KR20170031760A - Curable resin composition - Google Patents

Abstract

A material having excellent adhesion to a base material even in a cold region and having flexibility obtained by the obtained cured film. (A) a thioether-containing (meth) acrylate derivative having a specific structure, (B) a polyfunctional epoxy resin having a weight average molecular weight of 200 to 50000, and (C) an amine compound having a weight average molecular weight of 90 to 700 Curable resin composition. (A) / (B)) of the component (A) and the component (B) is 0.05 to 30 and the component (C) is 0.01 to 100 parts by mass based on 100 parts by mass of the total mass of the components (A) 50 parts by mass.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition having excellent adhesion to a base material even in a cold region and having a flexibility obtained by the obtained cured film.

Conventionally, there is a technique of adding a silane coupling agent in order to improve adhesion to an inorganic substrate such as a paint containing an epoxy resin as a main component (for example, Patent Document 1). However, a considerable number of silane coupling agents have a low boiling point, and therefore it has been necessary to add a large amount of the silane coupling agent to the thermosetting resin. Further, the adhesion improving effect is not sufficient. For example, when the adhesion property required at practical level can be attained by simultaneously adding a salt such as titanium · zirconium or an adhesion aid such as phosphate ester or urethane resin . 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.

Thus, Patent Document 2 proposes a curable resin composition in which a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative are mixed with an epoxy resin composition and an amine compound. As in the case of using a silane coupling agent, this curable resin composition does not need to be added with any other adhesion promoter or the like, and can exert excellent adhesion to an inorganic substrate.

Japanese Unexamined Patent Publication No. 7-300491 Japanese Laid-Open Patent Publication No. 2012-246464

However, as in Patent Document 2, a curable resin composition obtained by mixing a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative with an epoxy resin composition and an amine compound is excellent in adhesion to an inorganic substrate, However, it has been found that there is a problem that a cured film is liable to be cracked at the time of bending because of insufficient flexibility in a cold region, and that the adhesion is insufficient.

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 material having excellent adhesion to a base material even in cold regions and having flexibility obtained by the obtained cured film.

(A) a thioether-containing (meth) acrylate derivative represented by the following formula (1), (B) a polyfunctional epoxy resin having a weight average molecular weight of 200 to 50000, (C) (A) / (B)) of the component (A) and the component (B) is 0.05 to 30, and the component (A) (C) in an amount of 0.01 to 50 parts by mass based on 100 parts by mass of the total mass of the component (A).

[Chemical Formula 1]

(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R ¹ is a methylene group, R ² is a divalent functional group represented by the following formula 2 or 3: R ³ is a methyl group or an ethyl group, and R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms.

(2)

(R < ⁵ > is a hydrogen atom or a methyl group)

(3)

(R < ⁵ > is a hydrogen atom or a methyl group)

The curable resin composition of the present invention preferably further comprises (D) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 50000 in an amount of 2 to 100 parts by mass of the total mass of the component (A) To 300 parts by mass.

The curable resin composition of the present invention may further contain 0.01 to 10 parts by mass of the (E) photopolymerization initiator relative to 100 parts by mass of the total mass of the component (A) and the component (D).

In the present invention, "(meth) acrylate" means a generic term including both acrylate and methacrylate. The terms "(meth) acrylic acid" and "(meth) acryloxy group" are also used collectively. In the present invention, " xx to xx " indicating the numerical range is a concept including the lower limit value (" xx ") and the upper limit value (xx). That is, it means exactly "xx or more xx or less". In the present invention, " molecular weight " means a weight average molecular weight unless otherwise specified.

(B) a polyfunctional epoxy resin having a specific molecular weight; (C) a polyfunctional epoxy resin having a specific molecular weight; and (C) a polyfunctional epoxy resin having a specific molecular weight, The amine compound is well-balanced. Thereby, even when the conventional silane coupling agent is used, it has excellent adhesion to the substrate even if it does not contain any other adhesion promoting agent or the like. In particular, the curable resin composition using the conventional multifunctional thiol compound has insufficient adhesion to the base material under the cold condition, which is insufficient, and the obtained cured film has flexibility.

