CN105164168A - Curable resin composition - Google Patents

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

technical field

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

Background technique

Adhesives are used in various parts of electronic devices such as liquid crystal displays. Such an adhesive may be, for example, a photocurable resin composition containing an acrylic monomer or an acrylic oligomer, or the like.

For example, Patent Document 1 discloses a photocurable resin composition used as an adhesive for bonding displays such as liquid crystal displays and optical functional materials (claim 5, etc.), which contains polyurethane in its skeleton. (Meth)acrylate oligomers (i.e. urethane acrylates).

On the other hand, since electronic devices are often exposed to high-temperature environments, the adhesives used are required to have heat resistance.

For example, if the heat resistance of an adhesive used for an electronic device is insufficient, when the electronic device is exposed to a high temperature environment, the adhesive strength of the adhesive decreases, thereby causing problems such as poor operation of the electronic device. Therefore, it is required that the adhesive strength of the adhesive used for electronic equipment is not easily lowered even if it is exposed to a high-temperature environment.

In addition, if the heat resistance of the adhesive used in a display device such as a liquid crystal display is insufficient, when exposed to a high temperature environment, the cured product of the adhesive will be deteriorated and colored, and there will be a problem that the display performance such as visible objects will decrease. . Therefore, adhesives used for display devices such as liquid crystal displays are required not to be colored even when exposed to high-temperature environments.

prior art literature

patent documents

[Patent Document 1] International Publication No. 2010/027041

Contents of the invention

The problem to be solved by the invention

Referring to Patent Document 1, the present inventors studied curable resin compositions containing urethane acrylate, and found that when the cured product was exposed to a high temperature environment, the adhesive strength would decrease and coloration would occur. That is, it was found that the heat resistance of the cured product was insufficient.

In view of the above circumstances, an object of the present invention is to provide a curable resin composition whose cured product has excellent heat resistance.

A solution to the problem described

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the use of polysiloxane having a (meth)acryloyl group and a silicone resin represented by a specific average unit formula together can provide a cured product with excellent heat resistance. resin composition, thus completing the present invention.

That is, the inventors of the present invention found that the above-mentioned problems can be solved by the following configuration.

(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 …(1)

(In formula (1), R ¹ , R ² and R ³ independently represent groups selected from aryl groups, groups containing (meth)acryloyl groups, alkyl groups, cycloalkyl groups, groups containing vinyl groups and groups containing The organic group in the group that the group of epoxy group forms. Multiple R ² and R ³ can be identical or different respectively. The ratio of aryl group relative to all organic groups shown in R ¹ , R ² and R ³ is 15mol More than %. X ¹ represents a group selected from the group consisting of a hydrogen atom and an alkyl group. A, b, c, d and e satisfy the following relational formula:

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).

(2) The curable resin composition as described in said (1) whose said silicone resin (B) has a (meth)acryloyl group.

(3) The curable resin composition as described in said (1) or (2) whose said polysiloxane (A) has an aryl group.

(4) The curable resin composition as described in any one of said (1)-(3) whose said polysiloxane (A) has an alkoxy group.

(5) The curable resin composition as described in any one of said (1)-(4) whose said polysiloxane (A) has a urethane bond.

(6) The curable resin composition as described in any one of said (1)-(5) further containing a monofunctional (meth)acrylic monomer (C) and a photoinitiator.

(7) The curable resin composition as described in any one of said (1)-(6) which contains the (meth)acrylate monomer (D) which has several ester groups further.

Invention effect

As shown below, the present invention can provide a curable resin composition whose cured product has excellent heat resistance.

Detailed ways

The curable resin composition of the present invention (hereinafter simply referred to as "the composition of the present invention") will be described below. In addition, the numerical range represented by "-" in this specification is the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

The composition of the present invention is a curable resin combination 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) thing.

The composition of the present invention exhibits excellent heat resistance in its cured product by adopting such a constitution.

