KR101528737B1 - Curable resin composition - Google Patents

Abstract

A curable resin composition excellent in adhesion to an inorganic substrate is provided. The curable resin composition comprises a polyfunctional thiol compound (A) having a molecular weight of 200 to 2000, a polyfunctional epoxy resin (B) having a molecular weight of 200 to 50000, an epoxy equivalent of 80 to 6000 g / mol, An alkoxysilane derivative (C), and an amine compound (D) having a molecular weight of 90 to 700. 0.5 to 50 parts by weight of (C) and 0.01 to 50 parts by weight of (D) are contained per 100 parts by weight of 0.05 to 30 parts by weight (A) / (B)

Description

CURABLE RESIN COMPOSITION [0001]

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

BACKGROUND ART [0002] A silane coupling agent is conventionally added to an epoxy resin composition for the purpose of improving adhesion when various paints are applied to inorganic substrates such as glass (for example, Patent Document 1). Further, a thiol compound is conventionally used as a curing agent for an epoxy resin, and a basic substance such as an amine has been used as a catalyst for activating the reaction between an epoxy group and a thiol group (see, for example, Non-Patent Document 1). It is also known that a mixture of a thiol compound and a polyfunctional polyene having a plurality of double bonds is a curable resin composition which is cured by light (for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 7-300491 Japanese Patent Application Laid-Open No. 6-306172

 Epoxy Resin, Volume 1, Foundation I, P204-205, Epoxy Resin Technology Association

However, in the technique described in Patent Document 1, a large number of silane coupling agents have a low boiling point, and it is necessary to add a large amount of the silane coupling agent to the thermosetting resin. In addition, the adhesion improving effect is not sufficient. For example, when the adhesion property such as a salt of titanium, zirconium or the like, or an adhesion auxiliary agent such as a phosphate ester or a urethane resin is added at the same time, There were many. In this case, there is a problem that the addition of these adhesion adjuvants not only increases the number of steps, but also requires selection of the adhesion adjuvant species that does not impair the paint properties and a strict optimization of the addition amount.

On the other hand, the cured film of the curable composition using the thiol compound as the curing agent as in the non-patent document 1 is excellent in adhesion to organic matter. However, adhesion to inorganic substances such as glass, ITO, and aluminum is not sufficient. Particularly, since the cured film of the curable composition containing a thiol compound as a curing agent has a low water resistance, there is a problem that when the cured film is exposed to high temperature and high humidity, adhesiveness is largely lowered.

In addition, as in the case of Patent Document 2, the adhesion of the cured product to the inorganic material of the obtained photocurable curable resin composition obtained by mixing the thiol compound and the polyfunctional polyene was not sufficient.

Further, in the curable composition containing a thiol compound as a curing agent, since curing proceeds at room temperature when an amine is used as a catalyst, a curable composition having a long usable time (usable time in use environment) has been desired.

SUMMARY OF THE INVENTION The present invention has been accomplished in view of the above-described circumstances, and an object of the present invention is to provide a curable resin composition excellent in adhesion to inorganic substrates such as glass, indium tin oxide and aluminum.

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive investigations in order to solve the above problems. As a result, the present inventors have found that a cured resin composition containing a specific thioether-containing alkoxysilane derivative as an effective component in place of a conventional silane coupling agent or thiol compound And thus the present invention has been completed.

That is, the present invention provides a curable resin composition containing the following components (A), (B), (C) and (D), wherein the component (A) is a polyfunctional thiol compound having a molecular weight of 200 to 2000, Wherein the component (B) is a polyfunctional epoxy resin having a molecular weight of 200 to 50000 and an epoxy equivalent of 80 to 6000 g / mol, wherein the component (C) is a thioether-containing alkoxysilane derivative represented by the following general formula (1) , And the component (D) is an amine compound having a molecular weight of 90 to 700. And the weight ratio (A) / (B) of the component (A) to the component (B) is 0.05 to 30 and the total weight of the component (A) 0.5 to 50 parts by weight of the component (C), and 0.01 to 50 parts by weight of the component (D).

[Chemical Formula 1]

(Wherein a and b are integer from 0 to 2 in the formula, c is an integer from 1 ~ 3, a + b + c = 3 a. R is to a trivalent group represented by the general formula (2), R ¹ And R ² are each -CH ₂ -CH (CH ₃₎ independently _{-, -C (CH 3) 2} -, -CH 2 -CH 2 -, or -CH (CH ₃₎ - 2-valent indicating that any of the groups And R ³ is a methyl group or an ethyl group.

(2)

(Wherein m is 1 or 2)

As described above, since the specific thioether-containing alkoxysilane derivative (C) is used as an effective component and the components (A) to (D) are well-balanced, excellent adhesion to an inorganic substrate can be exhibited .

In the present invention, " equivalent amount " is the weight of a chemical substance required for the number of functional groups of a chemical substance to be 1 mol, and can be determined from (molecular weight) / (the number of functional groups in one molecule). The " molecular weight " in the case of a polymer means the weight average molecular weight.

The curable resin composition of the present invention may further contain the following component (E) in addition to the above components (A) to (D). The curable resin composition of the present invention which does not contain the component (E) is thermosetting. When the component (E) is also added thereto, the curable resin composition can be provided with photo- The curing reaction can be selected depending on the purpose and the like. Specifically, as the component (E), a polyfunctional (meth) acrylate compound having a molecular weight of 200 to 50000 and an equivalent (meth) acrylate of 80 to 6000 g / mol may be contained. The component (E) is blended in an amount of 2 to 300 parts by weight based on 100 parts by weight of the total weight of the component (A) and the component (B). In the present invention, " (meth) acrylate " means a generic term including both acrylate and methacrylate.

As the amine compound (D), an imidazole compound represented by the following general formula (2) is preferably used. According to this, although the curing resin composition does not proceed well in the use / storage temperature range of 35 ° C or lower and the usable time becomes long, the curing reaction proceeds at 60 ° C, And low temperature curing can be achieved at the same time.

(3)

(R ⁵ is a cyano group, an alkoxy group, or a hydrogen atom of a hydrocarbon group having 1 to 10 hydrocarbon group, a 2,3-diamino-tree of 1 to 10 carbon atoms substituted with a triazine, having a carbon number of 1 to 4, R ^4, R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and a hydrocarbon group having 2 to 8 carbon atoms when R ⁴ to R ⁷ are combined to form a ring )

As the polyfunctional thiol compound (A), it is preferable to use a polyfunctional thiol compound represented by the following general formula (3).

[Chemical Formula 4]

(Wherein n is an integer of 2 to 5, p is an integer of 2 to 10, and R ⁸ is a hydrocarbon group (? 1) having 2 to 30 carbon atoms, ether oxygen (-O-) having 2 to 40 carbon atoms and hydrocarbon (? 2), isocyanurate ring (? 3), or a group (? 4) composed of an isocyanurate ring and a hydrocarbon group only. With such a polyfunctional thiol compound, the storage stability of the curable resin composition is excellent.

As the polyfunctional epoxy resin (B), it is preferable to use a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin. If such a polyfunctional epoxy resin is used, the reactivity at room temperature is slow, and the usable time becomes longer.

In the present invention, " xx to xx " indicating the numerical range is a concept including a lower limit value (xx) and an upper limit value (xx). That is, it means exactly "xx or more xx or less".

 According to the present invention, since the essential thioether-containing alkoxysilane derivative (C) is used as an effective component and the essential components (A) to (D) are mixed in a good balance, It is not necessary to add other adhesion auxiliary agents or the like and excellent adhesion can be obtained while suppressing the addition amount of the active component (C) for improving the adhesion. In addition, in the case of using a conventional thiol compound, a novel curable resin composition which has not been conventionally excellent in adhesion to an inorganic substrate such as glass, indium tin oxide or aluminum, which was insufficient, can be obtained.

Further, since the curable resin composition of the present invention has a relatively long service life (usable time under the use environment), the curable resin composition has good workability and excellent storage stability. In addition, when thermally curing, it can be cured at a lower temperature than a conventional one and in a short time. That is, it is not well cured at room temperature and good in reactivity (curability) even at a low temperature of about 60 캜 when thermosetting. Further, the toughness, water resistance, heat resistance, flexibility, uniformity and the like of the cured film obtained by curing the curable resin composition of the present invention can also be improved. Thereby, sufficient adhesion can be maintained even when the cured film is formed on the inorganic substrate and then exposed to a severe environment such as under a high-temperature and high-humidity condition (for example, 120 占 폚 占 100 RH% 占 90 hours or so).

 Hereinafter, the present invention will be described in detail. The curable resin composition of the present invention is a curable resin composition containing the following components (A), (B), (C) and (D) as essential components and further containing component (E) as required.

<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, and more preferably 350 to 1600. Even if the molecular weight is less than 200, there is no problem in terms of adhesion, but the multifunctional thiol compound has a high volatility, and the odor tends to become strong. On the other hand, if the molecular weight is more than 2000, the solubility in the multifunctional epoxy resin (B) to be described later is lowered, and the adhesion to the inorganic substrate may be lowered.

Examples of the polyfunctional thiol compound (A) include polyfunctional thiol compounds represented by the following general formula (4). In addition, the polyfunctional thiol compound (A) may be used alone or in admixture of two or more.

[Chemical Formula 5]

(Wherein n is an integer of 2 to 5, p is an integer of 2 to 10, and R ⁸ is a hydrocarbon group (? 1) having 2 to 30 carbon atoms, ether oxygen (-O-) having 2 to 40 carbon atoms and hydrocarbon (? 2), isocyanurate ring (? 3), or a group (? 4) composed only of an isocyanurate ring and a hydrocarbon group)

The compound having n = 1 in the general formula (3) can be used without any problem, but the resulting polyfunctional thiol compound has a high reactivity, so that the storage stability of the curable resin composition containing the polyfunctional thiol compound tends to be slightly deteriorated. On the other hand, if n is in the range of 2 to 5, the storage stability is excellent and the thermosetting can be performed in a short time at a low temperature of about 60 캜. In addition, as the number of n increases, the reactivity of the obtained polyfunctional thiol compound decreases, and the curing time at the time of heat curing of the curable resin composition containing the same tends to become longer. Therefore, among the compounds represented by the above general formula (3), a compound of n = 2 is most preferable. When n = 2, the reactivity of the polyfunctional thiol compound is most suitable for both the storage stability and the shortening of the curing time at the time of thermosetting.

The polyfunctional thiol compound represented by the general formula (4) can be obtained by an esterification reaction of a mercaptocarboxylic acid represented by the following general formula (5) and a polyfunctional alcohol represented by the following general formula (6).

[Chemical Formula 6]

(Wherein n is an integer of 1 to 5)

(7)

(Wherein p is an integer of 2 to 10, R ⁸ is a hydrocarbon group (? 1) having 2 to 30 carbon atoms, ether oxygen (-O-) having 2 to 40 carbon atoms and a group (? 2) (Or a group consisting of an isocyanurate ring and a hydrocarbon group alone)

Among the compounds represented by the general formula (6), wherein p is 2-4, and also resulting compound (α1-1), p is 2 to 6 R ⁸ consisting of a hydrocarbon group having 2 to 20 carbon atoms, and the R ⁸ carbon atoms (Α2-1) which is a group consisting of only ether oxygen (-O-) of 2 to 30 and a hydrocarbon group only or a compound wherein p is 3 and R ⁸ is an isocyanurate ring and a hydrocarbon group having 1 to 3 carbon atoms The compound (4-1) is preferred. This is because such a compound has a high solubility with the polyfunctional epoxy resin (B).

(α1-1) include, for example, alkylenediols having 2 to 20 carbon atoms, glycerin, pentaerythritol, trimethylolpropane, and the like. (? 2-1) include, for example, polyethylene glycol, polypropylene glycol, dipentaerythritol and the like. (4-1) include, for example, tris (2-hydroxyethyl) isocyanurate and the like.

<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 50,000, preferably 200 to 48,000, and more preferably 200 to 46,000. Even if the molecular weight is less than 200, there is no problem in terms of adhesion, but the volatile property of the polyfunctional epoxy resin increases and the odor tends to become strong. On the other hand, if the molecular weight is larger than 50000, solubility in other components is lowered, and 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, more preferably 90 to 5000 g / mol. When the epoxy equivalent is less than 80 g / mol, the epoxy groups per unit volume become excessive, and a large amount of unreacted epoxy groups and thiol groups of the polyfunctional thiol compound (A) remain, whereby the toughness of the cured film composed of the curable resin composition is lowered , And when exposed under high temperature and high humidity conditions, there is a fear that the adhesiveness is lowered. On the other hand, when the epoxy equivalent is more than 6000 g / mol, the reaction efficiency with the thiol group of the polyfunctional thiol compound (A) is lowered because the epoxy group concentration is remarkably low, whereby the toughness of the cured film composed of the curable resin composition is lowered, There is a possibility that the adhesiveness is lowered when exposed under a high humidity condition.

Examples of the polyfunctional epoxy resin (B) include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and epoxy resins obtained by oxidizing a double bond of a double bond containing compound with a peroxide And an oxidized epoxy resin. Of these, glycidyl ether-type epoxy resins and glycidyl ester-type epoxy resins are preferable in that the reactivity at room temperature is slow and the usable time is prolonged. In particular, a glycidyl ether type epoxy resin does not have a functional group which reacts with the polyfunctional thiol compound (A), so that a uniform curable resin composition and, furthermore, a cured film can be obtained regardless of reaction conditions. The polyfunctional epoxy resin (B) may be used singly or in combination of two or more.

&Lt; Glycidyl ether type epoxy resin >

The glycidyl ether type epoxy resin is preferably a reaction product of epichlorohydrin and a compound represented by the following general formula (7).

[Chemical Formula 8]

(In the formula, q is an integer of 2 to 30, R ⁹ is a hydrocarbon group (? 1) having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a group An anilate ring (? 3), a group (? 4) composed of an isocyanurate ring and a hydrocarbon group only)

Among the compounds represented by the general formula (7), wherein q is 2-20, and R ⁹ and the resulting compound (β1-1), or q is 2 to 20 consisting of a hydrocarbon of a carbon number of 2 to 150, and R ⁹ is Is a group consisting only of a hydrocarbon group having 2 to 150 carbon atoms and ether oxygen (-O-), and the compound (2-1) is preferable because of its high solubility with other components. (? 1-1) include, for example, alkylenediols having 2 to 10 carbon atoms, glycerin, pentaerythritol, trimethylol propane, phenol novolac, bisphenol A and the like. (? 2-1) include, for example, polyethylene glycol, polypropylene glycol, and dipentaerythritol.

The reaction of the epichlorohydrin with the compound represented by the general formula (7) can be carried out by reacting the chlorohydrin obtained by the addition reaction of epichlorohydrin and the hydroxyl group of the compound represented by the general formula (7) with a base such as sodium oxide To obtain 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 above ring-closing reaction.

The reaction product of epichlorohydrin and the compound represented by the general formula (7) has a structure represented by the following general formula (8).

[Chemical Formula 9]

(In the formula, q is an integer of 2 to 30, R ⁹ is a hydrocarbon group (? 1) having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a group A pyridinium ring (? 3) or a group (? 4) composed of an isocyanurate ring and a hydrocarbon group only)

&Lt; Glycidyl ester type epoxy resin >

The glycidyl ester type epoxy resin is obtained by polymerizing a monomer having an epoxy group such as glycidyl (meth) acrylate alone or with an alkyl (meth) acrylate having 4 to 25 carbon atoms and having a weight average molecular weight of 3,000 to 20,000, The reaction product of chlorohydrin and the compound represented by the following general formula (9), and the like.

[Chemical formula 10]

(Wherein r is an integer of 2 to 8, R ¹⁰ is a hydrocarbon group (? 5) having 2 to 20 carbon atoms, ether oxygen (-O-) having 2 to 30 carbon atoms and a group (? (7), or a group consisting of an isocyanurate ring and a hydrocarbon group alone (? 8)

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

Among the compounds represented by the general formula (9), wherein r is 2-4, and R ¹⁰ is a group consisting of hydrocarbon groups having 2 to 10 carbon atoms, the compound (β5-1) wherein r is 2-6, and R ¹⁰ Wherein the compound (β6-1), or a compound wherein r is 3, and R ¹⁰ is a group consisting of an isocyanurate ring and a hydrocarbon group only, is a compound comprising only ether oxygen (-O-) having 2 to 30 carbon atoms and a hydrocarbon group, (? 8-1) is preferable because of its high solubility.

(? 5-1) include, for example, hydrophthalic acid and trimellitic acid. (beta 6-1) include, for example, a reaction product of pentaerythritol and trimellitic anhydride. (? 8-1) include, for example, 1,3,5-tris (2-carboxyethyl) isocyanurate and the like.

The reaction product of epichlorohydrin and the compound represented by the general formula (9) has a structure represented by the following general formula (10).

(11)

(Wherein r is an integer of 2 to 8, R ¹⁰ is a hydrocarbon group (? 5) having 2 to 20 carbon atoms, ether oxygen (-O-) having 2 to 30 carbon atoms and a group (? (7), or a group consisting of an isocyanurate ring and a hydrocarbon group alone (? 8)

<Thioether-containing alkoxysilane derivative (Component (C))>

The thioether-containing alkoxysilane derivative (C) is an adhesion improver 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 with a thioether group formed by a crosslinking reaction between the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B) by 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 adhesiveness improving effect is high. Further, the thioether-containing alkoxysilane derivative (C) has an alkoxysilyl group and reacts with the 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 crosslinking density and becomes a crosslinked product (cured product) having a high strength and a high water resistance. In addition, the alkoxysilyl group of the thioether-containing alkoxysilane derivative (C) can be chemically bonded to the inorganic substrate, and the adhesiveness to the inorganic substrate can be greatly improved.

The thioether-containing alkoxysilane derivative (C) in the curable resin composition of the present invention is a compound represented by the following general formula (1). The thioether-containing alkoxysilane derivative (C) may be used singly or in combination of two or more.

[Chemical Formula 12]

(Expression and of a and b is an integer of 0 ~ 2, c is a trivalent group represented an integer of 1 to 3, a + b + c = 3. R is to by the general formula (2), R ^1, and R ² each independently represents a divalent group represented by any of -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, -CH ₂ -CH ₂ - or -CH (CH ₃ ) , And R &lt; ³ &gt; is a methyl group or an ethyl group.

[Chemical Formula 13]

(Wherein m is 1 or 2)

Such a thioether-containing alkoxysilane derivative (C) is a compound having at least a double bond with an alkoxysilyl group [-Si (OR ⁴ ) ₃ ] (hereinafter may be referred to as an X component), a thiol group (-SH) (Hereinafter, may be referred to as Y component). Specifically, a compound wherein b is 0 can be obtained by reacting at least an alkoxysilyl group-containing compound (X) represented by the following general formula (11) with a polyhydric thiol compound (Y) represented by the following general formula (12). The compound in which b is not 0 is a compound having at least an alkoxysilyl group-containing compound (X) represented by the following general formula (11), a polyhydric thiol compound (Y) represented by the following general formula (12) Acrylate. Further, when the components (X) and (Y) are reacted, the double bond of the component (X) and the thiol group of the component (Y) react.

[Chemical Formula 14]

(Wherein R ³ is a methyl group or an ethyl group, and R ¹⁴ is a hydrogen atom or a methyl group)

[Chemical Formula 15]

(Wherein m is an integer of 1 or 2)

Examples of the alkoxysilyl group-containing compound (X) represented by the general formula (11) include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like can be used.

Examples of the polyhydric thiol compound (Y) represented by the general formula (12) include tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate of m = 2. Examples of the compound (Y) having m = 1 include a combination of isocyanuric acid tris (2-hydroxyethyl) and thioglycolic acid. When the compound represented by the general formula (12) is used, the number of hydrophobic and non-polar hydrocarbons increases, so that the orientation property of the thioether group to the base is weakened, making it difficult to obtain adhesion.

The components (X) and (Y) are preferably reacted in the presence of a catalyst or a radical generator. When the catalyst or the radical generator is added, the reaction can be performed in a shorter time and at a higher yield.

As the catalyst, an amine-based base catalyst is preferable, and primary, secondary or tertiary amines or imidazole-based compounds can be used. Examples of the primary amine include methylamine, ethylamine, propylamine, butylamine and ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine and diphenylamine; Examples of the amine include trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7,2,4,6-tris (dimethylaminomethyl) phenol And the like. Examples of the imidazole compound include imidazole analogs such as 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole and 1-phenylimidazole, Methyl-2-oxylmethylimidazole, and 1-methyl-2-oxyethylimidazole, 1-methyl-4 (5) -nitimidazole, 4) -aminoimidazole, benzoimidazole, 1-methylbenzoimidazole, 1-methyl-2-benzylbenzoimidazole and the like.

As the radical generator, a peroxide or an azo compound is preferable. As the peroxide, for example, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dilauryl peroxide, tert-butyl hydroperoxide and the like can be given. Examples of the azo compound include azobis (iso-butyronitrile) and 2,2'-azobis (2-methylbutanenitrile).

In the method for producing the thioether-containing alkoxysilane derivative (C), the reaction can be carried out at a temperature of 5 ° C or higher, but in order to react in a short time, the reaction is preferably carried out at 30 to 120 ° C, preferably 60 to 80 ° C .

In the method for producing the thioether-containing alkoxysilane derivative, although the reaction can proceed even if the solvent is not used, when the viscosity is to be lowered, for example, when the reaction is carried out at a low temperature, a solvent may be added and reacted. At this time, a solvent which does not react with an alkoxysilyl group, a double bond, or a thiol group, such as an alcohol, a ketone, an ester or an aromatic group is preferable.

As such alcohols, it is preferable that the number of carbon atoms is not more than 3, and it is preferable that the alcohol has a boiling point higher than the reaction temperature. It is more preferable that the reaction temperature is high in the temperature range. In addition, since alcohol and alkoxysilyl groups may cause ester exchange during the reaction and the yield of the desired product may decrease, it is preferable to have a structure of R ² OH in order to suppress the yield reduction. As the reaction solvent satisfying these conditions, for example, methanol, ethanol and the like can be given. The ketone preferably has a boiling point higher than the reaction temperature, and more preferably 6 or less carbon atoms from the viewpoint of solubility. Among these, methyl ethyl ketone, methyl isobutyl ketone and the like are exemplified. As the esters, the boiling point is preferably higher than the reaction temperature, and from the viewpoint of solubility, the number of carbon atoms in the linear chain is preferably 6 or less. Among these, for example, butyl acetate, ethyl acetate and the like can be given.

The esters not reacting with the alkoxysilyl group, the double bond and the thiol group preferably have a boiling point higher than the reaction temperature, and from the viewpoint of solubility, those having a linear carbon number of 6 or less are preferred. Examples which satisfy these include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate.

&Lt; Amine compound (Component (D)) >

The amine compound in the curable resin composition of the present invention is added in order to accelerate (catalyze) the reaction between the thiol group and the epoxy group. Examples of the amine compound (D) include monofunctional amines having a molecular weight of 90 to 700, preferably 100 to 690, more preferably 110 to 680, and polyamines having a plurality of amino groups. If the molecular weight of the amine compound (D) is less than 90, the volatility of the amine increases, which causes bad odor and voids. In addition, since the amine concentration at the time of heat curing is lowered, the crosslinking reaction does not proceed well, . When the molecular weight of the amine compound (D) exceeds 700, the water resistance is lowered and the adhesion is likely to be lowered.

Monofunctional amines include primary amines, secondary amines, and tertiary amines. The polyamines include primary amines, secondary amines, tertiary amines, and complex amines. The complex amine is an amine having at least two of a primary amino group, a secondary amino group and a tertiary amino group. Such complex amines include imidazoline compounds, imidazole compounds, N-substituted piperazine compounds, N, N-dimethylurea derivatives and the like. The amine compound (D) may be used singly or in combination of two or more.

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 to be reacted with the amine compound (D) in advance include aliphatic carboxylic acids having 1 to 20 carbon atoms and 1 to 5 carboxyl groups such as stearic acid and 2-ethylhexanoic acid, carboxyl groups having 1 to 20 carbon atoms, Aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 1 to 10 carbon atoms, and isocyanuric acid. The amine compound (D) may be added after forming an adduct with the polyfunctional epoxy resin (B) in order to adjust the catalytic activity.

<Imidazole compound>

Among the amine compounds (D), imidazole compounds are most suitable for compatibility between the storage stability and the curing time at low temperatures. An imidazole compound coated with a phenol resin or the like can also be used.

The imidazole compound is a compound represented by the following formula (3).

[Chemical Formula 16]

(R ⁵ is a cyano group, an alkoxy group, or a hydrogen atom of a hydrocarbon group having 1 to 10 hydrocarbon group, a 2,3-diamino-tree of 1 to 10 carbon atoms substituted with a triazine, having a carbon number of 1 to 4, R ^4, R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and a hydrocarbon group having 2 to 8 carbon atoms when R ⁴ to R ⁷ are combined to form a ring )

Specific examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) Imidazole, 1- (2-cyanoethyl) -2-undecylimidazole, 1- (2-cyanoethyl) Ethyl-4-methylimidazole, 2,3-dihydro-lH-pyrrolo [1,2-a] benz Imidazole, 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- Phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

<Polyfunctional (meth) acrylate compound (component (E))>

When the curable resin composition of the present invention contains a polyfunctional thiol compound (A), a polyfunctional epoxy resin (B), and an amine compound (D), it is cured by heat. On the other hand, when it is desired to impart a photo-curable property or a photo-thermal curable property to the curable resin composition of the present invention, a polyfunctional (meth) acrylate compound (E) may be added.

It is known that the thiol group undergoes addition reaction with a double bond by heat or light stimulus. Therefore, a 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 above 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 multiple double bond-containing compounds, the reason for selecting polyfunctional (meth) acrylate is that the polyfunctional thiol compound (A) in the curable resin composition of the present invention does not react well at room temperature, (A), the reaction with the polyfunctional thiol compound (A) is difficult to be catalyzed by the amine compound (D), the reaction between the polyfunctional epoxy resin (B) and the polyfunctional thiol compound ), And the like.

As such a polyfunctional (meth) acrylate (E), a compound represented by the following general formula (13) is preferably used. Further, the polyfunctional (meth) acrylate (E) may be used alone or in admixture of two or more.

[Chemical Formula 17]

(Wherein s is an integer of 2 to 30, R ¹² is a hydrocarbon group (∈1) having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a group (ε2) and isocyanurate rings (ε3), or isocyanurate rings and the group (ε4) made of a hydrocarbon deception, R ¹³ is a hydrogen atom or a methyl group)

As the polyfunctional (meth) acrylate (E), a polymer type may also be preferably used. Examples of the polymer type polyfunctional (meth) acrylate (E) include a (meth) acrylate compound having an epoxy group such as glycidyl (meth) acrylate or a group reacting with an epoxy group such as (meth) (Meth) acrylate compound, a (meth) acrylate compound having a hydroxyl group such as hydroxyethyl (meth) acrylate or a copolymer thereof with 2-methylpropene 2-isocyanatoethyl (Meth) acrylate compound having a group reacting with a hydroxyl group, a (meth) acrylate compound having a carboxyl group such as (meth) acrylic acid, or a copolymer of a carboxyl group and a glycidyl And a polymer obtained by reacting a (meth) acrylate compound having a reactive group.

The molecular weight of the polyfunctional (meth) acrylate compound (E) is from 200 to 50000, preferably from 220 to 40000, and more preferably from 240 to 30000. Even if the molecular weight of the polyfunctional (meth) acrylate compound (E) is smaller than 200, there is no problem in terms of adhesion, but the volatility tends to become strong and the offensive odor becomes strong. On the other hand, if the molecular weight is larger than 50,000, the solubility of the other components may be lowered.

The (meth) acrylate equivalent of the polyfunctional (meth) acrylate (E) is 80 to 6000 g / mol, preferably 80 to 4500, 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 the thiol group of the polyfunctional thiol compound (A) and the unreacted (meth) acryloxy group remain in a large amount , The toughness of the cured film made of the curable resin composition lowers, and when exposed under high temperature and high humidity conditions, there is a fear that the adhesiveness is lowered. On the other hand, when the (meth) acrylate equivalent is more 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 remarkably low, Toughness of the resulting cured film is lowered, and when exposed under high temperature and high humidity conditions, there is a fear that the adhesiveness is lowered.

<Composition ratio (compounding balance)>

The curable resin composition of the present invention is blended so that the weight ratio (A) / (B) of 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 values of (A) / (B) are the properties required for the curable resin composition, and the values of the polyfunctional (meth) acrylate (A) and the polyfunctional epoxy resin (B) It differs depending on the structure of the compound (E). The properties of the curable resin composition after curing are strictly a value of (thiol group number) / (epoxy group number + (meth) acryloxy group number) (hereinafter referred to as thiol / (epoxy + en) ratio) in the unit weight of the curable resin composition . &Lt; / RTI &gt; For example, when the ratio of thiol / (epoxy + ene) is in the range of 0.5 to 1.5, it is easy to form dense bridges and tends to be hardened. On the other hand, when the ratio of thiol / (epoxy + ene) is 0.1 or more and less than 0.5 or 1.5 or more and 2.0 or less, a flexible and adhesive cured product can be obtained. When the ratio of thiol / (epoxy + ene) is less than 0.1 or more than 2.0, gelation hardly occurs, and adhesion tends to decrease.

The curable resin composition of the present invention is characterized in that the amount of the thioether-containing alkoxysilane derivative (C) is 0.5% by weight based on 100 parts by weight of the total weight (A + B) of the polyfunctional thiol compound (A) and the polyfunctional epoxy resin To 50 parts by weight, preferably 0.5 to 45 parts by weight. When the amount of the component (C) is less than 0.5 parts by weight based on the amount of the component (A), the adhesion is not obtained. When the amount exceeds 50 parts by weight, the crosslinking density of the cured product is lowered and the toughness is lowered.

The curable resin composition of the present invention preferably contains 0.01 to 50 parts by weight of the amine compound (D) based on 100 parts by weight of the total weight (A + B) of the polyfunctional thiol compound (A) and the polyfunctional epoxy resin (B) By weight, preferably 0.01 to 45 parts by weight. If the compounding amount of the component (D) is less than 0.01, the time required for the reaction between the thiol group and the epoxy group to proceed, the curing is defective. When the amount is more than 50 parts by weight, the crosslinking density is low, There is a tendency to deteriorate.

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

<Curable resin composition>

When a thiol group of the polyfunctional thiol compound (A) reacts with an epoxy group of the polyfunctional epoxy resin (B), a thioether group or a hydroxyl group is produced. The thioether-containing alkoxysilane (C) also has a thioether group and is crosslinked by a disulfide bond with a thioether formed by the reaction of the thiol group and the epoxy group. Also, the thioether-containing alkoxysilane (C) has an alkoxysilyl group at the same time, and reacts with the hydroxyl group generated 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 increased heat resistance, toughness, water resistance and the like because the cross-linked product becomes dense. Further, since it is a cured product crosslinked with a thioether group or a disulfide bond, it has a high degree of flexibility and high adhesiveness. In addition, since the thioether-containing alkoxysilane (C) has a trialkoxysilyl group at the same time, it is possible to form a chemical bond with an inorganic substrate such as glass in particular, and the curable resin composition of the present invention is excellent in adhesion It is increasing.

In the curable resin composition of the present invention, the reaction of the (meth) acryloyl group of the polyfunctional (meth) acrylate compound (E) and the polyfunctional thiol compound (A) do. 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 which is cured in two steps of light and heat. Further, it is possible to control the degrees of photo-curing and thermosetting by controlling the respective component amounts.

Conventionally, various thiol compounds have been used as a curing agent (a compound added to cure a subject such as an epoxy resin or a (meth) acrylate compound). It is also generally known that a base material such as an amine has an effect of lowering (catalyzing) the reaction activation energy in any reaction of a thiol group, an epoxy group, or a thiol group and a (meth) acryloyl group.

The curable resin composition of the present invention may be diluted with an organic solvent so as to make the reaction system homogeneous and to facilitate application. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents and 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 based on 100 parts by weight of the curable resin composition. Basically, since the solvent volatilizes at the time of becoming a cured film, the physical properties of the cured film are not greatly affected. However, the use of a compound having a functional group reactive with a thiol group, an epoxy group, or a (meth) acryloyl group, and an amine compound as a solvent may hinder the effect of the present invention.

In the curable resin composition of the present invention, a viscosity adjusting agent such as silica powder may be added for the purpose of adjusting the viscosity. It is preferable that these viscosity modifiers are controlled to a blending amount of less than 300 parts by weight based on 100 parts by weight of the curable resin composition. If the blending amount of the viscosity adjusting agent exceeds 300 parts by weight, the adhesion may be deteriorated.

The curable resin composition of the present invention may be added with various additives used for ordinary paints and adhesives. Examples of such an additive include a surfactant for smoothing a coated surface, an aluminum salt for lengthening the usable time, a photo-radical generator for improving photoreactivity, a photo-base generator, and a photo acid generator. These additives are preferably suppressed to a blending amount of less than 80 parts by weight based on 100 parts by weight of the curable resin composition. If the blending amount of these additives exceeds 80 parts by weight, there is a possibility that the adhesiveness is lowered.

Example

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto. The reagents used in this Example and Comparative Example are as follows. Mw represents the weight average molecular weight.

<Polyfunctional Thiol Compound (Component A)>

(A-1, Mw: 372)

[Chemical Formula 18]

(A-2, Mw: 399)

[Chemical Formula 19]

(A-3, Mw: 526)

[Chemical Formula 20]

(A-4, Mw: 488)

[Chemical Formula 21]

(A-5, Mw: 784)

[Chemical Formula 22]

(A-6, Mw: 416)

(23)

(A-7, Mw: 785)

&Lt; EMI ID =

(A-8, Mw: 1584)

(25)

<Polyfunctional epoxy resin (component B)>

(B-1, Mw: 220, epoxy equivalent: 110)

(26)

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

(27)

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

(28)

(B-4, Mw: 5500, epoxy equivalent: 3000)

[Chemical Formula 29]

n is an average of 15

(B-5, Mw: 1500, epoxy equivalent: 186)

(30)

n is an average of 7

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

(31)

(B-7, Mw: 18000, epoxy equivalent: 250)

Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (a white solid reprecipitated with 50 wt% methyl isobutyl ketone solution in hexane).

(B-8, Mw: 45000, epoxy equivalent: 250)

Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid redissolved in 50 wt% methyl isobutyl ketone solution in hexane).

<Thioether-containing alkoxysilane derivative (Component C)>

(C-1)

(32)

(C-2)

(33)

(C-3)

(34)

(C-4)

(35)

(C-5)

(36)

(C-6)

(37)

(C-7)

(38)

<Amine compound (component D)>

(D-1, Mw: 136)

[Chemical Formula 39]

(D-2)

1: 1 equivalent of 1,8-diazabicyclo (5,4,0) undeca-7-ene and stearic acid

(D-3, Mw: 680)

(40)

n1, n2 and n3 are integers of 1 to 5,

(D'-1, Mw: 110)

(41)

(D'-2, Mw: 144)

(42)

(D'-3, Mw: 163)

(43)

(D'-4, Mw: 219)

(44)

(D'-5)

[Chemical Formula 45]

Salts of 2-phenylimidazole and pyromellitic acid

(D'-6, Mw: 158)

(46)

(D'-7, Mw: 306)

(47)

<Polyfunctional (meth) acrylate compound (component E)>

(E-1, Mw: 246, double bond equivalent: 123)

(48)

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

(49)

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

(50)

(E-4, Mw: 5000, double bond equivalent: 3000)

(51)

n is an average of 13

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

(52)

n is an average of 5

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

(53)

(E-7, Mw: 22000, double bond equivalent: 320)

A polymer (50 wt% methyl isobutyl ketone solution in hexane-refined white solid) of methacrylic acid in the presence of D-3 as a catalyst in the copolymer of glycidyl methacrylate and cyclohexyl methacrylate.

<Other reagents>

(F-1 (? Component))

(54)

(F-2 (? C component))

(55)

The components (A) to (E) were each mixed with the compounding balance shown in Tables 1 and 2, and stirred until they became homogeneous with a spatula. The following evaluation was conducted on the sample after stirring, and the results are also shown in Tables 1 and 2.

&Lt; Evaluation of adhesion &

Each of the examples and comparative examples was coated on a non-alkali glass (OA-10, manufactured by Nippon Electric Glass Company, thickness: 0.7 mm) and an aluminum plate (A5052P, manufactured by Nippon Test Panel Co., thickness: 2.0 mm) And heated at 140 占 폚 for 1 hour to obtain a cured film on each substrate. After the base material obtained the cured film was treated at 121 캜 x 100% RH for 90 hours, evaluation was conducted by the mechanical property-adhesion (crosscut method) test method of the coating film specified in JIS K5600-5-6. ⊚ indicates that there is no peeling at all, ◯ indicates that the peeling is not more than 1% of the total area, and × indicates the other peeling. Adhesiveness 1 in the table is a result on a non-alkali glass substrate, and adhesion 2 is a result on an aluminum plate substrate.

<Confirmation of Photocurability>

Each of the Examples and Comparative Examples was coated on a non-alkali glass to a thickness of 100 mu m with a bar coater and irradiated with light of 500 mJ / cm &lt; 2 &gt; (i line conversion) with a high-pressure mercury lamp. When the irradiated coating film was pressed with a spatula, a case in which the coating liquid did not adhere to the spatula was evaluated as &amp; cir &amp;

<Confirmation of Storage Stability (Storage Stability)>

The viscosity of each of the examples and comparative examples immediately after mixing was measured by the following viscometer. Each of the Examples and Comparative Examples were heated at 30 占 폚 for 12 hours and then viscosities were measured again. The values obtained by dividing the viscosity after heating by the viscosity after mixing were 1.0 to 1.8,?: 1.8 to 10, and?

Model: manufactured by Toki Industry Co., Ltd. (R type viscometer)

Temperature: 25 ℃

As evident from the results in Tables 1 and 2, high adhesion was confirmed in all Examples. It was also confirmed that the addition of the component (E) in Examples 2-1 to 2-8 can impart photocurability. It has also been found that the storage stability (storage stability) is improved by using amines as imidazole compounds in Examples 1-3 to 1-7 and 2-3 to 2-8. On the other hand, it was confirmed that, as in each of Comparative Examples, excellent adhesion to an inorganic substrate can not be obtained if the material does not contain any of the essential components (A) to (D) of the present invention or is a different material.

Claims (5)

A curable resin composition containing the following components (A), (B), (C) and (D)
The component (A) is a polyfunctional thiol compound having a molecular weight of 200 to 2000,
Wherein the component (B) is a polyfunctional epoxy resin having a molecular weight of 200 to 50000 and an epoxy equivalent of 80 to 6000 g / mol,
Wherein the component (C) is a thioether-containing alkoxysilane derivative represented by the following general formula (1)
The component (D) is an amine compound having a molecular weight of 90 to 700,
(A) / (B) of the component (A) and the component (B) is 0.05 to 30,
(C) is contained in an amount of 0.5 to 50 parts by weight and the component (D) is contained in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the total weight of the component (A) and the component (B) Curable resin composition.
[Chemical Formula 1]

(Expression and of a and b is an integer of 0 ~ 2, c is a trivalent group represented an integer of 1 to 3, a + b + c = 3. R is to by the general formula (2), R ^1, and R ² each independently represents a divalent group represented by any of -CH ₂ -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, -CH ₂ -CH ₂ - or -CH (CH ₃ ) , And R &lt; ³ &gt; is a methyl group or an ethyl group)
(2)

(Wherein m is 1 or 2) The method according to claim 1,
(Meth) acrylate compound having a molecular weight of 200 to 50000 and a (meth) acrylate equivalent of 80 to 6000 g / mol as the component (E) is added to the component (A) And 2 to 300 parts by weight based on 100 parts by weight of the total weight of the curable resin composition. The method according to claim 1,
Wherein the amine compound (D) is an imidazole compound represented by the following general formula (3).
(3)

(R ⁵ is a cyano group, an alkoxy group, or a hydrogen atom of a hydrocarbon group having 1 to 10 hydrocarbon group, a 2,3-diamino-tree of 1 to 10 carbon atoms substituted with a triazine, having a carbon number of 1 to 4, R ^4, R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and a hydrocarbon group having 2 to 8 carbon atoms when R ⁴ to R ⁷ are combined to form a ring ) The method according to claim 1,
Wherein the polyfunctional thiol compound (A) is a polyfunctional thiol compound represented by the following general formula (3).
[Chemical Formula 4]

(Wherein n is an integer of 2 to 5, p is an integer of 2 to 10, and R ⁸ is a hydrocarbon group (? 1) having 2 to 30 carbon atoms, ether oxygen (-O-) having 2 to 40 carbon atoms and hydrocarbon (? 2), isocyanurate ring (? 3), or a group (? 4) composed only of an isocyanurate ring and a hydrocarbon group) The method according to claim 1,
Wherein the polyfunctional epoxy resin (B) is a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin.