KR20150128672A - Curable resin composition - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition excellent in heat resistance of a cured product. The curable resin composition of the present invention contains a polysiloxane (A) having at least one (meth) acryloyl group in one molecule and a silicone resin (B) represented by a specific average unit formula.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition which can be suitably used as an adhesive for electronic devices such as a liquid crystal display.

In electronic devices such as liquid crystal displays, adhesives are used in various places. Examples of such an adhesive include a photo-curable resin composition containing an acrylic monomer or an acryl oligomer.

For example, Patent Document 1 discloses a photo-curable resin composition comprising a (meth) acrylate oligomer having a polyurethane skeleton (so-called urethane acrylate) as an adhesive for sticking an optical functional material to a display body such as a liquid crystal display (Claim 5, etc.).

On the other hand, since electronic devices are often exposed under a high temperature environment, the adhesive used is required to have heat resistance.

For example, when the heat resistance of the adhesive used in the electronic device is insufficient, the adhesive strength is lowered when the electronic device is exposed in a high temperature environment, and the adhesive is connected to a bad state such as an operation failure of the electronic device. Therefore, the adhesive used in electronic equipment is required to have a low adhesive strength even when exposed under a high-temperature environment.

Further, if the heat resistance of an adhesive used for a display device such as a liquid crystal display is insufficient, there is a problem that the cured product of the adhesive deteriorates and is colored when exposed under a high temperature environment, and the display performance such as visibility is lowered It happens. Therefore, it is required that an adhesive used for a display device such as a liquid crystal display does not cause coloring even when exposed to a high temperature environment.

Patent Document 1: WIPO International Publication No. 2010/027041

The present inventors have studied a curable resin composition containing urethane acrylate with reference to Patent Document 1. It has been found that when the cured product is exposed under a high temperature environment, the adhesion strength is reduced or colored. That is, it has been found that the heat resistance of the cured product is insufficient.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a curable resin composition which is excellent in heat resistance of a cured product in view of the above circumstances.

The present inventors have conducted intensive studies in order to achieve the above object. As a result, they have found that by using a polysiloxane having a (meth) acryloyl group together with a silicone resin represented by a specific average unit formula, And found that the resin composition can be obtained, leading to the present invention.

That is, the inventors of the present invention have found out that the above problems can be solved by the following constitution.

(1) A curable resin composition comprising a polysiloxane (A) having at least one (meth) acryloyl group in one molecule and a silicone resin (B) represented by the following average unit formula (1).

^{_{(R 1 SiO 3/2) a (}} R 2 2 SiO 2/2) b (R 3 3 SiO 1/2) c (SiO 4/2) d (X 1 O 1/2) e ... (One)

(Wherein R ¹ , R ² and R ³ are each independently selected from the group consisting of an aryl group, a (meth) acryloyl group-containing group, an alkyl group, a cycloalkyl group, a vinyl group-containing group and an epoxy group- It represents an organic group which is. a plurality of R ² and R ³ but may be the same or each proportion of the aryl group for groups total organic the R ^1, R ² and R ³ represents is at least 15mol%. X ¹ is hydrogen A, b, c, d and e represent a group selected from the group consisting of an alkyl group,

0 &lt; a <

0 < b &lt; 1,

0? C <1,

0? D <1,

0? E <1,

0? B / a? 10,

0? C / a? 5,

0? D / (a + b + c + d)? 0.3,

0? E / (a + b + c + d)? 0.4

Satisfies the following expression.

(2) The curable resin composition according to (1), wherein the silicone resin (B) has a (meth) acryloyl group.

(3) The curable resin composition according to (1) or (2), wherein the polysiloxane (A) has an aryl group.

(4) The curable resin composition according to any one of (1) to (3), wherein the polysiloxane (A) has an alkoxy group.

(5) The curable resin composition according to any one of (1) to (4), wherein the polysiloxane (A) has a urethane bond.

(6) The curable resin composition according to any one of (1) to (5), further comprising a monofunctional (meth) acrylic monomer (C) and a photopolymerization initiator.

(7) The curable resin composition according to any one of (1) to (6), further comprising (meth) acrylate monomer (D) having a plurality of ester groups.

As described below, according to the present invention, a curable resin composition excellent in heat resistance of a cured product can be provided.

Hereinafter, the curable resin composition of the present invention (hereinafter, simply referred to as the composition of the present invention) will be described. Incidentally, in this specification, the numerical range indicated by "~" means a range including numerical values before and after "~" as a lower limit value and an upper limit value.

The composition of the present invention is a curable resin composition containing a polysiloxane (A) having at least one (meth) acryloyl group in one molecule and a silicone resin (B) represented by the following average unit formula (1).