Although the detailed reason thereof is not clear, it can be roughly estimated as follows.

As described above, the composition of the present invention uses both the specific polysiloxane (A) and the specific silicone resin (B). The silicone resin (B) used in the present invention has a branched chain structure as described below.

Since the composition of the present invention uses these two components at the same time, its cured product is a siloxane skeleton formed by interweaving (meth)acryloyl crosslinked polysiloxane and specific silicone resin with branched chain structure. Complex, thereby improving chemical durability such as anti-free radical activity. This increased chemical durability will contribute to improved heat resistance.

This is also presumed as shown in Comparative Examples 1 and 2 below: when the above-mentioned specific polysiloxane (A) and the above-mentioned specific silicone resin (B) are not contained, the heat resistance of the cured product is insufficient.

In particular, in the present invention, the silicone resin (B) is characterized in that the aryl group ratio described below is 15 mol % or more. By using this type of silicone resin, aryl groups are deeply packed with each other during curing, resulting in a cured product that is less prone to structural changes even when exposed to high temperature environments. That is, a cured product having excellent heat resistance and excellent toughness is formed.

This point can also be presumed as shown in Comparative Example 3 below. Even if polysiloxane (A) and silicone resin are used together, when the aryl group ratio of the silicone resin is less than 15 mol%, the heat resistance of the cured product is insufficient.

Next, polysiloxane (A), silicone resin (B), and other components that may be contained as necessary will be described in detail.

<Polysiloxane (A)>

The polysiloxane (A) used in the composition of the present invention is not particularly limited except that it has at least one (meth)acryloyl group in one molecule. In addition, in this patent, a (meth)acryloyl group means an acryloyl group or a methacryloyl group. In addition, polysiloxane refers to a compound having two or more siloxane structures (-Si-O-) in the main chain.

As described above, when the polysiloxane (A) is cured, the (meth)acryloyl groups of the polysiloxane (A) react with each other to crosslink. In addition, when the following silicone resin (B) has a (meth)acryloyl group, not only the polysiloxanes (A) are crosslinked but also the silicone resin (B) is crosslinked.

The polysiloxane (A) may be a linear polysiloxane or a branched polysiloxane. Among them, straight-chain polysiloxane (linear polysiloxane) is preferable in order to provide a cured product with excellent elongation.

In polysiloxane (A), the position of the above-mentioned (meth)acryloyl group is not particularly limited. For example, polysiloxane (A) may have a (meth)acryloyl group at a terminal, and may have a (meth)acryloyl group at a side chain. Among them, it is preferable to have a (meth)acryloyl group at the terminal in order to make the cured product have excellent elongation. When the polysiloxane (A) is a linear polysiloxane, it preferably has (meth)acryloyl groups at both terminals.

The group bonded to the silicon atom in the polysiloxane (A) may be, for example, a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group which may have a heteroatom, or the like.

The aforementioned halogen atom may be, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

The heteroatom in the above-mentioned hydrocarbon group which may have a heteroatom may be, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or the like.

The hydrocarbon group in the above-mentioned hydrocarbon group which may have a heteroatom may be, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a group combining these groups, or the like.

The above-mentioned aliphatic hydrocarbon group may be any of linear, branched and cyclic. Specific examples of the aforementioned aliphatic hydrocarbon groups may be straight-chain or branched-chain alkyl groups (especially 1-10 carbon atoms), straight-chain or branched-chain alkenyl groups (2-10 carbon atoms), straight-chain or branched-chain alkynyl groups (especially having 2 to 10 carbon atoms), straight chain or branched cycloalkyl group, and the like.

The aforementioned aromatic hydrocarbon group may be, for example, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more specifically, an aryl group, a naphthyl group, or the like. The aforementioned aryl group may be, for example, an aryl group having 6 to 18 carbon atoms such as phenyl (hereinafter sometimes represented by "Ph"), tolyl, and xylyl, among which phenyl is preferred.

Polysiloxane (A) preferably has an aryl group. Specific examples and preferred forms of the aryl group are as described above.

Among them, 5 to 50 mol% of groups bonded to silicon atoms in the polysiloxane (A) are preferably aryl groups, and more preferably 10 to 30 mol% are aryl groups.

The polysiloxane (A) preferably has an alkoxy group in view of excellent adhesion to an adherend.

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

The polysiloxane (A) preferably has a urethane bond in view of the improvement of the adhesiveness of the cured product by forming hydrogen bonds in the cured product.

A preferable form of polysiloxane (A) may be, for example, a compound represented by the following formula (A1) or the like.

chemical formula 1

In the above formula (A1), R ²¹ represents a hydrogen atom or a methyl group (hereinafter sometimes represented by "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. Multiple 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. Multiple R ²³ may be the same or different.

In the above formula (A1), R ²⁴ represents a divalent organic group. The divalent organic group can be, for example, a substituted or unsubstituted aliphatic hydrocarbon group (such as an alkylene group, preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (such as an arylene group, preferably having 6 carbon atoms), ~12), -O-, -S-, -SO ₂ -, -N(R)-(R: alkyl), -CO-, -NH-, -COO-, -CONH-, or a combination of these group (eg, alkyleneoxy (-C _m H _2m O-: m is a positive integer), alkyleneoxycarbonyl, alkylenecarbonyloxy, etc.) and the like.

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

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

In said formula (A1), n represents the integer of 0-2. Among them, an integer of 1 or more is preferable in view of excellent adhesiveness with an adherend.

Considering the more excellent heat resistance and toughness of the cured product, preferably 5 to 50 mol% of the group bonded to the silicon atom of the compound represented by the above formula (A1) is an aryl group, more preferably 10 to 30 mol% is an aryl group .

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

In addition, the weight average molecular weight in this patent is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.

In addition, the polysiloxane (A) preferably has a viscosity at 25° C. of 20 to 1,000,000 mPa·s, more preferably 200 to 100,000 mPa·s.

In addition, in this patent, the viscosity is the viscosity measured at 25 degreeC based on 4.1 (Brookfield rotational viscometer) of JISK7117-1.

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

(Synthetic method of polysiloxane (A))

The synthesis method of polysiloxane (A) is not particularly limited, and the method can be, for example, reacting polysiloxane (a1) with a monomer (a2) having a (meth)acryloyl group to obtain a compound having At least one (meth)acryloyl polysiloxane and the like.

Among these, the method of making the polysiloxane (a11) which has a silanol group at a terminal (preferably both terminals) and the alkoxysilane (a21) which has a (meth)acryloyl group react is preferable. The alkoxysilane (a21) having a (meth)acryloyl group preferably has two or more alkoxy groups in view of excellent adhesion to an adherend.

Another preferred form of the method of synthesizing polysiloxane (A) after reacting polysiloxane (a1) with a monomer (a2) having a (meth)acryloyl group can be, for example, having Reaction of polysiloxane (a12) having a hydroxyalkyl group (-R-OH: R is an alkylene group) and isocyanate (a22) having a (meth)acryloyl group, etc.

In addition, another preferred form of the method for synthesizing polysiloxane (A) by reacting polysiloxane (a1) with monomer (a2) having a (meth)acryloyl group may be to make polysiloxane (a1) having an epoxy group Oxyalkylene (a13) reacts with (meth)acrylic acid, etc.

The above polysiloxane (a1) used in the synthesis of polysiloxane (A) preferably has an aryl group in view of excellent transparency of the cured product and more excellent heat resistance of the cured product. Specific examples and preferred forms 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). However, the following average unit formula (1) represents the number of moles of each siloxane unit when all the siloxane units constituting the silicone resin (B) are taken as 1 mol.

