JP5588646B2 - Thermosetting resin composition and dry film - Google Patents

Description

  The present invention relates to a thermosetting resin composition and a dry film.

  In recent years, with the increase in density and speed of semiconductor package substrates, the clearance of flip chip bumps connecting semiconductor chips and circuit boards has been narrowed. As described above, when the clearance becomes narrower, there is a problem in that the semiconductor package substrate has problems such as warpage and disconnection due to cracks due to the stress caused by the difference in the expansion amount due to the temperature change between different materials. For this reason, the insulating layer of a circuit board formed of a thermosetting resin has a linear expansion coefficient (thermal expansion coefficient) of other materials used for the circuit board (17 ppm / ° C. based on copper foil). It is required to reduce to a value close to. Further, regarding the linear expansion coefficient, it is required to reduce the linear expansion coefficient in a wide temperature range from the glass transition temperature to the normal temperature by expanding the application of the semiconductor package substrate and improving the performance. However, a cured product of a conventional thermosetting resin has a high linear expansion coefficient of about 45 to 65 ppm / ° C. in a region close to the glass transition temperature, and tends to increase the linear expansion coefficient.

  Also, with the miniaturization and multilayering of semiconductor package substrates, the semi-additive method has become the mainstream for circuit formation, and the formation of conductor layers by plating has become essential, improving the adhesion strength of conductor plating layers. Is required.

  Furthermore, the insulating layer of the circuit board is required to have mechanical strength (extensibility) in order to alleviate problems caused by the difference in expansion amount that occurs.

  On the other hand, the dry film used to form the insulating layer of the circuit board prevents damage caused by various mechanical and thermal shocks to the semiconductor package substrate during manufacturing. desired.

  Patent Document 1 discloses a method of reducing the linear expansion coefficient without using a large amount of inorganic filler by using a layered silicate compound having an exchangeable metal cation between crystals. However, this method has a problem that the elongation percentage is lowered and the adhesion strength of the conductor plating layer is greatly lowered.

  Patent Document 2 discloses a method of lowering the linear expansion coefficient by filling a thermosetting resin composition with spherical silica. However, since this method contains a large amount of spherical silica, the dry film composition before curing becomes brittle and there is a risk that the handling property may be reduced.

WO2005-056632 gazette JP 2001-49220 A

  The present invention can improve the handling property and adhesion (laminate property) of the dry film, and can reduce the linear expansion coefficient of a cured product (insulating layer) produced using this dry film. It aims at providing the thermosetting resin composition which was excellent also in adhesiveness and conductor plating adhesiveness (conductor plating peel strength).

  As a result of intensive studies in order to solve the above problems, the present inventors have made the thermosetting resin composition contain a layered silicate compound having an exchangeable metal cation between crystals according to Patent Document 1, Compared to silica, the effect of reducing the coefficient of linear expansion is large, but it does not lead to an improvement in the mechanical strength (elongation rate) of the coating film and the adhesion strength of the conductor plating layer, whereas by using talc in the layered silicate compound, It has been found that the adhesion strength of the conductor plating layer can be improved without reducing the linear expansion coefficient and without impairing the extensibility of the thermosetting resin itself.

  Further, in order to lower the linear expansion coefficient by filling the thermosetting resin composition with spherical silica according to Patent Document 2, it is necessary to fill the spherical silica in a large amount. As a result, the dry film-like composition before curing became brittle and the handling property was lowered. On the other hand, it was found that the handling property was improved by using silica and talc in combination, and the present invention was completed.

  That is, the present invention has the following configuration.

(1) A thermosetting resin composition comprising a thermosetting resin, a phenolic curing agent, amorphous silica and talc.

(2) The thermosetting resin composition according to (1), wherein the total amount of the amorphous silica and talc is 35 to 70% by mass in the nonvolatile content of the composition.

(3) The thermosetting resin composition according to (1), wherein the phenolic curing agent has a softening temperature of 120 ° C. or higher.

(4) The thermosetting resin composition according to (1), wherein the amount of talc in the total amount of the amorphous silica and talc is 5 to 90% by mass.

(5) A dry film produced using the thermosetting resin composition according to any one of (1) to (4).

(6) The dry film according to (5), wherein the linear expansion coefficient of the cured product at a curing temperature of 25 to 150 ° C is 17 to 30 ppm / ° C.

  In the thermosetting resin composition of the present invention, by using amorphous silica and talc in combination with the thermosetting resin, it is possible to improve dry film handling and adhesion (laminate), The linear expansion coefficient of the cured product (insulating layer) of the curable resin composition can be reduced, and the elongation rate, adhesion, and conductor plating adhesion (conductor plating peel strength) can be excellent.

  Hereinafter, embodiments of the present invention will be described in detail.

  The resin composition of the present invention contains a thermosetting resin, a phenol-based curing agent, amorphous silica, and talc.

(Thermosetting resin)
The thermosetting resin is not particularly limited as long as it causes a curing reaction with the thermosetting resin itself and the thermosetting resin and its curing agent by heating, but among them, a linear thermosetting resin is preferable. More preferably, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound is used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, phenol aralkyl type epoxy resin, naphthalene type epoxy resin, and heterocyclic ring Containing epoxy resin. In addition, it is also possible to use those having improved transparency and reduced viscosity by hydrogenating all or part of the aromatic rings in these skeletons. An episulfide resin in which the oxygen atom of the epoxy group is replaced with a sulfur atom can also be used.

  In the present invention, it is particularly preferable to use an epoxy resin having a bisphenol S type epoxy resin or a naphthalene skeleton, from the viewpoint of reducing the linear expansion coefficient among these.

  In the present invention, one type of thermosetting resin may be used, or a plurality of types of thermosetting resins may be used.

  Examples of commercially available polyfunctional epoxy compounds include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto YD- manufactured by Tohto Kasei Co., Ltd. 011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664, etc. (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical Company D. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide ECN1273, manufactured by Ciba Specialty Chemicals ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., YDF- 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all trade names); water such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Toto Kasei Bisphenol A type epoxy resin; jER604 manufactured by Japan Epoxy Resin Co., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-epoxy ELM-100 manufactured by Sumitomo Chemical Co., Ltd. All are trade names) Sidylamine type epoxy resin; Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Araldide CY175, CY179 manufactured by Ciba Specialty Chemicals (All trade names) alicyclic epoxy resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YX-4000 and YL-6121 manufactured by Japan Epoxy Resin Co., Ltd. Bixylenol type or biphenol type epoxy resins such as trade name) or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1517 manufactured by DIC, etc. Bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Product name) tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by KK; ESN-175, ESN-355, ESN-375 manufactured by Tohto Kasei Co., Ltd., HP-4032, HP-5000, EXA-4710, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resins such as EXA-7311 EXA-9900; Epoxy resins having an anthracene skeleton such as YX-8800 manufactured by Japan Epoxy Resin; Epoxy having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Resin; Japanese fat CP-50S, CP-50M, and other glycidyl methacrylate copolymer epoxy resins; a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries); Examples thereof include, but are not limited to, CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Tohto Kasei Co., Ltd.). These epoxy resins can be used alone or in combination of two or more. In addition, an episulfide resin in which the oxygen atom of the epoxy group of the epoxy resin is replaced with a sulfur atom can be used.

(Curing agent)
The curing agent for the thermosetting resin used in the thermosetting resin composition of the present invention is a phenolic curing agent. In particular, by using a phenolic curing agent containing a phenolic hydroxyl group as an epoxy resin curing agent, the linear expansion coefficient is reduced, and handling properties and laminating properties are excellent.

  Examples of the phenolic curing agent include phenol, 0-cresol, p-cresol, bisphenol A, bisphenol F, bisphenol S, bisphenol, naphthalenediol and the like. Further, phenol novolak resins, o-cresol novolak resins, m-cresol novolak resins, and naphthalene skeleton-containing phenol resins, which are polycondensates of these phenols and aldehydes, may be mentioned. Moreover, the triazine ring containing novolak resin which is a polycondensate of these phenols, aldehydes, and the compound which has a triazine ring is mentioned.

  In the present invention, a phenolic curing agent having a softening point temperature of 120 ° C. or higher is preferably used. The ring and ball method is generally used for the softening point temperature measurement. When it has the said value, reduction of the linear expansion coefficient in a wide temperature range can be aimed at by raising the glass transition temperature of hardened | cured material. Examples of such commercially available phenolic curing agents include cresol novolak resins such as GPX-41 manufactured by Gifu Seratech Co., Ltd., trisphenol methane type phenol resins such as MEH-7500H manufactured by Meiwa Kasei Co., Ltd., and products manufactured by Meiwa Kasei Co., Ltd. And biphenyl aralkyl type phenol resins such as MEH-7851-4H.

  When the phenolic curing agent is used in combination with an epoxy resin, the blending ratio is preferably 3: 1 to 0.75: 1 in terms of the number of moles of epoxy groups and the number of moles of phenolic hydroxyl groups, respectively. 5: 1 to 1: 1 are more preferable, and 2.3: 1 to 1.1: 1 are particularly preferable. When the blending ratio is out of the range of 3: 1 to 0.75: 1, there is a concern that the laminating property is lowered and the insulation reliability is lowered.

  The thermosetting resin composition of this invention can contain the hardening | curing agent of other thermosetting resins as needed with a phenol type hardening | curing agent. This thermosetting resin curing agent is not particularly limited, and examples thereof include amines, acid anhydrides, carboxyl group-containing compounds, and hydroxyl group-containing compounds.

(Curing accelerator)
The thermosetting resin composition of this invention can contain a hardening accelerator as needed. Examples of such effect promoters include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.

  Examples of commercially available effect promoters include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U- CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. It is not particularly limited to these, and any thermosetting resin or any one that promotes the reaction between the thermosetting resin and its curing agent may be used alone or in admixture of two or more. Absent. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used.

(Amorphous silica)
Amorphous silica used in the thermosetting resin composition of the present invention is amorphous silicon dioxide and can be distinguished by an X-ray diffractometer. The amorphous silica produced as described above is fine particles having an average particle size of about 0.1 to 10 μm. The amorphous silica is not particularly limited, and examples thereof include spherical silica, spherical porous silica, plate silica, layered silica, mesoporous silica, and hollow silica. Among these, spherical silica is preferably used because it has good dispersibility in the resin and imparts toughness of the resin. In the present invention, those having a sphericity of 0.8 or more are defined as spherical silica.

  The sphericity is measured as follows. A photograph is taken with an SEM, and is calculated as a value calculated by (sphericity) = {4π × (area) ÷ (perimeter) 2} from the area and perimeter of the observed particle. Specifically, an average value measured for 100 particles using an image processing apparatus is employed.

  The method for producing the amorphous spherical silica particles is not particularly limited, and methods known to those skilled in the art can be applied. For example, it can be manufactured by burning silicon powder by the VMC (Vap-erized Metal Combustion) method. In the VMC method, a chemical flame is formed by a burner in an oxygen-containing atmosphere, and metal powder that constitutes part of the target oxide particles is introduced into the chemical flame in such an amount that a dust cloud is formed. In this method, deflagration is caused to obtain oxide particles.

These amorphous silicas can be used alone or in combination of two or more.
Note that crystalline silica is not desirable because of concern about the influence on the human body.

(talc)
Talc used in the thermosetting resin composition of the present invention refers to fine particles obtained by pulverizing talc and means hydrous magnesium silicate (chemical formula: 3MgO.4SiO ₂ .H ₂ O). Talc is a kind of layered silicate, and since it does not contain exchangeable metal ions between crystals, it is characterized by being chemically stable.

  The talc is not particularly limited, but is preferably pulverized and classified to an average particle size of 2 μm or less, more preferably a maximum particle size of 10 μm or less.

  It is also possible to improve the dispersibility of the amorphous silica and talc in the components in the composition such as a thermosetting resin by performing a surface treatment. Silane compounds, titanate compounds and the like are known as compounds used for the surface treatment, and may be subjected to surface treatment in advance before blending, or may be added during blending of the composition.

(Blend ratio of amorphous silica and talc)
The non-crystalline silica and talc are preferably blended so that the total amount (total mass) of the non-crystalline silica and talc is 35 to 70% by mass in the nonvolatile components of the thermosetting resin composition. If it is less than 35% by mass, the effect of reducing the linear expansion coefficient of the cured product (insulating layer) of the thermosetting resin composition is poor. If it exceeds 70% by mass, the elongation percentage of the cured product (insulating layer) of the thermosetting resin composition is lowered and crack resistance is lowered. A more preferable blending amount is 55 to 70% by mass.

  The non-crystalline silica and talc are preferably blended in such a manner that the mass of talc is 5 to 90% by mass with respect to the total amount (total mass) of non-crystalline silica and talc. If it is less than 5% by mass, the effect of improving the handleability of the dry film is poor. If it exceeds 90% by mass, the effect of reducing the coefficient of linear expansion of the cured product (insulating layer) is saturated, but the adverse effect of decreasing the elongation rate of the cured product Becomes larger, and the balance of both characteristics deteriorates. A more preferable blending ratio is 10 to 70% by mass, and further preferably 15 to 60% by mass.

(Other ingredients)
In addition to the thermosetting resin, phenolic curing agent, amorphous silica and talc, which are essential components, the thermosetting resin composition of the present invention includes, for example, the thermosetting resin and You may contain resin polymerizable with the said phenol type hardening | curing agent. The polymerizable resin is not particularly limited. For example, cyanate ester resin, phenoxy resin, benzoxazine resin, modified polyphenylene ether resin, thermosetting modified amide imide resin, epoxidized polybutadiene rubber, rubber modified epoxy resin. Etc. These polymerizable resins can be blended alone or in combination of two or more.

  In addition to the thermosetting resin, phenolic curing agent, amorphous silica and talc, which are essential components, the thermosetting resin composition of the present invention includes an organic solvent for the purpose of adjusting viscosity and imparting coating properties. It may be contained. Examples of the organic solvent include ketones such as methyl ethyl ketone, cyclohexanone, acetone and methyl isobutyl ketone, acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate, and aromatics such as petroleum naphtha. Examples thereof include hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent individually or in combination of 2 or more types.

  In the thermosetting resin composition of the present invention, if necessary, silane coupling such as silicone-based, fluorine-based, polymer-based antifoaming agent and / or leveling agent, imidazole-based, thiazole-based, triazole-based, etc. Additives, phosphorus-based flame retardants, antimony flame retardants and other flame retardants, antioxidants, rust inhibitors and the like can be blended with known and conventional additives.

(Dry film of the present invention)
The thermosetting resin composition of the present invention can form an insulating layer in the production of a multilayer substrate, and can be used industrially as a dry film such as flatness and film thickness uniformity.

  The dry film of the present invention can be produced as follows by a known method. That is, a thermosetting resin composition varnish containing an organic solvent is applied to a support film as a support using a film coater, a film applicator, a bar coater, a die coater, etc., and is temporarily dried or temporarily cured. To form a dry film. And it is set as a 3 layer structure by laminating | stacking a protective film on the resin composition surface as needed.

  Examples of the support film or protective film include films made of polyester such as polyethylene, polypropylene, polypropylene, and polyethylene terephthalate. The support film and the protective film may be subjected to an embossing treatment, a corona treatment, a release agent treatment or the like so that they can be selectively peeled off when used.

  The thickness of the dry film of the present invention is not particularly limited, but is preferably 5 to 150 μm, more preferably 10 to 100 μm, and particularly preferably 15 to 75 μm. If it is thinner than 5 μm, the flatness after lamination becomes poor, and if it is thicker than 150 μm, the drying property of the varnish coated on the support film is lowered, and the productivity of the dry film is lowered.

  In this invention, the linear expansion coefficient between 25-150 degreeC of the hardened | cured material of this dry film is about 0.5-2 times (8-40 ppm / degrees C) of copper linear expansion coefficient, Especially 17-30 ppm / It is preferable that it is ° C. If the linear expansion coefficient exceeds 30 ppm / ° C, the semiconductor package substrate may be warped or broken due to cracks due to the stress caused by the difference in expansion due to temperature changes between different materials due to thermal history in the mounting process and reliability test. It tends to occur.

(Printed wiring board)
Next, a method for producing a multilayer printed wiring board through the roughening and plating steps using the dry film produced as described above will be described.

  First, using a vacuum laminator, a dry film is laminated on a wiring substrate that becomes a core substrate. Although there is no restriction | limiting in particular as a base material used for a wiring board, Generally a glass epoxy board | substrate, BT board | substrate etc. are mentioned. If the dry film has a roll and a protective film, the protective film is removed, cut to the required dimensions, and an auto-cut laminator that temporarily attaches improves productivity. Since many transport rollers are installed, excellent handling is required.

  After laminating the dry film on the wiring board, the insulating film can be formed on the wiring board by peeling the support film and thermosetting. The thermosetting conditions can be selected according to the type of the resin component, etc., but are generally set in the range of 140 to 200 ° C. for 15 to 180 minutes, preferably 160 to 190 ° C. for 30 to 120 minutes.

  After the insulating layer is formed, a via hole or a through hole is formed by drilling the insulating layer in order to obtain electrical connection with the core substrate. The drilling step can be generally performed by a known method such as a drill, a carbon dioxide laser, or a UV-YAG laser.

  Next, a conductor layer is formed by plating. In general, wet plating is performed, and first, the surface of the hardened insulating layer is roughened. As the roughening solution, a sodium hydroxide aqueous solution of permanganate is preferably used. Subsequently, conductor layers are formed by electroless copper plating after electroless copper plating. When a fine circuit is formed, a semi-additive method is used in which the resist is removed after patterning with a resist in advance and electroless plating is performed.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

Example 1
As a polyfunctional epoxy resin, 60 parts by mass of a bisphenol S type epoxy resin (DIC Corporation, EXA-1517, epoxy equivalent of about 237), as a liquid epoxy, a mixed epoxy resin of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin (Nippon Steel Chemical Co., Ltd., ZX-1059, epoxy equivalent of about 165) Using 40 parts by mass, as a phenolic resin, cresol novolak resin (Gifu Seratsuk Co., Ltd., GPX-41, hydroxyl equivalent of about 120) 13 parts by mass, 12 parts by mass of phenol novolak resin (Maywa Kasei Co., Ltd., HF-1M, hydroxyl equivalent: about 106, softening point temperature: 86 ° C.), amorphous silica (Admatechs Co., Ltd., SO- E2) 144 parts, talc (Nippon Talc Co., Ltd., SG-2000) 26 parts by mass, as a curing accelerator 1-benzyl-2-phenylimidazole (Shikoku Kasei Kogyo Co., Ltd., trade name 1B2PZ) 0.5 parts by mass, organic solvent (diethylene glycol monomethyl ether acetate, commonly used carbitol acetate) 20 parts by mass, additives (Bic Chemie) , BYK-352, leveling agent) 1.5 parts, and uniformly dispersed by a bead mill to produce a thermosetting resin composition varnish (total amount of silica and talc in the non-volatile component, about 58% by mass, The amount of talc in the total amount of silica and talc, about 15% by mass). Next, the obtained varnish was uniformly coated on a 38 μm-thick polyethylene terephthalate film (hereinafter abbreviated as PET film) using a bar coater, and dried at 80 ° C. for 15 minutes to produce a test dry film. did. The coating conditions of the bar coater were set so that the thickness of the thermosetting resin composition layer after drying was 25 μm.

(Example 2)
Non-volatile component in the same manner as in Example 1, except that 119 parts of amorphous silica (Admatechs Co., Ltd., SO-E2) and 51 parts by weight of talc (Nihon Talc Co., Ltd., SG-2000) were changed. A dry film having a total amount of silica and talc of about 58% by mass and a total amount of talc of silica and talc of about 30% by mass was obtained.

(Example 3)
A non-volatile component was obtained in the same manner as in Example 1 except that the amount was changed to 68 parts of amorphous silica (Admatechs Corporation, SO-E2) and 102 parts of talc (Nihon Talc Co., Ltd., SG-2000). A dry film having a total amount of silica and talc of about 58% by mass and a total amount of talc of silica and talc of about 60% by mass was obtained.

Example 4
As a polyfunctional epoxy resin, 60 parts by mass of a bisphenol S type epoxy resin (DIC Corporation, EXA-1517, epoxy equivalent of about 237), as a liquid epoxy, a p-aminophenol type epoxy resin (Sumitomo Chemical Co., Ltd.), ELM-100, epoxy equivalent of about 106) 40 parts by mass, and phenol resin, cresol novolac resin (Gifu Seratsuk Co., Ltd., GPX-41, hydroxyl equivalent of about 120) 18 parts by mass, phenol novolac resin (Maywa Kasei) Co., Ltd., HF-1M, hydroxyl equivalent of about 106, softening temperature 86 ° C. 15 parts by mass, amorphous silica (Admatechs Co., Ltd., SO-E2) 158 parts, talc (Nippon Talc ( Co., Ltd., SG-2000) 31 parts by mass, 1-benzyl-2-phenylimidazole (Shikoku) as a curing accelerator Industrial Co., Ltd., trade name 1B2PZ) 0.5 parts by mass, organic solvent (diethylene glycol monomethyl ether acetate, commonly used carbitol acetate) 20 parts by mass, additives (Bic Chemie, BYK-352, leveling agent) 5 parts was blended and uniformly dispersed by a bead mill to prepare a thermosetting resin composition varnish (total amount of silica and talc in the non-volatile component, about 56% by mass, amount of talc in the total amount of silica and talc, About 17% by mass). Next, the obtained varnish was uniformly coated on a 38 μm-thick polyethylene terephthalate film (hereinafter abbreviated as PET film) using a bar coater, and dried at 80 ° C. for 15 minutes to produce a test dry film. did. The coating conditions of the bar coater were set so that the thickness of the thermosetting resin composition layer after drying was 25 μm.

(Example 5)
Amorphous silica (Co., Ltd., Admatex Co., Ltd., SO-E2) 158 parts, talc (Nihon Talc Co., Ltd., SG-2000) mass part 34 parts changed to phenoxy resin (Toto Kasei Co., Ltd.) ), FX293AM40, high heat resistance grade, non-volatile content: 40% by mass) The total amount of silica and talc in the non-volatile component is about 58% by mass, and the total of silica and talc except that 11% by mass is added A dry film having a talc content of about 18% by mass was obtained.

(Example 6)
As a polyfunctional epoxy resin, 80 parts by mass of a naphthalene type epoxy resin (DIC Corporation, HP-4032 epoxy equivalent: about 140), as a liquid epoxy, a mixed epoxy resin of bisphenol A type epoxy resin and bisphenol F type epoxy resin (new Nichijo Chemical Co., Ltd., ZX-1059, epoxy equivalent of about 165) 20 parts by mass, and phenol resin, cresol novolac resin (Gifu Seratsuk Co., Ltd., GPX-41, hydroxyl equivalent of about 120) 20 mass Part, phenol novolak resin (Maywa Kasei Co., Ltd., HF-1M, hydroxyl equivalent of about 106, softening point temperature 86 ° C.) 18 parts by mass, amorphous silica (Admatechs Co., Ltd., SO-E2) 150 parts, 50 parts by mass of talc (Nippon Talc Co., Ltd., SG-2000), 1-ben as a curing accelerator 0.5 parts by mass of diru 2-phenylimidazole (Shikoku Kasei Kogyo Co., Ltd., trade name 1B2PZ), 20 parts by mass of organic solvent (diethylene glycol monomethyl ether acetate, commonly used carbitol acetate), additives (Bic Chemie, BYK) -352, leveling agent) 1.5 parts, and uniformly dispersed by a bead mill to prepare a thermosetting resin composition varnish (total amount of silica and talc in nonvolatile components, about 59% by mass, silica and The amount of talc in the total amount of talc, about 25% by mass). Next, the obtained varnish was uniformly coated on a 38 μm-thick polyethylene terephthalate film (hereinafter abbreviated as PET film) using a bar coater, and dried at 80 ° C. for 15 minutes to produce a test dry film. did. The coating conditions of the bar coater were set so that the thickness of the thermosetting resin composition layer after drying was 25 μm.

(Example 7)
Except for changing to amorphous silica (Admatechs Co., Ltd., SO-E2) 225 parts by mass, talc (Nippon Talc Co., Ltd., SG-2000) 75 parts by mass, non-volatile as in Example 6. A dry film in which the total amount of silica and talc in the components was about 68% by mass and the amount of talc in the total amount of silica and talc was about 25% by mass was obtained.

(Comparative Example 1)
The total amount of silica and talc in the non-volatile component was about 58% by mass, except that the talc which is the layered silicate in Example 1 was not blended and the mass of the talc was replaced with amorphous silica. A dry film having a talc amount of 0% by mass in the total amount of talc was obtained.

(Comparative Example 2)
A phenol novolak resin (Maywa Kasei Co., Ltd.) having the same number of hydroxyl groups without blending the cresol novolak resin (Gifu Seratsuk Co., Ltd., GPX-41, hydroxyl group equivalent of about 120) which is a phenolic resin in Example 1. HF-1M, hydroxyl group equivalent of about 106, softening point temperature of 86 ° C.), the total amount of silica and talc in the non-volatile component is about 58% by mass, and the amount of talc in the total amount of silica and talc is About 15% by mass of a dry film was obtained.

(Comparative Example 3)
The total amount of silica and talc in the non-volatile component was about 58% by mass, and the total amount of silica and talc was the same except that the amorphous silica in Example 1 was not blended and the mass of the amorphous silica was replaced with talc. A dry film having a talc content of 100% by mass was obtained.

(Comparative Example 4)
The total amount of silica and talc in the non-volatile component is approximately the same except that the talc that is the layered silicate in Example 6 is not blended and the mass of the talc is replaced by amorphous silica (no talc is blended). A dry film having 58% by mass and 0% by mass of talc in the total amount of silica and talc was obtained.

(Comparative Example 5)
Instead of talc, which is the layered silicate in Example 6, the mass fraction of talc by synthetic hectorite (Corp Chemical Co., Ltd., Lucentite STN), which is a layered silicate compound having an exchangeable metal cation between crystals. A dry film was obtained in the same manner except that the total amount of silica and talc in the non-volatile component was about 58% by mass and the amount of talc in the total amount of silica and talc was 0% by mass.

  Table 1 below shows each component constituting the thermosetting resin composition of each Example and each Comparative Example and the blending amount thereof, and Table 2 shows the evaluation results of each Example and each Comparative Example.

(Evaluation items and evaluation methods of Examples and Comparative Examples)
1. Linear expansion coefficient
The dry film obtained in each example and each comparative example was laminated on the glossy surface of the copper foil with a vacuum laminator (manufactured by Nichigo Morton, CVP-300), and then the PET film was peeled off and cured at 180 ° C. for 60 minutes. A cured product was obtained. The copper foil was removed from the cured product, cut into a test piece having a width of about 3 mm and a length of about 15 mm, and the linear expansion coefficient was measured using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., TMA-6000). . The heating rate was 5 ° C./min. The linear expansion coefficient (α1) was determined in the temperature range of 25 to 150 ° C.

2. Elongation at break (mechanical strength)
After laminating the dry film obtained in each Example and each Comparative Example on the glossy surface of the copper foil with a vacuum laminator (CVP-300, manufactured by Nichigo Morton), the PET film was peeled off and cured at 180 ° C. for 90 minutes. A cured product was obtained. Copper foil is removed from the cured product, cut into test pieces having a width of about 5 mm and a length of about 80 mm, and the elongation at break is measured using a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100N). did. The measurement conditions were a sample width of about 10 mm, a fulcrum distance of about 40 mm, a pulling speed of 1.0 mm / min, and the elongation rate until breakage was the elongation at breakage point.

3. Handleability
The dry film obtained in each example and each comparative example was cut into about 50 mm × about 200 mm, and evaluated using a cylindrical mandrel tester (BYK Gardner, No. 5710). The surface to which the composition was applied was placed on the outside, bent around the core bar, and evaluated for the occurrence of cracks. The diameter of the core rod was 2 to 16 mm, and the interval was 2 mm.
In Table 2,
○ is Φ6mm or less,
Δ is Φ8mm to Φ12mm,
X shows a thing of Φ16 mm or more.

4). Laminating property The dry film obtained in each Example and each Comparative Example was subjected to surface treatment (MEC, CZ-8101, etching amount: about 1.0 μm) on a copper clad laminate (manufactured by Nichigo Morton, After laminating using CVP-300), the PET film was peeled off and cured at 180 ° C. for 60 minutes to prepare an evaluation substrate. Lamination conditions were a temperature of 100 ° C., a lamination pressure of 0.5 MPa, a vacuum time of 20 seconds, a slap down of 1 second, and a pressurization time of 19 seconds, and the state of the cured product after curing was visually evaluated.

In Table 2,
○ indicates that there is no problem with adhesion,
△ indicates that the cured product is partially lifted or peeled off,
X shows what was not able to adhere | attach at all.

5. Conductor plating peel strength
A vacuum laminator (manufactured by Nichigo Morton, CVP-) was applied to a copper clad laminate obtained by subjecting the dry films obtained in each Example and each Comparative Example to surface treatment (MEC, CZ-8101, etching amount: about 1.0 μm). 300), the PET film was peeled off and cured at 180 ° C. for 60 minutes to prepare an evaluation substrate.

  The evaluation substrate is immersed in a swelling liquid (Atotech Japan, mixed solution of Swelling Dip Securigant P and aqueous sodium hydroxide (400 g / L)) at 80 ° C. for 10 minutes, and then a roughening liquid (Atotech Japan, Immerse it in a mixture of Concentrate Compact CP and aqueous sodium hydroxide (400 g / L) at 80 ° C. for 20 minutes, and finally put it in a reducing solution (Atotech Japan Co., Reduction Solution Securigant P500 and sulfuric acid) at 50 ° C. For 5 minutes to roughen the surface. Then, after dipping in a cleaner solution, a catalyst solution and a reducing solution for electroless copper plating, and then dipping in an electroless copper plating solution, after annealing at 100 ° C. for 30 minutes, copper sulfate electroplating is performed. Finally, an annealing treatment was performed at 180 ° C. for 60 minutes to form a conductor plating layer. The conductor thickness at this time was measured with a micrometer and found to be 25 μm ± 5 μm.

  The obtained conductor plating layer is cut at a depth of about 10 mm x about 80 mm to reach the dry film layer, and the end is slightly peeled off to secure a gripping margin, and then gripped with a gripping jig. The conductor plating peel strength was measured using (Autograph AGS-100N, manufactured by Shimadzu Corporation). The measurement conditions were room temperature, the pulling speed was 50 mm / min, and the average load when peeling 35 mm was measured.

In Table 2,
○ indicates that the peel strength exceeds 4 N / cm,
Δ is from 2 N / cm to 4 N / cm,
X shows less than 2 N / cm.

EXA-1517 DIC Corporation Bisphenol S type epoxy resin
HP-4032 DIC Corporation Naphthalene type epoxy resin
ZX-1059 Toto Kasei Co., Ltd. Bisphenol A type epoxy resin and bisphenol F type epoxy mixture
ELM-100 Sumitomo Chemical Co., Ltd. Aminophenol type epoxy resin
GPX-41 Gifu Seratsuk Co., Ltd. Cresol novolak resin
HF-1M Meiwa Kasei Co., Ltd. Phenol novolac resin
FX-293AM40 Toto Kasei Co., Ltd. Phenoxy resin
SO-E2 Admatechs Co., Ltd. Spherical silica fine particles
SG-2000 Nippon Talc Co., Ltd. Talcrucentite STN Corp Chemical Co., Ltd. Synthetic hectorite diethylene glycol monomethyl ether acetate Common name Carbitol acetate 1B2PZ Shikoku Chemicals Co., Ltd. 1-Benzyl-2-phenylimidazole
BYK-352 Big Chemie Japan Co., Ltd. Antifoam / Leveling Agent

  As is clear from the comparison of the above examples and comparative examples, the examples in which amorphous silica and talc are used in combination have both a linear expansion coefficient (α1) of 25 to 150 ° C. and handling properties, and breakage. The point elongation, laminating property, and conductor plating peel strength can be maintained well. On the other hand, Comparative Example 1 which does not contain talc and Comparative Example 2 in which the amount of talc is less than the blending amount of the present invention have a high linear expansion coefficient and are not sufficiently handled. Comparative Example 3 containing no amorphous silica can reduce the linear expansion coefficient, but has a low elongation at break and poor laminating properties. Comparative Example 4 which does not contain talc and is replaced with amorphous silica has a high linear expansion coefficient. Comparative Example 5 containing synthetic hectorite, which is the same layered silicate instead of talc, has a lower linear expansion coefficient than Comparative Example 4 having the same resin composition but no layered silicate, but the elongation at break and the peel strength of the conductor plating Is inferior.

Claims (3)

A compound having at least two epoxy groups in the molecule,
A phenolic curing agent having a softening point temperature of 120 ° C. or higher, selected from the group consisting of a phenol novolac resin, a cresol novolac resin, and a triazine ring-containing novolac resin ,
Amorphous silica, and
Contains talc ,
The ratio of the number of moles of epoxy groups of the epoxy compound to the number of moles of phenolic hydroxyl groups of the phenolic curing agent is 3: 1 to 0.75: 1;
The thermosetting resin composition, wherein the total amount of the amorphous silica and talc is 35 to 70% by mass in the nonvolatile content of the composition. A dry film produced using the thermosetting resin composition according to claim 1 . The dry film according to claim 2 , wherein the linear expansion coefficient of the cured product at a curing temperature of 25 to 150 ° C is 17 to 30 ppm / ° C.