It is considered that the composition of the present invention has such a constitution that the cured product exhibits excellent heat resistance.

This is not clear in detail, but is estimated to be approximately as follows.

As described above, the composition of the present invention uses a specific polysiloxane (A) and a specific silicone resin (B) in combination. Here, as described later, the silicone resin (B) used in the present invention has a branched structure.

Since the composition of the present invention uses these two components in combination, the cured product becomes a composite of a siloxane skeleton in which a polysiloxane crosslinked with a (meth) acryloyl group and a specific silicone resin having a branched structure are intertwined with each other, Chemical durability such as radicality is improved. It is considered that such improvement in chemical durability contributes to improvement in heat resistance.

This is presumed from the fact that the heat resistance of the cured product becomes insufficient when the specific polysiloxane (A) and the specific silicone resin (B) are not contained, as shown by Comparative Examples 1 and 2 described later.

Particularly in the present invention, the silicone resin (B) is characterized in that the aryl group ratio described later is set to 15 mol% or more. By using such a silicone resin, packing between the aryl groups at the time of curing proceeds, and a cured product hardly changes in structure even when exposed under a high temperature environment. That is, it is considered to be a cured product excellent in heat resistance and toughness.

This is presumably because, as will be described later in Comparative Example 3, even when polysiloxane (A) and silicone resin are used in combination, when the aryl group ratio of the silicone resin described below is less than 15 mol%, the heat resistance of the cured product becomes insufficient I guess.

Hereinafter, the polysiloxane (A) and the silicone resin (B) and other components which may optionally be contained will be described in detail.

&Lt; Polysiloxane (A) &gt;

The polysiloxane (A) used in the composition of the present invention is not particularly limited as long as it is a polysiloxane having at least one (meth) acryloyl group in one molecule. Incidentally, in the present application, the (meth) acryloyl group represents an acryloyl group or a methacryloyl group. The polysiloxane refers to a compound having two or more siloxane structures (-Si-O-) in the main chain (main chain).

As described above, the polysiloxane (A) is crosslinked by the reaction of the (meth) acryloyl groups of the polysiloxane (A) upon curing. When the silicone resin (B) to be described later has a (meth) acryloyl group, it is crosslinked not only with the polysiloxane (A) but also with the silicone resin (B).

The polysiloxane (A) may be either a straight chain polysiloxane or a branched polysiloxane. Among them, linear polysiloxane (straight-chain polysiloxane) is preferable because of the excellent elongation of the cured product.

In the polysiloxane (A), the position having the (meth) acryloyl group is not particularly limited. For example, the polysiloxane (A) may have a (meth) acryloyl group at the terminal or may have a (meth) acryloyl group at the side chain (side chain). Among them, it is preferable that the (meth) acryloyl group is at the terminal from the reason that the cured product is excellent in elongation. When the polysiloxane (A) is a linear polysiloxane, it preferably has a (meth) acryloyl group at both terminals.

Examples of the group bonded to the silicon atom in the polysiloxane (A) include a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, and a hydrocarbon group which may have a hetero atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hetero atom of the hydrocarbon group which may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.

The hydrocarbon group of the hydrocarbon group which may have a hetero atom includes, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.

The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (in particular, having 1 to 10 carbon atoms), a linear or branched alkenyl group (having 2 to 10 carbon atoms), a linear or branched alkynyl group (particularly, 2 to 10 carbon atoms), a linear or branched cycloalkyl group, and the like.

The aromatic hydrocarbon group includes, for example, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more specifically, an aryl group, a naphthyl group, and the like can be given. As the aryl group, for example, an aryl group having 6 to 18 carbon atoms such as a phenyl group (hereinafter sometimes referred to as "Ph"), a tolyl group, a xylyl group and the like can be given. desirable.

The polysiloxane (A) preferably has an aryl group. The specific examples of the aryl group and the preferred embodiment are as described above.

Among them, it is preferable that 5 to 50 mol% of the group bonding to the silicon atom of the polysiloxane (A) is an aryl group, and it is more preferable that 10 to 30 mol% is an aryl group.

The polysiloxane (A) is preferably one having an alkoxy group for reasons of excellent adhesion with an adherend.

From the viewpoint of transparency, it is preferable that the polysiloxane (A) has an aryl group and an alkoxy group.

It is preferable that the polysiloxane (A) has a urethane bond because a hydrogen bond is formed in the cured product to improve the adhesion of the cured product.

As a preferred embodiment of the polysiloxane (A), for example, a compound represented by the following formula (A1) can be given.

In the formula (A1), R ²¹ represents a hydrogen atom or a methyl group (hereinafter sometimes referred to as "Me"). The plural R &lt; ²¹ &gt; s may be the same or different.

In the formula (A1), R ²² represents a hydrocarbon group (preferably having 1 to 6 carbon atoms). Specific examples of the hydrocarbon group are as described above. The plural R &lt; ²² &gt; s may be the same or different.

In the formula (A1), R ²³ represents a hydrogen atom or a hydrocarbon group (preferably having 1 to 18 carbon atoms). Specific examples of the hydrocarbon group are as described above. The plurality of R ²³ may be the same or different.

In the formula (A1), R ²⁴ represents a divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (e.g., an alkylene group, preferably a C 1-8), a substituted or unsubstituted aromatic hydrocarbon group (e.g., an arylene group preferably the carbon atoms 6 ~ 12), -O-, -S- , -SO 2 -, -N (R) - (R: alkyl group), -CO-, -NH-, -COO-, -CONH- , Or a combination thereof (e.g., an alkyleneoxy group (-C _m H2 _m O-: m is a positive integer), an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.).

In the formula (A1), R ²⁵ and R ²⁶ represent a hydrocarbon group which may have a hetero atom. Specific examples of the hydrocarbon group which may have a hetero atom are as described above. R ²⁵ and R ²⁶ may be the same or different.

In the formula (A1), 1 represents a positive integer. Among these, an integer of 1 to 500 is preferable, and an integer of 3 to 300 is more preferable.

In the formula (A1), n represents an integer of 0 to 2. Among them, it is preferable that the number is an integer of 1 or more for reasons of excellent adhesion with an adherend.

The compound represented by the formula (A1) is preferably an aryl group in an amount of 5 to 50 mol% of the group bonded to the silicon atom, and preferably 10 to 30 mol% in the aryl group, for the reason that the cured product is more excellent in heat resistance and toughness More preferable.

The weight average molecular weight (Mw) of the polysiloxane (A) is not particularly limited, but is preferably from 100 to 1,000,000, more preferably from 500 to 50,000, from the viewpoint of excellent toughness and elongation of the cured product.

Incidentally, in the present invention, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.

The viscosity of the polysiloxane (A) at 25 캜 is preferably 20 to 1,000,000 mPa · s, more preferably 200 to 100,000 mPa · s.

Incidentally, in the present application, the viscosity is measured at 25 占 폚 in accordance with 4.1 (Brookfield rotational viscometer) of JIS K7117-1.

In the composition of the present invention, the content of the polysiloxane (A) is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 30 to 70% by mass, from the viewpoint of excellent toughness and elongation of the cured product.

(Synthesis method of polysiloxane (A)) [

The method of synthesizing the polysiloxane (A) is not particularly limited. For example, the polysiloxane (a1) and the monomer (a2) having a (meth) acryloyl group are reacted to form at least one (meth) acryloyl group And a method of obtaining a polysiloxane having a hydroxyl group.

Among them, a method of reacting a polysiloxane (a11) having a silanol group at a terminal (preferably both ends) with an alkoxysilane (a21) having a (meth) acryloyl group is preferable. The alkoxysilane (a21) having a (meth) acryloyl group is preferably one having two or more alkoxy groups from the viewpoint of excellent adhesion with an adherend.

Other preferred embodiments of the method for synthesizing the polysiloxane (A) by reacting the polysiloxane (a1) with the monomer (a2) having a (meth) acryloyl group include, for example, And a method of reacting a polysiloxane (a12) having an alkyl group (-R-OH: R is an alkylene group) with an isocyanate (a22) having a (meth) acryloyl group.

Another conventional method of synthesizing the polysiloxane (A) by reacting the polysiloxane (a1) with the monomer (a2) having a (meth) acryloyl group is a method of reacting a polysiloxane (a13) having an epoxy group with (meth) And the like.

The above polysiloxane (a1) used in the synthesis of the polysiloxane (A) is preferably one having an aryl group because of excellent transparency of the cured product and further excellent heat resistance of the cured product. Specific examples and preferred embodiments of the aryl group are as described above.

&Lt; Silicone Resin (B) &gt;

The silicone resin (B) used in the composition of the present invention is a silicone resin represented by the following average unit formula (1). Here, the following average unit formula (1) represents the number of moles of each siloxane unit when the total siloxane unit constituting the silicone resin (B) is 1 mole.

