JP6609993B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition capable of obtaining a cured film having excellent adhesion and flexibility to a substrate even in a cold region.

  Conventionally, there is a technique of adding a silane coupling agent in order to improve adhesion to an inorganic base material such as a paint mainly composed of an epoxy resin (for example, Patent Document 1). However, many of the silane coupling agents have a low boiling point, and it was necessary to add a large amount to the thermosetting resin. In addition, the adhesion improvement effect due to the addition of a silane coupling agent cannot be said to be sufficient. For example, the addition of an adhesion aid such as a salt of titanium / zirconium, a phosphate ester, a urethane resin, etc. is the first practical level. In many cases, it was possible to achieve the adhesion required in the above. In this case, the formulation of these adhesion assistants not only increases the number of steps, but also requires the selection of adhesion assistants that do not impair the paint properties and the strict optimization work of the amount added. There was a point.

  Therefore, 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 a polyfunctional polyene having a plurality of double bonds. ing. This curable resin composition does not require the addition of other adhesion assistants as in the case of using a silane coupling agent, and can exhibit excellent adhesion to an inorganic substrate.

JP-A-7-300491 JP 2012-246464 A

  However, as disclosed 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 a polyfunctional polyene having a plurality of double bonds is inorganic. Although it has excellent adhesion to the substrate and excellent storage stability of the resin composition, since the cured film is inflexible in cold regions, cracks are likely to occur when the cured film is bent, and the adhesion is poor. Turned out to be.

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

（式中のａは１〜３の整数であり、ｂは０または１であり、ｃは１〜３の整数であり、ａとｂとｃの和は４である。Ｒ^１は、メチレン基、エチレン基またはイソプロピレン基である。Ｒ^２は、下記式２または下記式３で表される２価の官能基である。Ｒ^３は、メチル基またはエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。）

（Ｒ^５は水素原子またはメチル基である。）

（Ｒ^５は水素原子またはメチル基である。）
なお、本発明において、分子量とは別途記載が無い限り重量平均分子量のことである。
The curable resin composition of the present invention to solve the above problems, (A) a thioether-containing represented by the following general formula 1 and (meth) acrylate derivatives, Ri (B) weight average molecular weight of 200 to 50,000 der , (Meth) acrylate equivalent is 80 to 6000 g / mol polyfunctional (meth) acrylate, and the mass ratio of the component (A) to the component (B) ((A) / (B)) Is 0.05-30.

(In the formula, 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 the following formula 3. R ³ is a methyl group or an ethyl group, and R ⁴ is carbon. It is a hydrocarbon group having a number of 1 to 12.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)
In the present invention, the molecular weight is a weight average molecular weight unless otherwise specified.

  The curable resin composition of the present invention can further contain (C) a photopolymerization initiator in addition to the components (A) to (B). The said (C) component mix | blends 0.01-10 mass parts with respect to 100 mass parts of total mass of the said (A) component and the said (B) component.

  In addition to the components (A) to (B) or the components (A) to (C), the curable resin composition of the present invention further comprises (D) an amine compound having a weight average molecular weight of 90 to 700. It can be included. The said (D) component is mix | blended 0.01-50 mass parts with respect to 100 mass parts of total mass of the said (A) component and the said (B) component.

  In the present invention, “(meth) acrylate” means a generic name including both acrylate and methacrylate. Similarly, “(meth) acryloxy group” means a generic name including both acryloxy group and methacryloxy group, and “(meth) acryl” means a generic name including both acrylic and methacrylic. In the present invention, “OO to XX” indicating a numerical range is a concept including a lower limit (“OO”) and an upper limit (“XX”) unless otherwise specified. In other words, it means “more than XX and less than xx”.

  According to the curable resin composition of the present invention, a specific (A) thioether-containing (meth) acrylate derivative is used as an active ingredient for improving adhesion, and a specific molecular weight (B) polyfunctional (meth) acrylate is balanced. Well formulated. Thereby, the outstanding adhesiveness with respect to a base material is realizable, without adding other adhesive adjuvant etc. like the case where the conventional silane coupling agent is used. In particular, even in cold regions, the obtained cured film exhibits excellent adhesion and flexibility to the substrate.

  The present invention is described in detail below. The curable resin composition of the present invention is a curable resin composition containing the following components (A) and (B) as essential components and optionally further containing at least one of components (C) and (D).

（式中のａは１〜３の整数であり、ｂは０または１であり、ｃは１〜３の整数であり、ａとｂとｃの和は４である。Ｒ^１は、メチレン基、エチレン基またはイソプロピレン基である。Ｒ^２は、下記式２または下記式３で表される２価の官能基である。Ｒ^３は、メチル基またはエチル基である。Ｒ^４は、炭素数が１〜１２の炭化水素基である。）

（Ｒ^５は水素原子またはメチル基である。）

（Ｒ^５は水素原子またはメチル基である。）
上記式１中のＲ^４である炭素数が１〜１２の炭化水素基としては、直鎖のアルキル基、側鎖を持つアルキル基、環状のアルキル基が挙げられる。上記式１中のＲ^１は、メチレン基、エチレン基、イソプロピレン基であり、密着性向上効果が高くなることから、エチレン基、イソプロピレン基が特に好ましい。 <Thioether-containing (meth) acrylate derivative (component (A))>
The (A) component thioether-containing (meth) acrylate derivative is a compound represented by the following formula 1.

(In the formula, 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 the following formula 3. R ³ is a methyl group or an ethyl group, and R ⁴ is carbon. It is a hydrocarbon group having a number of 1 to 12.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)
Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R ⁴ in Formula 1, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. R ¹ in the above formula 1 is a methylene group, an ethylene group, an isopropylene group, since the adhesion improving effect is high, an ethylene group, isopropylene group is particularly preferred.

（式中のｄは２〜３０の整数であり、Ｒ^６は炭素数２〜２００の炭化水素基、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、またはイソシアヌレート環若しくはイソシアヌレート環と炭化水素基のみからなる基であり、Ｒ^７は水素原子またはメチル基である。） <Multifunctional (meth) acrylate (component (B))>
The polyfunctional (meth) acrylate as the component (B) has a (meth) acryloxy group at the terminal, and preferred examples thereof include compounds represented by the following general formula 4. In addition, the polyfunctional (meth) acrylate which is (B) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

(In the formula, d is an integer of 2 to 30, and R ⁶ is a hydrocarbon group having 2 to 200 carbon atoms, a group consisting only of ether oxygen (—O—) having 2 to 300 carbon atoms and a hydrocarbon group, or An isocyanurate ring or a group consisting only of an isocyanurate ring and a hydrocarbon group, and R ⁷ is a hydrogen atom or a methyl group.)

  Moreover, as (B) polyfunctional (meth) acrylate, a polymer type thing can also be used conveniently. As a polymer type polyfunctional (meth) acrylate, a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate or a copolymer has a group that reacts with an epoxy group such as (meth) acrylic acid. Polymer obtained by reacting (meth) acrylate, (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, or a copolymer, reacting with a hydroxyl group like 2-methylpropenoic acid 2-isocyanatoethyl A polymer obtained by reacting a (meth) acrylate having a group to react, (meth) acrylate having a carboxyl group such as (meth) acrylic acid or a copolymer, and reacting with a carboxyl group like glycidyl (meth) acrylate Reacts with (meth) acrylates that have groups Allowed include polymers obtained.

  (B) The polyfunctional (meth) acrylate has a weight average molecular weight of 200 to 50,000. (B) Even if the weight average molecular weight of the polyfunctional (meth) acrylate is smaller than 200, there is no problem with respect to adhesion, but it is not preferable because the volatility tends to increase and the odor tends to increase. On the other hand, if the weight average molecular weight is larger than 50000, there is no problem with the adhesion, but the solubility in other components may be lowered, which is not preferable.

  Moreover, the (meth) acrylate equivalent of (B) polyfunctional (meth) acrylate is 80-6000 g / mol. 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 (A) thioether-containing (meth) acrylate derivative and the unreacted (meth) acryloxy group By remaining in a large amount, the toughness of the cured film made of the curable resin composition is lowered, and the adhesion may be lowered. On the other hand, when the (meth) acrylate equivalent is larger than 6000 g / mol, the (meth) acryloxy group concentration is extremely low, so that the reaction efficiency with the thiol group of the (A) thioether-containing (meth) acrylate derivative is reduced, thereby curing. There is a possibility that the toughness of the cured film made of the adhesive resin composition is lowered and the adhesiveness is lowered.

<Photopolymerization initiator (component (C))>
The photopolymerization initiator as the component (C) is added to promote the reaction between the thiol group and the (meth) acryloxy group, and can reduce the light irradiation necessary for curing the curable resin composition. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. The photoradical polymerization initiator is preferably used for shortening the reaction time, the photocationic polymerization initiator is preferably used for reducing curing shrinkage, and the photoanionic polymerization initiator is used in the field of electronic circuits and the like. It is preferable to use it when imparting adhesiveness.

  Examples of the radical photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. It is.

  Examples of the cationic photopolymerization initiator include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, and diphenyl. Iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, triphenylsulfonium tetrafluoroborate, Examples include triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, and the like.

  Examples of the photoanionic polymerization initiator include acetophenone o-benzoyloxime, nifedipine, 2- (9-oxoxanthen-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] guanidinium 2- (3-benzoylphenyl) propionate, 1,2 -Dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate and the like.

<Amine compound (component (D))>
The amine compound as component (D) is added to promote (catalyze) the reaction between the thiol group and the (meth) acryloxy group. Specifically, since the thiol group and the (meth) acryloxy group can be reacted at a low temperature by containing the component (D), the curable resin composition containing the component (A) and the component (B). An object can be cured at a low temperature. Examples of the amine compound as component (D) include monofunctional amines having a weight average molecular weight of 90 to 700 and polyamines having a plurality of amino groups. If the weight average molecular weight of the amine compound is less than 90, not only the volatility of the amine is increased, causing odor and void, but also the amine concentration at the time of heat curing is lowered, so that the crosslinking reaction is difficult to proceed and the adhesion is improved. It tends to decrease. When the weight average molecular weight of an amine compound exceeds 700, water resistance will become low and adhesiveness will fall easily.

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

  The amine compound may form a salt with an organic acid in advance in order to adjust the catalytic activity. The organic acid to be reacted with the amine compound in advance is an aliphatic carboxylic acid having 1 to 5 carbon atoms and 1 to 5 carboxyl groups in the molecule, and 1 to 10 carboxyl groups having 7 to 20 carbon atoms in the molecule. Aromatic carboxylic acid or isocyanuric acid may be mentioned.

  Among amine compounds, an imidazole compound having a high basicity is suitable for curing at the lowest temperature. Further, an imidazole compound coated with a phenol resin or the like can also be used.

（Ｒ⁹はシアノ基、炭素数１〜１０の炭化水素基、２,３−ジアミノトリアジンで置換された炭素数１〜１０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ⁸、Ｒ¹⁰、Ｒ¹¹は炭素数１〜２０の炭化水素基、炭素数１〜４のアルコキシ基、又は水素原子であり、Ｒ⁸〜Ｒ¹¹が結合して環を形成している場合には炭素数２〜８の炭化水素基である。）
具体的には、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、１,２−ジメチルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、１−（２−シアノエチル）−２−メチルイミダゾール、１−（２−シアノエチル）−２−ウンデシルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール、１−（２−シアノエチル−２−フェニルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール、２,３−ジヒドロ−１Ｈ−ピロロ［１,２−ａ］ベンズイミダゾール、２,４−ジアミノ−６−［２−メチルイミダゾリル−（１）］エチル−ｓ−トリアジン、２,４−ジアミノ−６−[２’−ウンデシルイミダゾリル−（１’）]−エチル−ｓ−トリアジン、２,４−ジアミノ−６−[２’−エチル−４'−メチルイミダゾリル−（１'）]−エチル−ｓ−トリアジン、２−フェニル−４,５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾールが挙げられる。 The imidazole compound is a compound represented by the following formula 5.

(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 with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom. R ⁸ , R ¹⁰ and R ¹¹ are each a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R ^{8 to} R ¹¹ are bonded to form a ring. If it is, it is a hydrocarbon group having 2 to 8 carbon atoms.)
Specifically, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-undecylimidazole, 1- ( 2-cyanoethyl) -2-ethyl-4-methylimidazole, 1- (2-cyanoethyl-2-phenylimidazole), 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2,3-dihydro-1H -Pyrrolo [1,2-a] benzimidazole, 2,4-diamino-6- [2- Methylimidazolyl- (1)] ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [ 2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole It is done.

<Composition ratio (mixing balance)>
The curable resin composition of the present invention has a mass ratio ((A) / (B)) of (A) thioether-containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate of 0.05 to 30. It mix | blends so that it may become. Here, “(A) / (B)” is a value obtained by dividing the mass of (A) the thioether-containing (meth) acrylate derivative by the mass of (B) polyfunctional (meth) acrylate. When (A) / (B) is less than 0.05 or more than 30, the adhesion tends to decrease. The optimum value of (A) / (B) varies depending on the characteristics required for the curable resin composition, the type of (A) thioether-containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate. Strictly speaking, the characteristics after curing the curable resin composition are the values of (number of thiol groups) / (number of (meth) acryloxy groups) (hereinafter referred to as thiol / ene ratio) in the unit weight of the curable resin composition. to be influenced. For example, when the thiol / ene ratio is in the range of 0.5 to 1.5, it is easy to form dense crosslinks and to become a tough cured product. On the other hand, if the thiol / ene ratio is 0.1 or more and less than 0.5 or more than 1.5 and 2.0 or less, a flexible and sticky cured product can be obtained. If the thiol / ene ratio is less than 0.1 or exceeds 2.0, gelation is difficult and adhesion tends to decrease.

  Moreover, when mix | blending (C) photoinitiator with respect to the curable resin composition of this invention, the total mass of (A) thioether containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate. It mix | blends so that it may become 0.01-10 mass parts of (C) photoinitiators with respect to 100 mass parts of ((A) + (B)). When the blending amount of the component (C) is less than 0.01 parts by mass with respect to 100 parts by mass of ((A) + (B)), a large amount of integrated light is required for the reaction between the thiol group and the (meth) acryloxy group to proceed. Is required, and if it exceeds 10 parts by mass, the crosslink density may be lowered and the adhesion may be lowered.

  Moreover, when mix | blending (D) amine compound with respect to the curable resin composition of this invention, the total mass ((A) thioether containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate (( A) + (B)) 100 parts by mass is blended so that (D) the amine compound is 0.01 to 50 parts by mass. When the blending amount of the component (D) is less than 0.01 with respect to ((A) + (B)), the function as a catalyst becomes insufficient, the curing is not accelerated by heating, and the amount exceeds 50 parts by mass. The storage stability of the curable resin composition is lowered.

<Formation of cured film>
The curable resin composition of the present invention can form a cured film by coating on a substrate and curing. The curable resin composition of the present invention exhibits adhesion to the substrate due to the thioether group of the (A) thioether-containing (meth) acrylate derivative. Therefore, a substrate that forms a chemical bond with the thioether group (high chemical affinity), for example, an inorganic substrate such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, It is excellent in the effect of improving the adhesion to an organic substrate such as an organic substance having a saturated 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 base material include glass, silicon, and various metals. Poly (meth) acrylic resins, triacetate cellulose (TAC) resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate, polycarbonate resins, polyimide resins, polyolefins such as polyethylene and polypropylene Resin, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride resin, polyacetal and the like. Moreover, as for the curable resin composition of this invention, a cured film is excellent in a softness | flexibility because (A) thioether containing (meth) acrylate derivative has a specific hydrocarbon group. Therefore, the cured film easily follows the substrate even under cold conditions, and has excellent adhesion to the substrate. Therefore, it can be particularly suitably used for coating flexible substrates that can be used under cold conditions.

The curable resin composition can be cured by irradiating light. Examples of the light to be irradiated include active energy rays such as UV (ultraviolet rays) and EB (electron beams). Further, if the curable resin composition comprises a component (C), it is possible to reduce the amount of light irradiation to be usually 2,500 mJ / cm ² about need to about 100 mJ / cm ^2. In addition, when the curable resin composition contains the component (D), it can be cured at a low temperature of about 80 ° C., and is cured through two stages of a curing process by light irradiation and a curing process by heating. It can also be made.

  The curable resin composition of the present invention may be used by diluting with an organic solvent in order to make the reaction system uniform and facilitate coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, ether ester solvents, ketone solvents, and phosphate ester solvents. These organic solvents are preferably suppressed to a blending amount of less than 10000 parts by mass with respect to 100 parts by mass of the curable resin composition, but basically the solvent is volatilized at the time of becoming a cured film. It does not have a big influence on the physical properties.

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

  Moreover, you may add various additives which are used for the usual coating material and adhesive agent to the curable resin composition of this invention. Examples of such an additive include a surfactant for smoothing the coated surface, and an aluminum salt for increasing 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. When the compounding amount of these additives exceeds 80 parts by mass, the adhesion may be lowered.

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

（Ａ−２：チオエーテル含有（メタ）アクリレート誘導体）

（Ａ−３：チオエーテル含有（メタ）アクリレート誘導体）

（Ａ−４：チオエーテル含有（メタ）アクリレート誘導体）

（Ａ’−５：多価チオール化合物）

（Ａ’−６：多価チオール化合物）

（Ａ’−７：チオエーテル含有アルコキシシラン誘導体）

（Ａ’−８：チオエーテル含有アルコキシシラン誘導体）

（Ａ’−９：チオエーテル含有（メタ）アクリレート誘導体）

<(A) component>
(A-1: (Meth) acrylate derivative containing thioether)

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

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

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

(A'-5: polyvalent thiol compound)

(A'-6: polyvalent thiol compound)

(A′-7: thioether-containing alkoxysilane derivative)

(A′-8: thioether-containing alkoxysilane derivative)

(A′-9: (meth) acrylate derivative containing thioether)

（Ｂ−１、Ｍｗ：５０００）
（ｎは平均１３）
（Ｂ−２、Ｍｗ：２４６）

（Ｂ−３、Ｍｗ：３５２）

（Ｂ−４、Ｍｗ：２２０００）
グリシジルメタクリレートとシクロヘキシルメタクリレートの共重合体に下記Ｄ−３を触媒としメタクリル酸を当モル付加したポリマー（５０ｗｔ％メチルイソブチルケトン溶液をヘキサンで再沈した白色固体）。
（Ｂ−５、Ｍｗ：４５０００）
グリシジルメタクリレートとシクロヘキシルメタクリレートの共重合体に下記Ｄ−３を触媒としメタクリル酸を当モル付加したポリマー（５０ｗｔ％メチルイソブチルケトン溶液をヘキサンで再沈した白色固体）。 <(B) component: polyfunctional (meth) acrylate>

(B-1, Mw: 5000)
(N is an average of 13)
(B-2, Mw: 246)

(B-3, Mw: 352)

(B-4, Mw: 22000)
A polymer obtained by adding equimolar amounts of methacrylic acid to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using the following D-3 as a catalyst (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).
(B-5, Mw: 45000)
A polymer obtained by adding equimolar amounts of methacrylic acid to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using the following D-3 as a catalyst (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).

<(C) component: photopolymerization initiator>
(C-1, Mw: 204)
1-hydroxy-cyclohexyl-phenyl-ketone (C-2, Mw: 348)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (C-3, Mw: 407)
2- (9-Oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] dec-5-ene

（Ｄ−２、Ｍｗ：１０２）
Ｎ，Ｎ−ジメチル−１，３−プロパンジアミン
（Ｄ−３、Ｍｗ：６８０）

（ｎ１、ｎ２、ｎ３は１〜５の整数であり、平均が３．５である混合物） <(D) component: amine compound>
(D-1, Mw: 110)

(D-2, Mw: 102)
N, N-dimethyl-1,3-propanediamine (D-3, Mw: 680)

(N1, n2, and n3 are integers of 1 to 5, and the average is 3.5)

  Components (A) to (D) were mixed at the blending ratios shown in Tables 1 to 4 and stirred with a spatula until uniform, to obtain samples of curable resin compositions of Examples and Comparative Examples. The following adhesiveness 1 (room temperature adhesiveness), adhesiveness 2 (cold region adhesiveness), flexibility, and storage stability were evaluated for the samples of the curable resin compositions obtained in Examples and Comparative Examples. went. The results are shown in Tables 1 to 4.

[Preparation of test specimen for evaluation]
Test pieces for evaluation of adhesion 1, adhesion 2, and flexibility were obtained as follows. Each sample of the curable resin composition was coated on a 25 mm wide PET film with a die coater to a thickness of 100 microns, and another PET film was overlaid thereon, followed by the curing conditions shown in Tables 1 to 4. A test piece for evaluation was obtained by curing. Note that Lumirror U46-100 manufactured by Toray Industries, Inc. was used as the PET film. For the light irradiation, a UV lamp system “Light Hammer 6” manufactured by Heraeus Noble Light Fusion Ubuy Co., Ltd. was used, and an H bulb was used as the lamp bulb.

[Adhesion 1 (room temperature adhesion)]
The test piece for evaluation was allowed to stand at 25 ° C. for 24 hours, then measured by a T-type peeling method according to JIS K6854-3, and evaluated as follows.
A: Tensile strength is 5 N / 25 mm or more (PET film breaks)
○: Tensile strength of 5 N / 25 mm or more (PET film does not break)
X: Less than 5N / 25mm

[Adhesion 2 (cold region adhesion)]
After leaving the said test piece for evaluation at -10 degreeC for 24 hours, it measured by the T-type peeling method according to JISK6854-3, and evaluated as follows.
A: Tensile strength is 5 N / 25 mm or more (PET film breaks)
○: Tensile strength of 5 N / 25 mm or more (PET film does not break)
X: Less than 5N / 25mm

[Flexibility]
The test piece for evaluation was allowed to stand at −10 ° C. for 24 hours, and then wound around a rod having a diameter of 8 mm for 1 minute, visually observed, and evaluated as follows.
○: No crack ×: There is a crack

[Storage stability]
About the sample of the curable resin composition of each Example and Comparative Example, immediately after mixing, the viscosity at 25 ° C. (viscosity immediately after mixing) was measured, and after heating at 40 ° C. for 12 hours, the viscosity again (viscosity after heating) ) Was measured, the viscosity after heating was divided by the viscosity immediately after mixing, and the rate of thickening was calculated and evaluated as follows. The viscosity was measured under the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.
Rotor used: 1 ° 34 '× R24
Measurement range: 0.5183 to 103.7 Pa · s
(Double-circle): Thickening rate 1.0-1.8
○: Thickening rate 1.8 to 10
×: Thickening rate outside the above range

  The curable resin compositions of Examples 1-1 to 1-12 were confirmed to have high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability. The curable resin compositions of Examples 2-1 to 2-5 were cured with a small amount of light irradiation, and high adhesion, good flexibility, and excellent storage stability under room temperature and cold conditions were confirmed. The curable resin compositions of Examples 3-1 to 3-6 were cured by low light irradiation and low-temperature heating, and confirmed high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability. It was done. On the other hand, in Comparative Example 1-1 in which the component (A) is too small relative to the component (B), and in Comparative Example 1-2 in which the component (A) is excessive relative to the component (B), not only in the cold condition. Adhesion was poor even at room temperature. In Comparative Examples 1-3 to 1-7 in which the compound having no structure of the above formula 1 was used as the component (A), the adhesion under cold conditions was inferior.

Claims (3)

(A) a thioether-containing (meth) acrylate derivative represented by the following formula 1,
(B) a weight average molecular weight of Ri der 200-50000, containing a polyfunctional (meth) acrylate which is a (meth) acrylate equivalent of 80~6000g / mol,
Curable resin composition whose mass ratio ((A) / (B)) of said (A) component and said (B) component is 0.05-30.

(In the formula, 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 the following formula 3. R ³ is a methyl group or an ethyl group, and R ⁴ is carbon. It is a hydrocarbon group having a number of 1 to 12.)

(R ⁵ is a hydrogen atom or a methyl group.)

(R ⁵ is a hydrogen atom or a methyl group.)   (C) Curing property of Claim 1 formed by mix | blending 0.01-10 mass parts with respect to 100 mass parts of total mass of the said (A) component and the said (B) component with a photoinitiator. Resin composition.   (D) The amine compound whose weight average molecular weight is 90-700 mix | blends 0.01-50 mass parts with respect to 100 mass parts of total mass of the said (A) component and the said (B) component, Item 3. The curable resin composition according to item 1 or 2.