JP5772235B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition having excellent adhesion to inorganic substrates such as glass, indium tin oxide (ITO), and aluminum.

  Conventionally, when various paints are applied to an inorganic base material such as glass, a silane coupling agent has been added to an epoxy resin composition for the purpose of improving adhesion (for example, Patent Document 1). In addition, thiol compounds have been used conventionally as curing agents for epoxy resins, and basic substances such as amines have been used as catalysts for activating the reaction between epoxy groups and thiol groups (for example, non-patent documents). 1). Furthermore, it is known that a mixture of a thiol compound and a polyfunctional polyene having a plurality of double bonds becomes a curable resin composition that is cured by light (for example, Patent Document 2).

JP-A-7-300491 JP-A-6-306172

Review Epoxy Resin, Volume 1, Basic I, P204-205, Epoxy Resin Technology Association

  However, in the technique such as Patent Document 1, many of the silane coupling agents have low boiling points, and it is necessary to add a large amount to the thermosetting resin. Moreover, it cannot be said that the effect of improving the adhesion is sufficient. For example, the adhesion required at a practical level is achieved only by adding an adhesion aid such as a salt such as titanium and zirconium, a phosphate ester, and a urethane resin at the same time. There were many cases where it was possible. In this case, the formulation of these adhesion assistants not only increases the number of steps, but also requires selection of adhesion assistant types that do not impair the coating properties and strict optimization of the amount added. There was a problem.

  On the other hand, the cured film of a curable composition using a thiol compound as a curing agent as in Non-Patent Document 1 has excellent adhesion to organic substances. However, the adhesion to inorganic materials such as glass, ITO and aluminum was not sufficient. In particular, a cured film of a curable composition using a thiol compound as a curing agent has low water resistance, so that there is a problem that adhesion is greatly reduced when exposed to high temperature and high humidity.

  In addition, as in Patent Document 2, the photocurable curable curable resin composition in which the thiol compound and the polyfunctional polyene are mixed also has insufficient adhesion to the inorganic substance of the obtained cured product.

  Furthermore, a curable composition using a thiol compound as a curing agent cures even at room temperature when an amine is used as a catalyst. Therefore, a curable composition having a long usable time (usable time in a use environment) is desired. It was rare.

  Therefore, the present invention has been accomplished in view of the above-described actual situation, and an object thereof is to provide a curable resin composition having excellent adhesion to an inorganic substrate such as glass, indium tin oxide, and aluminum.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cured resin composition containing a specific thioether-containing alkoxysilane derivative as an active ingredient instead of a conventional silane coupling agent or thiol compound. Then, it discovered that it had the adhesiveness outstanding with respect to the inorganic base material, and came to complete this invention.

（式中のａは１〜４の整数であり、ｂは０〜３の整数であり、ｃは０または１であり、ａ＋ｂ＋ｃ＝４である。ｍは１または２である。Ｒ^１は−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−ＣＨ_３−、−ＣＨ（ＣＨ_３）−、または、−ＣＨ（ＣＨ_３）−ＣＨ_２−のいずれかで表される２価の基であり、Ｒ^２はメチル基またはエチル基である。）

（式中のａ’は１〜３の整数であり、ｂ’は０〜２の整数であり、ｃ’は０または１であり、ａ’＋ｂ’＋ｃ’＝３である。ａ”は０〜３の整数であり、ｂ”は０〜２の整数であり、ｃ”は０または１であり、ａ”＋ｂ”＋ｃ”＝３である。ｍは１または２である。Ｒ^１は−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、または、−ＣＨ（ＣＨ_３）−ＣＨ_２−のいずれかで表される２価の基であり、Ｒ^２はメチル基またはエチル基である。） That is, this invention is curable resin composition containing the following (A), (B), (C), and (D) component, Comprising: The said (A) component is molecular weight 200-2000. It is a polyfunctional thiol compound, the component (B) is a polyfunctional epoxy resin having a molecular weight of 200 to 50,000 and an epoxy equivalent of 80 to 6000 g / mol, and the component (C) It is a thioether-containing alkoxysilane derivative represented by the formula (1) or the general formula (2), and the component (D) is an amine compound having a molecular weight of 90 to 700. And weight ratio ((A) / (B)) of said (A) component and said (B) component is 0.05-30, and the total weight of said (A) component and said (B) component The component (C) is blended in an amount of 0.5 to 50 parts by weight and the component (D) is blended in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight.

(In the formula, a is an integer of 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 3 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is 0 B ″ is an integer from 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

  Thus, the specific thioether-containing alkoxysilane derivative (C) is used as an active ingredient as an adhesion improver, and the ingredients (A) to (D) are blended in a well-balanced manner, which is superior to inorganic substrates. Adhesiveness can be expressed.

  In the present invention, the “equivalent” is the weight of a chemical substance necessary for the number of functional groups of a certain chemical substance to be 1 mol, and is obtained by (molecular weight) / (number of functional groups in one molecule). be able to. “Molecular weight” means a weight average molecular weight in the case of a polymer.

  The curable resin composition of the present invention can further contain the following component (E) in addition to the components (A) to (D). The curable resin composition of the present invention that does not contain the component (E) is thermosetting, but when the component (E) is also added thereto, the curable resin composition is photocurable or photothermal two-stage curable. The curing reaction can be selected according to the working environment, the purpose of use, and the like. Specifically, as the component (E), a polyfunctional (meth) acrylate compound having a molecular weight of 200 to 50,000 and a (meth) acrylate equivalent of 80 to 6000 g / mol may be contained. The component (E) is blended in an amount of 2 to 300 parts by weight with respect to 100 parts by weight as a total weight of the component (A) and the component (B). In the present invention, “(meth) acrylate” means a generic name including both acrylate and methacrylate.

（Ｒ^５はシアノ基、炭素数１〜１０の炭化水素基、２,３−ジアミノトリアジンで置換された炭素数１〜１０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ^４、Ｒ^６、Ｒ^７は炭素数１〜２０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ^４〜Ｒ^７が結合して環を形成している場合には炭素数２〜８の炭化水素基である。） As the amine compound (D), an imidazole compound represented by the following general formula (3) is preferably used. According to this, the curing reaction proceeds at 60 ° C. despite the fact that the curing reaction does not easily proceed in the use / storage temperature range of 35 ° C. or lower, and the usable time becomes longer. It becomes possible to achieve both time and storage stability and low-temperature curing.

(R ⁵ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom. R ⁴ , R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R ^{4 to} R ⁷ are bonded to form a ring. If it is, it is a hydrocarbon group having 2 to 8 carbon atoms.)

（式中のｎは２〜５の整数であり、ｐは２〜１０の整数であり、Ｒ^８は炭素数２〜３０の炭化水素基（α１）、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（α２）、イソシアヌレート環（α３）、又はイソシアヌレート環と炭化水素基のみからなる基（α４）のいずれかである。）このような多官能チオール化合物であれば、硬化性樹脂組成物の保存安定性に優れる。 Moreover, as said polyfunctional thiol compound (A), it is preferable to use the polyfunctional thiol compound represented by following General formula (4).

(In the formula, n is an integer of 2 to 5, p is an integer of 2 to 10, R ⁸ is a hydrocarbon group having 2 to 30 carbon atoms (α1), ether oxygen having 2 to 40 carbon atoms (- O-) and a group consisting only of a hydrocarbon group (α2), an isocyanurate ring (α3), or a group consisting only of an isocyanurate ring and a hydrocarbon group (α4).) Such a polyfunctional thiol. If it is a compound, it is excellent in the storage stability of curable resin composition.

  Moreover, it is preferable to use a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin as the polyfunctional epoxy resin (B). Such a polyfunctional epoxy resin has a low reactivity at room temperature and a longer usable time.

  In the present invention, “OO to XX” indicating a numerical range is a concept including a lower limit value (“OO”) and an upper limit value (“XX”). That is, it means “more than XX and less than xx”.

  According to the present invention, the essential components (A) to (D) are blended in a well-balanced manner with the specific thioether-containing alkoxysilane derivative (C) as an active ingredient, so that a conventional silane coupling agent can be used. It is not necessary to add other adhesion assistants or the like as in the case of use, and excellent adhesion can be obtained while suppressing the amount of the active ingredient (C) added as an adhesion improver. In addition, when a conventional thiol compound is used, a novel curable resin composition, which has not been conventionally used, is excellent in adhesion to an inorganic base material such as glass, indium tin oxide, and aluminum. It can be.

  Moreover, since the curable resin composition of this invention has a comparatively long usable time (usable time in use environment), workability | operativity is also favorable and it is excellent also in storage stability. And when making it thermoset, it can be hardened in a short time, although it is low temperature conventionally. That is, it is difficult to cure at room temperature, and the reactivity (curability) is good even at a low temperature of about 60 ° C. during thermosetting. In addition, the toughness, water resistance, heat resistance, flexibility, and uniformity of the cured film obtained by curing the curable resin composition of the present invention can be improved. Thereby, after forming a cured film on an inorganic substrate, sufficient adhesion even when exposed to harsh environments such as high-temperature and high-humidity conditions (for example, about 120 ° C. × 100 RH% × 90 hours) Can be maintained.

  The present invention is described in detail below. The curable resin composition of the present invention comprises the following components (A), (B), (C), and (D) as essential components, and further contains a component (E) as necessary. It is.

<Polyfunctional thiol compound (component (A))>
The polyfunctional thiol compound (A) in the curable resin composition of the present invention is an organic compound having two or more thiol groups (—SH groups). The molecular weight of the polyfunctional thiol compound is 200 to 2000, preferably 300 to 1800, more preferably 350 to 1600. Even if the molecular weight is smaller than 200, there is no problem with the adhesion, but the polyfunctional thiol compound has a high volatility and tends to have a strong odor. On the other hand, when the molecular weight is larger than 2000, the solubility in the later-described polyfunctional epoxy resin (B) is lowered, and the adhesion to the inorganic substrate may be lowered.

（式中のｎは２〜５の整数であり、ｐは２〜１０の整数であり、Ｒ^８は炭素数２〜３０の炭化水素基（α１）、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（α２）、イソシアヌレート環（α３）、又はイソシアヌレート環と炭化水素基のみからなる基（α４）のいずれかである。） As a polyfunctional thiol compound (A), the polyfunctional thiol compound represented, for example by following General formula (4) can be mentioned. In addition, a polyfunctional thiol compound (A) can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, n is an integer of 2 to 5, p is an integer of 2 to 10, R ⁸ is a hydrocarbon group having 2 to 30 carbon atoms (α1), ether oxygen having 2 to 40 carbon atoms (- O-) and a group consisting of only a hydrocarbon group (α2), an isocyanurate ring (α3), or a group consisting only of an isocyanurate ring and a hydrocarbon group (α4).

  In the above general formula (4), even if n = 1, the compound can be used without any major problems. However, due to the high reactivity of the resulting polyfunctional thiol compound, the storage stability of the curable resin composition containing the compound is slightly high. Tend to get worse. On the other hand, if it is a compound of the range of n = 2-5, while being excellent in storage stability, it can be thermoset at a low temperature of about 60 degreeC in a short time. In addition, the reactivity of the polyfunctional thiol compound obtained becomes low as n becomes large, and there exists a tendency for the curing time at the time of thermosetting of the curable resin composition containing this to become long. Therefore, among the compounds represented by the general formula (4), a compound with n = 2 is most preferable. This is because if n = 2, the reactivity of the polyfunctional thiol compound is most suitable for both storage stability and shortening of the curing time during thermal curing.

（式中のｎは1〜５の整数である。）

（式中のｐは２〜１０の整数であり、Ｒ^８は炭素数２〜３０の炭化水素基（α１）、炭素数２〜４０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（α２）、イソシアヌレート環（α３）、又はイソシアヌレート環と炭化水素基のみからなる基（α４）のいずれかである。） The polyfunctional thiol compound represented by the general formula (4) is obtained by an esterification reaction between a mercaptocarboxylic acid represented by the following general formula (5) and a polyfunctional alcohol represented by the following general formula (6). be able to.

(In the formula, n is an integer of 1 to 5.)

(In the formula, p is an integer of 2 to 10, and R ⁸ is composed only of a hydrocarbon group having 2 to 30 carbon atoms (α1), ether oxygen having 2 to 40 carbon atoms (—O—) and a hydrocarbon group. Any one of the group (α2), the isocyanurate ring (α3), or the group (α4) consisting only of the isocyanurate ring and the hydrocarbon group.)