^{_{(R 1 SiO 3/2) a (}} R 2 2 SiO 2/2) b (R 3 3 SiO 1/2) c (SiO 4/2) d (X 1 O 1/2) e ... (One)

R ¹ , R ² and R ³ each independently represent an aryl group, a (meth) acryloyl group-containing group, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group, And an organic group selected from the group consisting of an epoxy group-containing group. The plurality of R ² and R ³ may be the same or different.

In addition, when a plurality of units (R ¹ SiO _3/2 ) exist in the silicone resin (B), some units (R ¹ SiO _3/2 ) and other units (R ¹ SiO _3/2 ) It is acceptable. That is, R ¹ of any units (R ¹ SiO _3/2) R ¹ and the other units (R ¹ SiO _3/2) is of but may be the same. (R ² ₂ SiO _2/2 ), (R ³ ₃ SiO _1/2 ), and (X ¹ O _1/2 ).

Specific examples and preferred embodiments of the aryl group are as described above.

The (meth) acryloyl group-containing group is not particularly limited as long as it is a group containing a (meth) acryloyl group, but from the viewpoint of curability, it is preferably a hydrocarbon group having a (meth) acryloyloxy group as a substituent, More preferably an alkyl group having an acryloyloxy group as a substituent (particularly having 1 to 10 carbon atoms).

The preferred embodiment of the (meth) acryloyl group-containing group includes, for example, a group represented by the following formula (B1).

In the formula (B1), R ¹¹ represents a hydrogen atom or a methyl group.

In the above formula (B1), R ¹² represents a divalent organic group. Specific examples and preferred embodiments of the divalent organic group are the same as R ²⁴ in the formula (A1).

In the above formula (B1), * represents a bonding position.

The vinyl group-containing group is not particularly limited as long as it is a group containing a vinyl group (CH ₂ ═CH-) (hereinafter sometimes referred to as "Vi"). Examples of the vinyl group-containing group include a vinyl group and an allyl group, and among them, a vinyl group is preferable.

In the above formula (1), the ratio of the aryl group (hereinafter also referred to as the aryl group ratio) to the total organic groups represented by R ¹ , R ² and R ³ (in all organic groups) is 15 mol% or more. Among them, from the viewpoint of excellent adhesion and transparency of the cured product, it is preferably 25 mol% or more. The upper limit is not particularly limited, but is usually 80 mol% or less and preferably 70 mol% or less.

For example, the indicate an alkyl group as a silicone resin is a (meth) acryloyl group-containing group 2mol, R ³ as represented by R ¹ 3mol, R ² is an aryl group represented by the (B) is present 5mol, that in addition to R ^1, When the organic group represented by R ² or R ³ is not present, the total organic groups represented by R ¹ , R ² and R ³ are present in an amount of 10 mol, and 3 mol of the aryl group therein is present. Therefore, the aryl group ratio is 30 mol% 10).

In the formula (1), X ¹ represents a group selected from the group consisting of a hydrogen atom and an alkyl group (preferably having 1 to 10 carbon atoms). The alkyl group may be linear, branched or cyclic.

A, b, c, d and e in the formula (1)

0 &lt; a <

0 < b &lt; 1,

0? C <1,

0? D <1,

0? E <1,

0? B / a? 10,

0? C / a? 5,

0? D / (a + b + c + d)? 0.3,

0? E / (a + b + c + d)? 0.4

Lt; / RTI &gt;

b / a is preferably 0 to 1.0.

The value of c / a is preferably 0 to 1.0, more preferably 0.5 to 0.7.

d / (a + b + c + d) is preferably 0 to 1.0.

It is preferable that e / (a + b + c + d) is 0 to 1.0.

As described above, in the above formula (1), a is an integer (> 0). That is, the silicone resin (B) has a branched structure represented by (R ¹ SiO _3/2 ).

It is preferable that the silicone resin (B) has the above-mentioned (meth) acryloyl group-containing group for reasons of excellent adhesion of the cured product.

The weight average molecular weight (Mw) of the silicone resin (B) is not particularly limited, but is preferably 1,000 to 300,000, and more preferably 1,500 to 100,000 from the viewpoints of toughness and rigidity of the cured product.

In the composition of the present invention, the content of the silicone resin (B) is not particularly limited, but is preferably 10 to 200 mass%, more preferably 50 to 150 mass%, with respect to the content of the polysiloxane (A) .

(Method for synthesizing silicone resin (B)) [

The method for synthesizing the silicone resin (B) is not particularly limited, and for example, a method of subjecting a trialkoxysilane having an aryl group to a dealcohol condensation.

(B1) having an aryl group, (b2) a trialkoxysilane having a (meth) acryloyl group-containing group, and a polymerizable group (preferably a vinyl group) (B3) having a hydroxyl group and a hydroxyl group in the molecule. The definitions and preferred embodiments of the (meth) acryloyl group-containing group are as described above.

&Lt; Monofunctional (meth) acrylic monomer (C) &gt;

The composition of the present invention preferably contains a monofunctional (meth) acrylic monomer (C) because of the excellent flexibility of the cured product. Incidentally, the (meth) acrylic monomer refers to an acrylic monomer or a methacryl monomer.

Examples of the monofunctional (meth) acrylic monomer (C) include, but are not limited to, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, octadecyl (meth) acrylate, Hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate such as nonylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxy Roxy-3-phenoxif (Meth) acrylate such as phenyl (meth) acrylate, nonylphenoxyethyltetrahydrofurfuryl (meth) acrylate and phenoxyethyl (meth) acrylate, dicyclopentenyl (Alicyclic) (meth) acrylate such as dicyclopentyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexyl (Meth) acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxymethyl-isobornyl methacrylate, 2-methylbicycloheptaneadamantyl (meth) acrylate, and the like.

Incidentally, the monofunctional (meth) acrylic monomer (C) does not include monofunctional (meth) acrylic monomers having a plurality of ester groups.

In the composition of the present invention, the content of the monofunctional (meth) acrylic monomer (C) is not particularly limited, but is preferably 10 to 30 mass% with respect to the total amount of the composition from the viewpoints of toughness and flexibility of the cured product.

<(Meth) acrylate monomer (D) having a plurality of ester groups>

The composition of the present invention is preferably a (meth) acrylate monomer (D) having a plurality of ester groups (hereinafter, simply referred to as ester group-containing (meth) acrylate monomer) Acrylate monomer (D)).

The ester group-containing (meth) acrylate monomer (D) is not particularly limited, but is preferably a compound represented by the following formula (D1) from the viewpoints of the toughness and flexibility of the cured product and the adhesion with the adherend.

In the formula (D1), R ¹¹ represents a hydrogen atom or a methyl group.

In the formula (D1), R ¹² represents a single bond or a divalent organic group. Specific examples and preferred embodiments of the divalent organic group are the same as R ²⁴ in the formula (A1).

In the formula (D1), n represents an integer of 1 to 25.

In the composition of the present invention, the content of the ester group-containing (meth) acrylate monomer (D) is not particularly limited, but from the viewpoints of toughness and flexibility of the cured product and adhesion with an adherend, By mass to 30% by mass.

&Lt; Photopolymerization initiator &gt;

The composition of the present invention may further contain a photopolymerization initiator.

Examples of the photopolymerization initiator include, but are not limited to, acetophenones, benzoins, benzophenones (1-hydroxy-1,2,3,4,5,6-hexahydrobenzophenone, etc.) There may be mentioned peroxides, peroxides, peroxides, peroxides, peroxides, peroxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxide compounds, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, , Onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

In the composition of the present invention, the content of the photo initiator polymerization initiator is not particularly limited, but is preferably 1 to 5% by mass from the viewpoints of curability and storage stability.

<Other components>

If necessary, the composition of the present invention may further contain additives insofar as the effects and objects are not impaired.

Examples of the additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, antioxidants, radical inhibitors, An antiozonant, a thickener, a plasticizer, a radiopaque agent, a nucleating agent, a coupling agent, a conductivity imparting agent, a phosphorus peroxide decomposer, a pigment, a metal deactivator, and a physical property adjusting agent. The various additives are not particularly limited. For example, conventionally known ones can be mentioned.

The method for producing the composition of the present invention is not particularly limited, and for example, a method of producing the composition by mixing the above-described essential components and optional components may be mentioned.

The composition of the present invention can be suitably used for adhesives, primers, encapsulating materials, etc. for electronic devices such as liquid crystal displays, recording media, optical instruments and semiconductor integrated circuits.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis of polysiloxane A1)

(100 g), methylphenylpolysiloxane [HO (PhMeSiO) 7H] (100 g) having silanol groups at both terminals, 68 g of KBM5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., (1 g) were mixed and reacted at 140 DEG C for 4 hours to synthesize a methylphenylpolysiloxane having acryloyl groups at both terminals. The obtained methylphenylpolysiloxane is referred to as polysiloxane A1. The polysiloxane A1 has the following structure, and has an aryl group (phenyl group) and an alkoxy group (methoxy group), and further has acryloyl groups at both terminals.

(Synthesis of polysiloxane A2)

Both ends carbinol-modified methylphenyl polysiloxane _{[HOCH 2 CH 2 (PhMeSiO)} 6 PhMeSiCH 2 CH 2 OH, Mw: 5,000] (100g), 2- isocyanate ethyl acrylate (5g), neo Stan U-28 (inorganic metal catalyst, (Concentration for the reaction solution: 20 ppm) manufactured by Nitto Kasei Co., Ltd. (Nitto Kasei Co., Ltd.) were mixed and reacted at 70 ° C for 2 hours to synthesize a methylphenylpolysiloxane having acryloyl groups at both terminals. The obtained methylphenylpolysiloxane is referred to as polysiloxane A2. The polysiloxane A2 has the following structure, and has an aryl group (phenyl group) and a urethane bond, and further has an acryloyl group at both terminals. In addition, the polysiloxane A2 does not have an alkoxy group.

(Synthesis of polysiloxane A3)

(100 g), acrylic acid (20 g) and tetramethylphosphonium bromide (1 g) were mixed and reacted at 100 占 폚 for 5 hours to obtain a side chain , A phenyl group-containing polysiloxane having an acryloyl group was synthesized. The obtained phenyl group-containing polysiloxane is referred to as polysiloxane A3. The polysiloxane A3 has an aryl group (phenyl group) and further has an acryloyl group in its side chain. In addition, polysiloxane A3 does not have an alkoxy group.

(Synthesis of polysiloxane A4)

(100 g), dimethylpolysiloxane (trade name: KF9701, Shin-Etsu Chemical Co., Ltd.) having silanol groups at both ends, KBM5103 (3-acryloxypropyltrimethoxysilane, Shinetsu Kagakukogyo Co., Were mixed and reacted at 140 ° C for 4 hours to synthesize a dimethylpolysiloxane having acryloyl groups at both ends. The obtained dimethylpolysiloxane is referred to as polysiloxane A4. The polysiloxane A4 has an alkoxy group (methoxy group), and further has acryloyl groups at both ends. In addition, the polysiloxane A4 does not have an aryl group.

(Synthesis of urethane acrylate X1)

182.67g of polypropylene glycol having a number average molecular weight of 1000, 16.48g of polypropylene glycol having a number average molecular weight of 4000, 0.183g of 2,6-di-t-butyl-p-cresol, 255.14g of tolylene diisocyanate and 94.35 g of 2-ethylhexyl acrylate were placed, and the mixture was cooled with stirring until the liquid temperature reached 15 ° C. After 0.608 g of dibutyltin dilaurate was added, the mixture was stirred for about 1 hour while taking care not to cause the temperature to exceed 40 占 폚. After stirring to room temperature, 87.56 g of 2-hydroxypropyl acrylate was added dropwise while controlling the liquid temperature so as not to exceed 30 占 폚. After completion of dropwise addition, the mixture was stirred at a liquid temperature of 40 占 폚 for 1 hour. Then, 218.64 g of 2-hydroxyethyl acrylate was added dropwise while controlling the liquid temperature so as not to exceed 60 占 폚. After completion of the dropwise addition, the mixture was stirred at a liquid temperature of 60 ° C. When the residual isocyanate group concentration became 0.1 mass% or less, the reaction was terminated to obtain urethane acrylate. The obtained urethane acrylate is referred to as urethane acrylate X1.

(Synthesis of silicone resin B1)

In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet and a thermometer, 64.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 90 g of water, 0.14 g of trifluoromethanesulfonic acid, And 189 g of KBM103 (phenyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) and 38 g of KBM5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour while stirring After completion of dropwise addition, the mixture was heated under reflux for 1 hour. After cooling, the lower layer was separated, and the toluene solution layer was washed with water (water) three times. To the washed toluene solution layer was added 100 g of a 5% sodium hydrogencarbonate aqueous solution, and the mixture was heated to 75 캜 while stirring and refluxed for 1 hour. After cooling, the lower layer was separated and the upper toluene solution layer was washed three times. The remaining toluene solution layer was concentrated under reduced pressure to obtain a liquid silicone resin. The obtained silicone resin is referred to as silicone resin B1.

The silicone resin B1 was subjected to NMR analysis. The average unit formula was as follows.

(PhSiO _3/2 ) _0.53 (AcSiO _3/2 ) _0.09 (ViMe ₂ SiO _1/2 ) _0.38

Here, Ac represents -C ₃ H ₆ OC (= O) CH = CH ₂ .

The silicone resin B1 has an acryloyl group.

The aryl group ratio of the silicone resin B1 is 30 mol%.

(Synthesis of silicone resin B2)

A silicone resin was obtained in the same manner as in the synthesis of the silicone resin B1, except that the amount of KBM103 was 94.5 g and the amount of KBM5103 was 76 g. The obtained silicone resin is referred to as silicone resin B2.

The silicone resin B2 was subjected to NMR analysis. The average unit formula was as follows.

(PhSiO _3/2 ) _0.32 (AcSiO _3/2 ) _0.22 (ViMe ₂ SiO _1/2 ) _0.46

Here, Ac represents -C ₃ H ₆ OC (= O) CH = CH ₂ .

The silicone resin B2 has an acryloyl group.

The aryl group ratio of the silicone resin B2 is 17 mol%.

(Synthesis of silicone resin B3)

A silicone resin was obtained according to the same procedure as the synthesis of the silicone resin B1, except that KBM5103 was not added. The obtained silicone resin is referred to as silicone resin B3.

The silicone resin B3 was subjected to NMR analysis. The average unit formula was as follows.

(PhSiO _3/2 ) _0.58 (ViMe ₂ SiO _1/2 ) _0.42

Silicone resin B3 does not have a (meth) acryloyl group.

The aryl group ratio of the silicone resin B3 is 32 mol%.

(Synthesis of silicone resin X1)

Except that the amount of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was changed to 68 g, the amount of KBM103 was changed to 9.9 g, and the amount of KBM5103 was changed to 51 g. According to the same procedure as the synthesis, a silicone resin was obtained. The obtained silicone resin is referred to as silicone resin X1.

The silicone resin X1 was subjected to NMR analysis. The average unit formula was as follows.

(PhSiO _3/2 ) _0.05 (AcSiO _3/2 ) _0.22 (ViMe ₂ SiO _1/2 ) _0.73

Here, Ac represents -C ₃ H ₆ OC (= O) CH = CH ₂ .

The aryl group ratio of the silicone resin X1 is 2 mol%.

&Lt; Examples 1 to 10, Comparative Examples 1 to 3 &gt;

The components shown in the following Table 1 were used as amounts (unit: parts by mass) shown in the table, and they were uniformly mixed with a vacuum stirrer to prepare a curable resin composition.

<Adhesive strength>

The obtained curable resin composition was applied to a glass plate (coating area:? 5 mm, coating thickness: 0.3 mm), and another glass plate was affixed to the coated part by heat. Thereafter, light irradiation (amount of integrated light: 3,000 mJ / cm ² ) was performed using a light irradiation device (GS UVSYSTEM TYPE S250-01, light source: metal hydro lamp, manufactured by GS Yuasa International Ltd.) ) And cured. Thus, a sample for evaluating the adhesive strength was prepared.

The adhesive strength of the prepared samples was evaluated by tensile test. Specifically, one of the glass plates stuck to each other was fixed by using a tensile tester, and the other glass plate was pulled out at a pulling rate of 5 mm / min. When the glass plate stuck together was peeled off The maximum tensile strength was measured. This was regarded as an adhesive strength.

In addition, the produced samples were subjected to a high temperature and high humidity environment test (85 DEG C, RH 85%, 1000 hours), and then the bonding strength was evaluated by the same method as that described above.

Table 1 shows the adhesive strength before and after the high temperature and high humidity environment test and the adhesive strength retention (= adhesive strength after testing / adhesive strength before testing).

Practically, from the viewpoint of heat resistance, the adhesive strength retention ratio is preferably 80% or more.

<Appearance after high temperature and high humidity environment test>

A sample for evaluation was prepared by the same method as the above adhesive strength. The produced samples were subjected to a high temperature and high humidity environmental test (85 ° C, RH 85%, 1000 hours), and then the appearance was visually observed. The appearance after the high temperature and high humidity environment test is shown in Table 1.

<Transmittance>

A sample for evaluation was prepared by the same method as the above adhesive strength. The transmittance at a wavelength of 400 nm was measured using an ultraviolet / visible absorption spectrum measuring device (manufactured by Shimazu Seisho Shoji Co., Ltd.) in accordance with JIS K0115: 2004. The results are shown in Table 1.

Details of each component shown in the first table are as follows.

Polysiloxane A1: Polysiloxane A1 synthesized as described above

Polysiloxane A2: Polysiloxane A2 synthesized as described above

Polysiloxane A3: Polysiloxane A3 synthesized as described above

Polysiloxane A4: Polysiloxane A4 synthesized as described above

Urethane acrylate X1: urethane acrylate X1 synthesized as described above

Silicone Resin B1: Polysiloxane B1 synthesized as described above

Silicone Resin B2: Polysiloxane B2 synthesized as described above

Silicone resin B3: Polysiloxane B3 synthesized as described above

Silicone Resin X1: Polysiloxane X1 synthesized as described above

· Monofunctional acrylic monomer C1: Dicyclopentenyl acrylate

· Monofunctional acrylic monomer C2: Isobornyl acrylate

Monofunctional acrylic monomer C3: isodecyl acrylate

Ester group-containing acrylate monomer D1: Fraxel FM1 (compound represented by the formula (D1), molecular weight: 244, manufactured by DAICEL CORPORATION)

Ester group-containing acrylate monomer D2: Fraxel FM3 (compound represented by the above formula (D1), molecular weight: 473, Dicelsha)

Photopolymerization initiator: Irgacure 184 (BASF Corporation)

As can be seen from Table 1, in Comparative Examples 1 and 2 using urethane acrylate, the adhesive strength decreased after the high temperature and high humidity environment test, and the appearance changed from colorless transparent to light yellow transparent.

(A) containing at least one (meth) acryloyl group in one molecule but not containing the silicone resin (B) represented by the average unit formula (1) Also in Comparative Example 3, the adhesive strength was lowered after the high temperature and high humidity environment test, and the appearance changed from colorless transparent to pale yellow transparent.

On the other hand, in the present example in which the polysiloxane (A) having at least one (meth) acryloyl group in one molecule and the silicone resin (B) represented by the average unit formula (1) There was hardly any decrease in adhesive strength due to the high humidity environment test, and no change in appearance was observed by the high temperature and high humidity environmental test. That is, excellent heat resistance was exhibited.

Among them, in Examples 1 to 5 and 7 to 9, in which the polysiloxane (A) had a (meta) acryloyl group at an "end", the adhesion strength was higher and the adhesion was excellent It was. Among them, in Examples 1 to 5, 7 and 9 in which the silicone resin (B) had a (meth) acryloyl group, the bonding strength before the high temperature and high humidity environment test was higher and the adhesion was excellent.

The comparison between Examples 1 and 2 shows that Example 1 in which the aryl group ratio of the silicone resin (B) is 25 mol% or more as compared with Example 2 in which the aryl group ratio of the silicone resin (B) does not reach 25 mol% Both before and after the test), the adhesive strength was higher and the adhesiveness was excellent. In addition, the transmittance was high and transparency was excellent.

The comparison of Examples 5 and 6 and the comparison of Examples 9 and 10 shows that the polysiloxane (A) has a urethane bond in comparison with Examples 6 and 10 in which the polysiloxane (A) does not have a urethane bond Examples 5 and 9 (both before and after the high temperature and high humidity environment test) showed higher adhesive strength and excellent adhesion.

From the comparison of Examples 1 to 10, Examples 1 to 4 and 8, in which the polysiloxane (A) had an aryl group and an alkoxy group, showed high transmittance and excellent transparency.

Claims (7)

A curable resin composition comprising a polysiloxane (A) having at least one (meth) acryloyl group in one molecule and a silicone resin (B) represented by the following average unit formula (1).
^{_{(R 1 SiO 3/2) a (}} R 2 2 SiO 2/2) b (R 3 3 SiO 1/2) c (SiO 4/2) d (X 1 O 1/2) e ... (One)
(Wherein R ¹ , R ² and R ³ are each independently selected from the group consisting of an aryl group, a (meth) acryloyl group-containing group, an alkyl group, a cycloalkyl group, a vinyl group-containing group and an epoxy group- It represents an organic group which is. a plurality of R ² and R ³ but may be the same or each proportion of the aryl group for groups total organic the R ^1, R ² and R ³ represents is at least 15mol%. X ¹ is hydrogen A, b, c, d and e represent a group selected from the group consisting of an alkyl group,
0 &lt; a <
0 < b < 1,
0? C <1,
0? D <1,
0? E <1,
0? B / a? 10,
0? C / a? 5,
0? D / (a + b + c + d)? 0.3,
0? E / (a + b + c + d)? 0.4
Satisfies the following expression. The method according to claim 1,
Wherein the silicone resin (B) has a (meth) acryloyl group. 3. The method according to claim 1 or 2,
The polysiloxane (A) has an aryl group. 4. The method according to any one of claims 1 to 3,
Wherein the polysiloxane (A) has an alkoxy group. 5. The method according to any one of claims 1 to 4,
Wherein the polysiloxane (A) has a urethane bond. 6. The method according to any one of claims 1 to 5,
(C) and a photopolymerization initiator. The curable resin composition according to claim 1, wherein the curable resin composition further comprises a monofunctional (meth) acrylic monomer (C) and a photopolymerization initiator. 7. The method according to any one of claims 1 to 6,
(Meth) acrylate monomer (D) having a plurality of ester groups.