TW201725235A - Curable resin composition - Google Patents

Abstract

Provided is a material which has excellent adhesion to substrates even in a cold district and gives a cured film that is flexible. The material is a curable resin composition comprising (A) a thioether-containing (meth)acrylate derivative having a specific structure, (B) a polyfunctional epoxy resin having a molecular weight of 200-50,000, and (C) an amine compound having a molecular weight of 90-700. The mass ratio of the component (A) to the component (B), (A)/(B), is 0.05-30, and the component (C) is incorporated in an amount of 0.01-50 parts by mass per 100 parts by mass of the sum of the component (A) and the component (B).

Description

Curable resin composition

The present invention relates to a curable resin composition which is excellent in adhesion to a substrate even in a cold region and which has flexibility in the obtained cured film.

Conventionally, in order to improve the adhesion of a coating material containing an epoxy resin as a main component to an inorganic substrate, a technique of adding a decane coupling agent has been proposed (for example, Patent Document 1). However, most of the decane coupling agents have a low boiling point and require a large amount of addition to the thermosetting resin. Further, the effect of improving the adhesion cannot be said to be sufficient. For example, by adding a salt such as titanium or zirconium or a patching aid such as a phosphate ester or a urethane resin, it is possible to achieve a practical level of adhesion. . In this case, there is a problem in that the addition of these adhesion aids not only increases the number of processes, but also requires selection of the type of the adhesion aid which does not impair the characteristics of the coating, or strict optimization of the amount of addition.

Here, Patent Document 2 proposes a curable resin composition which has a polyfunctional thiol compound and a specific thioether-containing alkoxydecane derivative and an epoxy resin composition and has a plurality of double bonds The polyfunctional polyene is mixed. The curable resin composition can exhibit excellent adhesion to an inorganic substrate as in the case of using a decane coupling agent without adding another adhesion aid or the like.

Prior art document [Patent Document]

Patent Document 1: Japanese Patent Publication No. 7-300491

Patent Document 2: JP-A-2012-246464

[Problems to be solved by the invention]

However, it has been clarified that a curable resin in which a polyfunctional thiol compound and a specific thioether-containing alkoxydecane derivative are mixed with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds is disclosed in Patent Document 2. Although the composition is excellent in adhesion to an inorganic substrate and excellent in storage stability of a resin composition, there is a technical problem that cracks are likely to occur during bending due to lack of flexibility of the cured film in cold regions, and Lack of attachment.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a material which is excellent in adhesion to a substrate even in a cold region and which has flexibility in the obtained cured film.

[Technical means to solve technical problems]

The present invention is the following [1] to [3].

[1] A curable resin composition comprising (A) a sulfide-containing (meth) acrylate derivative of the following formula 1, (B) a polyfunctional epoxy resin having a molecular weight of 200 to 50,000, (C) an amine compound having a molecular weight of 90 to 700, and the mass ratio ((A)/(B)) of the component (A) to the component (B) is 0.05 to 30, with respect to the components (A) and (B) The total mass is 100 parts by mass, and 0.01 to 50 parts by mass (C) is added.

In the formula, a is an integer of 1 to 2, b is an integer of 1 to 2, a+b=3; R ¹ is a trivalent group represented by the following formula 2, and R ² is a following formula 3 or the following formula 4 In the divalent group shown, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group.

Further, in the present invention, the molecular weight is a weight average molecular weight.

[2] The curable resin composition of the present invention may further contain the following component (D) in addition to the components (A) to (C). The (D) component may contain a polyfunctional (meth) acrylate compound having a molecular weight of 200 to 50,000. The component (D) is added in an amount of 2 to 300 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B).

[3] The curable resin composition of the present invention may further contain the following component (E) in addition to the components (A) to (D). As the component (E), a photoinitiator may be contained. 0.01 to 10 parts by mass of the component (E) is added to 100 parts by mass of the total mass of the component (A) and the component (D).

Further, "(meth) acrylate" in the present invention means a general term including both acrylate and methacrylate. Further, "○○~××" indicating a numerical range in the present invention is a concept including a lower limit value ("○○") and an upper limit value ("××"). That is, the correct meaning is "○○ or more × × or less".

[effect of the invention]

According to the curable resin composition of the present invention, a specific thioether-containing (meth) acrylate derivative (A) can be used as an active ingredient for improving adhesion, and a polyfunctional ring having a specific molecular weight can be added in a well-balanced manner. An oxygen resin (B) and an amine compound (C) having a specific molecular weight. Therefore, it is not necessary to add another adhesive auxiliary agent like the conventional decane coupling agent, and it is excellent in the adhesiveness with respect to a base material. In particular, the curable resin composition using a polyfunctional thiol compound in the past is also excellent in cold regions where the adhesion to the substrate is insufficient, and the obtained cured film has flexibility.

The invention is described in detail below. The curable resin composition of the present invention contains the following components (A), (B), and (C) as essential components, and if necessary, the component (D) and the (E) component are further contained. <Sulfur ether-containing (meth) acrylate derivative ((A) component)>

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

In the formula, a is an integer of 1 to 2, b is an integer of 1 to 2, a+b=3; R ¹ is a trivalent group represented by the following formula 2, and R ² is a following formula 3 or the following formula 4 In the divalent group shown, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group.

The hydrocarbon group having 1 to 12 carbon atoms of R ³ in the formula 1 may, for example, be a linear alkyl group, an alkyl group having a side chain or a cyclic alkyl group.

R ⁴ in the formula 2 is a methylene group, an ethylene group or an isopropylidene group, and is particularly preferably an ethylene group or an isopropylidene group from the viewpoint of a high effect of improving adhesion. <Multifunctional epoxy resin ((B) component)>

The polyfunctional epoxy resin as the component (B) is an organic compound having two or more epoxy groups (oxirane rings). The molecular weight of the multifunctional epoxy resin is from 200 to 50,000, preferably from 200 to 48,000, more preferably from 200 to 46,000. Although the molecular weight is less than 200, there is no problem concerning adhesion, but the volatility of the polyfunctional epoxy resin is high, and the odor tends to be strong. On the other hand, when the molecular weight is more than 50,000, the solubility in other components is lowered, and the adhesion to the substrate may be lowered.

The polyfunctional epoxy resin has an epoxy equivalent of from 80 to 6000 g/mol, preferably from 85 to 5500 g/mol, more preferably from 90 to 5000 g/mol. When the epoxy equivalent is less than 80 g/mol, the epoxy group per unit volume is excessively large, and the epoxy group which is not reacted with the thiol group of the (A) thioether-containing (meth) acrylate derivative remains in a large amount, and thus The cured film composed of the curable resin composition may have lower toughness and lower adhesion. On the other hand, when the epoxy equivalent is more than 6000 g/mol, the epoxy group concentration is remarkably lowered, and thus the reaction efficiency with the thiol group of the (A) thioether-containing (meth) acrylate derivative is lowered, whereby The cured film composed of the curable resin composition has a lowered toughness and a possibility of lowering the adhesion to the substrate.

Examples of the polyfunctional epoxy resin as the component (B) include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, or a double bond by a peroxide. An oxidized epoxy resin obtained by oxidizing a double bond of a compound. Among them, a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin is preferred from the viewpoint that the reactivity is slow at room temperature and the usable time is long. Further, the polyfunctional epoxy resin may be used alone or in combination of two or more.

[Glycidyl ether epoxy resin]

The glycidyl ether type epoxy resin is preferably a reaction product of epichlorohydrin and a compound represented by the following formula 5.

In the formula, c is an integer of 2 to 30, and R ⁶ is a hydrocarbon group (β1) having 2 to 200 carbon atoms, and a group consisting of ether oxygen (-O-) and a hydrocarbon group having 2 to 300 carbon atoms (β2). ), an isocyanurate ring (β3), a group consisting of only an isocyanurate ring and a hydrocarbon group (β4).

In the compound of the formula 5, c is 2 to 20 and R ⁶ is a compound (β1-1) of a hydrocarbon group having 2 to 150 carbon atoms, or c is 2 to 20 and R ⁶ is carbon. The compound (β2-1) having only a group of a hydrocarbon group and an ether acid (-O-) having 2 to 150 atoms is preferred because it has high solubility with other components. Examples of (β1-1) include an alkylene glycol having 2 to 10 carbon atoms, glycerin, pentaerythritol, trimethylolpropane, phenol novolac, and bisphenol A. Examples of (β2-1) include polyethylene glycol, polypropylene glycol, and dipentaerythritol.

The reaction of the epichlorohydrin with the compound of the formula 5 can be carried out by ring-closing the chlorohydrin obtained by subjecting the epichlorohydrin to a hydroxyl group of the compound of the formula 5 by a base such as sodium oxide. Obtained epoxy resin. Further, the glycidyl ether type epoxy resin may be an epoxy resin obtained by subjecting a partial epoxy group of the epoxy resin obtained after the ring closure reaction to ring-opening polymerization.

The reaction product of epichlorohydrin and the compound represented by Formula 5 is a structure of the following Formula 6.

In the formula, c is an integer of 2 to 30, and R ⁶ is a hydrocarbon group (β1) having 2 to 200 carbon atoms, and a group consisting of ether oxygen (-O-) and a hydrocarbon group having 2 to 300 carbon atoms (β2). ), an isocyanurate ring (β3), or a group consisting of an isocyanurate ring and a hydrocarbon group (β4).

[Glycidyl Ester Resin]

The glycidyl ester type epoxy resin is a weight average molecular weight of 3000 obtained by copolymerizing a monomer having an epoxy group such as glycidyl (meth)acrylate alone or with an alkyl (meth) acrylate having 4 to 25 carbon atoms. a polymer of ~20000 or a reaction product of epichlorohydrin and a compound represented by the following formula 7.

In the formula, d is an integer of 2 to 8, and R ⁷ is a hydrocarbon group having 2 to 20 carbon atoms (β5), and a group having 2 to 30 carbon atoms and consisting only of ether oxygen (-O-) and a hydrocarbon group (β6) Any one of an isocyanurate ring (β7) or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group.

The reaction of the epichlorohydrin with the compound of the formula 7 can be carried out by ring-closing a chlorohydrin obtained by subjecting epichlorohydrin to a carboxyl group of the compound of the formula 7 with a base such as sodium hydroxide. Glycidyl ester type epoxy resin. Further, an epoxy resin obtained by subjecting a partial epoxy group of a glycidyl ester type epoxy resin to ring-opening polymerization can also be used.

In the compound represented by Formula 7, a compound (β5-1) and d in which d is 2 to 4 and R ⁷ is a group of a hydrocarbon group of 2 to 10, and d is preferably a compound having a high solubility. 2 to 6 and R ⁷ is a compound having a group of 2 to 30 carbon atoms and having only a group consisting of an ether oxygen (-O-) and a hydrocarbon group (β6-1), or d is 3 and R ⁷ is only an isocyanuric acid. A compound (β8-1) of a group consisting of an acid ester ring and a hydrocarbon group.

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

The reaction product of epichlorohydrin and the compound represented by Formula 7 is a structure of the following Formula 8.

In the formula, d is an integer of 2 to 8, and R ⁷ is a hydrocarbon group having 2 to 20 carbon atoms (β5), and a group having 2 to 30 carbon atoms and consisting only of ether oxygen (-O-) and a hydrocarbon group (β6) Any one of an isocyanurate ring (β7) or a group (β8) consisting only of an isocyanurate ring and a hydrocarbon group. <Amine compound ((C) component)>

The amine compound as the component (C) is used to promote (catalyze) the reaction of a thiol group with an epoxy group. The amine compound as the component (C) may, for example, be a monofunctional amine having a molecular weight of 90 to 700, preferably 100 to 690, more preferably 110 to 680, or a polyamine having a plurality of amino groups. When the molecular weight of the amine compound is less than 90, the volatility of the amine becomes high, which causes not only odor or pores, but also an amine concentration at the time of heat curing, which makes it difficult to carry out a crosslinking reaction, and the adhesion is liable to lower. When the molecular weight of the amine compound exceeds 700, the water resistance is lowered, and the adhesion is liable to lower.

The monofunctional amine may, for example, be a primary amine, a secondary amine or a tertiary amine. Examples of the polyamine include a primary amine, a secondary amine, a tertiary amine, and a complex amine. The complex amine means an amine having two or more kinds of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such a complex amine include an imidazoline compound, an imidazole compound, an N-substituted pyridazine compound, and an N,N-dimethylurea derivative. Further, the amine compounds may be used alone or in combination of two or more.

Further, in order to adjust the activity of the catalyst, the amine compound may be previously formed as a salt with an organic acid. Examples of the organic acid previously reacted with the amine compound include an aliphatic carboxylic acid such as stearic acid or 2-ethylhexanoic acid having 1 to 20 carbon atoms and 1 to 5 carboxyl groups in the molecule, and the number of carbon atoms is 1 ~20, an aromatic carboxylic acid or isocyanuric acid such as pyromellitic acid, trimellitic acid or benzoic acid containing 1 to 10 carboxyl groups in the molecule. Further, in order to adjust the catalyst activity, the amine compound as the component (C) may be added after forming an adduct of the polyfunctional epoxy resin of the component (B).

[Imidazole compound]

Among the amine compounds, the imidazole compound is most suitable for both storage stability and curing time at low temperatures. Further, an imidazole compound coated with a phenol resin or the like can also be used.

This imidazole compound is a compound represented by the following formula 9.

R ⁹ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted by 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms or a hydrogen atom; 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 in the case of synthesizing a ring of R ⁸ to R ¹¹ , R ⁸ , R ¹⁰ and R ¹¹ is a hydrocarbon group having 2 to 8 carbon atoms.

Specific examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4. -methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2 -methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2 - cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a Benzimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2'-undecane Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl -s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole. <Polyfunctional (meth) acrylate compound (( D) Ingredients)>

The curable resin composition of the present invention can be cured by heat if it has (A) a sulfide-containing (meth) acrylate derivative, (B) a polyfunctional epoxy resin, and (C) an amine compound. On the other hand, when it is desired to impart photocurability or photothermal double curability to the curable resin composition of the present invention, a polyfunctional (meth) acrylate compound may be added as the component (D).

Among the many double bond-containing compounds of the present invention, the reason why the polyfunctional (meth) acrylate is selected as the component (D) is that it is difficult to form a composition with the curable resin of the present invention at room temperature ( A) a thioether-containing (meth) acrylate derivative is reacted, and a long-term usable time can be set; and a tough cured product is formed upon reaction with (A) a thioether-containing (meth) acrylate derivative; It is difficult to catalyze the reaction with (A) a sulfide-containing (meth) acrylate derivative by (C) an amine compound; it does not react with (B) a polyfunctional epoxy resin, or the like.

As such a polyfunctional (meth)acrylate, a compound represented by the following formula 10 is preferable. Further, the polyfunctional (meth) acrylate as the component (D) may be used alone or in combination of two or more.

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

Further, as the (D) polyfunctional (meth) acrylate, a polymer type polyfunctional (meth) acrylate can be applied. The polymer type polyfunctional (meth) acrylate is exemplified by a homopolymer or a copolymer of a (meth) acrylate compound having an epoxy group such as glycidyl (meth)acrylate. a polymer obtained by reacting a (meth) acrylate compound having a group reactive with an epoxy group such as (meth)acrylic acid; (meth)acrylic acid having a hydroxyl group such as hydroxyethyl (meth)acrylate a polymer obtained by reacting a (meth) acrylate compound having a group reactive with a hydroxyl group such as 2-isocyanatoethyl 2-methacrylate in a homopolymer or a copolymer of an ester compound; (meth)acrylic acid having a group reactive with a carboxyl group such as glycidyl (meth)acrylate in a homopolymer or copolymer of a (meth) acrylate compound having a carboxyl group such as (meth)acrylic acid A polymer obtained by reacting an ester compound.

The molecular weight of the (D) polyfunctional (meth) acrylate compound is from 200 to 50,000, preferably from 220 to 40,000, more preferably from 240 to 30,000. (D) When the molecular weight of the polyfunctional (meth) acrylate compound is less than 200, there is no problem concerning adhesion, but the volatility tends to be high and the odor tends to be strong. On the other hand, when the molecular weight is more than 50,000, the solubility to other components may be lowered.

Further, the (meth) acrylate equivalent of the (D) polyfunctional (meth) acrylate is 80 to 6000 g/mol, preferably 80 to 4,500, more preferably 85 to 3,000. If the (meth) acrylate equivalent is less than 80 g/mol, the (meth) propylene oxime per unit volume becomes excessive, and the thiol of the (meth) acrylate derivative which is not (A) thioether-containing When the (meth) propylene oxime group of the base reaction remains in a large amount, the cured film composed of the curable resin composition may have a lowered toughness and a decrease in adhesion. On the other hand, if the (meth) acrylate equivalent is more than 6000 g/mol, the (meth) propylene oxime group is significantly lower in concentration, and (A) the thioether-containing (meth) acrylate derivative thiol When the reaction efficiency of the base is lowered, the toughness of the cured film composed of the curable resin composition may be lowered, and the adhesion may be lowered. <Photoinitiator ((E) component)>

In order to promote the reaction of the thiol group with the (meth) propylene decyloxy group, the (E) component photoinitiator may be added. As a photoinitiator, it is a photo radical initiator, a photocation initiator, a photoanion initiator, etc. When the photoradical initiator is preferably used to shorten the reaction time, the photocationic initiator is preferably used for reducing the curing shrinkage, and the photoanion initiator is preferably used for imparting adhesion in the field of circuits and the like.

Examples of the photo radical initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-hydroxy- 2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one , 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 2-methyl 1-[4-(methylthio)phenyl]-2-morpholinan-1-one, bis(2,4,6-trimethylbenzhydrazide)-phenylphosphine oxide, 2,4 , 6-trimethyl benzamidine-diphenyl-phosphine oxide, and the like.

Examples of the photocationic initiator include bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and cyclopropyldiene. Phenylhydrazine tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2-(3,3-dimethoxystyryl)-4,6-double (trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, triphenylphosphonium bromide, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethyl Sulfonate and the like.

Examples of the photoanion initiator include acetophenone O-benzhydrazide, nifedipine, and 2-(9-oxanthon-2-yl)propionic acid 1,5,7-triazabicyclo ring. [4.4.0] 癸-5-ene, 2-nitrophenylmethyl 4-methylpropenyl acridine-1-carboxylate, 1,2-diisopropyl-3-[double (two Methylamino)methylene]indole 2-(3-benzhydrylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbis-n-butyltriphenyl Borate, etc. <composition ratio (equal ratio)>

The curable resin composition of the present invention has a mass ratio ((A)/(B)) of (A) a sulfide-containing (meth) acrylate derivative to (B) a polyfunctional epoxy resin of 0.05 to 30. The way to add. Here, "(A)/(B)" means 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 value of the optimum (A) / (B), depending on the desired properties of the curable resin composition, (A) a sulfide-containing (meth) acrylate derivative or (B) a polyfunctional epoxy resin and, as the case may be, The structure of the (D) polyfunctional (meth) acrylate compound added is different. The properties of the curable resin composition after curing are strictly controlled by the number of (thiol groups) / (number of epoxy groups + number of (meth) acryloxy groups) per unit weight of the curable resin composition (hereinafter referred to as thiol / (ring) The effect of the value of oxygen + ene). For example, if the thiol/(epoxy+ene) ratio is in the range of 0.5 to 1.5, it is easy to form a close crosslink, and it is easy to form a tough cured product. On the other hand, when the thiol/(epoxy+ene) ratio is 0.1 or more and less than 0.5, or more than 1.5 and 2.0 or less, a soft viscous cured product can be obtained. When the thiol/(epoxy+ene) ratio is less than 0.1 or exceeds 2.0, gelation is difficult, and the adhesion tends to be lowered.

Further, the curable resin composition of the present invention has a total mass ((A) + (B)) 100 relative to (A) a sulfide-containing (meth) acrylate derivative and (B) a polyfunctional epoxy resin. The (C) 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) added is less than 0.01 parts by mass based on 100 parts by mass of ((A)+(B)), it takes a long time to cause a curing failure by reacting a thiol group with an epoxy group, and if it exceeds 50%, In the case of the mass portion, the crosslinking density tends to be low, and the adhesion tends to decrease.

Further, in the case where the (D) polyfunctional (meth) acrylate compound is further added to the curable resin composition, (A) a thioether-containing (meth) acrylate derivative and (B) The total mass of the polyfunctional epoxy resin ((A) + (B)) 100 parts by mass, and the (D) polyfunctional (meth) acrylate compound is 2 to 300 parts by mass, preferably 2 to 250 parts by mass. The way to add. When the amount of the component (D) added is less than 2 parts by mass based on 100 parts by mass of ((A) + (B)), it is difficult to impart photocurability, and if it exceeds 300 parts by mass, the adhesion tends to be lowered.

Further, in the case where the (E) photoinitiator is further added to the curable resin composition, the (A) thioether-containing (meth) acrylate derivative and (D) polyfunctional (A) 100 parts by mass of the total mass ((A) + (D)) of the acrylate compound, 0.01 to 10 parts by mass of (E) photoinitiator is added. When the (E) component is less than 0.01 parts by mass based on 100 parts by mass of ((A) + (D)), the reaction promoting action of the thiol group and the (meth) propylene decyloxy group is small, and if it exceeds 10 parts by mass, There is a case where the crosslinking density is lowered and the adhesion is lowered. <Formation of cured film>

The curable resin composition of the present invention can be formed into a cured film by coating and curing on a substrate. The curable resin composition of the present invention exhibits adhesion to a substrate by (A) a thioether group of a thioether-containing (meth) acrylate derivative. Therefore, it is excellent in the adhesion improving effect on a (chemically high affinity) substrate which forms a chemical bond with a thioether group, and as a base material, for example, a transition metal or its alloy, a telluride, a phosphide, a sulfide, or a boride, etc. A substrate, an organic substance having an unsaturated bond (including an aromatic ring), 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, enamel, various metals, and the like. As the organic substrate, a poly(meth)acrylic resin, a cellulose triacetate (TAC) resin, polyethylene terephthalate (PET) or polybutylene terephthalate is preferably used. Polyester resin such as ester, polycarbonate resin, polyimide resin, polyolefin resin such as polyethylene or polypropylene, polycarbonate, polyimine, ABS resin, polyvinyl alcohol, vinyl chloride Resin, polyacetal, etc. Further, in the curable resin composition of the present invention, the (A) thioether-containing (meth) acrylate derivative has a specific hydrocarbon group, and the cured film is excellent in flexibility. Therefore, even in cold conditions, the cured film easily follows the substrate and is excellent in adhesion to the substrate. Therefore, it is particularly applicable to the application of a flexible substrate which can be used under cold conditions.

The curable resin composition can be cured by heating. The heating temperature is about 25~250 °C. Further, when the curable resin composition contains the component (D), it can be cured by irradiation with light. Examples of the light to be irradiated include active energy rays such as UV (ultraviolet rays) or EB (electron beams). In the case where the curable resin composition contains the component (D), it can be cured by a dual process of a heating curing process and a light irradiation curing process.

In order to make the reaction system uniform and easy to apply, the curable resin composition of the present invention can be used by diluting it with an organic solvent. Examples of such an organic solvent include an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, an ether ester solvent, a ketone solvent, and a phosphate solvent. The organic solvent is preferably inhibited from being added in an amount of less than 10,000 parts by mass based on 100 parts by mass of the curable resin composition. However, since the solvent is substantially volatilized when the cured film is formed, it does not greatly affect the physical properties of the cured film. Further, when a compound having a functional group reactive with a thiol group, an epoxy group or a (meth) acryloyl group and an amine compound are used as a solvent, the effects of the present invention may be impaired.

Further, in the curable resin composition of the present invention, a viscosity adjusting agent such as cerium oxide powder may be added for the purpose of adjusting the viscosity. The viscosity adjusting agent is preferably suppressed to be added in an amount of less than 300 parts by mass based on 100 parts by mass of the curable resin composition. When the amount of the viscosity modifier added is more than 300 parts by mass, the adhesion may be lowered.

Further, the curable resin composition of the present invention may be added with various additives used in usual paints or adhesives. Examples of such an additive include a surfactant for smoothing the coated surface, an aluminum salt for extending the usable time, a photo radical initiator for improving photoreactivity, a photobase generator, and a photoacid generator. Wait. The additive is preferably inhibited from being added in an amount of less than 80 parts by mass based on 100 parts by mass of the curable resin composition. When the amount of the additive added exceeds 80 parts by mass, the adhesion may be lowered. Example

Next, the present invention will be further specifically described by way of examples and comparative examples, but the present invention is not limited thereto. The reagents used in the examples and comparative examples are as follows. Further, Mw represents a weight average molecular weight. <(A) component>

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

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

(A-3: (meth) acrylate derivative containing a sulfide)

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

(A-5: a thioether-containing (meth) acrylate derivative)

(A-6: polythiol compound)

(A-7: polythiol compound)

(A-8: alkoxydecane derivative containing a sulfide)

(A-9: alkoxydecane derivative containing a sulfide) <Multifunctional epoxy resin ((B) component)>

(B-1, Mw: 5500)

(B-2, Mw: 220)

(B-3, Mw: 18000) Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid reprecipitated with 50 wt% methyl isobutyl ketone solution using hexane)

(B-4, Mw: 45000) Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid reprecipitated with 50 wt% methyl isobutyl ketone solution using hexane) <Amine compound ( (C) component)>

(C-1, Mw: 110)

(C-2, Mw: 102) N,N-dimethyl-1,3-propanediamine

(C-3, Mw: 680) N1, n2, and n3 are integers of 1 to 5, and the average is 3.5. <Polyfunctional (meth) acrylate compound ((D) component)>

(D-1, Mw: 352)

(D-2, Mw: 246)

(D-3, Mw: 5000) n is an average of 13.

(D-4, Mw: 22000) On a copolymer of glycidyl methacrylate and cyclohexyl methacrylate, a catalyst such as D-3 as a catalyst, and a molar addition of methacrylic acid (using hexane) A white solid which was reprecipitated on a 50 wt% methyl isobutyl ketone solution). <Photoinitiator ((E) component)>

(E-1, Mw: 204) 1-hydroxy-cyclohexyl-phenyl-one

(E-2, Mw: 348) 2,4,6-trimethylbenzhydrazide-diphenyl-phosphine oxide

(E-3, Mw: 407) 2-(9-oxanthene-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]non-5-ene

The components (A) to (D) were mixed in a balanced ratio shown in Tables 1 to 4, and the mixture was stirred until uniform to obtain a curable resin composition sample of Examples and Comparative Examples. Each of the curable resin composition samples of the obtained Examples and Comparative Examples was subjected to the following adhesion 1 (room temperature adhesion), adhesion 2 (cold area adhesion), flexibility, and storage stability. evaluation of. Further, each of the curable resin composition samples of Examples 2-1 to 2-9 and Examples 3-1 to 3-5 was further evaluated for photocurability. The results are shown in Tables 1 to 4.

[Production of test piece for evaluation]

The test pieces for adhesion evaluation, adhesion 2, and softness evaluation were obtained in the following manner. Each of the samples of the curable resin composition was applied to a thickness of 100 μm on a 25 mm-wide PET film by a die coater, and another PET film was superposed thereon, and then allowed to stand at 150 ° C for 1 hour. The test piece was evaluated by curing. In addition, as the PET film, lumirror U46-100 manufactured by Toray Industries, Inc. was used.

[Adhesiveness 1 (room temperature attachment)]

The test piece for evaluation was allowed to stand at 25 ° C for 24 hours, and then measured by a T-peel method prescribed by JIS K6854-3 within 5 minutes, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PET film breakage)

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

×: less than 5N/25mm

[Attach 2 (cold area attachment)]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then measured by a T-peel method prescribed by JIS K6854-3 within 5 minutes, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PET film breakage)

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

×: less than 5N/25mm

[softness]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then wound on a rod having a diameter of 8 mm for 1 minute in 5 minutes, and evaluated in the following manner.

○: 0 cracks

×: 1 or more cracks

[save stability]

The sample of the curable resin composition of each of the examples and the comparative examples was measured immediately after mixing, and the viscosity (mixed viscosity) at 25 ° C was measured, and the viscosity was measured again after heating at 40 ° C for 12 hours (after heating) Viscosity), the viscosity after heating is divided by the viscosity just after mixing, and the thickening rate is calculated. Evaluation was performed as follows. In addition, the viscosity was measured by the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

Use rotor: 1°34′×R24

Measuring range: 0.5183~103.7 Pa·s

◎: Thickening rate 1.0~1.8

○: Thickening rate 1.8~10

×: the thickening rate is outside the above range

[Photocuring]

Each sample of the curable resin composition was applied to a thickness of 100 μm on a PET film having a width of 25 mm and a length of 150 mm by using a die coater, and another PET film was superposed thereon, and then irradiated with a high-pressure mercury lamp at 500 mJ/cm. ² (I-line conversion) light, the test piece for evaluation was obtained. One PET film of the test piece was stretched in the width direction, and the relative displacement (displacement in the width direction) with respect to the other PET film was evaluated in the following manner. In addition, as the PET film, lumirror U46-100 manufactured by Toray Industries, Inc. was used.

◎: no misplacement

○: Dislocation within 2mm

×: Dislocation 3mm or more

[Table 1]

[Table 2]

[table 3]

[Table 4]

According to the results of the examples, the (meth) acrylate derivative containing the thioether of the formula (1) as the component (A), and the polyfunctional epoxy resin having a molecular weight of 200 to 50,000 as the component (B) and The curable resin composition of the amine compound having a molecular weight of 90 to 700 in the component (C) can be confirmed to have high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability. On the other hand, in Comparative Examples 1-5 to 1-8 using the other material having a partial common structure with the formula (1) as the component (A), the adhesion and the flexibility were insufficient under cold conditions. Therefore, from the comparison of Examples 1-7 and Examples 1-10 to 1-13 with Comparative Examples 1-5, it is understood that the thioether-containing (meth)acrylic acid in which R3 is a hydrocarbon group in the formula (1) is used. As the (A) component, the ester derivative can obtain flexibility of the curable resin composition and is excellent in adhesion under cold conditions.

Further, according to the comparison of Examples 1-1 to 1-5 with Comparative Examples 1-1 and 1-2, it was confirmed that the mass ratio of (A) component to (B) component ((A)/(B)) was 0.05. ~30. In Comparative Examples 1-1 and 1-2 in which (A)/(B) did not satisfy the range, the adhesion was poor not only in cold conditions but also in adhesion at normal temperature. However, in Comparative Example 1-1 in which the component (A) was too small relative to the component (B), flexibility was absent.

Further, by comparison of Examples 1-6 to 1-9 with Comparative Examples 1-3 and 1-4, it was confirmed that 0.05 to 30 parts by mass is added to 100 parts by mass of the total mass of the components (A) and (B). Parts by mass of component (C). The adhesion was absent in Comparative Example 1-3 in which the component (C) was not added. The storage stability was absent in Comparative Examples 1-4 in which the component (C) was excessively added.

Further, in Examples 2-1 to 2-9, it was confirmed that by adding the component (D), in addition to high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability, Provides photocurability. Further, in Examples 3-1 to 3-5, it was confirmed that even if the component (E) was further added, it had high adhesion at room temperature and cold conditions, good flexibility, excellent storage stability, and light. Curability.

no.

no.

no.

Claims (3)

A curable resin composition comprising: (A) a thioether-containing (meth) acrylate derivative of the following formula 1; (B) a polyfunctional epoxy resin having a molecular weight of 200 to 50,000; and (C) An amine compound having a molecular weight of 90 to 700, wherein the mass ratio (A)/(B) of the component (A) to the component (B) is 0.05 to 30, relative to the component (A) and the (B) 100 parts by mass of the total mass of the component, and 0.01 to 50 parts by mass of the component (C) is added. In the formula, a is an integer of 1 to 2, b is an integer of 1 to 2, a+b=3; R ¹ is a trivalent group represented by the following formula 2, and R ² is a following formula 3 or a divalent group represented by the following formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms; Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group. R ⁵ is a hydrogen atom or a methyl group. The curable resin composition according to claim 1, wherein 2 to 300 parts by mass of the component (D) is further added to 100 parts by mass of the total mass of the component (A) and the component (B). The polyfunctional (meth) acrylate compound having a molecular weight of 200 to 50,000. The curable resin composition according to claim 2, wherein 0.01 to 10 parts by mass of the component (E) is further added to 100 parts by mass of the total mass of the component (A) and the component (D). Photoinitiator.