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

<Thioether-containing (meth) acrylate derivative (component (A))>

The (A) thioether-containing (meth) acrylate derivative of the present invention is a compound represented by the following formula (1).

[Chemical Formula 4]

(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R ¹ is a methylene group, R ² is a divalent functional group represented by the following formula 2 or 3: R ³ is a methyl group or an ethyl group, and R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms.

[Chemical Formula 5]

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)

[Chemical Formula 6]

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R &lt; ⁴ &gt; in the formula (1) include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. R ¹ in the formula 1 is a methylene group, an ethylene group, an isopropylene group, is improved in that the adhesion increasing effect, an ethylene group, an isopropylene group is particularly preferred.

The thioether-containing (meth) acrylate derivative represented by the above-mentioned formula (1) exerts a high adhesiveness improving effect on the base material without being added with an adhesion aid even when it is incorporated into a paint or the like, for example, in a cold environment such as -10 ° C The effect of imparting flexibility to the obtained coating film is excellent. Further, the thioether-containing (meth) acrylate derivative represented by the above formula (1) is excellent in solubility in other components because of its small molecular weight. Therefore, the thioether-containing (meth) acrylate derivative represented by the formula (1) has high compatibility with many resins, so that it can be used for a wide range of paints and has high versatility.

<Polyfunctional epoxy resin (component (B))>

The polyfunctional epoxy resin as the component (B) is an organic compound having two or more epoxy groups (oxirane rings). The weight average molecular weight of the polyfunctional epoxy resin is 200 to 50000, preferably 200 to 48000, and more preferably 200 to 46000. Even if the weight average molecular weight is less than 200, there is no problem in adhesion, but the volatile property of the polyfunctional epoxy resin is high, and the odor tends to become strong. On the other hand, if the weight average molecular weight is larger than 50,000, solubility in other components is lowered, and adhesion to a 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. If the epoxy equivalent is less than 80 g / mol, the epoxy group per unit volume becomes excessive, and (A) a thiol group of the thioether-containing (meth) acrylate derivative and a large amount of unreacted epoxy groups remain, There is a fear that the toughness of the film is deteriorated and the adhesiveness is lowered. On the other hand, if the epoxy equivalent is more than 6000 g / mol, the epoxy group concentration is remarkably low, and (A) the reaction efficiency of the thioether-containing (meth) acrylate derivative with the thiol group is lowered, and the toughness of the cured film made of the curable resin composition is lowered And adhesion to the substrate may be deteriorated.

Examples of the polyfunctional epoxy resin as the component (B) include epoxy resins such as glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, or a double bond of a double bond containing compound as a peroxide And an oxidized epoxy resin obtained by oxidation. Of these, glycidyl ether type epoxy resins and glycidyl ester type epoxy resins are preferable from the viewpoint of low reactivity at room temperature and high storage stability. The polyfunctional epoxy resin may be used alone or in combination of two or more.

&Lt; Glycidyl ether type epoxy resin &gt;

As the glycidyl ether type epoxy resin, a reaction product of epichlorohydrin and a compound represented by the following formula 4 is preferable.

(7)

(Wherein d is an integer of 2 to 30, R ⁶ is a hydrocarbon group (? 1) having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a group (? 2) A pyridinium ring (? 3) or a group (? 4) composed of an isocyanurate ring and a hydrocarbon group only)

Among the compounds represented by the above formula 4, and d is 2-20, and R ⁶ is a hydrocarbon group having 2 to compound 150 (β1-1), or a d is 2-20, and R ⁶ is of a carbon number of 2 to 150 The compound (? 2-1) which is a group consisting only of a hydrocarbon group and ether oxygen (-O-) is preferable because of 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.

By reacting epichlorohydrin with the compound represented by the formula 4, the epichlorohydrin and the hydroxyl group of the compound represented by the formula 4 are subjected to an addition reaction to obtain the chlorohydrin, and the resulting chlorohydrin is reacted with a base such as sodium oxide An epoxy resin can be obtained. The glycidyl ether type epoxy resin may be an epoxy resin obtained by ring-opening polymerization of a part of epoxy groups of the epoxy resin obtained after the cyclization reaction.

The reaction product of epichlorohydrin and the compound represented by the formula (4) has a structure represented by the following formula (5).

[Chemical Formula 8]

(Wherein d is an integer of 2 to 30, R ⁶ is a hydrocarbon group (? 1) having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a group (? 2) A pyridinium ring (? 3) or a group (? 4) composed of an isocyanurate ring and a hydrocarbon group only)

[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 an alkyl (meth) acrylate having 4 to 25 carbon atoms and having a weight average molecular weight of 3000 to 20000 or The reaction product of epichlorohydrin and the compound represented by the following formula 6, and the like.

[Chemical Formula 9]

(In the formula, e is an integer of 2 to 8, R ⁷ 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 only (? 8)

Epichlorohydrin and the carboxyl group of the compound of the formula 6 are subjected to an addition reaction by reacting epichlorohydrin with the compound represented by the formula 6 to obtain a chlorohydrin, and the obtained chlorohydrin is subjected to a ring-closing reaction with a base such as sodium hydroxide Whereby a glycidyl 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.

Of the compounds represented by the formula 6, compounds (β5-1) wherein e is 2 to 4 and R ⁷ is a hydrocarbon group of 2 to 10 carbon atoms, e is 2 to 6, and R ⁷ is an ether of 2 to 30 carbon atoms A compound (β6-1) which is a group consisting of only oxygen (-O-) and a hydrocarbon group or a compound (β8-1) in which e is 3 and R ⁷ is a group consisting of an isocyanurate ring and a hydrocarbon group only, It is preferable because it is high.

(? 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 formula 6 has a structure represented by the following formula (7).

[Chemical formula 10]

(In the formula, e is an integer of 2 to 8, R ⁷ 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 only (? 8)

&Lt; Amine compound (Component (C)) &gt;

The amine compound as the component (C) accelerates (catalyses) the reaction between the thiol group and the epoxy group. Examples of the amine compound as the component (C) include monofunctional amines having a weight average molecular weight of 90 to 700, preferably 100 to 690, and more preferably 110 to 680, and polyamines having a plurality of amino groups. If the weight average molecular weight of the amine compound is less than 90, the volatility of the amine compound becomes high, which causes bad odor and voids. In addition, since the amine concentration at the time of heat curing lowers, the crosslinking reaction becomes difficult to proceed and the adhesion tends to decrease . When the weight average molecular weight of the amine compound is more than 700, the water resistance is lowered and the adhesiveness 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. In addition, the amine compound may be used alone or in admixture of two or more.

The amine compound may form a salt with an organic acid in advance to adjust the catalytic activity. Examples of the organic acid to be reacted with the amine compound in advance include aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 20 carbon atoms and 1 to 5 carboxyl groups, 1 to 20 carbon atoms, Aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 10 carbon atoms, or isocyanuric acid. Further, the amine compound as the component (C) may be added after forming an adherend with the polyfunctional epoxy resin as the component (B) to adjust the catalytic activity.

[Imidazole compound]

Among the amine compounds, imidazole compounds are most suitable for compatibility between storage stability and curing in a short time under low temperature conditions. An imidazole compound coated with a phenol resin or the like can also be used. This imidazole compound is a compound represented by the following formula (8).

(11)

(R ⁹ 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 ^8, R ¹⁰ and R ¹¹ 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 ⁸ to R ¹¹ are combined to form a ring )

Specific examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2- Benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl Methylimidazole, 1- (2-cyanoethyl) -2-undecylimidazole, 1- (2-cyanoethyl) (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- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

<Multifunctional (meth) acrylate (Component (D))>

The curable resin composition of the present invention comprising (A) a thioether-containing (meth) acrylate derivative, (B) a polyfunctional epoxy resin, and (C) an amine compound can be cured by heating. By adding (D) a polyfunctional (meth) acrylate to the curable resin composition, photo-curable or photo-thermal two-stage curing properties can be imparted.