(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 independently represent groups selected from aryl groups, groups containing (meth)acryloyl groups, alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups, , an organic group in the group consisting of a vinyl group-containing group and an epoxy group-containing group. A 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), one unit (R ¹ SiO _3/2 ) may be the same as or different from the other unit (R ¹ SiO _3/2 ). That is, R ¹ of one unit (R ¹ SiO _3/2 ) and R ¹ of the other unit (R ¹ SiO _3/2 ) may be the same or different. The same is true for (R ² ₂ SiO _2/2 ), (R ³ ₃ SiO _1/2 ), (X ¹ O _1/2 ).

Specific examples and preferred forms of the above-mentioned aryl group are as described above.

The above-mentioned (meth)acryloyl group-containing group is not particularly limited except for a (meth)acryloyl group-containing group, and a hydrocarbon group having a (meth)acryloyloxy group as a substituent is preferable from the viewpoint of curability. , more preferably an alkyl group (especially having 1 to 10 carbon atoms) having a (meth)acryloyloxy group as a substituent.

A preferable form of the above-mentioned (meth)acryloyl group-containing group may be, for example, a group represented by the following formula (B1).

chemical formula 2

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 forms of the divalent organic group are the same as R ²⁴ in the above formula (A1).

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

The above-mentioned vinyl group-containing group is not particularly limited except for a group containing a vinyl group (CH ₂ =CH—) (hereinafter sometimes represented by “Vi”). The aforementioned vinyl group-containing group may be, for example, vinyl group, propenyl group, etc., among which vinyl group is preferred.

In the above formula (1), the ratio of aryl groups (hereinafter referred to as "aryl ratio") to all organic groups represented by R ¹ , R ² and R ³ (out of all organic groups) is 15 mol% or more. Among them, 25 mol% or more is preferable in consideration of excellent adhesiveness and transparency of the cured product. Although the upper limit is not particularly limited, it is usually 80 mol% or less, preferably 70 mol% or less.

For example, in the silicone resin (B), there are 3 mol of aryl groups represented by R ¹ , ² mol of (meth)acryloyl-containing groups represented by R 2 , and 5 mol of alkyl groups represented by R ³ , and in addition When there is no organic group shown in other R ¹ , R ² or R ³ , there are 10 mol of all organic groups shown in R ¹ , R ² and R ³ , and 3 mol of aryl groups exist, so the aryl ratio 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 above-mentioned alkyl group may be any of linear, branched and cyclic.

In the above formula (1), a, b, c, d and e satisfy the following relationship:

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.

b/a is preferably 0 to 1.0.

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.

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

As mentioned 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 above-mentioned (meth)acryloyl group-containing group in view of excellent adhesiveness of a 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, more preferably 1,500 to 100,000 from the viewpoint 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% by mass, more preferably 50 to 150% by mass based on the content of the polysiloxane (A).

(Synthesis method of silicone resin (B))

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

A preferred form of the method for synthesizing the silicone resin (B) is to make a trialkoxysilane (b1) having an aryl group, a trialkoxysilane (b2) having a (meth)acryloyl group-containing group, a polymerizable group Group (preferably vinyl) disiloxane (b3) three are dealcoholized and condensed. The definition and preferred forms of the above-mentioned (meth)acryloyl group-containing group are as described above.

<Monofunctional (meth)acrylic monomer (C)>

In view of the excellent flexibility of the cured product, the composition of the present invention preferably further contains a monofunctional (meth)acrylic monomer (C). In addition, a (meth)acrylic monomer means an acrylic monomer or a methacrylic monomer.

The above-mentioned monofunctional (meth)acrylic acid monomer (C) is not particularly limited, and it may be ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Nonyl methacrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, octadecyl (meth)acrylate, isopentyl (meth)acrylate, isodecyl (meth)acrylate ester, isostearate (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (methyl) aliphatic (meth)acrylates such as acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, benzyl (meth)acrylate; nonylphenoxy Ethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Glycidyl (meth)acrylate, 2-Hydroxy-3-phenoxypropyl (meth)acrylate, Nonylphenoxy Aromatic (meth)acrylates such as tetrahydrofurfuryl alcohol ethyl (meth)acrylate and phenoxyethyl (meth)acrylate; dicyclopentenyl (meth)acrylate, bicyclo (meth)acrylate Alicyclic (meth)acrylates such as pentyl ester, dicyclopentenyloxyethyl (meth)acrylate, tetracyclododecyl (meth)acrylate, and cyclohexyl (meth)acrylate; Lactone modified tetrahydrofurfuryl (meth)acrylate, acryloylmorpholine, isobornyl (meth)acrylate, norbornyl (meth)acrylate, 2-(meth)acryloyloxymethyl- 2-methylbicycloheptyl adamantyl (meth)acrylate, etc.

In addition, 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, although the content of the monofunctional (meth)acrylic monomer (C) is not particularly limited, from the viewpoint of the toughness and flexibility of the cured product, it is preferably 10 to 30% relative to the total amount of the composition. quality%.

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

From the perspective of the toughness and flexibility of the cured product, and the adhesiveness with the adherend, the composition of the present invention may also contain a (meth)acrylate monomer (D) having a plurality of ester groups (hereinafter referred to as It is called "ester group-containing (meth)acrylate monomer (D)").

Although the ester group-containing (meth)acrylate monomer (D) is not particularly limited, it is preferred to use the following formula (D1 ) represented by the compound.

chemical formula 3

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 forms of the divalent organic group are the same as R ²⁴ in the above formula (A1).

In said formula (D1), n represents the integer of 1-25.

In the composition of the present invention, although the content of the ester group-containing (meth)acrylate monomer (D) is not particularly limited, from the viewpoint of the toughness and flexibility of the cured product and the adhesion to the adherend On the other hand, it is preferably 5 to 30% by mass based on the total amount of the composition.

<Photoinitiator>

The compositions of the present invention may also contain a photoinitiator.

The photoinitiator is not particularly limited, and it can be, for example, acetophenones, benzoins, benzophenones (1-hydroxyl-1,2,3,4,5,6-hexahydrobenzophenone, etc. ), phosphorus oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldiketone compounds, disulfide compounds, fluoroamine compounds, Aromatic sulfonium salts, profen base dimers, Salts, borates, active lipids, active halogens, inorganic complexes, coumarins, etc.

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

<other ingredients>

The composition of the present invention may contain additives as necessary within a range not impairing the effect or purpose.

Additives can be, for example, inorganic fillers, antioxidants, slip agents, ultraviolet absorbers, light and heat stabilizers, dispersants, antistatic agents, polymerization inhibitors, defoamers, hardening accelerators, solvents, inorganic phosphors, antiaging agents , free radical inhibitors, adhesion modifiers, flame retardants, surfactants, storage stability modifiers, ozone anti-aging agents, tackifiers, plasticizers, radiation barriers, nucleating agents, coupling agents, conductive Property imparting agent, phosphorus peroxide decomposing agent, pigment, metal deactivator, physical property regulator. Various additives are not particularly limited. For example, existing well-known substances may be used.

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

The composition of the present invention can be preferably used in adhesives, surface treatment agents, sealing materials, and the like for electronic devices such as liquid crystal displays, storage media, optical devices, and semiconductor integrated circuits.

Example

The present invention will be described in more detail below based on examples, but the present invention is not limited thereto.

(Synthesis of polysiloxane A1)

Methylphenyl polysiloxane [HO(PhMeSiO) ₇ H] (100 g) having silanol groups at both ends, KBM5103 (3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) ( 68 g) and acetic acid (1 g) were mixed and reacted at 140° C. for 4 hours to synthesize methylphenylpolysiloxane having acryloyl groups at both ends. The obtained methylphenyl polysiloxane was designated as polysiloxane A1. Polysiloxane A1 has a structure that has an aryl group (phenyl) and an alkoxy group (methoxy group), and also has acryloyl groups at both terminals.

chemical formula 4

(Synthesis of polysiloxane A2)

Two-terminal methanol-modified methylphenyl polysiloxane [HOCH ₂ CH ₂ (PhMeSiO) ₆ PhMeSiCH ₂ CH ₂ OH, Mw: 5,000] (100 g), 2-isocyanate ethyl acrylate (5 g), NEOSTANNU- 28 (inorganic metal catalyst, manufactured by Nitto Kasei Co., Ltd.) (concentration relative to the reaction solution: 20 ppm) was mixed and reacted at 70° C. for 2 hours to synthesize methylphenylpolysiloxane having acryloyl groups at both terminals. The obtained methylphenyl polysiloxane was designated as polysiloxane A2. Polysiloxane A2 has a structure that has an aryl group (phenyl) and a urethane bond, and also has acryloyl groups at both terminals. In addition, polysiloxane A2 does not have an alkoxy group.

chemical formula 5

(Synthesis of Polysiloxane A3)

Phenyl-containing epoxy-modified polysiloxane (trade name: X-22-2000, manufactured by Shin-Etsu Chemical Co., Ltd.) (100 g), acrylic acid (20 g), and tetramethylphosphorus bromide (1 g) were mixed to make This was reacted at 100° C. for 5 hours to synthesize a phenyl group-containing polysiloxane having an acryloyl group in a side chain. The obtained phenyl group-containing polysiloxane was designated as polysiloxane A3. Polysiloxane A3 has an aryl group (phenyl group), and also has an acryloyl group in a side chain. In addition, polysiloxane A3 does not have an alkoxy group.

(Synthesis of Polysiloxane A4)

Dimethicone (trade name: KF9701, manufactured by Shin-Etsu Chemical Co., Ltd.) (100 g), KBM5103 (3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Manufacture) (17 g) and acetic acid (1 g) were mixed and reacted at 140° C. for 4 hours to synthesize dimethylpolysiloxane having acryloyl groups at both terminals. The obtained dimethyl polysiloxane was designated as polysiloxane A4. Polysiloxane A4 has an alkoxy group (methoxy group), and also has acryloyl groups at both terminals. In addition, polysiloxane A4 does not have an aryl group.

(Synthesis of urethane acrylate X1)

182.67 g of polypropylene glycol with a number average molecular weight of 1000, 16.48 g of polypropylene glycol with a number average molecular weight of 4000, 0.183 g of 2,6-di-tert-butyl-p-cresol, 255.14 g of toluene diisocyanate, 94.35 g of 2-ethylhexyl acrylate, and the liquid temperature was cooled to 15° C. while stirring. After adding 0.608 g of dibutyltin dilaurate, stir for about 1 hour while taking care to prevent the temperature from rising above 40°C. After stirring to reach room temperature, the temperature of the liquid was adjusted not to exceed 30° C., and 87.56 g of 2-hydroxypropyl acrylate was added dropwise. After completion of the dropwise addition, 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 temperature of the liquid to not exceed 60°C. After completion of the dropwise addition, it was stirred at a liquid temperature of 60°C. When the residual isocyanate group concentration was reduced to 0.1% by mass or less, the reaction was considered to be complete, and urethane acrylate was obtained. The obtained urethane acrylate was designated as urethane acrylate X1.

(Synthesis of silicone resin B1)

Add 64.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 90 g of water, and three After mixing 0.14 g of fluoromethanesulfonic acid and 200 g of toluene, 189 g of KBM103 (phenyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), KBM5103 (3-acryloyloxypropyltrimethoxy Silane (manufactured by Shin-Etsu Chemical Co., Ltd.) 38 g, after the dropwise addition was completed, heating and reflux was performed for 1 hour. After cooling, the lower layer was separated, and the toluene solution layer was washed with water three times. After adding 100 g of 5% sodium bicarbonate aqueous solution to the toluene solution layer after water washing, it heated up to 75 degreeC 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 residual toluene solution layer was concentrated under reduced pressure to obtain a liquid silicone resin. The obtained silicone resin was designated as silicone resin B1.

After carrying out NMR analysis to silicone resin B1, the average unit formula obtained is as follows:

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

Wherein, 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 was 30 mol%.

(Synthesis of silicone resin B2)

Except that the amount of KBM103 was changed to 94.5g and the amount of KBM5103 was changed to 76g, the same procedure as the synthesis of the silicone resin B1 was adopted to obtain the silicone resin. The obtained silicone resin was designated as silicone resin B2.

After carrying out NMR analysis to silicone resin B2, obtain the average unit formula as follows:

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

Wherein, 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 was 17 mol%.

(Synthesis of silicone resin B3)

Except that KBM5103 was not added, the same procedure as that of the silicone resin B1 was used to obtain the silicone resin. The obtained silicone resin was designated as silicone resin B3.

After carrying out NMR analysis to silicone resin B3, obtain average unit formula 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 was 32 mol%.

(Synthesis of silicone resin X1)

In addition to changing the amount of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane to 68g, changing the amount of KBM103 to 9.9g, and changing the amount of KBM5103 to 51g , the rest of the steps were the same as the synthesis of the silicone resin B1 to obtain the silicone resin. The obtained silicone resin was designated as silicone resin X1.

After carrying out NMR analysis to silicone resin X1, the average unit formula obtained is as follows:

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

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

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

<Examples 1-10, Comparative Examples 1-3>

Using the components shown in Table 1 below, the curable resin composition was prepared by mixing these components uniformly using a vacuum stirrer according to the amounts (unit: parts by mass) shown in the table.

<Adhesive Strength>

The obtained curable resin composition was coated on a glass plate (coating area: 5 mm, coating thickness: 0.3 mm), and another glass plate was bonded to the above-mentioned coated portion in a cross shape. Thereafter, light irradiation (estimated light amount: 3,000 mJ/cm ² ) was performed using a light irradiation device (device name: GSUV SYSTEMTYPES250-01, light source: metal halide lamp, manufactured by GS-YUASALighting Co., Ltd.) to cure. Samples for evaluation of adhesive strength were thus prepared.

Adhesive strength was evaluated on the prepared samples by tensile test. Specifically, using a tensile tester, one of the glass plates bonded in a cross shape was fixed, and the other glass plate was stretched at a tensile speed of 5 mm/min to measure the thickness of the glass plate bonded in a cross shape. The maximum tensile strength of the board when it is peeled off. Take this as the bond strength.

In addition, a high-temperature and high-humidity environment test (85° C., RH 85%, 1000 hours) was performed on the prepared sample, and then the adhesive strength was evaluated in the same manner as the above-mentioned method.

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

In practical use, the adhesive strength maintenance rate is preferably 80% or more from the viewpoint of heat resistance. <Appearance after high temperature and high humidity environment test>

Samples for evaluation were prepared by the same method as the above-mentioned adhesive strength. The prepared samples were subjected to a high-temperature and high-humidity environment test (85°C, RH85%, 1000 hours), and then the appearance was observed with the naked eye. The appearance after the high temperature and high humidity environment test is shown in Table 1.

<Transmittance>

Samples for evaluation were prepared by the same method as the above-mentioned adhesive strength. The transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible light absorption spectrometer (manufactured by Shimadzu Corporation) in accordance with JIS K0115:2004. The results are shown in Table 1.

The details of each component shown in Table 1 above are as follows.

· Polysiloxane A1: Polysiloxane A1 synthesized as above

· Polysiloxane A2: Polysiloxane A2 synthesized as above

· Polysiloxane A3: Polysiloxane A3 synthesized as above

· Polysiloxane A4: Polysiloxane A4 synthesized as above

Urethane acrylate X1: Urethane acrylate X1 synthesized as above

・Silicone resin B1: Polysiloxane B1 synthesized as above

・Silicone resin B2: polysiloxane B2 synthesized as above

・Silicone resin B3: Polysiloxane B3 synthesized as above

・Silicone resin X1: Polysiloxane X1 synthesized as 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: PLACCELFM1 (a compound represented by the above formula (D1), molecular weight: 244, manufactured by DAICEL Corporation)

・Ester group-containing acrylate monomer D2: PLACCELFM3 (a compound represented by the above formula (D1), molecular weight: 473, manufactured by DAICEL Corporation)

Photoinitiator: IRGACURE184 (Yanjiagu 184) (manufactured by BASF)

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

In addition, the polysiloxane (A) having at least one (meth)acryloyl group in one molecule does not contain the silicone resin (B) represented by the above-mentioned average unit formula (1) (the aryl group content is less than 15 mol%) The comparative example 3 of the silicone resin) also lowered the adhesive strength after the high-temperature and high-humidity environment test, and in addition, the appearance changed from colorless and transparent to pale yellow and transparent.

On the other hand, in the examples of this patent containing polysiloxane (A) having at least one (meth)acryloyl group in one molecule and silicone resin (B) represented by the above-mentioned average unit formula (1), any In all of the examples, there was basically no decrease in adhesive strength due to the high temperature and high humidity environment test, and no change in appearance due to the high temperature and high humidity environment test was found. That is, excellent heat resistance is exhibited.

Among them, the polysiloxane (A) has a (meth)acryloyl group at the "terminus" of Examples 1-5 and 7-9 (before and after the high-temperature and high-humidity environment test) with higher adhesive strength and excellent adhesion . 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, high-humidity environment test, and were excellent in adhesiveness.

According to the comparison of Examples 1 and 2, it is found that compared with Example 2 whose aryl group rate of the silicone resin (B) is less than 25 mol%, the aryl rate of the silicone resin (B) is more than 25 mol% in Example 1 (in High-temperature and high-humidity environment test before and after) the adhesive strength is higher and the adhesion is excellent. In addition, the transmittance is high and the transparency is also excellent.

According to the comparison of Examples 5 and 6 and the comparison of Examples 9 and 10, it is found that compared with Examples 6 and 10 in which polysiloxane (A) does not have urethane bonds, polysiloxane (A) has urethane bonds. Bonding Examples 5 and 9 (before and after the high-temperature and high-humidity environment test) had higher adhesive strength and excellent adhesion.

From the comparison of Examples 1 to 10, it was found that 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 (7)

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 …(1) (In formula (1), R ¹ , R ² and R ³ independently represent groups selected from aryl groups, groups containing (meth)acryloyl groups, alkyl groups, cycloalkyl groups, groups containing vinyl groups and groups containing The organic groups in the group consisting of epoxy groups, multiple R ² and R ³ can be the same or different respectively, the ratio of all organic groups represented by R ¹ , R ² and R ³ is more than 15 mol%, and X ¹ represents a group selected from the group consisting of a hydrogen atom and an alkyl group, and a, b, c, d and e satisfy the following relational formula: 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). 2. The curable resin composition according to claim 1, wherein the silicone resin (B) has a (meth)acryloyl group. 3. The curable resin composition according to claim 1 or 2, wherein the polysiloxane (A) has an aryl group. 4. The curable resin composition according to any one of claims 1 to 3, wherein the polysiloxane (A) has an alkoxy group. 5. The curable resin composition according to any one of claims 1 to 4, wherein the polysiloxane (A) has a urethane bond. 6 . The curable resin composition according to claim 1 , further comprising a monofunctional (meth)acrylic monomer (C) and a photoinitiator. 7 . The curable resin composition according to claim 1 , further comprising a (meth)acrylate monomer (D) having a plurality of ester groups.