Among the compounds represented by the general formula (6), the compound (α1-1) in which p is 2 to 4 and R ⁸ is a group composed of a hydrocarbon group having 2 to 20 carbon atoms, p is 2 it is 6, and the compound ^{R 8} is a group consisting of only hydrocarbon groups and oxygen ethers having 2 to 30 carbon atoms (-O-) (α2-1), or p is 3, and ^{R 8} is A compound (α4-1) which is a group consisting only of an isocyanurate ring and a hydrocarbon group having 1 to 3 carbon atoms is preferred. This is because such a compound has high solubility with the polyfunctional epoxy resin (B).

  Examples of (α1-1) include alkylene diols having 2 to 20 carbon atoms, glycerin, pentaerythritol, or trimethylolpropane. Examples of (α2-1) include polyethylene glycol, polypropylene glycol, and dipentaerythritol. Examples of (α4-1) include tris (2-hydroxyethyl) isocyanurate.

<Polyfunctional epoxy resin (component (B))>
The polyfunctional epoxy resin (B) in the curable resin composition of the present invention is an organic compound having two or more epoxy groups (oxirane rings). The molecular weight of the polyfunctional epoxy resin is 200 to 50000, preferably 200 to 48000, more preferably 200 to 46000. Even if the molecular weight is less than 200, there is no problem with the adhesion, but the volatility of the polyfunctional epoxy resin tends to increase and the odor tends to increase. On the other hand, when the molecular weight is larger than 50000, the solubility in other components is lowered, and the adhesion to an inorganic substrate may be lowered.

  The epoxy equivalent of the polyfunctional epoxy resin is 80 to 6000 g / mol, preferably 85 to 5500 g / mol, and more preferably 90 to 5000 g / mol. When the epoxy equivalent is less than 80 g / mol, the epoxy group per unit volume becomes excessive, and a large amount of thiol groups and unreacted epoxy groups remain in the polyfunctional thiol compound (A), so that the curable resin composition. The toughness of the cured film consisting of the above may decrease, and the adhesiveness may decrease when exposed to high temperature and high humidity conditions. On the other hand, when the epoxy equivalent is larger than 6000 g / mol, the reaction efficiency with the thiol group of the polyfunctional thiol compound (A) decreases because the epoxy group concentration is extremely low, and thus the cured film made of the curable resin composition The toughness is lowered, and the adhesion may be lowered when exposed to high temperature and high humidity conditions.

  As the polyfunctional epoxy resin (B), for example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or an oxidation obtained by oxidizing a double bond of a double bond-containing compound with a peroxide. Type epoxy resin. Among these, a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin are preferable because reactivity at room temperature is slow and usable time is long. In particular, a glycidyl ether type epoxy resin does not have a functional group that reacts with the polyfunctional thiol compound (A), so that a uniform curable resin composition and a cured film can be obtained regardless of reaction conditions. it can. In addition, a polyfunctional epoxy resin (B) can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

（式中のｑは２〜３０の整数であり、Ｒ^９は炭素数２〜２００の炭化水素基（β１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β２）、イソシアヌレート環（β３）、イソシアヌレート環と炭化水素基のみからなる基（β４）である。） <Glycidyl ether type epoxy resin>
As the glycidyl ether type epoxy resin, a reaction product of epichlorohydrin and a compound represented by the following general formula (7) is preferable.

(In the formula, q is an integer of 2 to 30, and R ⁹ is composed only of a hydrocarbon group having 2 to 200 carbon atoms (β1), ether oxygen having 2 to 300 carbon atoms (—O—) and a hydrocarbon group. A group (β4), an isocyanurate ring (β3), and a group (β4) consisting only of an isocyanurate ring and a hydrocarbon group.)

Among the compounds represented by the general formula (7), a compound (β1-1) in which q is 2 to 20 and R ⁹ is a group consisting of a hydrocarbon group having 2 to 150 carbon atoms, or q is 2 to 20, and R ⁹ is a group consisting only of a hydrocarbon group having 2 to 150 carbon atoms and ether oxygen (—O—), and the compound (β2-1) has high solubility with other components. This is preferable. Examples of (β1-1) include alkylene diols having 2 to 10 carbon atoms, glycerin, pentaerythritol, trimethylolpropane, phenol novolac, and bisphenol A. Examples of (β2-1) include polyethylene glycol, polypropylene glycol, or dipentaerythritol.

  The reaction between the epichlorohydrin and the compound represented by the general formula (7) is performed by adding chlorohydrin obtained by addition reaction of epichlorohydrin and the hydroxyl group of the compound represented by the general formula (7). Ring closure with a base such as sodium oxide provides an epoxy resin. The glycidyl ether type epoxy resin may be an epoxy resin obtained by ring-opening polymerization of a part of the epoxy group of the epoxy resin obtained after the ring-closing reaction.

（式中のｑは２〜３０の整数であり、Ｒ^９は炭素数２〜２００の炭化水素基（β１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β２）、イソシアヌレート環（β３）、又はイソシアヌレート環と炭化水素基のみからなる基（β４）である。） A reaction product of epichlorohydrin and the compound represented by the general formula (7) has a structure represented by the following general formula (8).

(In the formula, q is an integer of 2 to 30, and R ⁹ is composed only of a hydrocarbon group having 2 to 200 carbon atoms (β1), ether oxygen having 2 to 300 carbon atoms (—O—) and a hydrocarbon group. A group (β2), an isocyanurate ring (β3), or a group (β4) consisting only of an isocyanurate ring and a hydrocarbon group.)

（式中のrは２〜８の整数であり、Ｒ^１０は炭素数２〜２０の炭化水素基（β５）、炭素数２〜３０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β６）、イソシアヌレート環（β７）、又はイソシアヌレート環と炭化水素基のみからなる基（β８）のいずれかである。） <Glycidyl ester type epoxy resin>
The glycidyl ester type epoxy resin is a polymer or epi having a weight average molecular weight of 3000 to 20000 obtained by copolymerizing an epoxy group monomer such as glycidyl (meth) acrylate alone or with an alkyl (meth) acrylate having 4 to 25 carbon atoms. Reaction products of chlorohydrin and a compound represented by the following general formula (9).

(In the formula, r is an integer of 2 to 8, and R ¹⁰ consists only of a hydrocarbon group having 2 to 20 carbon atoms (β5), ether oxygen having 2 to 30 carbon atoms (—O—) and a hydrocarbon group. Any one of a group (β6), an isocyanurate ring (β7), or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group.)

  The reaction between epichlorohydrin and the compound represented by the general formula (9) is carried out by adding chlorohydrin obtained by addition reaction of epichlorohydrin and the carboxyl group of the compound of the general formula (9) to sodium hydroxide or the like. The glycidyl ester type epoxy resin can be obtained by ring closure with the above base. An epoxy resin obtained by ring-opening polymerization of a part of the epoxy group of the glycidyl ester type epoxy resin can also be used.

Among the compounds represented by the general formula (9), r is 2 to 4 and R ¹⁰ is a group composed of a hydrocarbon group having 2 to 10 carbon atoms, and the compound (β5-1), r is 2 And R ¹⁰ is a group consisting of ether oxygen (—O—) having 2 to 30 carbon atoms and a hydrocarbon group, compound (β6-1), or r is 3, and R ¹⁰ is A compound (β8-1), which is a group consisting only of an isocyanurate ring and a hydrocarbon group, is preferred because of its high solubility.

  Examples of (β5-1) include hydrophthalic acid and trimellitic acid. Examples of (β6-1) include a reaction product of pentaerythritol and trimellitic anhydride. Examples of (β8-1) include 1,3,5-tris (2-carboxyethyl) isocyanurate.

（式中のrは２〜８の整数であり、Ｒ^１０は炭素数２〜２０の炭化水素基（β５）、炭素数２〜３０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β６）、イソシアヌレート環（β７）、又はイソシアヌレート環と炭化水素基のみからなる基（β８）のいずれかである。） A reaction product of epichlorohydrin and the compound represented by the general formula (9) has a structure represented by the following general formula (10).

(In the formula, r is an integer of 2 to 8, and R ¹⁰ consists only of a hydrocarbon group having 2 to 20 carbon atoms (β5), ether oxygen having 2 to 30 carbon atoms (—O—) and a hydrocarbon group. Any one of a group (β6), an isocyanurate ring (β7), or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group.)

<Thioether-containing alkoxysilane derivative (component (C))>
The thioether-containing alkoxysilane derivative (C) is an adhesion improver that is added to improve the adhesion to an inorganic substrate when the curable resin composition of the present invention is cured. The thioether-containing alkoxysilane derivative (C) has a thioether group and is chemically bonded to the thioether group generated by the crosslinking reaction between the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B) through a disulfide bond. . At this time, since the thioether-containing alkoxysilane derivative (C) has high compatibility with the polyfunctional thiol compound (A) and high reaction efficiency, the resulting adhesion improvement effect is high. Furthermore, the thioether-containing alkoxysilane derivative (C) has an alkoxysilyl group and reacts with a hydroxyl group generated by the reaction of the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B). As a result, the obtained resin cured product has a high cross-linking density, and becomes a cross-linked product (cured product) having toughness and high water resistance. In addition, the alkoxysilyl group of the thioether-containing alkoxysilane derivative (C) can be chemically bonded to the inorganic base material, and the adhesion with the inorganic base material can be greatly improved.

（式中のａは１〜４の整数であり、ｂは０〜３の整数であり、ｃは０または１であり、ａ＋ｂ＋ｃ＝４である。ｍは１または２である。Ｒ^１は−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−ＣＨ_３−、−ＣＨ（ＣＨ_３）−、または、−ＣＨ（ＣＨ_３）−ＣＨ_２−のいずれかで表される２価の基であり、Ｒ^２はメチル基またはエチル基である。）

（式中のａ’は１〜３の整数であり、ｂ’は０〜２の整数であり、ｃ’は０または１であり、ａ’＋ｂ’＋ｃ’＝３である。ａ”は０〜３の整数であり、ｂ”は０〜２の整数であり、ｃ”は０または１であり、ａ”＋ｂ”＋ｃ”＝３である。ｍは１または２である。Ｒ^１は−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、または、−ＣＨ（ＣＨ_３）−ＣＨ_２−のいずれかで表される２価の基であり、Ｒ^２はメチル基またはエチル基である。） The thioether-containing alkoxysilane derivative (C) in the curable resin composition of the present invention is a compound represented by the general formula (1) or the formula (2). In addition, a thioether containing alkoxysilane derivative (C) can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, a is an integer of 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 3 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is 0 B ″ is an integer from 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

  Since the thioether-containing alkoxysilane derivative (C) of the general formula (1) has a low molecular weight and high compatibility with the epoxy resin, it is preferably used when it is desired to increase the toughness of the cured product. Further, the thioether-containing alkoxysilane derivative (C) of the general formula (2) is suitably used when it is desired to obtain high adhesion with a smaller amount of addition.

  Since the thioether-containing alkoxysilane derivative (C) where b is not 0 in the general formula (1) also has a thiol group, it can also react with the polyfunctional epoxy resin (B). Therefore, the crosslinking density can be further improved, and a tough cured product can be obtained. Similarly, the thioether-containing alkoxysilane derivative (C) in which b ′ or b ″ is not 0 in the above general formula (2) also has a thiol group, and thus can react with the polyfunctional epoxy resin (B). Therefore, the crosslink density can be further improved and a tough cured product can be obtained.

（式中のＲはビニル基またはアリル基であり、Ｒ^２はメチル基またはエチル基である。）

（式中のｍは１または２であり、ｄは３または４、ｅは０または１、ｄ＋ｅ＝４である。）

（式中のｍは１または２であり、ｄ’は２または３、ｅ’は０または１、ｄ’+ｅ’＝３、ｄ”は２または３、ｅ”は０または１、ｄ”+ｅ”＝３である。） The thioether-containing alkoxysilane derivative (C) in the curable resin composition of the present invention includes the alkoxysilyl group-containing compound (X) represented by the general formula (11) and the general formula (12) or the general formula (13). It can be obtained by reacting the represented polyfunctional thiol compound (Y).

(In the formula, R is a vinyl group or an allyl group, and R ² is a methyl group or an ethyl group.)