(Meth) acrylate as the component (D), among the double bond-containing compounds having a large number of double bond-containing compounds, it is preferable that the curing resin composition of the present invention contains (Meth) acrylate derivative (A) to form a strong cured product when reacted with the thioether-containing (meth) acrylate derivative, (A) a thioether The reaction between the (meth) acrylate derivative (D) and the polyfunctional (meth) acrylate is difficult to be catalyzed by the amine compound (C), and (B) does not react with the polyfunctional epoxy resin .

A preferred example of such a polyfunctional (meth) acrylate is a compound represented by the following formula (9). The polyfunctional (meth) acrylate as the component (D) may be used singly or in a mixture of two or more kinds.

[Chemical Formula 12]

(Wherein f 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 (D), a polymer type may also be preferably used. Examples of the polymer type polyfunctional (meth) acrylate include (meth) acrylates having epoxy groups such as glycidyl (meth) acrylate or the like having a group reacting with an epoxy group such as (meth) (Meth) acrylate, a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, or a copolymer obtained by reacting with a hydroxyl group such as 2-methylpropene 2-isocyanatoethyl (Meth) acrylate having a group capable of reacting with a carboxyl group such as glycidyl (meth) acrylate on a (meth) acrylate having a carboxyl group such as (meth) acrylic acid or the like, (Meth) acrylate, and the like.

The weight average molecular weight of the polyfunctional (meth) acrylate (D) is 200 to 50000, preferably 220 to 40000, and more preferably 240 to 30000. (D) a polyfunctional (meth) acrylate having a weight average molecular weight of less than 200, there is no problem in terms of adhesion, but there is a tendency that the volatility increases and the offensive odor becomes strong. On the other hand, if the weight average molecular weight is more than 50,000, solubility in other components may be lowered.

The (meth) acrylate equivalent of the (D) polyfunctional (meth) acrylate is 80 to 6000 g / mol, preferably 80 to 4500, more preferably 85 to 3000. If the (meth) acrylate equivalent is less than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive and (A) the thiol group of the thioether-containing (meth) If a large amount of the curing agent remains, the toughness of the cured film formed of the curable resin composition may deteriorate and the adhesion may deteriorate. On the other hand, when the (meth) acrylate equivalent is more than 6000 g / mol, the reaction efficiency with the thiol group of the thioether-containing (meth) acrylate derivative is lowered because (A) the (meth) The toughness of the cured film made of the curable resin composition may decrease, and the adhesion may be lowered.

&Lt; Photopolymerization initiator (Component (E)) &gt;

The photopolymerization initiator as the component (E) is added to promote the reaction between the thiol group and the (meth) acryloxy group. Examples of the photopolymerization initiator include photo radical initiators, photocathion initiators, photoanionic initiators, and the like. The photo-radical initiator is preferably used when shortening the reaction time. The photo-cation initiator is preferably used when the curing shrinkage is reduced. The photoanionic initiator is preferably used in adhesiveness It is preferable to use it when giving.

Examples of photo radical initiators include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -hydroxy-cyclohexyl- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- Methyl-1- [4- (methylthio) phenyl] -2-methyl-propan- ] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide .

Examples of the photocathion initiator include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1, 2,4,6-tetramethyluronium hexafluorophosphate, tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2- , Triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, etc., .

Examples of the photoinitiator include acetophenone-o-benzoyloxime, nifedipine, 2- (9-oxo xanthene-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] deca- 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] -Benzoylphenyl) propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanium n-butyltriphenylborate, and the like.

<Composition ratio (compounding balance)>

The curable resin composition of the present invention is formulated so that the mass ratio (A) / (B) of the (A) thioether-containing (meth) acrylate derivative and the (B) polyfunctional epoxy resin is 0.05 to 30. Here, "(A) / (B)" is a value obtained by dividing the mass of the (A) thioether-containing (meth) acrylate derivative by the mass of the (B) polyfunctional epoxy resin. The optimum value of (A) / (B) is the property required for the curable resin composition, and the value of (A) / (B) It differs depending on the structure of the functional (meth) acrylate. The properties of the curable resin composition after curing are strictly referred to as (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 The value is affected. 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 to less than 0.5 or more than 1.5 to 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 becomes difficult and adhesiveness tends to decrease.

(C) relative to 100 parts by mass of the total mass of the (A) thioether-containing (meth) acrylate derivative and the (B) polyfunctional epoxy resin, The amine compound is added in an amount of 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass. When the amount of the component (C) is less than 0.01 parts by mass based on 100 parts by mass of (A) + (B), it takes time for the reaction between the thiol group and the epoxy group to proceed, If the amount is more than 100 parts by weight, the storage stability may be lowered.

When the polyfunctional (meth) acrylate (D) is also blended in the curable resin composition of the present invention, the total mass of the (A) thioether-containing (meth) acrylate derivative and the polyfunctional epoxy resin (Meth) acrylate is added in an amount of 2 to 300 parts by mass, preferably 2 to 250 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate (A) + (B). If the blending amount of the component (D) is less than 2 parts by mass based on 100 parts by mass of (A) + (B), it is difficult to impart photo-curability, and if it exceeds 300 parts by mass, the adhesion tends to decrease.

When the photopolymerization initiator (E) is added to the curable resin composition of the present invention, the total mass of the (A) thioether-containing (meth) acrylate derivative and (D) the polyfunctional (meth) (E) is added in an amount of 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, per 100 parts by mass of (A) + (D). If the blending amount of the component (E) is less than 0.01 part by mass based on 100 parts by mass of (A) + (D), it is difficult to promote photo-curing, and if it exceeds 10 parts by mass, the amount becomes unnecessarily large.

&Lt; Formation of cured film &

The curable resin composition of the present invention can be coated on a substrate and cured to form a cured film. The curable resin composition of the present invention exhibits adhesion to a substrate due to the thioether group of the (A) thioether-containing (meth) acrylate derivative. Therefore, examples of the substrate include inorganic substrates such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound that forms a chemical bond with a thioether group (having a high chemical affinity) An organic substance having an unsaturated bond (including aromatic rings), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone. Specifically, examples of the inorganic substrate include glass, silicon, various metals, and the like. Examples of the organic base material include poly (meth) acrylic resins, triacetate cellulose (TAC) resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate, polycarbonate resins, polyimide resins, Polyolefin resin such as polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride resin, polyacetal and the like are preferable. In addition, the curable resin composition of the present invention has excellent flexibility because the (A) thioether-containing (meth) acrylate derivative has a specific hydrocarbon group. Therefore, even under a cold condition, the cured film is easy to follow the substrate, and the adhesion to the substrate is excellent. Therefore, it can be particularly preferably used for coating of a flexible substrate which can be used particularly under cold conditions.

The curable resin composition of the present invention can be cured by heating. The heating temperature is about 25 to 250 ° C. When the curable resin composition contains the component (D), it may be cured by irradiation with light. Examples of light to be irradiated include active energy rays such as UV (ultraviolet rays) and EB (electron beams). When the curable resin composition contains the component (D), the curable resin composition may be cured through a two-step process of a curing process by light irradiation and a curing process by heating.

The curable resin composition of the present invention may be diluted with an organic solvent so as to make the reaction system uniform and facilitate the coating. 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 mass based on 100 parts by mass of the curable resin composition. Basically, since the solvent is volatile 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.

The curable resin composition of the present invention may be blended with a viscosity adjusting agent such as silica powder 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 mass based on 100 parts by mass of the curable resin composition. If the blending amount of the viscosity adjusting agent exceeds 300 parts by mass, the adhesion may possibly decrease.

In the curable resin composition of the present invention, various additives used for ordinary paints and adhesives may be added. Examples of such an additive include a surfactant for smoothing the coated surface and an aluminum salt for prolonging the usable time. These additives are preferably suppressed to a blending amount of less than 80 parts by mass with respect to 100 parts by mass of the curable resin composition. If the blending amount of these additives exceeds 10 parts by mass, 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.

&Lt; Component (A) &gt;

(A-1: thioether-containing (meth) acrylate derivative)

[Chemical Formula 13]

(A-2: thioether-containing (meth) acrylate derivative)

[Chemical Formula 14]

(A-3: thioether-containing (meth) acrylate derivative)

[Chemical Formula 15]

(A-4: thioether-containing (meth) acrylate derivative)

[Chemical Formula 16]

(A'-1: polyvalent thiol)

[Chemical Formula 17]

(A'-2: a thioether-containing alkoxysilane derivative)

[Chemical Formula 18]

(A'-3: thioether-containing alkoxysilane derivative)

[Chemical Formula 19]

(A'-4: thioether-containing (meth) acrylate derivative)

[Chemical Formula 20]

<Polyfunctional epoxy resin (component (B))>

(B-1, Mw: 5500)

[Chemical Formula 21]

(B-2, Mw: 220)

[Chemical Formula 22]

(B-3, Mw: 18000)

A copolymer of glycidyl methacrylate and cyclohexyl methacrylate (functional group ratio 1: 1) (white solid obtained by re-precipitating a 50 wt% methyl isobutyl ketone solution in hexane)

(B-4, Mw: 45000)

A copolymer of glycidyl methacrylate and cyclohexyl methacrylate (functional group ratio 1: 1) (white solid obtained by re-precipitating a 50 wt% methyl isobutyl ketone solution in hexane)

&Lt; Amine compound (Component (C)) &gt;

(C-1, Mw: 110)

(23)

(C-2, Mw: 102)

N, N-dimethyl-1,3-propanediamine

(C-3, Mw: 680)

&Lt; EMI ID =

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

<Multifunctional (meth) acrylate (Component (D))>

(D-1, Mw: 352)

(25)

(D-2, Mw: 246)

(26)

(D-3, Mw: 5000)

(27)

(n is an average of 13)

(D-4, Mw: 22000)

A polymer (50 wt% methyl isobutyl ketone solution, reprecipitated with hexane as a 50 wt% solution of methacrylic acid) in the copolymer of glycidyl methacrylate and cyclohexyl methacrylate with C-3 as a catalyst,

(D-5, Mw: 45000)

A polymer (50 wt% methyl isobutyl ketone solution, reprecipitated with hexane as a 50 wt% solution of methacrylic acid) in the copolymer of glycidyl methacrylate and cyclohexyl methacrylate with C-3 as a catalyst,

&Lt; Photopolymerization initiator (Component (E)) &gt;

(E-1, Mw: 204)

1-Hydroxy-cyclohexyl-phenyl-ketone

(E-2, Mw: 348)

2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

(E-3, Mw: 407)

2- (9-oxo-xanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] deca-

<Curable resin composition>

The components (A) to (E) were each mixed with the composition and blending amount shown in Tables 1 to 4 below and stirred until uniform with a spatula to obtain curable resin compositions of each of Examples and Comparative Examples. The obtained curable resin composition was used to evaluate the following adhesiveness 1 (adhesion at room temperature), adhesion 2 (cold weather adhesion), adhesion 3 (light curability), flexibility and storage stability. The results are shown in Tables 1 to 4.

[Production of test piece 1 for evaluation]

Adhesion 1, adhesion 2, and test piece for evaluation of flexibility were obtained as follows. Each of the curable resin compositions was coated on a PET film having a width of 25 mm at a thickness of 100 microns with a die coater, and another PET film was laminated thereon, and then cured at 150 DEG C for 1 hour, . As the PET film, Lumirror U46-100 manufactured by Toray Industries, Inc. was used.

[Preparation of test piece 2 for evaluation]

A test piece for evaluation of adhesion 3 was obtained as follows. Each of the curable resin compositions was coated on a PET film having a width of 25 mm and a length of 150 mm at a thickness of 100 microns by a die coater and a separate PET film was laminated thereon and then light of a high pressure mercury lamp Irradiation amount: 500 mJ / cm &lt; 2 &gt;, and the test specimen 2A for evaluation was irradiated with 3000 mJ / cm2 to obtain test specimen 2B for evaluation. As the PET film, Lumirror U46-100 manufactured by Toray Industries, Inc. was used.

[Adhesiveness 1 (Adhesion at room temperature)]

The test piece for evaluation 1 was stopped at 25 캜 for 24 hours and then measured according to the T-type peeling method defined in JIS K6854-3, and evaluated as follows.

⊚: tensile strength of 5 N / 25 mm or more (breakage of PET film)

?: Tensile strength of 5 N / 25 mm or more (PET film is not broken)

X: less than 5 N / 25 mm

[Adhesiveness 2 (Adhesion of Cold Paper)]

The test piece for evaluation 1 was stopped at -10 deg. C for 24 hours and then measured according to the T-type peeling method defined in JIS K6854-3, and evaluated as follows.

⊚: tensile strength of 5 N / 25 mm or more (breakage of PET film)

?: Tensile strength of 5 N / 25 mm or more (PET film is not broken)

X: less than 5 N / 25 mm

[Adhesiveness 3 (light curing property)]

In each of the evaluation test pieces 2A and 2B for evaluation, one PET film was pulled in the width direction while holding the test piece for evaluation with both hands, and the relative displacement (width direction deviation) with respect to the other PET film was visually Observed and evaluated.

&Amp; cir &amp;: All of the test pieces 2A and 2B for evaluation were not deviated

O: Only test piece 2B for evaluation is not misaligned

X: Deviation of both test pieces 2A and 2B for evaluation

[flexibility]

The test piece for evaluation 1 was stopped at -10 deg. C for 24 hours and then wrapped in a rod having a diameter of 8 mm for 1 minute and observed with naked eyes and evaluated as follows.

○: No crack

X: With crack

[Storage stability]

Immediately after mixing, the viscosity (viscosity after mixing) at 25 ° C was measured and the viscosity (viscosity after heating) was measured again after heating at 40 ° C for 12 hours to each of the curable resin compositions of Examples and Comparative Examples , And the viscosity after heating was divided by the viscosity immediately after mixing to calculate the increasing ratio and evaluated as follows. The viscosity was measured using an R-type viscometer manufactured by Toray Industries, Ltd. under the following conditions.

Used rotor: 1 ° 34 '× R24

Measuring range: 0.5183 to 103.7 Pa · s

◎: Increase ratio 1.0 to 1.8

○: Increase ratio 1.8 to 10

×: Increase ratio Out of the above range

The curable resin compositions of Examples 1-1 to 1-17 exhibit high adhesiveness under room temperature and cold conditions, good flexibility, and excellent storage stability. On the other hand, in Comparative Examples 1-5 to 1-8 in which a compound not corresponding to the formula 1 was used as the component (A), adhesiveness and flexibility under a cold condition were insufficient. In Comparative Examples 1-1 and 1-2 in which the component (A) is excessively small or excessive relative to the component (B), the adhesiveness is poor not only in a cold condition but also at a room temperature. Among them, in Comparative Example 1-1 in which the component (A) is too small relative to the component (B), flexibility is also insufficient. In Comparative Example 1-3 in which the component (C) is not blended, the adhesion is insufficient. In Comparative Example 1-4 in which the component (C) was blended excessively with respect to the component (A) and the component (B), storage stability was insufficient. It was also confirmed that the photocurability can be imparted by adding the component (D) in Examples 2-1 to 2-10. In Examples 3-1 to 3-5, it was confirmed that the addition of the component (E) enables curing with less light irradiation.

Claims (3)

(A) a thioether-containing (meth) acrylate derivative represented by the following formula (1)
(B) a polyfunctional epoxy resin having a weight average molecular weight of 200 to 50000,
(C) an amine compound having a weight average molecular weight of 90 to 700,
(A) / (B)) of the component (A) and the component (B) is 0.05 to 30,
, And 0.01 to 50 parts by mass of the component (C) relative to 100 parts by mass of the total mass of the component (A) and the component (B).
[Chemical Formula 1]

(Wherein a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a, b and c is 4. R ¹ is a methylene group, R ² is a divalent functional group represented by the following formula 2 or 3: R ³ is a methyl group or an ethyl group, and R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms.
(2)

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)
(3)

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group) The method according to claim 1,
(D) 2 to 300 parts by mass of a multifunctional (meth) acrylate having a weight average molecular weight of 200 to 50000 in combination with 100 parts by mass of the total mass of the component (A) and the component (B) Composition. 3. The method of claim 2,
(E) a photopolymerization initiator in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (D).