, the polyurethane polyol obtained by making it react with 0.9 or less is mentioned.

Examples of the vegetable oil-based polyol include castor oil, castor oil-modified polyol, dimer acid-modified polyol, and soybean oil-modified polyol. Among them, the vegetable oil-based polyol is preferably a castor oil-modified polyol, and more preferably a castor oil-modified diol.

Among the above, as the component (O), a phenol resin or a resin containing a hydroxystyrene skeleton is preferable, a novolak resin or a resin containing a hydroxystyrene skeleton is more preferable, and hydroxystyrene or hydroxystyrene is preferable. Derivative polymers are more preferable, and polyhydroxystyrene resins are particularly preferable.

(O) As a component, 1 type may be used independently and 2 or more types may be used together.

50-90 mass % is preferable with respect to the total mass (100 mass %) of adhesive composition (a), and, as for content of (O) component in adhesive composition (a), 50-85 mass % is more preferable, , 60-85 mass % is more preferable. (O) Sclerosis|hardenability of an adhesive composition (a) becomes favorable as content of a component is more than the said lower limit. (I) It becomes it easy to balance with another component that content of a component is below the said upper limit.

It is preferable that the molar ratio (NCO/OH) of the hydroxyl group (-OH) in the (O) component to the isocyanate group (-NCO) in the (I) component contained in the adhesive composition (a) is 0.1 to 1, It is more preferable that it is 0.3-0.7.

It is preferable that mass ratio of content of (I) component and (O) component in adhesive composition (a) is the range of ((I):(O))=1:10-10:1, 2:8- It is more preferable that it is 8:2, and it is still more preferable that it is 2:8-5:5.

<Adhesive composition (b)>

The adhesive composition (b) contains a light absorber, a urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. In the adhesive composition (b), the urethane resin containing a polymerizable carbon-carbon unsaturated bond polymerizes and crosslinks by heating or the like. Thereby, the adhesive composition layer is hardened|cured, and the adhesive layer which temporarily adheres a support body, a semiconductor substrate, etc. is formed. On the other hand, when the adhesive layer is irradiated with light such as laser light, the light absorber absorbs the light and the adhesive layer is altered. Thereby, the support body and the semiconductor substrate and the like can be separated. In addition, the residue of the adhesive layer adhering to a semiconductor substrate etc. can be removed by decomposing|disassembling a urethane bond with an acid or alkali.

≪Light Absorber: (B) Component≫

The adhesive composition (b) contains a light absorber (component (B)). (B) As a component, the thing similar to the said adhesive composition (a) is mentioned. Further, the component (B) absorbs at least a part of light within a wavelength range of 300 to 800 nm, and the compound (B1) containing a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as “component (B1)”). ) may be included.

· (B1) component

(B1) Component is a compound which absorbs at least one part light within the range of wavelength 300-800 nm, and contains a polymerizable carbon-carbon unsaturated bond. In addition, (B1) component is a compound which does not correspond to (P1) component mentioned later.

Since component (B1) contains a polymerizable carbon-carbon unsaturated bond, it reacts with a urethane resin (P1) containing a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as “component (P1)”) described later. It is cured and can form an adhesive layer together with the component (P1). Thereby, a semiconductor substrate or an electronic device and a support body can be temporarily adhered. In addition, since component (B1) absorbs at least a part of light within a wavelength range of 300 to 800 nm, by irradiating the adhesive layer with light within a wavelength range of 300 to 800 nm, component (B1) absorbs light and generates heat. do. Thereby, the adhesive layer can be altered.

Component (B1) acts as a light absorber that absorbs light having a wavelength of 300 to 800 nm. The component (B1) can absorb light within a wavelength range of 300 to 800 nm, and can be converted into thermal energy to the extent that the adhesive layer can be altered. It is preferable that component (B1) can absorb light in the wavelength range of 300-700 nm, It is more preferable that it can absorb light in the wavelength range of 300-600 nm, It is more preferable that it absorbs light in the wavelength range of 300-550 nm. It is more preferable that it is possible, and it is especially preferable that it can absorb light in the wavelength range of 300-400 nm. (B1) component, Preferably, it has an absorption peak in the said wavelength range. As component (B1), according to the wavelength of the light used at the time of separation|separation of a support body, a semiconductor substrate, etc., what can absorb the light of the said wavelength can be used. (B1) As a component, the thing which absorbs light with a wavelength of 355 nm, converts it into thermal energy, and can change a quality of an adhesive layer is mentioned, for example.

Although the polymerizable carbon-carbon unsaturated bond contained in compound (B1) is not specifically limited, It is preferable that it is radically polymerizable. Examples of the polymerizable carbon-carbon unsaturated bond include a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. Examples of the polymerizable carbon-carbon double bond include, but are not limited to, a vinyl group, a methacryloyl group, and an acryloyl group. Examples of the polymerizable carbon-carbon triple bond include, but are not limited to, an ethynyl group and a propargyl group.

As a compound (B1), what is represented by the following general formula (b1) is mentioned, for example.

[Formula 4]

[wherein W is a monovalent group containing a polymerizable carbon-carbon unsaturated bond; Y is a single bond or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n is an integer of 1-6; X is an n-valent atomic group having aromatic condensed ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in the structure. When n is 2 or more, a plurality of W and Y may be the same as or different from each other.]

In general formula (b1), W is a polymerizable group containing group containing a polymerizable carbon-carbon unsaturated bond. Examples of the polymerizable carbon-carbon unsaturated bond included in W include a polymerizable carbon-carbon double bond and a polymerizable carbon-carbon triple bond. As W, an alkenyl group, an alkynyl group, etc. are mentioned, for example. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 or 3 carbon atoms. As a specific example of an alkenyl group, a vinyl group, an isopropenyl group, etc. are mentioned, for example. The alkynyl group preferably has 2 to 6 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms. As a specific example of an alkynyl group, an ethynyl group, 1-propynyl group, etc. are mentioned, for example.

In the general formula (b1), Y is a single bond or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-. Especially, a single bond, -COO-, or -CONH- is preferable and, as for Y, a single bond or -CONH- is more preferable.

In general formula (b1), n is an integer of 1-6. 1-5 are preferable, as for n, 1-3 are more preferable, 1 or 2 is still more preferable, and 1 is especially preferable. When n is 2 or more, although W which exists in multiple numbers may mutually be same or different, the same thing is preferable. When n is 2 or more, although Y which exists in multiple numbers may mutually be same or different, the same thing is preferable.

In the general formula (b1), X is an n-valent atomic group having aromatic condensed ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in the structure.

[N-valent atom group having aromatic condensed ring skeleton]

Condensed ring skeleton which has aromaticity contains the condensed ring which has at least 1 aromatic ring. The said aromatic ring will not specifically limit if it is a cyclic conjugated system which has 4n+2 pieces of (pi) electrons, An aromatic hydrocarbon ring may be sufficient and an aromatic heterocyclic ring may be sufficient as it. 2-10 are preferable, as for the number of the aromatic rings in a condensed ring, 2-6 are more preferable, 2-4 are still more preferable, 2 or 3 are especially preferable. The condensed ring may be composed of only an aromatic ring or may be a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, but a condensed ring composed of only an aromatic ring is preferable. Specific examples of the condensed ring include naphthalene, anthracene, phenanthrene, and pyrene. Among these, anthracene or phenanthrene is preferable.

As X which has condensed-ring frame|skeleton which has aromaticity, what is represented by the following general formula (Xa-1) or (Xa-2) is mentioned. X represented by the general formula (Xa-1) is an atomic group having an anthracene skeleton, and X represented by the general formula (Xa-2) is an atomic group having a phenanthrene skeleton.

[Formula 5]

[Wherein, L ^a1 and L ^a2 each independently represent a single bond or a divalent linking group, and R ^a1 and R ^a2 each independently represent a substituent. n is the same as n in the formula (b1). m represents the integer of 0-9, and is m+n<=10. When n is 2 or more, two or more L ^a1 and L ^a2 may be the same or different from each other. When m is 2 or more, two or more R ^a1 and R ^a2 may be the same or different from each other. * is a bond bonded to Y in the general formula (b1).]

In the general formulas (Xa-1) and (Xa-2), L ^a1 and L ^a2 each independently represent a single bond or a divalent linking group. As said divalent coupling group, the hydrocarbon group which may have a substituent is mentioned. An aliphatic hydrocarbon group may be sufficient as the said hydrocarbon group, and an aromatic hydrocarbon group may be sufficient as it.

Although saturated or unsaturated may be sufficient as the said aliphatic hydrocarbon group, it is preferable that it is saturated. The aliphatic hydrocarbon group may be linear, branched, or may have a ring in its structure. As a linear aliphatic hydrocarbon group, C1-C10 is preferable, C1-C6 is more preferable, C1-C3 is still more preferable. As a branched aliphatic hydrocarbon group, C2-C10 is preferable, C2-C6 is more preferable, C2 or C3 is still more preferable. As an aliphatic hydrocarbon group containing a ring structure, C3-C10 is preferable and C3-C6 is preferable.

The aliphatic hydrocarbon group may have a substituent. The substituent may substitute a hydrogen atom, or may substitute a methylene group (-CH ₂ -) in the carbon chain. As a substituent for substituting a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxy group, a cyano group etc. are mentioned, for example, A hydroxyl group or an amino group is preferable. As a substituent for substituting the methylene group (-CH ₂ -) in the carbon chain, -O-, -CO-, -NH-, -COO-, -CONH- etc. are mentioned, for example.

The said aromatic hydrocarbon group is a hydrocarbon group containing at least 1 aromatic ring. The aromatic ring contained in the said aromatic hydrocarbon group may be monocyclic or polycyclic may be sufficient as it. An aromatic hydrocarbon ring may be sufficient as the said aromatic ring, and an aromatic heterocyclic ring may be sufficient as it. Although the number of the aromatic rings contained in an aromatic hydrocarbon group is not specifically limited, 1-3 pieces are preferable, and 1 or 2 pieces are more preferable. An aromatic hydrocarbon group may also contribute to which an aromatic ring and an aliphatic hydrocarbon group were connected.

The said aromatic hydrocarbon group may have a substituent. The substituent may substitute a hydrogen atom of the aromatic ring, or may substitute a hetero atom for a carbon atom constituting the ring of the aromatic ring. As a substituent for substituting a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxy group, a cyano group etc. are mentioned, for example, A hydroxyl group or an amino group is preferable. As a hetero atom which substitutes the ring of an aromatic ring, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned, A nitrogen atom is preferable.

In the general formulas (Xa-1) and (Xa-2), R ^a1 and R ^a2 each independently represent a substituent. Examples of R ^a1 and R ^a2 include an alkyl group, a hydroxyl group, an amino group, an alkoxy group, a halogen atom, a carboxy group, a cyano group, a nitrile group, a nitrilealkyl group, and an alicyclic group. As said alkyl group, an alkoxy group, and a nitrile alkyl group, C1-C5 is preferable and C1-C3 is more preferable. As said alicyclic group, C1-C6 is preferable. As a nitrile alkyl group, a malonyl nitrile group is mentioned, for example. An alicyclic group may be an alicyclic hydrocarbon ring, or an alicyclic heterocyclic ring may be sufficient as it. Examples of the alicyclic heterocyclic ring include those containing a sulfur atom, a nitrogen atom, or an oxygen atom. Tidiorane is mentioned as a specific example of an alicyclic heterocyclic ring.

In general formulas (Xa-1) and (Xa-2), m represents the integer of 0-9. 0-6 are preferable, as for m, 0-5 are more preferable, 0-3 are still more preferable, and 0-2 are especially preferable.

In the general formulas (Xa-1) and (Xa-2), n is the same as n in the formula (b1).

m and n have a relationship of m + n ≤ 10.

[N-valent atomic group having benzophenone skeleton]

As X which has a benzophenone skeleton, what is represented by the following general formula (Xb) is mentioned.

[Formula 6]

[Wherein, L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group, and R ^b1 and R ^b2 each independently represent a substituent. p and q each independently represent the integer of 0-5, and p+q=n. n is the same as n in the formula (b1). m1 and m2 each independently represent an integer of 0 to 5, and m1 + p ≤ 5 and m2 + q ≤ 5. When p is 2 or more, two or more L ^b1s may be the same as or different from each other. When q is 2 or more, two or more L ^b2s may be the same as or different from each other. When m1 is 2 or more, two or more R ^b1s may be the same as or different from each other. When m2 is 2 or more, two or more R ^b2s may be the same as or different from each other. * is a bond bonded to Y in the general formula (b1).]

In general formula (Xb), L ^b1 and L ^b2 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include the same groups as those mentioned for L ^a1 and L ^a2 in the formulas (Xa-1) and (Xa-2). L ^b1 and L ^b2 are preferably an aliphatic hydrocarbon group which may have a single bond or a substituent, and preferably an alkyl group which may have a single bond or a substituent. As an alkyl group which may have a substituent, C1-C5 is preferable and C1-C3 is more preferable. As the alkyl group which may have a substituent, a part of the alkyl group or the methylene group (-CH ₂ -) constituting the carbon chain is substituted with -O-, -CO-, -NH-, -COO-, -CONH- An alkyl group is preferred.

In general formula (Xb), R ^b1 and R ^b2 each independently represent a substituent. Examples of R ^b1 and R ^b2 include the same ones mentioned for R ^a1 and R ^a2 in the formulas (Xa-1) and (Xa-2).

In general formula (Xb), p and q each independently represent the integer of 0-5, and p+q=n. Said n is the same as n in said Formula (b1).

In the general formula (Xb), m1 and m2 each independently represent an integer of 0 to 5, and m1 + p ≤ 5 and m2 + q ≤ 5. 0-3 are preferable, as for m1 and m2, 0-2 are more preferable, 0 or 1 is still more preferable.

[N-valent atomic group having dibenzoylmethane skeleton]

Examples of X having a dibenzoylmethane skeleton include those represented by the following general formula (Xc).

[Formula 7]

[Wherein, L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group, and R ^c1 and R ^c2 each independently represent a substituent. p and q each independently represent the integer of 0-5, and p+q=n. n is the same as n in the formula (b1). m1 and m2 each independently represent an integer of 0 to 5, and m1 + p ≤ 5 and m2 + q ≤ 5. When p is 2 or more, two or more L ^c1 may be mutually the same or different. When q is 2 or more, two or more L ^c2 may be the same as or different from each other. When m1 is 2 or more, two or more R ^c1 may be the same as or different from each other. When m2 is 2 or more, two or more R ^c2 may be mutually the same or different. * is a bond bonded to Y in the general formula (b1).]

In general formula (Xc), L ^c1 and L ^c2 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include the same groups as those mentioned for L ^a1 and L ^a2 in the formulas (Xa-1) and (Xa-2). L ^c1 and L ^c2 are preferably an aliphatic hydrocarbon group which may have a single bond or a substituent, and preferably an alkyl group which may have a single bond or a substituent. As an alkyl group which may have a substituent, C1-C5 is preferable and C1-C3 is more preferable. As the alkyl group which may have a substituent, a part of the alkyl group or the methylene group (-CH ₂ -) constituting the carbon chain is substituted with -O-, -CO-, -NH-, -COO-, -CONH- An alkyl group is preferred.

In general formula (Xc), R ^c1 and R ^c2 each independently represent a substituent. Examples of R ^c1 and R ^c2 include the same ones mentioned for R ^a1 and R ^a2 in the formulas (Xa-1) and (Xa-2).

In general formula (Xc), p and q each independently represent the integer of 0-5, and p+q=n. Said n is the same as n in said Formula (b1).

In the general formula (Xc), m1 and m2 each independently represent an integer of 0 to 5, and m1 + p ≤ 5 and m2 + q ≤ 5. 0-3 are preferable, as for m1 and m2, 0-2 are more preferable, 0 or 1 is still more preferable.

[N-valent atomic group having dibenzoylbenzene skeleton]

As X which has dibenzoylbenzene skeleton, what is represented by the following general formula (Xd) is mentioned.

[Formula 8]

[Wherein, L ^d1 , L ^d2 and L ^d3 each independently represent a single bond or a divalent linking group, and R ^d1 , R ^d2 and R ^d3 each independently represent a substituent. p and q each independently represent the integer of 0-5, r represents the integer of 0-4, and p+q+r=n. n is the same as n in the formula (b1). m1 and m2 each independently represent an integer of 0 to 5, m3 represents an integer of 1 to 4, m1 + p ≤ 5, m2 + q ≤ 5, and m3 + r = 4. When p is 2 or more, two or more L ^d1 may be mutually the same or different. When q is 2 or more, two or more L ^d2 may be the same as or different from each other. When r is 2 or more, two or more L ^d3 may be mutually the same or different. When m1 is 2 or more, two or more R ^d1 may be mutually the same or different. When m2 is 2 or more, two or more R ^d2 may be mutually the same or different. When m3 is 2 or more, two or more R ^d3 may be mutually the same or different. * is a bond bonded to Y in the general formula (b1).]

In general formula (Xd), L ^d1 , L ^d2 and L ^d3 each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include the same groups as those mentioned for L ^a1 and L ^a2 in the formulas (Xa-1) and (Xa-2). L ^d1 , L ^d2 and L ^d3 are preferably an aliphatic hydrocarbon group which may have a single bond or a substituent, and preferably an alkyl group which may have a single bond or a substituent. As an alkyl group which may have a substituent, C1-C5 is preferable and C1-C3 is more preferable. As the alkyl group which may have a substituent, a part of the alkyl group or the methylene group (-CH ₂ -) constituting the carbon chain is substituted with -O-, -CO-, -NH-, -COO-, -CONH- An alkyl group is preferred.

In general formula (Xd), R ^d1 , R ^d2 , and R ^d3 each independently represent a substituent. Examples of R ^d1 , R ^d2 and R ^d3 include the same ones mentioned for R ^a1 and R ^a2 in the formulas (Xa-1) and (Xa-2).

In general formula (Xd), p and q each independently represent the integer of 0-5, r represents the integer of 0-4, and p+q+r=n. Said n is the same as n in said Formula (b1).

In the general formula (Xd), m1 and m2 each independently represent an integer of 0 to 5, m3 represents an integer of 1 to 4, m1 + p ≤ 5, m2 + q ≤ 5, m3 + r = 4 0-3 are preferable, as for m1, m2, and m3, 0-2 are more preferable, 0 or 1 is still more preferable.

[N-valent atom group having benzotriazole skeleton]

As X which has benzotriazole skeleton, what is represented by the following general formula (Xe) is mentioned.

[Formula 9]

[In the formula, L ^e represents a single bond or a divalent linking group, and R ^e represents a substituent. n is the same as n in the formula (b1). m represents the integer of 0-4, and is m+n<=5. When n is 2 or more, two or more L ^e may be the same as or different from each other. When m is 2 or more, two or more R ^e may be mutually the same or different. * is a bond bonded to Y in the general formula (b1).]

In general formula (Xe), L ^e represents a single bond or a divalent linking group. Examples of the divalent linking group include the same groups as those mentioned for L ^a1 and L ^a2 in the formulas (Xa-1) and (Xa-2). L ^e is preferably a single bond or a hydrocarbon group which may have a substituent, and preferably a single bond, an alkyl group which may have a substituent, or a group in which one of the hydrogen atoms of the benzene ring is substituted with an alkyl group. As an alkyl group couple|bonded with the alkyl group which may have a substituent, and a benzene ring, C1-C5 is preferable and C1-C3 is more preferable.

In general formula (Xe), R ^e represents a substituent. Examples of R ^e include the same ones as mentioned for R ^a1 and R ^a2 in the formulas (Xa-1) and (Xa-2).

In general formula (Xe), m represents the integer of 0-4. 0-3 are preferable, as for m, 0-2 are more preferable, and 0 or 1 is still more preferable.

In general formula (Xe), n is the same as n in said formula (b1). In this case, n is an integer of 1-5.

m and n have a relationship of m + n ≤ 5.

The compound (B1) is preferably a compound represented by the following general formula (b1-1) or (b1-2).

[Formula 10]

[wherein, R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y ¹ is a single bond or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-, n ¹ is an integer of 1 to 6; X ¹ is an n ¹ valent atomic group having aromatic condensed ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in the structure. When n ¹ is 2 or more, a plurality of R ¹¹ , R ¹² , and R ¹³ and Y ¹ may be the same as or different from each other.]

[Formula 11]

[In the formula, R ²¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Y ² is a single bond or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n ² is an integer of 1 to 6; X ² is an n ^-divalent atomic group having aromatic condensed ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in the structure. When n ² is 2 or more, two or more R ²¹ and Y ² may be the same as or different from each other.]

In general formula (b1-1), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ and R ¹² are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. A hydrogen atom, a methyl group, or an ethyl group is preferable, and, as for R ¹³ , a hydrogen atom or a methyl group is more preferable.

In the general formula (b1-1), Y ¹ is the same as Y in the general formula (b1).

In the general formula (b1-1), X ¹ is the same as X in the general formula (b1).

In the general formula (b1-1), n ¹ is the same as n in the general formula (b1). When n ¹ is 2 or more, two or more R ¹¹ , R ¹² , and R ¹³ may be the same as or different from each other. When n< ¹ > is 2 or more, Y< ¹ > which exists two or more may mutually be same or different. When n ¹ is 2 or more, two or more X ¹ may be the same as or different from each other.

In general formula (b1-2), R ²¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ²¹ is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

In the general formula (b1-2), Y ² is the same as Y in the general formula (b1).

In the general formula (b1-2), X ² is the same as X in the general formula (b1).

In the general formula (b1-2), n ² is the same as n in the general formula (b1). When n ² is 2 or more, two or more R ²¹ may be the same as or different from each other. When n2 is ² or more, ^two or more Y2s may mutually be same or different. When n ² is 2 or more, two or more X ² may be the same as or different from each other.

Although the specific example of the compound (B1) containing the condensed ring skeleton which has aromaticity is shown below, it is not limited to these.

[Formula 12]

[Formula 13]

[Formula 14]

Although the specific example of the compound (B1) containing a benzophenone skeleton is shown below, it is not limited to these.

[Formula 15]

Although the specific example of the compound (B1) containing a dibenzoylmethane skeleton is shown below, it is not limited to these.

[Formula 16]

Although the specific example of the compound (B1) containing a dibenzoylbenzene skeleton is shown below, it is not limited to these.

[Formula 17]

Although the specific example of the compound (B1) containing a benzotriazole skeleton is shown below, it is not limited to these.

[Formula 18]

(B1) A component may be used individually by 1 type, and may use 2 or more types together.

1 mass part or more is preferable with respect to 100 mass parts of polyurethane resin (P1) mentioned later, as for content of (B1) component in an adhesive composition, 3 mass parts or more are more preferable, 5 mass parts or more are further It is preferable, and 10 mass parts or more, or 15 mass parts or more may be sufficient. (B1) Although the upper limit of content of a component is not specifically limited, For example, 30 mass parts or less or 20 mass parts or less are mentioned with respect to 100 mass parts of polyurethane resins (P1) mentioned later. (B1) As a range of content of a component, 1-30 mass parts is preferable with respect to 100 mass parts of polyurethane resin (P1) mentioned later, 3-20 mass parts is more preferable, 5-15 mass parts is still more preferable. . (B1) The light absorption efficiency in a contact bonding layer improves that content of a component is more than the said lower limit, and the quality change of a contact bonding layer becomes favorable. (B1) When content of a component is below the said upper limit, it will become easy to balance with another component.

(B) A component may be used individually by 1 type, and may use 2 or more types together.

1-20 mass % is preferable with respect to the total mass (100 mass %) of adhesive composition (b), and, as for content of (B) component in adhesive composition (b), 2-15 mass % is more preferable, , 3-15 mass % is more preferable. (B) The light absorption efficiency in a contact bonding layer improves that content of a component is more than the said lower limit, and the quality change of a contact bonding layer becomes favorable. (B) When content of a component is below the said upper limit, it will become easy to balance with another component.

Moreover, 5 mass % or more may be sufficient as content of (B) component in adhesive composition (b) with respect to the gross mass (100 mass %) of adhesive composition (b), and 10 mass % or more may be sufficient as it.

«Polymerizable carbon-urethane resin containing carbon unsaturated bond: (P1) component»

The adhesive composition (b) contains the urethane resin (henceforth "(P1) component") containing a polymerizable carbon-carbon unsaturated bond. The component (P1) can be cured by polymerization by a polymerizable carbon-carbon unsaturated bond to form an adhesive layer. Thereby, a semiconductor substrate or an electronic device and a support body can be temporarily adhered. In addition, the urethane bond in the component (P1) has a property of being decomposed by acid or alkali. Therefore, the adhesive layer can be easily removed by a treatment liquid containing an acid or an alkali.

Although the polymerizable carbon-carbon unsaturated bond contained in (P1) component is not specifically limited, It is preferable that it is radically polymerizable. The polymerizable carbon-carbon unsaturated bond may be a polymerizable carbon-carbon double bond or a polymerizable carbon-carbon triple bond, but a polymerizable carbon-carbon double bond is preferable. As a polymerizable carbon-carbon double bond, a methacryloyl group and an acryloyl group are mentioned, for example. (P1) The number of polymerizable carbon-carbon unsaturated bonds which a component contains may be one, or 2 or more types may be sufficient as it.

(P1) The equivalent of the polymerizable carbon-carbon unsaturated bond contained in a component is 200-2000 g/eq. The above is preferable, and 300-1500 g/eq. The above is more preferable, and 400-1200 g/eq. More preferably, 500-1000 g/eq. is particularly preferred. When the polymerizable carbon-carbon unsaturated bond equivalent is equal to or more than the lower limit of the preferred range, the elastic modulus, heat resistance, and the like of the adhesive layer are further improved. If the polymerizable carbon-carbon unsaturated bond equivalent is equal to or less than the upper limit of the above-mentioned preferred range, the adhesive layer does not become too hard, and the washability becomes good. The number of equivalents is the molecular weight of the urethane resin per equivalent of the polymerizable carbon-carbon unsaturated bond.

(P1) 5,000-100,000 are preferable, as for the weight average molecular weight (Mw) of a component, 1,000-50,000 are more preferable, 12,000-30,000 are still more preferable, 13,000-25,000 are especially preferable.

The component (P1) is compoundable by polymerization addition reaction of a polyisocyanate compound (component (I)) and a polyol (component (O)). That is, the (P1) component may be a reaction product of the (I) component and the (O) component. It is preferable that at least 1 sort(s) of (I) component and (O) component contain a polymerizable carbon-carbon unsaturated bond.

・Polyisocyanate compound: (I) component

As (I) component used for the synthesis|combination of (P1) component, the thing similar to what was mentioned as (I) component in the said adhesive composition (a) is mentioned.

(I) A component may be used individually by 1 type, and may use 2 or more types together. For example, as component (I), a mixture of an aliphatic diisocyanate and an aromatic diisocyanate can be used. As said aliphatic diisocyanate, hydrogenated xylene diisocyanate is preferable. As said aromatic diisocyanate, 4, 4- diphenylmethane diisocyanate is preferable.

Polyol: (O) component

As the (O) component used in the synthesis of the component (P1), a polyol containing a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as “(O1) component”), and other polyols (hereinafter referred to as “(O2) ) component") can be mentioned.

Polyol containing a polymerizable carbon-carbon unsaturated bond (component (O1))

(O1) As a component, the polyol containing at least 1 sort(s) chosen from the group which consists of a methacryloyl group and an acryloyl group is mentioned. (O1) The number of polymerizable carbon-carbon unsaturated bonds which a component has may be one, and two or more may be sufficient as it.

(O1) As a component, the ester etc. of a polyol more than trivalence, methacrylic acid, acrylic acid, or these derivatives are mentioned, for example. The trivalent or higher polyol is preferably a trivalent or higher molecular weight polyol. As said trihydric or more low molecular polyol, Trihydric alcohols, such as glycerol and a trimethylol propane; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerol; pentahydric alcohols such as xylitol; hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol; Heptahydric alcohols, such as perceitol; and octahydric alcohols such as sucrose; and the like.

Specific examples of the component (O1) include glycerin mono(meth)acrylate, diglycerin tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, diglycerin di (meth) acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol mono (meth) acrylate, sorbitol di ( Meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, etc. are mentioned.

"(meth)acrylate" is a concept containing a methacrylate and an acrylate, and means a methacrylate or an acrylate.

(O1) A component may be used individually by 1 type, and may use 2 or more types together.

Especially, as (O1) component, it is preferable that it is a diol containing a methacryloyl group or an acryloyl group, and glycerol mono(meth)acrylate or pentaerythritol di(meth)acrylate is more preferable.

・・Other polyols ((O2) component)

The component (O2) is a polyol other than the component (O1). The component (O2) is not particularly limited, and may be an aliphatic polyol or an aromatic polyol. The component (O2) may be a low molecular polyol (eg, molecular weight less than 500) or a high molecular polyol (eg, molecular weight 500 or more).

Examples of the low-molecular polyol include the same as those mentioned in the description of the component (O) in the adhesive composition (a). As a low molecular polyol, dihydric alcohol (diol) is preferable.

When a low molecular weight polyol is used as the component (O2), the ratio of the low molecular weight polyol to the component (O1) (low molecular weight polyol/(O1) component (mass ratio)) is preferably 0.01 to 0.1, more preferably 0.03 to 0.08. .

Examples of the polymer polyol include the same as those mentioned in the description of the component (O) in the adhesive composition (a) (however, those corresponding to the component (O1) are excluded).

As the polymer polyol, polycarbonate polyol and vegetable oil-based polyol are preferable. As a polycarbonate polyol, an aliphatic polycarbonate polyol is preferable and an aliphatic polycarbonate diol is more preferable. As the vegetable oil-based polyol, a castor oil-modified polyol is preferable, and a castor oil-modified diol is more preferable.

When using a polycarbonate polyol as the component (O2), the ratio of the polycarbonate polyol to the component (O1) (polycarbonate polyol/component (O1) (mass ratio)) is preferably 0.1 to 5, and 0.3 to 3 More preferably, 0.4-3 are still more preferable.

When a vegetable oil-based polyol is used as the (O2) component, the ratio of the vegetable oil-based polyol to the (O1) component (vegetable oil-based polyol/(O1) component (mass ratio)) is preferably 0.1 to 5, and 0.3 to 3 This is more preferable, and 0.4-2.5 are still more preferable.

(O2) A component may be used individually by 1 type, and may use 2 or more types together.

Among the above, as component (O2), a polycarbonate polyol and a low molecular weight polyol are preferable from a viewpoint of adjusting the viscosity of an adhesive composition (b), and the hardness of an adhesive layer. Moreover, you may use a castor oil-modified polyol as a component (O2) from a viewpoint of improving the heat resistance of an adhesive layer.

The component (O) is preferably a combination of the component (O1) and the component (O2) from the viewpoint of adjusting the viscosity of the adhesive composition (b) and the heat resistance of the adhesive layer. As the component (O2), a low-molecular polyol, polycarbonate polyol, or castor oil-modified polyol, or a combination thereof is preferable. Specific examples of the component (O2) to be combined with the component (O1) include a combination of a polycarbonate polyol, a castor oil-modified polyol, and a low molecular weight polyol; Combination of polycarbonate polyol and castor oil-modified polyol; And polycarbonate polyol etc. are mentioned.

The mass ratio of the component (O1) to the component (O2) is preferably (O1): (O2) = 1:5 to 5: 1, more preferably 1:4 to 2: 1, and 1:4 to 1: 1 is more preferable, and 1:4 - 1:2 are especially preferable. When the mass ratio of the component (O1) to the component (O2) falls within the above range, the elastic modulus and heat resistance of the adhesive layer can be improved.

(P1) A component is compoundable by mixing (I) component and (O) component, and making it copolymerize according to the synthesis method of a well-known urethane resin. It is preferable to perform copolymerization of (I) component and (O) component in presence of well-known urethanization catalysts, such as a bismuth catalyst. Moreover, in order to avoid superposition|polymerization of the polymerizable carbon-carbon unsaturated bond in (O1) component, you may add a polymerization inhibitor to a reaction system.

(P1) The ratio (mass ratio) of the component (I) to the component (O) used for the synthesis of the component is, for example, (I): (O) = 10: 90 to 60: 40, preferably 20: 80-50:50 is more preferable, and 25:75-45:55 is still more preferable. The molar ratio (NCO/OH) of the hydroxyl group (-OH) in the component (O) to the isocyanate group (-NCO) in the component (I) is preferably 60:40 to 40:60, and 55:45: It is more preferable that it is -45:55.

(P1) A component may be used individually by 1 type, and may use 2 or more types together.

Content of (P1) component in adhesive composition (b) will not be specifically limited if it is a density|concentration which can be apply|coated to a support body etc. As content of (P1) component in adhesive composition (b), 10-60 mass % is preferable with respect to the gross mass (100 mass %) of adhesive composition (b), and 20-60 mass % is more preferable and 30-60 mass % is more preferable.

«Polymerization initiator: (A) component»

The adhesive composition (b) contains a polymerization initiator (hereinafter also referred to as (A) component). A polymerization initiator means the component which has a function which accelerates|stimulates a polymerization reaction. (A) As a component, a thermal polymerization initiator, a photoinitiator, etc. are mentioned.

As a thermal polymerization initiator, a peroxide, an azo polymerization initiator, etc. are mentioned, for example.

Examples of the peroxide in the thermal polymerization initiator include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and peroxyester. Specific examples of such peroxides include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4 peroxide -Chlorobenzoyl, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methyl Propyl-1-hydroperoxide, pertriphenylacetic acid-tert-butyl, tert-butylhydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, per tert-butyl 4-methoxyacetate and tert-butyl perN-(3-toluyl)carbamate; and the like.

The above-mentioned peroxides include, for example, Nippon Yushi Co., Ltd. trade name "Percumyl (registered trademark)", brand name "Perbutyl (registered trademark)", brand name "Peroyl (registered trademark)", and brand name "Perocta (registered trademark)" )" and the like can be used.

Examples of the azo polymerization initiator in the thermal polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methyl Ethyl) diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2' -Azobisisobutylamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate methyl, 2,2'-dichloro-2,2'-azobisbutane, 2 ,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyrate dimethyl, 1,1'-azobis(1-methylbutyronitrile-3-sulfonate sodium), 2-(4 -Methylphenylazo)-2-methylmalonodinitrile 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis -2-methylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid dimethyl, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexane Nitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis -1-chlorophenylethane, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-cycloheptanenitrile, 1,1'-azobis-1-phenylethane, 1 , 1'-azobiscumene, 4-nitrophenylazobenzylcyanoethyl acetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1 , 2-diphenylethane, poly(bisphenol A-4,4'-azobis-4-cyanopentanoate), poly(tetraethylene glycol-2,2'-azobisisobutyrate), etc. are mentioned. .

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecyl) Phenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, eta Non 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, o-benzoyl Methyl benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothiok Santhene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3- Diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl ) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimida Sol dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e. Michler ketone), 4,4'-bisdiethylaminobenzophenone (ie ethylmichler ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-t-butylacetophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone , α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p -Methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-( 5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis (trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[ 2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl )-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloro Methyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s -triazine, 2, 4-bis- trichloromethyl-6-(2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. are mentioned.

The photopolymerization initiator includes, for example, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (all trade names, manufactured by BASF) and "NCI-831" (trade names, Co., Ltd.) A commercially available thing, such as ADEKA make) can be used.

(A) A component may be used individually by 1 type, and may be used in combination of 2 or more type. (A) As a component, a thermal-polymerization initiator is preferable and a peroxide is more preferable. The usage-amount of this (A) component can be adjusted with the usage-amount of (P1) component. It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of (P1) component, and, as for content of the polymerization initiator in adhesive composition (b), it is more preferable that it is 0.5-5 mass parts.

<Optional ingredients>

In addition to the said component, adhesive composition (a) and adhesive composition (b) may contain arbitrary components in the range which does not impair the effect of this invention. Although an arbitrary component is not specifically limited, For example, a polymerization inhibitor, a solvent component, a plasticizer, an adhesion|attachment adjuvant, a stabilizer, a coloring agent, surfactant, etc. are mentioned.

≪Polymerization inhibitor≫

A polymerization inhibitor means the component which has a function which prevents the radical polymerization reaction by a heat|fever or light. A polymerization inhibitor shows high reactivity with respect to a radical.

As a polymerization inhibitor, it is preferable to have a phenol skeleton. For example, as such a polymerization inhibitor, it is possible to use a hindered phenolic antioxidant, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, Amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4'-(1-methylethylidene)bis(2-methylphenol), 4,4'-(1- Methylethylidene)bis(2,6-dimethylphenol), 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]bisphenol, 4 ,4',4"-ethylidentris(2-methylphenol), 4,4',4"-ethylidentrisphenol, 1,1,3-tris(2,5-dimethyl-4-hydroxy Phenyl)-3-phenylpropane, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylly Denbis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-(3-tert) -Butyl-4-hydroxy-5-methylphenyl)-propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro (5,5) undecane, triethylene glycol-bis -3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, n-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Pentaerythryltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name IRGANOX1010, manufactured by BASF), tris(3,5-di-tert-butylhydride) Roxybenzyl) isocyanurate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc. are mentioned.

A polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.

What is necessary is just to determine content of a polymerization inhibitor suitably according to the kind of resin component, the use of adhesive composition, and use environment.

≪Surfactant≫

As surfactant, a fluorochemical surfactant, silicone type surfactant, etc. are mentioned, for example.

As the fluorine-based surfactant, for example, BM-1000, BM-1100 (all manufactured by BM Chemi Co., Ltd.), Megapac F142D, Megapac F172, Megapac F173, Megapac F183 (all manufactured by DIC Corporation), Fluorado FC -135, Fluorado FC-170C, Fluorado FC-430, Fluorado FC-431 (all manufactured by Sumitomo 3M), Sufflon S-112, Sufflon S-113, Sufflon S-131, Sufflon S- 141, Surflon S-145 (all manufactured by Asahi Glass Corporation), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicones), and other commercially available fluorine-based surfactants. can

As the silicone-based surfactant, for example, unmodified silicone-based surfactant, polyether-modified silicone-based surfactant, polyester-modified silicone-based surfactant, alkyl-modified silicone-based surfactant, aralkyl-modified silicone-based surfactant, reactive silicone-based surfactant, etc. can be heard A commercially available silicone surfactant can be used. Specific examples of commercially available silicone-based surfactants include, for example, Paintard M (manufactured by Toray Dow Corning), Topeka K1000, Topeka K2000, Topeka K5000 (all manufactured by Takachiho Industrial Co., Ltd.), XL-121 (polyether-modified silicone based) Surfactant, the Clariant company make), BYK-310 (polyester modified silicone type surfactant, the Bikchemi company make), etc. are mentioned.

Surfactant may be used individually by 1 type, and may be used in combination of 2 or more type. As surfactant, silicone type surfactant is preferable and polyester-modified silicone type surfactant is more preferable. When adhesive composition (a) contains surfactant, it is preferable that content of surfactant is 0.01-1 mass part with respect to the total mass (100 mass parts) of (I) component and (O) component, 0.5- It is more preferable that it is 0.5 mass part. When adhesive composition (b) contains surfactant, it is preferable that it is 0.01-1 mass part with respect to 100 mass parts of (P1) component, and, as for content of surfactant, it is more preferable that it is 0.5-0.5 mass part.

≪Solvent ingredient≫

As a solvent component, a hydrocarbon solvent, a petroleum solvent, and other solvents other than the said solvent are mentioned, for example. Hereinafter, the hydrocarbon solvent and the petroleum solvent are collectively referred to as "(S1) component". (S1) Solvent components other than a component are also called "(S2) component."

Examples of the hydrocarbon solvent include linear, branched, or cyclic hydrocarbons. Examples of the hydrocarbon solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched chain hydrocarbons such as isooctane, isononane, and isododecane; p-mentane, o-mentane, m-mentane, diphenylmentane, 1,4-terpine, 1,8-terpine, bornan, norbornane, finan, tuyan, karan, longi polen, α-terpinene alicyclic hydrocarbons such as , β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thuone, β-thuone, cyclohexane, cycloheptane, and cyclooctane; and aromatic hydrocarbons such as toluene, xylene, indene, pentalene, indane, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetralin), and decahydronaphthalene (decalin).

The petroleum solvent is a solvent refined from heavy oil, and examples thereof include white kerosene, a paraffinic solvent, and an isoparaffinic solvent.

(S2) As a component, the terpene solvent which has an oxygen atom, a carbonyl group, an acetoxy group etc. as a polar group is mentioned, For example, geraniol, nerol, linalol, citral, citronerol, menthol, Isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineol , 1,8-cineol, borneol, carvone, yonone, tuyon, camphor, and the like.

Moreover, as a component (S2), Lactones, such as (gamma)-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; A compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ether, monoethyl ether of the polyhydric alcohol or compound having an ester bond, Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monopropyl ether and monobutyl ether or monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable); cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; Aromatic organic solvents, such as anisole, ethyl benzyl ether, crezyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, and butylphenyl ether, are also mentioned.

A solvent component may be used individually by 1 type, and may be used in combination of 2 or more type. As a solvent component, it is preferable with respect to said (B) component, (I) component, and (O) component, or said (B) component, and an inactive thing with respect to (P1) component. Preferred solvent components include, for example, ester solvents, ketone solvents, aromatic hydrocarbon solvents, PGMEA, PGME, and mixed solvents thereof.

Adhesive composition (a) can be prepared by adding and mixing an arbitrary component suitably to the said (B) component, (I) component, and (O) component.

The adhesive composition (b) can be prepared by dissolving and mixing the component (B), the component (P1), the component (A), and, if necessary, an optional component in a solvent component.

What is necessary is just to adjust content of the solvent component in adhesive composition (b) suitably according to the thickness of an adhesive composition layer. As content of a solvent component, it is preferable to exist in the range of 40-90 mass % with respect to the gross mass (100 mass %) of an adhesive composition, for example. That is, it is preferable that the adhesive composition of this embodiment exists in the range whose solid content (total amount of compounding components except a solvent component) density|concentration is 10-80 mass %. When content of a solvent component is in the said preferable range, viscosity adjustment becomes easy.

When using a polymerization initiator, a polymerization initiator can be mix|blended by a well-known method just before using an adhesive composition. You may mix|blend a polymerization initiator or a polymerization inhibitor in the form of the solution previously melt|dissolved in the said (S2) component. (S2) What is necessary is just to adjust the usage-amount of component suitably according to the kind etc. of a polymerization initiator or polymerization inhibitor, For example, 1-50 mass parts is preferable with respect to 100 mass parts of (S1) component, 5-30 mass parts more preferably. (S2) A polymerization initiator or a polymerization inhibitor can fully be melt|dissolved as the usage-amount of a component is in the said preferable range.

According to the adhesive composition of this embodiment, when temporarily bonding a semiconductor substrate etc., a support body, an adhesive composition layer is formed between the said semiconductor substrate etc. and a support body, and it is made to harden|cure. Thereby, an adhesive layer for temporarily adhering the semiconductor substrate or the like to the support is formed. Since the said adhesive layer is hardened|cured by a crosslinked structure, heat resistance is high, and the elasticity modulus does not fall even at high temperature (for example, 200 degreeC or more). Therefore, even when a high-temperature process is performed at the time of processing a semiconductor substrate or an electronic device, it is hard to produce problems, such as a position shift and settling.

On the other hand, when the adhesive layer is irradiated with light such as laser light, the component (B) in the adhesive layer absorbs the light and the adhesive layer is altered. Thereby, the adhesive force of an adhesive layer falls, and a semiconductor substrate etc. can be separated from a support body. Therefore, it is not necessary to form a separation layer.

In addition, since the adhesive layer contains a urethane resin, the adhesive layer can be decomposed by decomposing the urethane bond with an acid or alkali. Therefore, even when the residue of the adhesive layer adheres to the semiconductor substrate separated from the support, the residue of the adhesive layer can be easily removed by washing with acid or alkali.

(laminate)

The laminate according to the second aspect of the present invention is a laminate in which a light transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order, wherein the adhesive layer is a cured product of the adhesive composition according to the first aspect. characterized in that

1 : has shown one Embodiment of the laminated body which concerns on a 2nd aspect.

The laminated body 100 shown in FIG. 1 is equipped with the support body 1 which transmits light, the adhesive layer 3, and the semiconductor substrate 4. As shown in FIG. In the laminated body 100, the support body 1, the adhesive layer 3, and the semiconductor substrate 4 are laminated|stacked in this order.

2 : has shown another embodiment of the laminated body which concerns on a 2nd aspect.

The laminated body 200 shown in FIG. 2 is a laminated body except that the electronic device 456 which consists of the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6 is laminated|stacked on the adhesive layer 3. (100) has the same configuration.

3 : has shown still another embodiment of the laminated body which concerns on a 2nd aspect.

The laminated body 300 shown in FIG. 3 has the same structure as the laminated body 100 except that an electronic device consists of the wiring layer 6 .

4 : has shown still another embodiment of the laminated body which concerns on a 2nd aspect.

The laminated body 400 shown in FIG. 4 is a laminated body except that the electronic device 645 which consists of the wiring layer 6, the semiconductor substrate 4, and the sealing material layer 5 is laminated|stacked on the adhesive layer 3. (100) has the same configuration.

<Support>

A support body is a member which supports a semiconductor substrate or an electronic device. The support has a property of transmitting light. A support body is bonded to a semiconductor substrate or an electronic device via an adhesive layer. Therefore, as a support body, when thinning a device, conveying a semiconductor substrate, mounting on a semiconductor substrate, etc., it is preferable to have the intensity|strength required in order to prevent the damage or deformation|transformation of a semiconductor substrate.

As a material of a support body, glass, silicone, an acrylic resin, etc. are used, for example. As a shape of a support body, although rectangular, circular, etc. are mentioned, for example, It is not limited to these. As the support, for the purpose of further high-density integration or improvement of production efficiency, a large-sized panel having a larger size of a circular support and a rectangular shape in plan view can also be used.

<Adhesive layer>

The adhesive layer is formed in order to temporarily bond a semiconductor substrate or an electronic device to a support body. The adhesive layer is a cured product of the adhesive composition according to the first embodiment. The adhesive composition according to the first embodiment can be cured by heating the adhesive composition. It is preferable to exist in the range of 1 micrometer or more and 200 micrometers or less, for example, and, as for the thickness of a contact bonding layer, it is more preferable to exist in the range of 5 micrometers or more and 150 micrometers or less.

Although the adhesive layer is a cured product of the adhesive composition as described above, it is preferable that the material (cured body) constituting the adhesive layer satisfies the following characteristics.

That is, when the complex elastic modulus of the cured product is measured under the following conditions, the complex elastic modulus at 200°C is preferably 1.0 × 10 ⁴ Pa or more, more preferably 5.0 × 10 ⁴ Pa or more, and 1.0 × 10 ⁵ Pa or more. It is more preferable that it is more than that. Moreover, as for the complex elastic modulus in 200 degreeC, it is more preferable that it is 1.0 x 10 ⁶ Pa or more, It is still more preferable that it is 5.0 x 10 ⁶ Pa or more, It is especially preferable that it is 1.0 x 10 ⁷ Pa or more. As an upper limit of the complex elastic modulus in 200 degreeC, it is 1.0x10< ¹⁰ >Pa or less, for example.

Moreover, when the complex elastic modulus of a hardening body is measured on the following conditions, it is preferable that it is 5.0 x 10 ⁶ Pa or more, and it is more preferable that it is 1.0 x 10 ⁷ Pa or more of the complex elastic modulus in 250 degreeC. As an upper limit of the complex elastic modulus in 250 degreeC, it is 1.0x10< ¹⁰ >Pa or less, for example.

The complex elastic modulus of a hardening body can be measured using the dynamic viscoelasticity measuring apparatus Rheogel-E4000 (made by UBM Corporation). Specifically, with respect to the adhesive composition, the adhesive composition is coated on a PET film with a mold release agent, and heated in an oven under a nitrogen atmosphere at 180° C. for 1 hour to form a 50 μm-thick test piece, and then peeled off from the PET film. About (size 5 mm x 40 mm, thickness 50 micrometers), it can measure using the measuring apparatus mentioned above. What is necessary is just to employ|adopt the conditions which heat up from the starting temperature of 50 degreeC to 300 degreeC at the temperature increase rate of 5 degree-C/min in tension conditions with a frequency of 1 Hz as measurement conditions.

<Semiconductor substrate or electronic device>

A semiconductor substrate or an electronic device is temporarily adhered to a support body via an adhesive layer.

≪Semiconductor substrate≫

There is no restriction|limiting in particular as a semiconductor substrate, The thing similar to what was illustrated by said "(adhesive agent composition)" is illustrated. The semiconductor substrate may be a semiconductor element or another element, and may have a structure of a single layer or a plurality of layers.

≪Electronic device≫

There is no restriction|limiting in particular as an electronic device, The thing similar to what was illustrated by the said "(adhesive agent composition)" is illustrated. It is preferable that an electronic device is a composite_body|complex of the member comprised by a metal or a semiconductor, and resin which seals or insulates the said member. Specifically, an electronic device may contain at least one of a sealing material layer and a wiring layer, and also contain a semiconductor substrate.

In the laminated body 200 shown in FIG. 2, the electronic device 456 is comprised by the semiconductor substrate 4, the sealing material layer 5, and the wiring layer 6. In the laminate 300 shown in FIG. 3 , the electronic device 6 is configured by the wiring layer 6 . In the laminated body 400 shown in FIG. 4, the electronic device 645 is comprised by the wiring layer 6, the semiconductor substrate 4, and the sealing material layer 5. As shown in FIG.

[Encapsulant Layer]

A sealing material layer is formed in order to seal a semiconductor substrate, and is formed using a sealing material. As a sealing material, the member which can insulate or seal the member comprised by a metal or a semiconductor is used.

As a sealing material, a resin composition can be used, for example. It is preferable that the sealing material layer 5 is not formed for every individual semiconductor substrate 4, but is formed so that all of the semiconductor substrates 4 on the contact bonding layer 3 may be covered. The resin used for the sealing material is not particularly limited as long as it can seal and/or insulate a metal or a semiconductor, and examples thereof include an epoxy resin or a silicone resin.

The sealing material may contain other components, such as a filler other than resin. As a filler, a spherical silica particle etc. are mentioned, for example.

≪Wiring layer≫

The wiring layer is also called RDL (Redistribution Layer), and is a thin-film wiring body constituting the wiring connected to the substrate, and may have a structure of a single layer or a plurality of layers. The wiring layer includes a conductor (for example, aluminum, copper, titanium, nickel, metals such as gold and silver, silver-tin alloy, etc.) between dielectrics (such as silicon oxide (SiO _x ) and photosensitive resin such as photosensitive epoxy). of the alloy) may be formed by wiring, but is not limited thereto.

In addition, in the laminated body of FIGS. 1-4, although the support body 1 and the adhesive layer 3 adjoin, it is not limited to this, Another layer is further formed between the support body 1 and the adhesive layer 3, there may be In this case, the other layer may be composed of a material that transmits light. According to this, the layer which provides desirable properties, etc. to the laminated bodies 100-400 can be added suitably, without obstructing the incident of light to the contact bonding layer 3 . The wavelength of the light that can be used differs depending on the kind of material constituting the adhesive layer 3 . Therefore, the material constituting the other layer does not need to transmit light of all wavelengths, and can be appropriately selected from materials which transmit light of a wavelength capable of altering the material constituting the adhesive layer 3 .

(Method for producing a laminate (1))

A method for manufacturing a laminate according to a third aspect of the present invention is a method for manufacturing a laminate in which a light transmitting support, an adhesive layer and a semiconductor substrate are laminated in this order, the support or semiconductor substrate according to the first aspect A step of forming an adhesive composition layer by applying an adhesive composition (hereinafter, also referred to as an “adhesive composition layer forming step”), and a step of placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween (hereinafter, It is characterized by having a "semiconductor substrate mounting step") and a step of curing the adhesive composition layer by polymerization of the urethane resin to form the adhesive layer (hereinafter also referred to as "adhesive layer forming step"). .

5-6 are schematic process diagrams explaining one Embodiment of the manufacturing method of the laminated body which concerns on this embodiment.

5A to 5B are views for explaining the manufacturing process of the laminate 100' in which the support 1, the adhesive composition layer 3', and the semiconductor substrate 4 are laminated in this order. It is a figure explaining the adhesive composition layer formation process. It is a figure explaining a semiconductor substrate mounting process.

6 : is a figure explaining a contact bonding layer formation process. The adhesive composition layer 3' in the laminated body 100' is thermosetted, the contact bonding layer 3 is formed, and the laminated body 100 is obtained.

[Adhesive composition layer forming process]

The manufacturing method of the laminated body which concerns on this embodiment includes the adhesive composition layer formation process. An adhesive composition layer forming process is a process of apply|coating an adhesive composition to a support body or a semiconductor substrate, and forming an adhesive composition layer.

In FIG. 5A, the adhesive composition layer 3' is formed on the support body 1 using the adhesive composition.

Although the formation method of the adhesive composition layer 3' with respect to the support body 1 is not specifically limited, For example, methods, such as spin coating, dipping, a roller blade, spray coating, and slit coating, are mentioned.

The adhesive composition layer may be formed in the semiconductor substrate 4 by the same method.

You may perform a baking process after adhesive composition layer formation. Bake temperature conditions are made into temperature lower than the heating temperature in the contact bonding layer formation process mentioned later. Although it can change with the kind of sclerosing|hardenable component which adhesive composition contains as baking conditions, For example, it is 70-100 degreeC temperature conditions, and 1 to 10 minutes etc. are mentioned.

[Semiconductor substrate placement process]

The manufacturing method of the laminated body which concerns on this embodiment includes a semiconductor substrate mounting process. A semiconductor substrate mounting process is a process of mounting a semiconductor substrate on a support body through an adhesive composition layer. Thereby, the laminated body 100' can be obtained.

In FIG.5(c), the semiconductor substrate 4 is mounted on the support body 1 via the adhesive composition layer 3' formed on the support body 1. As shown in FIG.

The method for mounting the semiconductor substrate 4 on the support 1 via the adhesive composition layer 3' is not particularly limited, and a method generally used as a method for arranging the semiconductor substrate at a predetermined position is adopted. can do.

[Adhesive layer forming process]

The manufacturing method of the laminated body which concerns on this embodiment includes a contact bonding layer formation process. A contact bonding layer formation process is a process of hardening the inside of an adhesive composition layer, and forming a contact bonding layer. Thereby, the laminated body 100 can be obtained.

In FIG. 6, the adhesive layer 3 is formed by hardening of the adhesive composition layer 3'.

The curing reaction of the adhesive composition layer can be carried out by selecting an appropriate method according to the type of curing component.

When the curing component is the component of the above (a), the curing reaction can be advanced by heating. Heating temperature can be made more than the temperature at which the crosslinking reaction of (I) component and (O) component starts. For example, when component (I) contains a blocked polyisocyanate, heating temperature can be made into the temperature more than the dissociation temperature of the thermally dissociable blocking agent which blocks the isocyanate group in the said blocked polyisocyanate. The heating temperature may change depending on the type of the thermally dissociable blocking agent, and examples thereof include 80°C or higher, 100°C or higher, 130°C or higher, or 150°C or higher. Although the upper limit of heating temperature is not specifically limited, From a viewpoint of energy consumption, 350 degrees C or less, 300 degrees C or less, 250 degrees C or less, etc. are mentioned, for example. As a range of heating temperature, 80-350 degreeC, 100-300 degreeC, 130-300 degreeC, or 150-300 degreeC etc. are mentioned, for example.

Heating time will not be specifically limited if it is sufficient time for thermosetting of (I)component and (O)component. The heating time can be, for example, 15 minutes or more, 30 minutes or more, or 45 minutes or more. The upper limit of the heating time is not particularly limited, but can be, for example, 120 minutes or less, 100 minutes or less, 80 minutes or less, or 60 minutes or less from the viewpoint of working efficiency. As a range of heating time, 15-120 minutes, 30-120 minutes, or 45-120 minutes etc. are mentioned, for example.

When the curing component is the component of (b), and the component (P1) contains a methacryloyl group or an acryloyl group, the curing reaction can be advanced by heating. As heating temperature, 80-350 degreeC, 100-300 degreeC, 130-300 degreeC, or 150-300 degreeC etc. are mentioned, for example. The heating time is not particularly limited as long as it is sufficient time for the component (P1) to polymerize and harden. As heating time, 30-180 minutes are preferable, for example, 45-120 minutes are more preferable, 60-120 minutes are still more preferable. The curing reaction can be carried out, for example, in a nitrogen atmosphere.

By this step, component (I) and component (O) or component (P1) in the adhesive composition layer 3' is crosslinked and cured, and the adhesive layer 3, which is a cured product of the adhesive composition layer 3', is formed. do. Thereby, the support body 1 and the semiconductor substrate 4 are temporarily adhered. As a result, the laminate 100 can be obtained.

In addition, when the curing component is the component of (b) above, and the component (B1) includes the component (B1) as the component (B), the component (P1) and the component (B1) in the adhesive composition layer (3') are crosslinked and cured, The adhesive layer 3 which is a hardening body of the adhesive composition layer 3' is formed. Thereby, the support body 1 and the semiconductor substrate 4 are temporarily adhered. As a result, the laminate 100 can be obtained.

[Random process]

The manufacturing method of the laminated body which concerns on this embodiment may include other processes in addition to the said process. Other processes include, for example, various mechanical or chemical treatments (thinning treatment such as grinding or chemical mechanical polishing (CMP), etc., and treatment under high temperature and vacuum such as chemical vapor deposition (CVD) or physical vapor deposition (PVD)). , organic solvent, treatment using chemicals such as acidic treatment liquid or basic treatment liquid, plating treatment, irradiation with actinic light, heating/cooling treatment, and the like).

(Method for manufacturing laminate (2))

In the manufacturing method of the laminated body which concerns on the 4th aspect of this invention, after obtaining a laminated body by the manufacturing method of the laminated body which concerns on the said 3rd aspect, the member comprised by a metal or a semiconductor, and the said member are sealed or insulated. It is characterized in that it further has an electronic device forming step of forming an electronic device, which is a composite of the resin to be used.

The laminate obtained by the manufacturing method of the laminated body of this embodiment is a laminated body in which the support body, the contact bonding layer, and the electronic device were laminated|stacked in this order. The said laminated body can be obtained by implementing an electronic device formation process with respect to the laminated body obtained by the manufacturing method of the laminated body which concerns on the said 3rd aspect.

[Electronic Device Formation Process]

The manufacturing method of the laminated body which concerns on this embodiment includes an electronic device formation process. An electronic device formation process is a process of forming the electronic device which is a composite_body|complex of the member comprised with a metal or a semiconductor, and resin which seals or insulates the said member.

The electronic device forming process may include any of a sealing process, a grinding process, and a wiring layer forming process. In one embodiment, the electronic device forming process includes a substrate fixing process and an encapsulating process. In this case, the electronic device forming step may further include a grinding step and a wiring layer forming step.

・About the sealing process

A sealing process is a process of sealing the board|substrate fixed on the support body using a sealing material.

In FIG. 7A, the laminated body 110 in which the whole semiconductor substrate 4 temporarily adhered to the support body 1 via the adhesive layer 3 was sealed by the sealing material layer 5 is obtained.

In the sealing process, for example, the sealing material heated to 130-170 degreeC is supplied on the adhesive layer 3 so that it may cover the semiconductor substrate 4 while maintaining a high-viscosity state, By compression-molding, the adhesive layer 3 ) The laminated body 110 in which the sealing material layer 5 was formed is produced.

In that case, temperature conditions are 130-170 degreeC, for example.

The pressure applied to the semiconductor substrate 4 is, for example, 50 to 500 N/cm 2 .

It is preferable that the sealing material layer 5 is not formed for every individual semiconductor substrate 4, but is formed so that all of the semiconductor substrates 4 on the contact bonding layer 3 may be covered.

・About the grinding process

A grinding process is a process of grinding the sealing material part (sealing material layer 5) in a sealing body after the said sealing process so that a part of a semiconductor substrate may be exposed.

Grinding of a sealing material part is performed by shaving the sealing material layer 5 until it becomes the thickness substantially equivalent to the semiconductor substrate 4, as shown to FIG. 7B, for example.

・About the wiring layer forming process

The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor substrate after the grinding step.

In FIG. 7C , the wiring layer 6 is formed on the semiconductor substrate 4 and the sealing material layer 5 . Thereby, the laminated body 120 can be obtained. In the laminated body 120 , the semiconductor substrate 4 , the sealing material layer 5 , and the wiring layer 6 constitute the electronic device 456 .

As a method of forming the wiring layer 6, the following method is mentioned, for example.

First, a dielectric layer such as silicon oxide (SiO _x ) or a photosensitive resin is formed on the encapsulant layer 5 . The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like. The dielectric layer made of the photosensitive resin can be formed by, for example, coating the photosensitive resin on the sealing material layer 5 by a method such as spin coating, dipping, roller blade, spray coating, or slit coating.

Then, wiring is formed in the dielectric layer with a conductor such as a metal. As a method of forming the wiring, for example, a lithography process such as photolithography (resist lithography) or a known semiconductor process method such as an etching process can be used. As such a lithographic process, a lithographic process using a positive resist material and a lithographic process using a negative resist material are mentioned, for example.

In the manufacturing method of the laminated body which concerns on this embodiment, formation of bumps on the wiring layer 6 or mounting of an element can be performed further. The element mounting on the wiring layer 6 can be implemented using a chip mounter etc., for example.

(Method for producing laminate (3))

A method for manufacturing a laminate according to a fifth aspect of the present invention is a method for manufacturing a laminate in which a support, an adhesive layer and an electronic device are laminated in this order, wherein the adhesive composition according to the first aspect is applied on the support, A step of forming a layer of the adhesive composition (adhesive composition layer forming step), a member composed of a metal or semiconductor, and an electronic device that is a composite of a resin sealing or insulating the member is formed on the adhesive composition layer It is characterized by having an electronic device forming step (electronic device forming step) to be performed, and a step of curing the adhesive composition layer to form an adhesive layer (adhesive layer forming step).

The laminate obtained by the manufacturing method of the laminated body of this embodiment is a laminated body in which the support body, the adhesive layer, and the electronic device were laminated|stacked in this order similarly to the manufacturing method which concerns on the said 4th aspect.

In the manufacturing method of this embodiment, the adhesive composition layer formation process can be implemented similarly to the thing in the manufacturing method of the laminated body which concerns on the said 3rd aspect.

In the manufacturing method of this embodiment, an electronic device formation process is implemented after an adhesive agent composition layer formation process. Such an electronic device forming process may include a wiring layer forming process. The electronic device formation step may further include a semiconductor substrate mounting step, a sealing step, a grinding step, and the like. Moreover, the process of mounting the sealing body by which the semiconductor substrate sealed with the sealing material on the support body through the adhesive composition layer may be sufficient as an electronic device formation process.

The adhesive layer formation process can be performed similarly to the thing in the manufacturing method of the laminated body which concerns on the said 3rd aspect.

After a contact bonding layer formation process, you may implement an electronic device formation process further as needed. The electronic device forming process may include, for example, a semiconductor substrate mounting process, an encapsulation process, and a grinding process.

According to the method for manufacturing a laminate according to the third to fifth aspects, the support and the semiconductor substrate or electronic device are temporarily bonded via an adhesive layer having high heat resistance. It is possible to stably manufacture a laminate formed by laminating with Such a laminate is a laminate manufactured in a process based on a fan-out type technology, in which terminals formed on a semiconductor substrate are mounted on a wiring layer extending out of a chip area.

(Manufacturing method of electronic components)

In the manufacturing method of the electronic component which concerns on the 6th aspect of this invention, after obtaining a laminated body by the manufacturing method of the laminated body which concerns on any one of the said 3rd - 5th aspect, light is irradiated to the said adhesive layer through the said support body. Thus, a step of separating the electronic device and the support by altering the adhesive layer (hereinafter also referred to as a “separation step”), and a step of removing the adhesive layer by decomposing the urethane bond in the adhesive layer with an acid or alkali (hereinafter also referred to as “adhesive layer removal step”) is characterized.

8 is a schematic process diagram illustrating an embodiment of a method for manufacturing a semiconductor package (electronic component). 8A is a diagram illustrating the laminate 120, FIG. 8B is a diagram illustrating a separation step, and FIG. 8C is a diagram illustrating an adhesive removal step.

[Separation process]

A separation process is a process of isolate|separating the electronic device 456 and the support body 1 by irradiating light (arrow) to the adhesive layer 3 through the support body 1, and changing the adhesive layer 3 in quality.

As shown to FIG. 8A, in a separation process, the adhesive layer 3 is changed in quality by irradiating light (arrow) to the adhesive layer 3 through the support body 1 which transmits light.

What is necessary is just to select the wavelength of the light used in a separation process according to the wavelength of the light which (B) component which the contact bonding layer 3 contains absorbs. For example, light in a wavelength range of 300 to 800 nm can be used.

The type of light to be irradiated may be appropriately selected according to the transmittance of the support 1, for example, a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser, a dye laser, etc. A liquid laser, a CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as a He-Ne laser, laser light such as a semiconductor laser, a free electron laser, or a non-laser light can be used. Thereby, the adhesive layer 3 can be changed in quality, and the support body 1 and the electronic device 456 can be made into the easily separable state.

When irradiating a laser beam, the following conditions are mentioned as an example of laser beam irradiation conditions.

1.0 W or more and 5.0 W or less are preferable, and, as for the average output value of a laser beam, 3.0 W or more and 4.0 W or less are more preferable. 20 kHz or more and 60 kHz or less are preferable, and, as for the repetition frequency of a laser beam, 30 kHz or more and 50 kHz or less are more preferable. As for the scanning speed of a laser beam, 100 mm/s or more and 10000 mm/s or less are preferable.

After the adhesive layer 3 is irradiated with light (arrow) to alter the adhesive layer 3 , as shown in FIG. 8B , the support 1 is separated from the electronic device 456 .

For example, by applying a force in a direction in which the support body 1 and the electronic device 456 move away from each other, the support body 1 and the electronic device 456 are separated. Specifically, in a state in which one of the support body 1 or the electronic device 456 side (wiring layer 6) is fixed to the stage, the other is held while adsorbed and held by a separation plate provided with a suction pad such as a bellows pad. By lifting, the support 1 and the electronic device 456 can be separated.

The force applied to the layered product 200 may be appropriately adjusted depending on the size of the layered product 200 and the like, and is not limited. For example, if it is a layered product having a diameter of about 300 mm, 0.1 to 5 kgf (0.98 to By applying a force of about 49 N), the support 1 and the electronic device 456 can be preferably separated.

[Adhesive layer removal process]

The manufacturing method of the electronic component which concerns on this embodiment has a contact bonding layer removal process. The adhesive layer removal step is a step of decomposing the urethane bond in the adhesive layer with an acid or alkali, and removing the adhesive layer.

In FIG. 8B , the adhesive layer 3 is attached to the electronic device 456 after the separation step. At this process, the contact bonding layer 3 is removed by decomposing|disassembling the contact bonding layer 3 using an acid or an alkali, and the electronic component 50 is obtained.

In this step, the urethane bond in the adhesive layer 3 is decomposed with acid or alkali. The adhesive layer (3) contains a urethane resin formed by copolymerization of the component (I) and the component (O), or a crosslinked urethane resin formed by polymerization of the component (P1). When these urethane resins are treated with an acid or an alkali, the urethane bond is cut and decomposed. Thereby, the adhesive layer 3 can be decomposed|disassembled, and the residue of the adhesive layer 3 adhering to the electronic device 456 can be removed.

The acid or alkali used in this process will not be specifically limited if a urethane bond can be decomposed|disassembled. Examples of the acid capable of decomposing the urethane bond include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid and the like. Moreover, as an alkali which can decompose|disassemble a urethane bond, Inorganic bases, such as potassium hydroxide and sodium hydroxide; and organic amines such as tetramethylammonium hydroxide and monoethanolamine, but is not limited thereto.

The acid or alkali can be dissolved in a solvent and used as a treatment liquid for removing the adhesive layer. The solvent is preferably a polar solvent, for example, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), diethylene glycol monobutyl ether, diethylene glycol, ethylene glycol, propylene glycol, etc. can be heard

The processing liquid for adhesive removal may contain well-known additives, such as surfactant, in addition to the said component.

Although it does not specifically limit as content of the acid or alkali in the said process liquid, For example, 1-50 mass % is mentioned. Moreover, as content of the polar solvent in the said process liquid, 50-99 mass % is mentioned.

As the treatment liquid for removing the adhesive layer, a commercially available alkaline treatment liquid or acidic treatment liquid may be used. As a commercially available processing liquid, ST-120, ST-121 (all are the Tokyooka Industrial Co., Ltd. make) etc. are mentioned, for example.

By bringing the above treatment liquid containing an acid or alkali into contact with the adhesive layer 3 , the urethane bond in the adhesive layer 3 is decomposed and the adhesive layer 3 can be removed.

The manufacturing method of the electronic component of this embodiment may perform processing, such as solder ball formation, dicing, or oxide film formation, with respect to the electronic component 50 further after the said contact bonding layer removal process.

According to the manufacturing method of the electronic component which concerns on this embodiment, (a) a light absorber, a polyisocyanate, and a polyol, or (b) a light absorber, the urethane resin containing a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator contain A semiconductor substrate and the like are temporarily bonded to a support by curing the adhesive composition using an adhesive composition. Therefore, it is possible to form an adhesive layer with high heat resistance that can withstand high-temperature treatment in an electronic device forming process or the like.

Moreover, since the said adhesive composition contains a light absorber, by irradiating light, an adhesive layer changes quality, and adhesive force falls. Therefore, even without a separation layer, the temporarily bonded semiconductor substrate and the like can be easily separated from the support.

In addition, the residue of the adhesive layer attached to the semiconductor substrate or the like separated from the support can be easily removed by decomposing the urethane bond in the adhesive layer with an acid or alkali.

Example

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Synthesis example of urethane resin (component (P1))>

In a flask equipped with a stirrer, dropping funnel, cooling tube and thermometer, propylene glycol monomethyl ether acetate (PGMEA), castor oil-modified diol 36 parts, polycarbonate diol (Mw 1,000) 17 parts, pentaerythritol diacrylate 18 parts , neopentyl glycol 1 part, and an inhibitor were added, and uniformly mixed under a nitrogen stream. Next, 7 parts of diphenylmethane diisocyanate (MDI) and 21 parts of hydrogenated xylylene diisocyanate (H6XDI) were poured into the dropping funnel, and it was dripped at constant velocity over 30 minutes. Aging was performed for 30 minutes after completion|finish of dripping. Then, the bismuth catalyst was added, the temperature was raised to 65°C, and aging was performed for 4 to 5 hours. Next, 2HEA (2-hydroxyethyl acrylate) was added, aging was performed for 1 hour, and reaction was complete|finished when the isocyanate group (NCO) lose|disappeared. The weight average molecular weight (Mw) of the obtained urethane resin (P1)-1 was 20,000. The C=C equivalent of the urethane resin (P1)-1 (molecular weight of the urethane resin per equivalent of the polymerizable carbon-carbon double bond) was 600 g/eq. It was.

The polycarbonate diol (Mw 1,000) used in the synthesis of the urethane resin (P1)-1 is a polycarbonate diol represented by the following formula (PC-1-1) (R=-(CH ₂ ) ₆ -, -( CH ₂ ) ₅ -).

[Formula 19]

<Preparation of adhesive composition (1)>

(Examples 1 to 6, Comparative Example 1)

The components shown in Table 1 were mixed, and the adhesive composition of each example was prepared, respectively. More specifically, it prepared as follows. First, (P1) component, (A) component, (Ad) component, and (S) component were mixed by the compounding quantity described in Table 1. Then, (B) component was added so that it might become the ratio shown in Table 1, and it mixed so that the whole composition might become uniform.

In Table 1, each symbol has the following meaning, respectively. Numerical values in [ ] are compounding amounts (parts by mass). In addition, the numerical value of wt% in ( ) is the ratio (mass %) of the pigment solid content with respect to the gross mass (100 mass %) of an adhesive composition.

(P1)-1: The urethane resin synthesized in the above synthesis example (P1)-1.

(A)-1: Peroxide (Percumyl (registered trademark) D, Nippon Yushi Co., Ltd.).

(Ad)-1: polyester-modified polydimethylsiloxane (BYK-310 (trade name), Big Chemis Co.).

(S)-1: PGMEA (propylene glycol monomethyl ether acetate).

(B)-1: carbon black (acrylic resin dispersion volume average particle diameter 150 nm or less).

(B)-2: perylene-based black pigment (volume average particle diameter 150 nm).

<Evaluation>

≪Measurement of light transmittance≫

The adhesive composition of each example was respectively apply|coated on the bare glass support body by the spin coater method. It was cured by heating at 180°C for 1 hour in an oven under a nitrogen atmosphere to form adhesive layers each having the film thicknesses shown in Table 2. About the said contact bonding layer, the transmittance|permeability of the light of wavelength 532nm was evaluated by irradiating the light of wavelength 380-780nm using spectroscopic-analysis measuring apparatus UV-3600 (made by Shimadzu Corporation). The results are shown in Table 2.

From the result shown in Table 2, the light transmittance of the contact bonding layer formed using the adhesive composition of Examples 1-6 fell large, and it was confirmed that it is absorbing the light of wavelength 532nm.

≪Evaluation of cleanliness≫

The adhesive composition of Example 6 was apply|coated by the spin coater method on the glass support body (size diameter 30 cm, thickness 700 micrometers). It was cured by heating at 180°C for 1 hour in an oven under a nitrogen atmosphere to form an adhesive layer (film thickness: 18 µm). The support of this adhesive layer forming agent was mixed at 50°C with a treatment solution (tetramethylammonium hydroxide (TMAH), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and propylene glycol (PG)) It was treated with a solvent (NMP:DMS:PG=10:78:12 (mass ratio)) and diluted to a concentration of 2% by mass), and the time for complete dissolution was measured. The dissolution rate of the adhesive layer was calculated from the dissolution time with respect to the film thickness. If the dissolution rate is 50 nm/sec or more, it is judged that the cleaning property is good.

The dissolution rate of the adhesive layer was 70 nm/sec. Therefore, it was confirmed that the washability of the adhesive layer formed using the adhesive composition of Example 6 was favorable.

<Preparation of adhesive composition (2)>

(Examples 7 to 9, Comparative Example 2)

The components shown in Table 3 were mixed, and the adhesive composition of each example was prepared, respectively.

In Table 3, each abbreviation has the following meaning, respectively. Numerical values in [ ] are compounding amounts (parts by mass).

(P1)-1: The urethane resin synthesized in the above synthesis example (P1)-1.

(A)-1: Peroxide (Percumyl (registered trademark) D, Nippon Yushi Co., Ltd.).

(Ad)-1: polyester-modified polydimethylsiloxane (BYK-310 (trade name), Big Chemis Co.).

(S)-1: PGMEA (propylene glycol monomethyl ether acetate).

(B1)-1: the following compound (B1-1).

[Formula 20]

<Evaluation>

≪Measurement of light transmittance≫

The adhesive composition of each example was respectively apply|coated on the bare glass support body by the spin coater method. It was cured by heating at 180°C for 1 hour in an oven under a nitrogen atmosphere to form adhesive layers each having the film thicknesses shown in Table 2. This adhesive layer was irradiated with light having a wavelength of 300 to 800 nm using a spectroscopic analyzer UV-3600 (manufactured by Shimadzu Corporation), and the transmittance of the light at a wavelength of 355 nm was measured. The results are shown in Table 4 below.

From the result shown in Table 4, the adhesive layer formed using the adhesive composition of Examples 7-9 became a low level of the light transmittance of a measurement wavelength, and it was confirmed that it is absorbing the light of this wavelength range.

«Evaluation of laser reactivity»

An adhesive layer was formed from the adhesive composition of Example 9 and Comparative Example 2 under the same conditions as <<Measurement of light transmittance>> described above. The adhesive layer was irradiated with a 355 nm laser beam using Talon (registered trademark) 355-12 manufactured by Spectra Physics. The adhesive layer was observed and the dent was confirmed. The result is shown in Table 5 together with the transmittance|permeability in 355 nm.

From the result shown in Table 5, it was confirmed that the adhesive layer formed using the adhesive composition of Example 9 has a laser reactivity of 355 nm. On the other hand, in the adhesive layer formed using the adhesive composition of Comparative Example 2, laser reactivity was not confirmed.

1: support
3: adhesive layer
3': adhesive composition layer
4: semiconductor substrate
5: encapsulant layer
6: wiring layer
20: laminate
50: electronic components
100: laminate
100': laminate
110: laminate
120: laminate
200: laminate
300: laminate
400: laminate
456: electronic device
645: electronic device

Claims (10)

An adhesive composition used to form an adhesive layer for temporarily bonding a semiconductor substrate or electronic device and a support that transmits light,
(a) light absorbers, polyisocyanates, and polyols, or
(b) an adhesive composition comprising a light absorber, a urethane resin comprising a polymerizable carbon-carbon unsaturated bond, and a polymerization initiator. The method of claim 1,
The adhesive composition contains the component of (b),
Compound (B1) wherein the light absorber absorbs at least a part of light within a wavelength range of 300 to 800 nm, and contains a polymerizable carbon-carbon unsaturated bond (however, except for those corresponding to the urethane resin). Containing, the adhesive composition. 3. The method of claim 2,
The said compound (B1) is an adhesive composition represented by the following general formula (b1).

[wherein W is a monovalent group containing a polymerizable carbon-carbon unsaturated bond; Y is a single bond or a divalent linking group selected from the group consisting of -O-, -CO-, -COO-, and -CONH-; n is an integer of 1-6; X is an n-valent atomic group having aromatic condensed ring skeleton, benzophenone skeleton, dibenzoylmethane skeleton, dibenzoylbenzene skeleton, or benzotriazole skeleton in the structure. When n is 2 or more, a plurality of W and Y may be the same or different from each other.] 4. The method according to any one of claims 1 to 3,
The adhesive composition contains the component of (b),
The urethane resin is a reaction product of a polyol and a polyisocyanate,
At least one of the said polyol and the said polyisocyanate contains the said polymerizable carbon-carbon unsaturated bond, The adhesive composition. 5. The method according to any one of claims 1 to 4,
The adhesive composition contains the component of (b),
An adhesive composition comprising a thermal polymerization initiator as the polymerization initiator. 6. The method according to any one of claims 1 to 5,
The electronic device, wherein a composite of a member made of a metal or a semiconductor and a resin for sealing or insulating the member is laminated on the support with the adhesive layer interposed therebetween. A laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate or electronic device are laminated in this order,
The said adhesive layer is a hardening body of the adhesive composition in any one of Claims 1-6, The laminated body. A method for producing a laminate in which a light-transmitting support, an adhesive layer, and a semiconductor substrate are laminated in this order,
A step of applying the adhesive composition according to any one of claims 1 to 6 to the support or semiconductor substrate to form an adhesive composition layer;
a step of placing the semiconductor substrate on the support with the adhesive composition layer interposed therebetween;
The manufacturing method of the laminated body which has the process of hardening the said adhesive composition layer and forming the said adhesive layer. After obtaining a laminate by the method for manufacturing a laminate according to claim 8, further comprising a step of forming an electronic device, which is a composite of a member made of a metal or semiconductor, and a resin that seals or insulates the member ,
A method for producing a laminate in which a light-transmitting support, an adhesive layer, and an electronic device are laminated in this order. After obtaining a laminated body by the manufacturing method of the laminated body of Claim 8,
separating the electronic device from the support by irradiating light to the adhesive layer through the support to modify the adhesive layer;
and decomposing the urethane bond in the adhesive layer with an acid or alkali to remove the adhesive layer adhering to the electronic device.

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