(In the formula, m is 1 or 2, d is 3 or 4, e is 0 or 1, and d + e = 4.)

(Where m is 1 or 2, d 'is 2 or 3, e' is 0 or 1, d '+ e' = 3, d "is 2 or 3, e" is 0 or 1, d " + e ″ = 3.)

Examples of the alkoxysilyl group-containing compound (X) represented by the general formula (11) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri An example is isopropoxysilane. In the general formula (11), when R ² is a compound other than a methyl group, an ethyl group, or an isopropyl group, the reactivity between the alkoxysilyl group and the inorganic base material or between the alkoxysilylsilyl groups is lowered, so It becomes difficult to obtain.

  Examples of the polyfunctional thiol compound (Y) represented by the general formula (12) include trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate). Examples of the polyfunctional thiol compound (Y) represented by the general formula (13) include ditrimethylolpropane hexakis (3-mercaptopropionate and dipentaerythritol hexakis (3-mercaptopropionate). When a compound with m ≧ 3 in the general formula (12) or (13) is used, the number of hydrophobic and nonpolar hydrocarbons in the resulting thioether-containing alkoxysilane derivative increases, thereby increasing the base material of the thioether group. Orientation is weakened and it is difficult to obtain an effect of improving adhesion .

  The alkoxysilyl group-containing compound (X) and the polyfunctional thiol compound (Y) are preferably reacted in the presence of a catalyst or a radical generator. This is because if a catalyst or a radical generator is added, the reaction can be performed in a shorter time and with a higher yield.

  The catalyst is preferably an amine base catalyst, and primary, secondary or tertiary amines, or imidazole compounds can be used. For example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine etc. as primary amine, dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine etc. as secondary amine, trimethylamine, triethylamine, tripropylamine, triamine as tertiary amine, etc. Examples include phenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, 2,4,6-tris (dimethylaminomethyl) phenol. Examples of imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, imidazole analogues such as 1-phenylimidazole, 1-methyl-2-oxymethylimidazole, Oxyalkyl derivatives such as 1-methyl-2-oxyethylimidazole, nitro and amino derivatives such as 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 (4) -aminoimidazole, benzimidazole, Examples thereof include 1-methylbenzimidazole and 1-methyl-2-benzylbenzimidazole.

  As the radical generator, a peroxide or an azo compound is preferable. Examples of the peroxide include dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, dilauroyl peroxide, tert-butyl hydroperoxide, and the like. Examples of the azo compound include azobis (iso-butyronitrile) and 2,2'-azobis (2-methylbutanenitrile).

  As a method for producing a thioether-containing alkoxysilane derivative, the reaction can be carried out at a temperature of 5 ° C. or higher. However, in order to react in a short time (for example, within 5 hours), a base catalyst such as amine or a radical generator is reacted. More preferably, it is added to the system and reacted at 60-80 ° C.

  In the method for producing a thioether-containing alkoxysilane derivative, the reaction can be allowed to proceed even without a solvent, but when the viscosity is to be lowered, for example, when the reaction is carried out at a low temperature, the reaction can be carried out by adding a solvent. In that case, a solvent that does not react with an alkoxysilyl group, a double bond, or a thiol group, for example, alcohols, ketones, esters, or aromatics is preferable.

  As alcohols that do not react with alkoxysilyl groups, double bonds, and thiol groups, those having an appropriate boiling point with respect to the reaction temperature are preferred, and those having a boiling point of 50 to 180 ° C. are particularly preferred. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes.

  As the ketones that do not react with the alkoxysilyl group, double bond, and thiol group, those having an appropriate boiling point with respect to the reaction temperature are preferable, and those having a boiling point of 50 to 180 ° C. are particularly preferable. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. Examples include methyl ethyl ketone and methyl isobutyl ketone.

  As the esters that do not react with the alkoxysilyl group, double bond, and thiol group, those having an appropriate boiling point with respect to the reaction temperature are preferable, and those having a boiling point of 50 to 180 ° C. are particularly preferable. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. Examples thereof include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, and isopropyl acetate.

<Amine compound (component (D))>
The amine compound in the curable resin composition of the present invention is added to promote (catalyze) the reaction between the thiol group and the epoxy group. Examples of the amine compound (D) include polyfunctional amines having a molecular weight of 90 to 700, preferably 100 to 690, more preferably 110 to 680, and a monofunctional amine and a plurality of amino groups. If the molecular weight of the amine compound (D) is less than 90, the volatility of the amine is increased, which not only causes odors and voids, but also decreases the amine concentration at the time of heat curing, so that the crosslinking reaction does not proceed easily and adhesion Tends to decrease. When the molecular weight of the amine compound (D) exceeds 700, the water resistance becomes low and the adhesion tends to be lowered.

  Monofunctional amines include primary amines, secondary amines, or tertiary amines. Examples of polyamines include primary amines, secondary amines, tertiary amines, and complex amines. A complex amine is an amine having two or more of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such complex amines include imidazoline compounds, imidazole compounds, N-substituted piperazine compounds, N, N-dimethylurea derivatives, and the like. In addition, an amine compound (D) can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

  In addition, the amine compound (D) may form a salt with an organic acid in advance in order to adjust the catalytic activity. Examples of the organic acid that is reacted in advance with the amine compound (D) include aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 20 carbon atoms and 1 to 5 carboxyl groups in the molecule, and 1 to 1 carbon atoms. Examples 20 include aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 1 to 10 carboxyl groups in the molecule, or isocyanuric acid. Moreover, an amine compound (D) may be mix | blended, after forming an adduct with a polyfunctional epoxy resin (B), in order to adjust catalyst activity.

<Imidazole compound>
Among the amine compounds (D), imidazole compounds are most suitable for achieving both storage stability and curing time at low temperatures. Further, an imidazole compound coated with a phenol resin or the like can also be used.

（Ｒ^５はシアノ基、炭素数１〜１０の炭化水素基、２,３−ジアミノトリアジンで置換された炭素数１〜１０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ^４、Ｒ^６、Ｒ^７は炭素数１〜２０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ^４〜Ｒ^７が結合して環を形成している場合には炭素数２〜８の炭化水素基である。） The imidazole compound is a compound represented by the following general formula (3).

(R ⁵ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom. R ⁴ , R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R ^{4 to} R ⁷ are bonded to form a ring. If it is, it is a hydrocarbon group having 2 to 8 carbon atoms.)

  Specifically, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-undecylimidazole, 1- ( 2-cyanoethyl) -2-ethyl-4-methylimidazole, 1- (2-cyanoethyl-2-phenylimidazole), 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,3-dihydro-1H -Pyrrolo [1,2-a] benzimidazole, 2,4-diamino-6- [2- Methylimidazolyl- (1)] ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole It is done.

<Polyfunctional (meth) acrylate compound (component (E))>
If there are a polyfunctional thiol compound (A), a polyfunctional epoxy resin (B), and an amine compound (D), the curable resin composition of the present invention is cured by heat. On the other hand, when it is desired to impart photocurability or photothermal two-stage curability to the curable resin composition of the present invention, a polyfunctional (meth) acrylate compound (E) may be added.

  It is known that a thiol group undergoes an addition reaction to a double bond by heat or light stimulation. Therefore, the mixture of the polyfunctional thiol compound (A) and the polyfunctional double bond-containing compound can be a cured resin composition. In the present invention, among the double bonds, a polyfunctional (meth) acrylate compound (E) which is a compound having two or more acryloxy groups or methacryloxy groups is preferable. Among the many double bond-containing compounds, the reason for selecting polyfunctional (meth) acrylate is that it is difficult to react with the polyfunctional thiol compound (A) in the curable resin composition of the present invention at room temperature, and the usable time is set longer. It is possible to form a tough cured product when reacted with the polyfunctional thiol compound (A), the reaction with the polyfunctional thiol compound (A) is not easily catalyzed by the amine compound (D), a polyfunctional epoxy resin ( For example, it does not react with B).

（式中のｓは２〜３０の整数であり、Ｒ^１２は炭素数２〜２００の炭化水素基（ε１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（ε２）、イソシアヌレート環（ε３）、又はイソシアヌレート環と炭化水素基のみからなる基（ε４）であり、Ｒ^１３は水素原子またはメチル基である。） As such a polyfunctional (meth) acrylate (E), a compound represented by the following general formula (14) is preferably exemplified. In addition, polyfunctional (meth) acrylate (E) can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, s is an integer of 2 to 30, R ¹² is composed of only a hydrocarbon group having 2 to 200 carbon atoms (ε1), ether oxygen having 2 to 300 carbon atoms (—O—) and a hydrocarbon group. A group (ε2), an isocyanurate ring (ε3), or a group (ε4) consisting only of an isocyanurate ring and a hydrocarbon group, and R ¹³ is a hydrogen atom or a methyl group.)

  Moreover, as a polyfunctional (meth) acrylate (E), a polymer type thing can also be used conveniently. As the polymer type polyfunctional (meth) acrylate (E), a (meth) acrylate compound having an epoxy group such as glycidyl (meth) acrylate or a copolymer reacts with an epoxy group like (meth) acrylic acid. A polymer obtained by reacting a (meth) acrylate compound having a group capable of reacting, a (meth) acrylate compound having a hydroxyl group such as hydroxyethyl (meth) acrylate alone or a copolymer, 2-methylpropenoic acid 2-isocyanatoethyl To a polymer obtained by reacting a (meth) acrylate compound having a group that reacts with a hydroxyl group, a (meth) acrylate compound having a carboxyl group such as (meth) acrylic acid alone or a copolymer, and glycidyl (meth) A group that reacts with a carboxyl group like acrylate To (meth) polymers obtained by reacting an acrylate compound.

  The molecular weight of the polyfunctional (meth) acrylate compound (E) is 200 to 50000, preferably 220 to 40000, and more preferably 240 to 30000. Even if the molecular weight of the polyfunctional (meth) acrylate compound (E) is smaller than 200, there is no problem with the adhesion, but the volatility tends to increase and the odor tends to increase. On the other hand, if the molecular weight is larger than 50000, the solubility in other components may be lowered.

  The polyfunctional (meth) acrylate (E) has a (meth) acrylate equivalent of 80 to 6000 g / mol, preferably 80 to 4500, and more preferably 85 to 3000. When the (meth) acrylate equivalent is less than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive, and a large amount of thiol groups and unreacted (meth) acryloxy groups remain in the polyfunctional thiol compound (A). By doing so, the toughness of the cured film made of the curable resin composition is lowered, and the adhesion may be lowered when exposed to high temperature and high humidity conditions. On the other hand, when the (meth) acrylate equivalent is larger than 6000 g / mol, the reaction efficiency with the thiol group of the polyfunctional thiol compound (A) is lowered because the (meth) acryloxy group concentration is extremely low, so that the curable resin composition The toughness of the cured film made of a product is lowered, and the adhesion may be lowered when exposed to high temperature and high humidity conditions.

<Composition ratio (mixing balance)>
The curable resin composition of the present invention is blended so that the weight ratio ((A) / (B)) between the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B) is 0.05 to 30. . Here, “(A) / (B)” is a value obtained by dividing the weight of the polyfunctional thiol compound (A) by the weight of the polyfunctional epoxy resin (B). The optimum value of (A) / (B) depends on the characteristics required for the curable resin composition, the polyfunctional thiol compound (A), the polyfunctional epoxy resin (B), and the polyfunctional (meta) added in some cases. ) Varies depending on the structure of the acrylate compound (E). Strictly speaking, the characteristics after curing the curable resin composition are (thiol group number) / (epoxy group number + (meth) acryloxy group number) (hereinafter referred to as thiol / (epoxy + ene)) in the unit weight of the curable resin composition. It is influenced by the value of the ratio. For example, when the thiol / (epoxy + ene) ratio is in the range of 0.5 to 1.5, it is easy to form dense crosslinks and to become a tough cured product. On the other hand, if the thiol / (epoxy + ene) ratio is 0.1 or more and less than 0.5 or more than 1.5 and 2.0 or less, a flexible and sticky cured product can be obtained. If the thiol / (epoxy + ene) ratio is less than 0.1 or exceeds 2.0, gelation is difficult and adhesion tends to decrease.

  Moreover, the curable resin composition of this invention has 0 thioether containing alkoxysilane derivative (C) with respect to 100 weight part of total weight (A + B) of a polyfunctional thiol compound (A) and a polyfunctional epoxy resin (B). 5 to 50 parts by weight, preferably 0.5 to 45 parts by weight. When the blending amount of the component (C) is less than 0.5 parts by weight with respect to (A + B), excellent adhesion cannot be obtained. Therefore, there exists a tendency for adhesiveness to fall.

  Moreover, the curable resin composition of the present invention has an amine compound (D) of 0.01 to 100 parts by weight with respect to 100 parts by weight of the total weight (A + B) of the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B). It mix | blends so that it may become 50 weight part, Preferably 0.01-45 weight part. When the blending amount of the component (D) is less than 0.01 with respect to (A + B), it takes time for the reaction between the thiol group and the epoxy group to proceed, resulting in poor curing. There is a tendency for adhesion to be lowered.

  Moreover, when mix | blending a polyfunctional (meth) acrylate compound (E) with respect to the curable resin composition of this invention, the total weight (A + B) of a polyfunctional thiol compound (A) and a polyfunctional epoxy resin (B). ) The polyfunctional (meth) acrylate compound (E) is blended in an amount of 2 to 300 parts by weight, preferably 2 to 250 parts by weight per 100 parts by weight. When the blending amount of the component (E) is less than 2 with respect to (A + B), it is difficult to impart photocurability, and when it exceeds 300 parts by weight, the adhesion tends to decrease.

<Curable resin composition>
When the thiol group of the polyfunctional thiol compound (A) reacts with the epoxy group of the polyfunctional epoxy resin (B), a thioether group or a hydroxyl group is generated. The thioether-containing alkoxysilane (C) also has a thioether group, and crosslinks with the thioether produced by the reaction of the thiol group and the epoxy group with a disulfide bond. The thioether-containing alkoxysilane (C) also has an alkoxysilyl group and reacts with the hydroxyl group produced by the reaction of the thiol group and the epoxy group to crosslink. As a result, a dense crosslinked body can be formed. The cured product obtained by curing the curable resin composition of the present invention has high heat resistance, toughness, water resistance, and the like because the crosslinked body becomes dense. Furthermore, since it is a cured product cross-linked with a thioether group or a disulfide bond, it has high flexibility and high adhesion. Furthermore, since the thioether-containing alkoxysilane (C) also has a trialkoxysilyl group at the same time, it can form a chemical bond with an inorganic base material such as glass in particular, and the curable resin composition of the present invention. Has particularly high adhesion to inorganic substrates.

  Further, in the curable resin composition of the present invention, the (meth) acryloyl group of the polyfunctional (meth) acrylate compound (E) and the thiol group of the polyfunctional thiol compound (A) added as necessary are also stimulated by light. React by. Therefore, the mixture of the polyfunctional thiol compound (A), the polyfunctional epoxy resin (B), and the polyfunctional (meth) acrylate compound (E) becomes a cured resin that is cured in two stages of light and heat. Furthermore, it is possible to control the degree of photocuring and thermosetting by controlling the amount of each component.

  Conventionally, various thiol compounds have been used as curing agents (compounds added to cure main agents such as epoxy resins and (meth) acrylate compounds). It is generally known that amines and other basic substances have an effect of reducing (catalyzing) reaction activation energy in any reaction of thiol group and epoxy group or thiol group and (meth) acryloyl group. ing.

  Further, the curable resin composition of the present invention may be used after diluting with an organic solvent in order to make the reaction system uniform and facilitate coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, ether ester solvents, ketone solvents, and phosphate ester solvents. These organic solvents are preferably suppressed to a blending amount of less than 10000 parts by weight with respect to 100 parts by weight of the curable resin composition. It does not have a big influence on the physical properties. However, the compound having a functional group that reacts with a thiol group, an epoxy group, or a (meth) acryloyl group, and an amine compound may impair the effects of the present invention when used as a solvent.

  In addition, the curable resin composition of the present invention may contain a viscosity modifier such as silica powder for the purpose of adjusting the viscosity. These viscosity modifiers are preferably suppressed to less than 300 parts by weight with respect to 100 parts by weight of the curable resin composition. If this value exceeds 300 parts by weight of the viscosity modifier, the adhesion may be lowered.

  Moreover, you may add various additives which are used for the usual coating material and adhesive agent to the curable resin composition of this invention. Such additives include surfactants for smoothing the coated surface, aluminum salts for extending the usable time, photoradical generators for improving photoreactivity, photobase generators, light An acid generator etc. are mentioned. These additives are preferably suppressed to a blending amount of less than 80 parts by weight with respect to 100 parts by weight of the curable resin composition. When the compounding amount of these additives exceeds 80 parts by weight, the adhesion may be lowered.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to this. The reagents used in the examples and comparative examples are as follows. Mw represents a weight average molecular weight.

<Polyfunctional thiol compound (component A)>
(A-1, Mw: 372)

(A-2, Mw: 399)

(A-3, Mw: 526)

(A-4, Mw: 488)

(A-5, Mw: 784)

(A-6, Mw: 416)

(A-7, Mw: 785)

(A-8, Mw: 1584)

<Polyfunctional epoxy resin (component B)>
(B-1, Mw: 220, epoxy equivalent: 110)

(B-2, Mw: 360, epoxy equivalent: 90)

(B-3, Mw: 350, epoxy equivalent: 175)

ｎは平均１５ (B-4, Mw: 5500, epoxy equivalent: 3000)

n is an average of 15

ｎは平均７ (B-5, Mw: 1500, epoxy equivalent: 186)

n is 7 on average

(B-6, Mw: 220, epoxy equivalent: 110)

(B-7, Mw: 18000, epoxy equivalent: 250)
A copolymer of glycidyl methacrylate and cyclohexyl methacrylate (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).

(B-8, Mw: 45000, epoxy equivalent: 250)
A copolymer of glycidyl methacrylate and cyclohexyl methacrylate (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).

<Thioether-containing alkoxysilane derivative (component C)>
(C-1)

(C-2)

(C-3)

(C-4)

(C-5)

(C-6)

(C-7)

(C'-1)

(C'-2)

(C'-3)

(C'-4)

(C'-5)

<Amine compound (component D)>
(D-1, Mw: 136)

(D-2)
1: 1 equivalent reactant of 1,8-diazabicyclo (5,4,0) undec-7-ene and stearic acid

ｎ１、ｎ２、ｎ３は１〜５の整数であり、平均が３．５混合物 (D-3, Mw: 680)

n1, n2, and n3 are integers of 1 to 5, and the average is 3.5 mixture

(D'-1, Mw: 110)

(D'-2, Mw: 144)

(D'-3, Mw: 163)

(D'-4, Mw: 219)

２−フェニルイミダゾールとピロメリット酸の塩 (D'-5)

2-Phenylimidazole and pyromellitic acid salt

(D'-6, Mw: 158)

(D'-7, Mw: 306)

<Polyfunctional (meth) acrylate compound (E component)>
(E-1, Mw: 246, double bond equivalent: 123)

(E-2, Mw: 352, double bond equivalent: 88)

(E-3, Mw: 376, double bond equivalent: 183)

ｎは平均１３ (E-4, Mw: 5000, double bond equivalent: 3000)

n is 13 on average

ｎは平均５ (E-5, Mw: 1200, double bond equivalent: 180)

n is an average of 5

(E-6, Mw: 586, double bond equivalent: 195)

(E-7, Mw: 22000, double bond equivalent: 320)
Polymer obtained by adding equimolar amount of methacrylic acid using D-3 as a catalyst to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).

<Other reagents>
(F-1 (≈A component))

(F-2 (≈ C component)

  Components (A) to (E) were mixed in the blending balance shown in Tables 1 and 2, and stirred with a spatula until uniform. The following evaluation was performed on the sample after stirring, and the results are also shown in Tables 1 and 2.

<Adhesion evaluation>
Each example and comparative example is a bar coater on alkali-free glass (OA-10, manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm) and an aluminum plate (A5052P, manufactured by Nippon Test Panel Co., Ltd., thickness 2.0 mm). The coating was applied to a thickness of 100 μm and heated at 140 ° C. for 1 hour to obtain a cured film on each substrate. After the base material from which the cured film was obtained was treated at 121 ° C. × 100 RH% × 90 hours, it was evaluated by the mechanical property-adhesiveness (cross-cut method) test method of the coating film specified in JIS K5600-5-6. It was. The case where there was no peeling at all was marked with ◎, the peeling at 10% or less of the total area was marked with ○, and the others were marked with ×. Adhesion 1 in the table is the result with an alkali-free glass substrate, and Adhesion 2 is the result with an aluminum plate substrate.

<Confirmation of photocurability>
Each Example and Comparative Example were coated on an alkali-free glass with a bar coater so as to have a thickness of 100 μm, and irradiated with light of 500 mJ / cm 2 (i-line conversion) with a high-pressure mercury lamp. When the irradiated coating film was suppressed with a spatula, the case where the coating liquid was not applied to the spatula was evaluated as “◯”.

<Confirmation of storage stability (storage stability)>
The viscosity immediately after mixing of each Example and Comparative Example was measured with the following viscometer. Each Example and Comparative Example was heated at 30 ° C. for 12 hours, and then the viscosity was measured again. Those having a thickening ratio of 1.0 to 1.8 obtained by dividing the viscosity after heating by the viscosity after mixing were evaluated as ◎, those with 1.8 to 10 as ○, and the others as ×.
Model: Toki Sangyo Co., Ltd. (R type viscometer)
Temperature: 25 ° C

As is clear from the results in Tables 1 and 2, high adhesion was confirmed in all Examples. Moreover, it was confirmed that photocurability can be provided by adding the component (E) in Examples 2-1 to 2-16. In Examples 1-5 to 1-14 and 2-5 to 2-16, it was also found that storage stability (storage stability) was improved by using an amine as an imidazole compound. On the other hand, as in each comparative example, if any one of the essential components (A) to (D) in the present invention does not contain or is a different material, excellent adhesion to the inorganic substrate is obtained. It was confirmed that it was not possible.

Claims (4)

A curable resin composition containing the following components (A), (B), (C), and (D),
Wherein component (A) is represented by the following general formula (4), a polyfunctional thiol compound having a weight average molecular weight of 200 to 2000,
The component (B) is a polyfunctional epoxy resin having a weight average molecular weight of 200 to 50,000 and an epoxy equivalent of 80 to 6000 g / mol,
The component (C) is a thioether-containing alkoxysilane derivative represented by the following general formula (1) or general formula (2):
The component (D) is an amine compound having a weight average molecular weight of 90 to 700,
The weight ratio ((A) / (B)) between the component (A) and the component (B) is 0.05 to 30,
The total weight of the component (A) and the component (B) is 100 parts by weight, and the component (C) is added in an amount of 0.5 to 50 parts by weight, and the component (D) is mixed in an amount of 0.01 to 50 parts by weight. A curable resin composition characterized by comprising:

(In the formula, a is an integer of 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 3 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is 0 B ″ is an integer from 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. R ¹ is −. _{CH 2 -CH 2 -, - CH} 2 -CH 2 -CH 2 -, - CH (CH 3) -, _{or, -CH (CH 3) -CH 2} - in the divalent group represented by any one of And R ² is a methyl group or an ethyl group.)

(In the formula, n is an integer of 2 to 5, p is an integer of 2 to 10, R ⁸ is a hydrocarbon group having 2 to 30 carbon atoms (α1), ether oxygen having 2 to 40 carbon atoms (- O-) and a group consisting of only a hydrocarbon group (α2), an isocyanurate ring (α3), or a group consisting only of an isocyanurate ring and a hydrocarbon group (α4). Furthermore, as the component (E), a polyfunctional (meth) acrylate compound having a weight average molecular weight of 200 to 50,000 and a (meth) acrylate equivalent of 80 to 6000 g / mol is used as the component (A) and The curable resin composition according to claim 1, wherein 2 to 300 parts by weight is blended with respect to 100 parts by weight of the total weight of component B). The resin composition according to claim 1 or 2, wherein the amine compound (D) is an imidazole compound represented by the following general formula (3).

(R ⁵ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom. R ⁴ , R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R ^{4 to} R ⁷ are bonded to form a ring. If it is, it is a hydrocarbon group having 2 to 8 carbon atoms.) The curable resin composition according to any one of claims 1 to 3, wherein the polyfunctional epoxy resin (B) is a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin.