CN116194523A - Ultraviolet curable organically modified silicone composition and cured product - Google Patents

Abstract

Containing (A) a polymer represented by formula (1) [wherein, X is each independently a divalent group represented by formula (2), and Y is each independently represented by formula (3) to (5) In any one of the monovalent groups represented, Y' is each independently a divalent group represented by formula (6) or (7), and m is an integer of 0-12. ], (B) an organosilicon compound having at least 3 hydrogen atoms bonded to a terminal silicon atom in one molecule, and (C) a platinum group metal catalyst activated by light with a wavelength of 200 to 500 nm, and not having HRSiO _2/2 (In the formula, R represents an organic group.) The UV-curable organically modified silicone composition represented by an organohydrogensiloxane unit undergoes curing by a hydrosilylation reaction rapidly after ultraviolet irradiation, without High hardness cured products can be formed when post-curing is required.

Description

Ultraviolet curable organically modified silicone composition and cured product

technical field

The present invention relates to an ultraviolet curable organically modified silicone composition and its cured product. UV-curable organically modified silicone compositions and cured products thereof, such as agents and mold materials for nanoimprint applications.

Background technique

Organo-modified silicones such as alkylene-modified silicones and arylene-modified silicones have the characteristics of high hardness, high toughness, and high gas barrier properties compared with dimethyl silicone. Due to these characteristics, organo-modified silicones are used as coating materials for electronic components and sealing materials for light-emitting diodes.

On the other hand, organo-modified silicone needs to be cured by addition crosslinking reaction, and in order to obtain a cured product with sufficient hardness, it must be cured by heating at a high temperature such as 150°C for several hours. Therefore, there is a problem that it cannot be applied to applications where the size of the device is large and it is difficult to put it into a curing furnace, or where low-temperature curability is required due to the heat resistance of the device.

In contrast, ultraviolet-curable addition-curable silicones use ultraviolet-activated platinum catalysts, and crosslinking begins with ultraviolet irradiation, so they can be cured at relatively low temperatures. In addition, since it does not have oxygen curing inhibition, the step of replacing the inside of the system with an inert gas during curing and the equipment used therefor are unnecessary.

Hitherto, it has been known that a composition comprising an addition polymer of vinylnorbornene and bis(dimethylsilyl)benzene and an organohydrogenpolysiloxane can be used as an addition-curable material of the UV-active type (patent Literature 1).

However, this material has insufficient curability after ultraviolet irradiation, and post-curing is required to obtain a cured product.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2019-108471

Contents of the invention

The problem to be solved by the invention

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ultraviolet-curable organo-modified silicone composition that rapidly undergoes curing by a hydrosilylation reaction after ultraviolet irradiation, and can be cured without post-curing. Form a cured product with high hardness.

means to solve the problem

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention found that the following composition can be rapidly cured after irradiation with ultraviolet rays to form a cured product with excellent hardness, and completed the present invention.

That is, the present invention provides:

1. An ultraviolet curable organically modified silicone composition, which contains:

(A) A polymer represented by the following structural formula (1):

[chemical 1]

[wherein, X is each independently a divalent group represented by the following structural formula (2), and Y is each independently a monovalent group represented by any one of the following structural formulas (3) to (5), Y' is each independently a divalent group represented by the following structural formula (6) or (7), and Me represents a methyl group. m is an integer of 0-12.

[Chem 2]

(In the formula, an asterisk (*) indicates a bonding site with a silicon atom.)

[Chem 3]

(In the formulas (3) to (7), the asterisk (*) represents the bonding site with the silicon atom, and the stereo configuration of each chiral carbon can be in the cis (external form) or trans (inner form) Either.)]

(B) an organosilicon compound having at least 3 hydrogen atoms bonded to a terminal silicon atom in 1 molecule, and

(C) using a photoactivated platinum group metal catalyst with a wavelength of 200 to 500 nm,

And it does not have an organohydrogensiloxane unit represented by HRSiO _2/2 (wherein, R represents an organic group.);

2. The ultraviolet curable organo-modified silicone composition according to 1, wherein the component (B) contains a compound represented by the following formula (I), a phenyl triphenyl compound represented by the following formula (II), The addition reaction product of vinylsilane and 1,4-bis(dimethylsilyl)benzene, or both,

[chemical 4]

[chemical 5]

(In formula (II), n is an integer of 1 to 20.)

3. The ultraviolet curable organically modified silicone composition according to 1 or 2, wherein the component (C) contains a (η ⁵ -cyclopentadienyl) trialiphatic platinum compound or a bis(β-di Keto) platinum compounds,

4. A cured product of the ultraviolet curable organically modified silicone composition according to any one of 1 to 3.

The effect of the invention

According to the present invention, it is possible to obtain a cured product of an organically modified silicone resin having sufficient hardness in a short period of time, and therefore it is possible to solve the technical and production problems that conventional materials had. In addition, since it can be cured at room temperature, it can also be applied to substrates with low heat resistance.

Therefore, the ultraviolet curable organically modified silicone composition of the present invention can be used as a material for optical devices or optical parts, an insulating material for electronic devices or electronic parts, a coating material, an adhesive, and a mold for nanoimprint applications. materials etc.

Detailed ways

The present invention will be specifically described below.

[1] (A) Component

(A) component in the ultraviolet curable silicone resin composition of this invention is a polymer represented by following structural formula (1).

[C61

In formula (1), X is each independently a divalent group represented by the following structural formula (2), and Y is each independently a monovalent group represented by any one of the following structural formulas (3) to (5). group, Y' each independently is a divalent group represented by the following structural formula (6) or (7), and Me represents a methyl group (the same applies hereinafter).

[chemical 7]

(In the formula, an asterisk (*) indicates a bonding site with a silicon atom.)

[chemical 8]

(In the formulas (3) to (7), the asterisk (*) represents the bonding site with the silicon atom, and the stereo configuration of each chiral carbon can be in the cis (external form) or trans (inner form) either.)

In addition, the bonding direction of the divalent group represented by the said structural formula (6) or (7) is not limited to the said description, The structure which rotated each structure by 180 degrees on paper is also included.

Moreover, m is an integer of 0-12, Preferably it is 1-5. When m exceeds 12, it will become a high-viscosity liquid at room temperature and it will be difficult to handle.

The kinematic viscosity of the component (A) is not particularly limited, but is preferably 1,000 to 100,000 mm ² /s, more preferably 5,000 to 30,000 mm ² /s. In addition, in this invention, a kinematic viscosity is the value in 23 degreeC measured with the Cannon-Fenske type viscometer (the same applies hereinafter).

The (A) component can be used, for example, as an addition reaction product of (a): bis(dimethylsilyl)benzene and (b): vinyl norbornene, according to a known method (Japanese Patent Laid-Open No. 2005-133073 etc.) to prepare.

The component (a) is ortho-, meta-, or para-substituted bis(dimethylsilyl)benzene represented by the following structural formula (8), and either a single structure or two or more can be used. Mixture of isomers.

[chemical 9]

The component (b) is 5-vinylbicyclo[2.2.1]hept-2-ene represented by the following structural formula (9), and either a single structure or a mixture of two or more isomers may be used.

[chemical 10]

The component (A) of the present invention can be obtained, for example, by having two addition-reactive carbon-carbon double bonds in one molecule relative to 1 mole of the component (a) having two SiH groups in one molecule. The (b) component is added in the presence of a hydrosilylation reaction catalyst in the presence of a hydrosilylation reaction catalyst in excess of more than 1 mol and 10 mol or less, preferably more than 1 mol and 5 mol or less.

A known catalyst can be used as a hydrosilylation reaction catalyst. Examples include platinum metal-supported carbon powder, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum diacetoacetate Platinum-based catalysts such as palladium-based catalysts, rhodium-based catalysts and other platinum-group metal-based catalysts, etc. In addition, addition reaction conditions, use of a solvent, and the like are not particularly limited, and can be carried out under known conditions.

As described above, when the component (A) is prepared, the molar excess of the component (b) is used relative to the component (a), so the component (A) has two additions to the structure of the component (b) in one molecule. Reactive carbon-carbon double bonds.

In addition, in the case of using a compound having an addition-reactive carbon-carbon double bond as the (B) component described later, etc., the addition-reactive carbon-carbon double bond derived from the (A) component is present in the composition of the present invention. The proportion of the addition-reactive carbon-carbon double bonds in the total amount is preferably 20 to 100 mol%, more preferably 40 to 100 mol%.

The said (A) component may be used individually by 1 type, and may use it in combination of 2 or more types.

[2] (B) component

The component (B) of the present invention is an organosilicon compound having at least three hydrogen atoms (hydrosilyl groups) bonded to terminal silicon atoms. Since such a terminal hydrosilyl group has high reactivity of the hydrosilylation reaction, formation of three-dimensional crosslinking proceeds rapidly, and a hardened cured product is formed.

In addition, (B) component is an organosilicon compound which does not have the organohydrogensiloxane unit (D ^H unit) represented by HRSiO _2/2 (wherein, R represents an organic group), For example, the following The compound represented by formula (I), the addition reaction product of phenyltrivinylsilane represented by the following formula (II) and 1,4-bis(dimethylsilyl)benzene, and the compound represented by the following formula ( Compounds represented by III), etc.

[chemical 11]

[chemical 12]

(In formula (II), n is an integer of 1 to 20, preferably an integer of 1 to 10, and the dotted line indicates a bonding terminal.)

[chemical 13]

The kinematic viscosity of the component (B) is not particularly limited, but is preferably 0.1 to 100000 mm ² /s, more preferably 0.1 to 3000 mm ² /s, and still more preferably 0.5 to 500 mm ² /s.

The compounding quantity of (B) component is preferable so that the quantity of the hydrogen atom bonded to a silicon atom shall be 0.5-1.5 mol with respect to 1 mol of addition-reactive carbon-carbon double bonds of (A) component in the composition of this invention. The amount is more preferably 0.8 to 1.2 moles.

The said (B) component may be used individually by 1 type, and may use it in combination of 2 or more types.

[3] (C) Component

The platinum group metal catalyst for the hydrosilylation reaction of component (C) is a platinum catalyst that is inactive under light-shielding and becomes active by irradiating light with a wavelength of 200 to 500 nm to promote the addition reaction in component (A) Catalyst for hydrosilylation reaction of permanent carbon-carbon double bond and silicon atom-bonded hydrogen atom in (B) component.

Specific examples of such component (C) include (η ⁵ -cyclopentadienyl)trialiphatic platinum compounds, derivatives thereof, and the like.

Among these, cyclopentadienyltrimethylplatinum complexes, methylcyclopentadienyltrimethylplatinum complexes, and derivatives obtained by modifying their cyclopentadienyl groups are particularly preferable. .

In addition, bis(β-diketonate)platinum compounds are also cited as examples of preferable (C)components, and bis(acetylacetonate)platinum compounds and derivatives thereof modified with acetylacetonate groups are particularly preferable. .

The compounding quantity of (C) component is not limited as long as it is the quantity which accelerates the hardening (hydrosilylation reaction) of this composition, Preferably it is the total mass of (A) component and (B) component with respect to this composition. , the amount of platinum group metal atoms in this component is in the range of 0.01 to 500 ppm by mass unit, more preferably in the range of 0.05 to 100 ppm, and still more preferably in the range of 0.01 to 50 ppm.

The said (C)component may be used individually by 1 type, and may use it in combination of 2 or more types.

[4] (D) Component

In the composition of the present invention, a reaction controller of component (D) may be added as necessary in order not to cause thickening or gelation before heating and curing when the composition is formulated or applied to a substrate.

Specific examples thereof include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3 -alcohol, 1-ethynylcyclohexanol, ethynylmethyldecylmethanol, 3-methyl-3-trimethylsilyloxy-1-butyne, 3-methyl-3-trimethylmethanol Silyloxy-1-pentyne, 3,5-dimethyl-3-trimethylsilyloxy-1-hexyne, 1-ethynyl-1-trimethylsilyloxycyclohexane, Bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane , 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, etc.

Among them, 1-ethynylcyclohexanol, ethynylmethyldecylmethanol, 3-methyl-1-butyn-3-ol, bis(2,2-dimethyl-3-butynyloxy ) Dimethylsilane.

It is preferable that the compounding quantity of (D)component is 0.01-2.0 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 0.01-0.1 mass part. Within such a range, the effect of reaction control can be fully exhibited.

In addition, the ultraviolet curable organo-modified silicone composition of the present invention basically does not have an organohydrogensiloxane unit (D ^H unit) represented by HRSiO _2/2 (where R represents an organic group). Since such a side chain hydrosilyl group is inferior in reactivity compared with the terminal hydrosilyl group in the said (B) component, it may hinder progress of an addition reaction.

[5] Other ingredients

The composition of the present invention may contain other components exemplified below as long as the object of the present invention is not impaired in addition to the above-mentioned (A) to (C) components and (D) component used as needed.

Examples include: an adhesiveness-imparting agent having one or more functional group groups consisting of an alkenyl group, (meth)acryloyl group, carbonyl group, epoxy group, alkoxysilyl group, and amido group in one molecule; Thixotropy control agents such as fumed silica; Enhancers such as crystalline silica; Antioxidants such as hindered phenols and hindered amines; Light stabilizers; Heat resistance improvers such as metal oxides and metal hydroxides; Titanium oxide Colorants such as aluminum oxide and crystalline silica; thermal conductivity imparting fillers such as alumina and crystalline silica; viscosity modifiers such as non-reactive silicone oils that do not have reactive functional groups; conductivity imparting agents such as metal powders such as silver and gold; used for coloring Pigments, dyes, etc.

The ultraviolet curable organically modified silicone composition of the present invention is applied to various substrates, and can be used in materials for optical devices or optical parts, insulating materials for electronic devices or electronic parts, coating materials, and nanoimprint applications mold materials, etc.

As the substrate, composite materials, metal members, plastic members, ceramic members, quartz glass, casings or members for electrical applications, electronic applications, optical applications, etc., can be used in the fields of coating, casting, bonding and sealing. Substrate etc.

The composition of the present invention can also be used on substrates activated by known pretreatment steps such as primer treatment, plasma treatment, and excimer phototreatment.

When curing the ultraviolet curable organically modified silicone composition of the present invention, a UV-LED lamp, a metal halide lamp, a mercury lamp, etc. can be used, and a photoactivator with a wavelength of 200 to 500 nm, preferably 200 to 370 nm, can be used for the photoactivation of the platinum catalyst. Light.

From the viewpoint of curing speed of the composition and prevention of discoloration, the irradiation intensity is preferably 30-2000 mW/cm ² , and the irradiation dose is preferably 3000-100000 mJ/cm ² . The temperature at the time of irradiation is preferably 10 to 60°C, more preferably 20 to 40°C.

Example

The following examples and comparative examples are given to describe the present invention in detail, but the present invention is not limited to the following examples. In addition, in the following formulae, Ph represents a phenyl group.

[Examples 1-3, Comparative Examples 1-4]

The following (A)-(D) components were mixed in the compounding quantity (parts by mass) shown in Table 1, and the ultraviolet-curable organomodified silicone composition was prepared.

(A) Ingredients

A mixture of polymers in which m in the above structural formula (1) is 1 to 5 (the content ratio of addition-reactive carbon-carbon double bonds is 0.47 mol/100g)

(B) Ingredients

(B-1) A compound represented by the following structural formula (I) (kinematic viscosity at 23° C.: 1.8 mm ² /s, content of silicon atom-bonded hydrogen atoms: 0.0092 mol/g)

[Chem. 141

(B-2) is an addition product of phenyltrivinylsilane and 1,4-bis(dimethylsilyl)benzene, and is a mixture of compounds represented by the following structural formulas (a) to (d) [(a):(b):(c):(d)=55:25:10:15 (molar ratio), kinematic viscosity at 23°C: 30000mm ² /s, average content of hydrogen atoms bonded to silicon atoms : 0.0035 mol/g]

[chemical 15]

(a)

[chemical 16]

(b)

[chemical 17]

(c)

[chemical 18]

(d)

(n=4～10, the dotted line indicates the bonding end.)

(B-3) A compound represented by the following structural formula (kinematic viscosity at 23° C.: 21.4 mm ² /s, content of silicon-bonded hydrogen atoms: 0.0069 mol/g)

[Chem. 191

(In the formula, the arrangement of each siloxane unit with brackets is random, alternate or block)

(B-4) A compound represented by the following structural formula (kinematic viscosity at 23°C: 65 mm ² /s, content of silicon-bonded hydrogen atoms: 0.0116 mol/g)

[chemical 20]

(In the formula, the arrangement of each siloxane unit with brackets is random, alternate or block)

(C) Ingredients

Toluene Solution of Methylcyclopentadienyltrimethylplatinum Complex with a Platinum Element Content of 0.5% by Mass

(D) Ingredients

Bis(2,2-Dimethyl-3-butynyloxy)dimethylsilane

[cured state of composition]

8 g of each of the obtained compositions was irradiated with ultraviolet light at room temperature (23° C.) using a UV-LED lamp with a wavelength of 365 nm so that the irradiation intensity became 100 mW/cm ² and the dose became 30,000 mJ/cm ² . The cured state of the finished composition.

Moreover, the hardness of the hardened|cured material in 23 degreeC was evaluated with the JIS hardness meter Durometer type. The results are also listed in Table 1.

[Table 1]

As shown in Table 1, it can be seen that the compositions prepared in Examples 1 to 3 cured rapidly after being irradiated with ultraviolet rays at 23° C., and formed cured products with high hardness.

On the other hand, it turned out that the compositions prepared in Comparative Examples 1 to 4 did not cure immediately after ultraviolet irradiation.

Claims (4)

1. An ultraviolet curable organically modified silicone composition, which contains: (A) A polymer represented by the following structural formula (1): [chemical 1]

In the formula, X is each independently a divalent group represented by the following structural formula (2), Y is each independently a monovalent group represented by any one of the following structural formulas (3) to (5), and Y ' are each independently a divalent group represented by the following structural formula (6) or (7), Me represents a methyl group, and m is an integer of 0 to 12, [Chem 2]

In the formula, the asterisk (*) indicates the bonding site with the silicon atom, [Chem 3]

In formulas (3) to (7), the asterisk (*) represents the bonding site with the silicon atom, and the stereo configuration of each chiral carbon can be any of cis (external form) or trans (inner form). A sort of, (B) an organosilicon compound having at least 3 hydrogen atoms bonded to terminal silicon atoms in 1 molecule, and (C) using a photoactivated platinum group metal catalyst with a wavelength of 200 to 500 nm, And it does not have an organohydrogensiloxane unit represented by HRSiO _2/2 , where R represents an organic group. 2. The ultraviolet curable organically modified silicone composition according to claim 1, wherein the component (B) contains a compound represented by the following formula (I), a benzene compound represented by the following formula (II), The addition reaction product of trivinylsilane and 1,4-bis(dimethylsilyl)benzene, or both, [chemical 4]

[chemical 5]

In formula (II), n is an integer of 1-20. 3. The ultraviolet curable organically modified silicone composition according to claim 1 or 2, wherein the (C) component comprises (η ⁵ -cyclopentadienyl) trialiphatic platinum compound or bis(β - diketo) platinum compounds. 4. A cured product of the ultraviolet curable organically modified silicone composition according to any one of claims 1 to 3.