WO2014141819A1

WO2014141819A1 - Curable resin composition

Info

Publication number: WO2014141819A1
Application number: PCT/JP2014/053648
Authority: WO
Inventors: つばさ伊藤; 石川　和憲
Original assignee: 横浜ゴム株式会社
Priority date: 2013-03-15
Filing date: 2014-02-17
Publication date: 2014-09-18
Also published as: CN105164168A; KR102180721B1; JPWO2014141819A1; TW201441328A; JP6269652B2; TWI613271B; KR20150128672A

Abstract

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

Description

Curable resin composition

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

Adhesives are used in various parts of electronic devices such as liquid crystal displays. Examples of such an adhesive include a photocurable resin composition containing an acrylic monomer or an acrylic oligomer.

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

On the other hand, since electronic devices are often exposed to a high temperature environment, heat resistance is required for the adhesive used.
For example, if the heat resistance of an adhesive used in an electronic device is insufficient, the adhesive strength is lowered when the electronic device is exposed to a high temperature environment, leading to problems such as malfunction of the electronic device. Therefore, the adhesive used for the electronic device is required to have a low adhesive strength even when exposed to a high temperature environment.
In addition, if the heat resistance of the adhesive used for display devices such as liquid crystal displays is insufficient, the cured product of the adhesive will deteriorate and become colored when exposed to high-temperature environments, and display performance such as visibility Problem arises. Therefore, an adhesive used for a display device such as a liquid crystal display is required not to be colored even when exposed to a high temperature environment.

International Publication No. 2010/027041

When the present inventors examined the curable resin composition containing a urethane acrylate with reference to patent document 1, when a hardened | cured material is exposed to high temperature environment, it is clear that the fall of adhesive strength and coloring arise. It became. That is, it was revealed that the heat resistance of the cured product was insufficient.
Then, an object of this invention is to provide the curable resin composition which is excellent in the heat resistance of hardened | cured material in view of the said situation.

As a result of earnest research to achieve the above-mentioned problems, the inventor of the present invention uses a polysiloxane having a (meth) acryloyl group and a silicone resin represented by a specific average unit formula, whereby the heat resistance of the cured product is improved. The inventors have found that an excellent curable resin composition can be obtained, and have reached the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) 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).
(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 (1)
(In formula (1), R ¹ , R ² and R ³ each independently comprise an aryl group, a (meth) acryloyl group-containing group, an alkyl group, a cycloalkyl group, a vinyl group-containing group and an epoxy group-containing group. Represents an organic group selected from the group, and a plurality of R ² and R ³ may be the same or different, and the ratio of the aryl group to the total organic group represented by R ¹ , R ² and R ³ is 15 mol. X ¹ represents a group selected from the group consisting of a hydrogen atom and an alkyl group, a, b, c, d and e are
0 <a ≦ 1,
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
Is satisfied. )
(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 the above (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 a (meth) acrylate monomer (D) having a plurality of ester groups.

As described below, according to the present invention, it is possible to provide a curable resin composition excellent in heat resistance of a cured product.

Hereinafter, the curable resin composition of the present invention (hereinafter, also simply referred to as the composition of the present invention) will be described. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The 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 an average unit formula (1) described later. It is an adhesive resin composition.
The composition of the present invention is considered to exhibit excellent heat resistance when the composition has such a configuration.
This is not clear in detail, but is estimated to be 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 will be 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 is a composite of a siloxane skeleton in which a polysiloxane having a (meth) acryloyl group crosslinked and a specific silicone resin having a branched structure are entangled. And chemical durability such as radical resistance is improved. Such an improvement in chemical durability is considered to contribute to an improvement in heat resistance.
This indicates that the heat resistance of the cured product is insufficient when the specific polysiloxane (A) and the specific silicone resin (B) are not contained, as shown in Comparative Examples 1 and 2 described later. It is guessed from that.
In particular, the present invention is characterized in that in the silicone resin (B), the aryl group ratio described later is 15 mol% or more. By using such a silicone resin, the packing of aryl groups proceeds during curing, and a cured product that does not easily change its structure even when exposed to a high temperature environment is obtained. That is, it is considered that the cured product is excellent in heat resistance and toughness.
As shown in Comparative Example 3 to be described later, this indicates that even if polysiloxane (A) and silicone resin are used in combination, if the aryl group ratio to be described later of the silicone resin is less than 15 mol%, it is cured. It is also speculated that the heat resistance of the object becomes insufficient.

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

<Polysiloxane (A)>
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. 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.

As described above, the polysiloxane (A) is crosslinked by the reaction between the (meth) acryloyl groups of the polysiloxane (A) at the time of curing. Moreover, when the silicone resin (B) mentioned later has a (meth) acryloyl group, not only polysiloxane (A) but also silicone resin (B) are bridge | crosslinked.

The polysiloxane (A) may be a linear polysiloxane or a branched polysiloxane. Among these, a linear polysiloxane (linear polysiloxane) is preferable because the elongation of the cured product is excellent.

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 a (meth) acryloyl group in the side chain. Especially, since it is excellent in the elongation of hardened | cured material, it is preferable that it has a (meth) acryloyl group at the terminal. When polysiloxane (A) is a linear polysiloxane, it is preferable that it has (meth) acryloyl groups at both ends.

Examples of the group bonded to the silicon atom in the polysiloxane (A) include a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, and a hydrocarbon group which may have a hetero atom.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Examples of the hetero atom of the hydrocarbon group that may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
Examples of the hydrocarbon group of the hydrocarbon group that may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which these are combined.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly, having 1 to 10 carbon atoms), a linear or branched alkenyl group (having 2 to 10 carbon atoms), and a linear chain. And linear or branched alkynyl groups (particularly 2 to 10 carbon atoms), linear or branched cycloalkyl groups, and the like.
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more specifically, an aryl group and a naphthyl group. Examples of the aryl group include a phenyl group (hereinafter sometimes referred to as “Ph”), an aryl group having 6 to 18 carbon atoms such as a tolyl group, and a xylyl group. It is preferable.

The polysiloxane (A) preferably has an aryl group. Specific examples and preferred embodiments of the aryl group are as described above.
Among them, 5 to 50 mol% of the group bonded to the silicon atom of the polysiloxane (A) is preferably an aryl group, and more preferably 10 to 30 mol% is an aryl group.

The polysiloxane (A) preferably has an alkoxy group because of its excellent adhesion to the adherend.

The polysiloxane (A) preferably has an aryl group and an alkoxy group from the viewpoint of transparency.

The polysiloxane (A) preferably has a urethane bond because hydrogen bonds are formed in the cured product to improve the adhesion of the cured product.

As a suitable aspect of polysiloxane (A), the compound etc. which are represented by a following formula (A1) are mentioned, for example.

In the above formula (A1), R ²¹ represents a hydrogen atom or a methyl group (hereinafter sometimes referred to as “Me”). A plurality of R ²¹ may be the same or different.
In the above 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. A plurality of R ²² may be the same or different.
In the above 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. A plurality of R ²³ may be the same or different.
In the above formula (A1), R ²⁴ represents a divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (for example, an arylene group). Preferably 6 to 12 carbon atoms), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH -, or a group comprising a combination thereof (e.g., alkyleneoxy group (-C _m H _2m O-: _m is a positive integer), alkyleneoxy carbonyl group, an alkylene carbonyl group) and the like.
In the above formula (A1), R ²⁵ and R ²⁶ represents 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 said formula (A1), l 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 above formula (A1), n represents an integer of 0 to 2. Especially, since it is excellent in adhesiveness with a to-be-adhered body, it is preferable that it is an integer greater than or equal to 1.

The compound represented by the above formula (A1) is preferably a compound in which 5 to 50 mol% of the groups bonded to the silicon atom are aryl groups because the cured product is more excellent in heat resistance and toughness. More preferably, ˜30 mol% is an aryl group.

The weight average molecular weight (Mw) of the polysiloxane (A) is not particularly limited, but is preferably from 100 to 1,000,000, and preferably from 500 to 50,000, because the toughness and elongation of the cured product are excellent. Is more preferable.
In addition, in this application, a weight average molecular weight is taken as the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) which uses chloroform as a solvent.
The viscosity of the polysiloxane (A) at 25 ° C. is preferably 20 to 1,000,000 mPa · s, more preferably 200 to 100,000 mPa · s.
In the present application, the viscosity is measured at 25 ° C. according to JIS K7117-1 4.1 (Brookfield rotary viscometer).

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 preferably 30 to 70% by mass because of excellent toughness and elongation of the cured product. It is more preferable.

(Method for synthesizing polysiloxane (A))
The method for 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 in one molecule. And a method for obtaining a polysiloxane having a group.
Among these, a method of reacting a polysiloxane (a11) having a silanol group at the terminal (preferably both terminals) and an alkoxysilane (a21) having a (meth) acryloyl group is preferable. The alkoxysilane (a21) having a (meth) acryloyl group preferably has two or more alkoxy groups from the viewpoint of excellent adhesion to the adherend.
As another preferred embodiment of the method of synthesizing the polysiloxane (A) by reacting the polysiloxane (a1) and the monomer (a2) having a (meth) acryloyl group, for example, at the terminals (preferably both terminals) Examples thereof include a method of reacting a polysiloxane (a12) having a hydroxyalkyl group (—R—OH: R is an alkylene group) with an isocyanate (a22) having a (meth) acryloyl group.
Another preferred embodiment of the method for synthesizing the polysiloxane (A) by reacting the polysiloxane (a1) with the monomer (a2) having a (meth) acryloyl group includes a polysiloxane having an epoxy group (a13). ) And (meth) acrylic acid.
The polysiloxane (a1) used for the synthesis of the polysiloxane (A) is preferably one having an aryl group because the cured product has excellent transparency and the cured product has more excellent heat resistance. . Specific examples and preferred embodiments of the aryl group are as described above.

<Silicone resin (B)>
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 number of siloxane units 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 (1)

In the above formula (1), R ¹ , R ² and R ³ are each independently an aryl group, a (meth) acryloyl group-containing group, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group or a vinyl group. An organic group selected from the group consisting of a containing group and an epoxy group-containing group. A plurality of R ² and R ³ may be the same or different.
When a plurality of units (R ¹ SiO _3/2 ) are present in the silicone resin (B), one unit (R ¹ SiO _3/2 ) and another unit (R ¹ SiO _3/2 ) are the same. Or different. That, R ¹ of a certain unit (R ¹ SiO _3/2) of R ¹ and other units (R ¹ SiO _3/2) may be different even in the same. The same applies to (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 is a hydrocarbon group having a (meth) acryloyloxy group as a substituent from the viewpoint of curability. And an alkyl group (particularly having 1 to 10 carbon atoms) having a (meth) acryloyloxy group as a substituent is more preferable.

As a suitable aspect of the above (meth) acryloyl group-containing group, for example, a group represented by the following formula (B1) can be mentioned.

In the above 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 formula (A1) described above.
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”). As said vinyl group containing group, a vinyl group, an allyl group, etc. are mentioned, for example, It is preferable that it is a vinyl group especially.

In the above formula (1), the ratio of aryl groups (in the total organic groups) to the total organic groups represented by R ¹ , R ² and R ³ (hereinafter also referred to as aryl group ratio) is 15 mol% or more. Especially, it is preferable that it is 25 mol% or more from the reason which the adhesiveness and transparency of hardened | cured material are excellent. The upper limit is not particularly limited, but is usually 80 mol% or less, and preferably 70 mol% or less.
For example, in the silicone resin (B), 3 mol of an aryl group represented by R ¹ , ² mol of a (meth) acryloyl group-containing group represented by R 2, 5 mol of an alkyl group represented by R ³ are present, When there is no organic group represented by R ¹ , R ² or R ^3, there are 10 mol of all organic groups represented by R ¹ , R ² and R ³ , of which 3 mol of aryl groups are present. The rate is 30 mol% (= 3/10).

In the above 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.

In the above formula (1), a, b, c, d and e are
0 <a ≦ 1,
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
Is satisfied.

b / a is preferably 0 to 1.0.
c / a is preferably 0 to 1.0, and more preferably 0.5 to 0.7.
d / (a + b + c + d) is preferably 0 to 1.0.
e / (a + b + c + d) is preferably 0 to 1.0.

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

The silicone resin (B) preferably has the (meth) acryloyl group-containing group described above for the reason 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 preferably 1,500 to 100,000 from the viewpoint of toughness and rigidity of the cured product. It is more preferable.

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

(Synthesis method of silicone resin (B))
The method for synthesizing the silicone resin (B) is not particularly limited, and examples thereof include a method of dealcoholizing a trialkoxysilane having an aryl group.
Preferred embodiments of the method for synthesizing the silicone resin (B) include trialkoxysilane (b1) having an aryl group, trialkoxysilane (b2) having a (meth) acryloyl group-containing group, and a polymerizable group (preferably vinyl). And a method of dealcoholizing with a disiloxane (b3) having a group. The definition and preferred embodiments of the (meth) acryloyl group-containing group are as described above.

<Monofunctional (meth) acrylic monomer (C)>
The composition of the present invention preferably further contains a monofunctional (meth) acrylic monomer (C) for the reason that the cured product is excellent in flexibility. In addition, a (meth) acryl monomer represents an acrylic monomer or a methacryl monomer.

The monofunctional (meth) acrylic monomer (C) is not particularly limited, but ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate , Hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3 -Aliphatic (meth) acrylates such as chloro-2-hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, benzyl (meth) acrylate, etc. Nonylphenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) acrylate, phenoxyethyl ( Aromatic (meth) acrylates such as (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexyl ( Alicyclic (meth) acrylates such as (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine, isobornyl (meta) Acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxy-2-methyl bicycloheptane adamantyl (meth) acrylate, and the like.

The monofunctional (meth) acrylic monomer (C) does not include a monofunctional (meth) acrylic monomer 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 10 to 30% by mass with respect to the total amount of the composition from the viewpoint of toughness and flexibility of the cured product. It is preferable.

<(Meth) acrylate monomer (D) having a plurality of ester groups>
The composition of the present invention is a (meth) acrylate monomer having a plurality of ester groups (D) (hereinafter simply referred to as ester groups) from the viewpoint of toughness and flexibility of the cured product and adhesion to the adherend. (Meth) acrylate monomer (D) may also be contained.

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

In the above formula (D1), R ¹¹ represents a hydrogen atom or a methyl group.
In the above 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 formula (A1) described above.
In the above 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 viewpoint of toughness and flexibility of the cured product and adhesion to the adherend, The content is preferably 5 to 30% by mass with respect to the total amount.

<Photopolymerization initiator>
The composition of the present invention may further contain a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and examples thereof include acetophenones, benzoins, benzophenones (such as 1-hydroxy-1,2,3,4,5,6-hexahydrobenzophenone), phosphine oxides, ketals. , Anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, activity Examples include esters, active halogens, inorganic complexes, and coumarins.

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

<Other ingredients>
If necessary, the composition of the present invention may further contain an additive within a range not impairing its effects and purposes.
Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property-imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.

The method for producing the composition of the present invention is not particularly limited, and examples thereof include a method for producing the composition by mixing the above-described essential components and optional components.

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

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

(Synthesis of polysiloxane A1)
Mixing methylphenylpolysiloxane having silanol groups at both ends [HO (PhMeSiO) ₇ H] (100 g), KBM5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) (68 g), and acetic acid (1 g) The mixture was reacted at 140 ° C. for 4 hours to synthesize methylphenylpolysiloxane having acryloyl groups at both ends. The obtained methylphenyl polysiloxane is designated as polysiloxane A1. Polysiloxane A1 has the following structure, has an aryl group (phenyl group) and an alkoxy group (methoxy group), and further has an acryloyl group at both ends.

(Synthesis of polysiloxane A2)
Both ends carbinol-modified methyl phenyl polysiloxane [HOCH ₂ CH ₂ (PhMeSiO) ₆ PhMeSiCH ₂ CH ₂ OH, Mw: 5,000] (100 g), 2-isocyanatoethyl acrylate (5 g), neostan U-28 (inorganic metal) Catalyst, manufactured by Nitto Kasei Co., Ltd. (concentration with respect to the reaction solution: 20 ppm) were mixed and reacted at 70 ° C. for 2 hours to synthesize methylphenylpolysiloxane having acryloyl groups at both ends. The obtained methylphenyl polysiloxane is designated as polysiloxane A2. Polysiloxane A2 has the following structure, has an aryl group (phenyl group) and a urethane bond, and further has an acryloyl group at both ends. In addition, polysiloxane A2 does not have an alkoxy group.

(Synthesis of polysiloxane A3)
Phenyl group-containing epoxy-modified polysiloxane (trade name: X-22-2000, manufactured by Shin-Etsu Chemical Co., Ltd.) (100 g), acrylic acid (20 g), tetramethylphosphonium bromide (1 g) are mixed and reacted at 100 ° C. for 5 hours. Thus, a phenyl group-containing polysiloxane having an acryloyl group in the side chain was synthesized. The obtained phenyl group-containing polysiloxane is designated as polysiloxane A3. Polysiloxane A3 has an aryl group (phenyl group), and further has an acryloyl group in the side chain. Polysiloxane A3 does not have an alkoxy group.

(Synthesis of polysiloxane A4)
Dimethylpolysiloxane having silanol groups at both ends (trade name: KF9701, manufactured by Shin-Etsu Chemical Co., Ltd.) (100 g), KBM5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) (17 g), acetic acid (1 g) ), And reacted at 140 ° C. for 4 hours to synthesize dimethylpolysiloxane having acryloyl groups at both ends. The obtained dimethylpolysiloxane is designated as polysiloxane A4. Polysiloxane A4 has an alkoxy group (methoxy group), and further has an acryloyl group at both ends. Polysiloxane A4 does not have an aryl group.

(Synthesis of urethane acrylate X1)
In a reaction vessel equipped with a stirrer, 182.67 g of polypropylene glycol having a number average molecular weight of 1000, 16.48 g of polypropylene glycol having a number average molecular weight of 4000, 0.183 g of 2,6-di-t-butyl-p-cresol, tolylene diisocyanate 255.14 g and 2-ethylhexyl acrylate 94.35 g were charged, and the mixture was cooled to a liquid temperature of 15 ° C. while stirring. After adding 0.608 g of dibutyltin dilaurate, the mixture was stirred for about 1 hour, taking care not to increase the temperature to 40 ° C. or higher. After stirring to room temperature, 87.56 g of 2-hydroxypropyl acrylate was added dropwise while adjusting the liquid temperature so as not to exceed 30 ° C. After completion of dropping, the mixture was stirred at a liquid temperature of 40 ° C. for 1 hour. Next, 218.64 g of 2-hydroxyethyl acrylate was added dropwise while adjusting the liquid temperature so as not to exceed 60 ° C. After completion of dropping, the mixture was stirred at a liquid temperature of 60 ° C. When the residual isocyanate group concentration was 0.1% by mass or less, the reaction was terminated, and urethane acrylate was obtained. Let the obtained urethane acrylate be urethane acrylate X1.

(Synthesis of silicone resin B1)
In a four-necked flask equipped with a stirrer, reflux condenser, inlet, thermometer, 64.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 90 g of water, 0.14 g of trifluoromethanesulfonic acid and toluene 200 g was added and mixed, and 189 g of KBM103 (phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 38 g of KBM5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise over 1 hour with stirring. After completion of the dropwise addition, the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated, and the toluene solution layer was washed with water three times. 100 g of 5% aqueous sodium hydrogen carbonate solution was added to the toluene solution layer that had been washed with water, and the mixture was heated to 75 ° C. with stirring and refluxed for 1 hour. After cooling, the lower layer was separated, and the upper toluene solution layer was washed with water three times. The remaining toluene solution layer was concentrated under reduced pressure to obtain a liquid silicone resin. Let the obtained silicone resin be silicone resin B1.
When the NMR analysis was performed about silicone resin B1, 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 .
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 according to the same procedure as the synthesis of silicone resin B1, except that the amount of KBM103 was 94.5 g and the amount of KBM5103 was 76 g. Let the obtained silicone resin be silicone resin B2.
When NMR analysis was performed on the silicone resin B2, 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 .
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 silicone resin B1, except that KBM5103 was not added. Let the obtained silicone resin be silicone resin B3.
When NMR analysis was performed on the silicone resin B3, 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)
Synthesis of silicone resin B1 except that the amount of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is 68 g, the amount of KBM103 is 9.9 g, and the amount of KBM5103 is 51 g A silicone resin was obtained according to the procedure described in 1. Let the obtained silicone resin be silicone resin X1.
NMR analysis of the silicone resin X1 revealed that 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%.

<Examples 1 to 10, Comparative Examples 1 to 3>
The components shown in Table 1 below were used in the amounts shown in the same table (unit: parts by mass), and these 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 (application area: φ5 mm, application thickness: 0.3 mm), and another glass plate was bonded to the applied part in a cross shape. Thereafter, light irradiation (integrated light amount: 3,000 mJ / cm ² ) was performed using a light irradiation device (device name: GS UVSYSTEM TYPE S250-01, light source: metal hydrolamp, manufactured by GS Yuasa Lighting Co., Ltd.) and cured. . In this way, a sample for evaluating the adhesive strength was prepared.
The adhesive strength was evaluated by the tensile test about the produced sample. Specifically, using a tensile tester, one of the glass plates bonded to the cross is fixed, the other glass plate is pulled at a tensile speed of 5 mm / min, and the glass plate bonded to the cross is peeled off. The maximum tensile strength was measured. This was defined as adhesive strength.
Moreover, the high-temperature, high-humidity environment test (85 degreeC, RH85%, 1000 hours) was done about the produced sample, and adhesive strength was evaluated by the method similar to the method mentioned above after that.
Table 1 shows the adhesive strength before and after the high-temperature and high-humidity environment test and the adhesive strength maintenance rate (= post-test adhesive strength / pre-test adhesive strength).
Practically, from the viewpoint of heat resistance, the adhesive strength maintenance rate is preferably 80% or more.

<Appearance after high temperature and high humidity environment test>
A sample for evaluation was produced by the same method as the adhesive strength. About the produced sample, the high temperature, high humidity environment test (85 degreeC, RH85%, 1000 hours) was done, and the external appearance was observed visually after that. Table 1 shows the appearance after the high temperature and high humidity environment test.

<Transmissivity>
A sample for evaluation was produced by the same method as the adhesive strength. Based on JIS K0115: 2004, the transmittance | permeability in wavelength 400nm was measured using the ultraviolet-visible absorption spectrum measuring apparatus (made by Shimadzu Corp.). The results are shown in Table 1.

Details of each component shown in Table 1 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: Plaxel FM1 (represented by the above formula (D1) Compound, molecular weight: 244, manufactured by Daicel)
Ester group-containing acrylate monomer D2: Plaxel FM3 (compound represented by the above formula (D1), molecular weight: 473, manufactured by Daicel Corporation)
Photoinitiator: Irgacure 184 (manufactured by BASF)

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 and transparent to light yellow and transparent.
Further, it contains polysiloxane (A) having at least one (meth) acryloyl group in one molecule, but does not contain the silicone resin (B) represented by the above average unit formula (1) (aryl group ratio is Also in Comparative Example 3 (containing a silicone resin of less than 15 mol%), the adhesive strength decreased after the high temperature and high humidity environment test, and the appearance changed from colorless and transparent to light yellow and transparent.
On the other hand, in this application example containing polysiloxane (A) having at least one (meth) acryloyl group in one molecule and silicone resin (B) represented by the above average unit formula (1), However, there was almost no decrease in the adhesive strength due to the high temperature and high humidity environment test, and no change in the appearance due to the high temperature and high humidity environment test was observed. That is, it showed excellent heat resistance.
Among them, Examples 1 to 5 and 7 to 9 in which the polysiloxane (A) has a (meth) acryloyl group at “terminal” have higher adhesive strength (before and after the high-temperature and high-humidity environment test), and adhesion. It was excellent. Among them, Examples 1 to 5, 7 and 9 in which the silicone resin (B) has a (meth) acryloyl group had higher adhesive strength before the high-temperature and high-humidity environment test and excellent adhesion.
From the comparison between Examples 1 and 2, an example in which the silicone resin (B) has an aryl group ratio of 25 mol% or more as compared with Example 2 in which the silicone resin (B) has an aryl group ratio of less than 25 mol%. No. 1 (both before and after the high temperature and high humidity environment test) had higher adhesive strength and excellent adhesion. Moreover, the transmittance was high and the transparency was excellent.
From the comparison between Examples 5 and 6 and the comparison between Examples 9 and 10, the polysiloxane (A) is urethane compared to Examples 6 and 10 where the polysiloxane (A) does not have a urethane bond. Examples 5 and 9 having a bond had higher adhesive strength (before and after the high-temperature and high-humidity environment test) and were excellent in adhesion.
From the comparison with Examples 1 to 10, Examples 1 to 4 and 8 in which the polysiloxane (A) has an aryl group and an alkoxy group have high transmittance and excellent transparency.

Claims

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).
(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 (1)
(In formula (1), R 1 , R 2 and R 3 each independently comprise an aryl group, a (meth) acryloyl group-containing group, an alkyl group, a cycloalkyl group, a vinyl group-containing group and an epoxy group-containing group. Represents an organic group selected from the group, and a plurality of R 2 and R 3 may be the same or different, and the ratio of the aryl group to the total organic group represented by R 1 , R 2 and R 3 is 15 mol. X 1 represents a group selected from the group consisting of a hydrogen atom and an alkyl group, a, b, c, d and e are
0 <a ≦ 1,
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
Is satisfied. )
The curable resin composition according to claim 1, wherein the silicone resin (B) has a (meth) acryloyl group.
The curable resin composition according to claim 1 or 2, wherein the polysiloxane (A) has an aryl group.
The curable resin composition according to any one of claims 1 to 3, wherein the polysiloxane (A) has an alkoxy group.
The curable resin composition according to any one of claims 1 to 4, wherein the polysiloxane (A) has a urethane bond.
The curable resin composition according to any one of claims 1 to 5, further comprising a monofunctional (meth) acrylic monomer (C) and a photopolymerization initiator.
The curable resin composition according to any one of claims 1 to 6, further comprising a (meth) acrylate monomer (D) having a plurality of ester groups.