JP6531400B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition having excellent adhesion to a substrate even in cold regions, and the resulting cured film having flexibility.

  Conventionally, there is a technique of adding a silane coupling agent in order to improve the adhesion to an inorganic substrate such as a paint containing an epoxy resin as a main component (for example, Patent Document 1). However, many of the silane coupling agents have low boiling points, and have to be added in large amounts to thermosetting resins. In addition, the adhesion improvement effect can not be said to be sufficient. For example, by simultaneously adding an adhesion auxiliary agent such as a salt such as titanium and zirconium, phosphate ester, urethane resin, etc., the adhesion required at the practical level is achieved for the first time. There were many cases where I could do it. In this case, not only does the addition of these adhesion aids increase the number of steps, but it is also necessary to select the kind of adhesion aid so as not to impair the paint properties and strictly optimize the addition amount thereof. There was a problem.

  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 an amine compound. This curable resin composition does not need to add other adhesion aids and the like as in the case of using a silane coupling agent, and can exhibit excellent adhesion to an inorganic substrate. .

Japanese Patent Application Laid-Open 7-300491 JP 2012-246464 A

  However, as in Patent Document 2, 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 has excellent adhesion to an inorganic base material, and a resin composition Although it is excellent in the storage stability of a thing, in a cold district, since a cured film is poor in flexibility, it is easy to produce a crack at the time of bending, and it turned out that there is a subject that adhesion is poor further.

  The present invention has been achieved in view of the above-mentioned circumstances, and an object thereof is to provide a material having excellent adhesion to a substrate even in a cold region, and the resulting 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。） The curable resin composition of the present invention comprises (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 50,000, and (C) And an amine compound having a weight average molecular weight of 90 to 700, and a mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.05 to 30, The component (C) is blended in an amount of 0.01 to 50 parts by mass with respect to 100 parts by mass of the total mass of the component (A) and the component (B).

(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 the following formula 3. R ³ is a methyl group or an ethyl group R ⁴ is carbon 1 to 12 hydrocarbon groups.)

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

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

  The curable resin composition of the present invention further comprises (D) a multifunctional (meth) acrylate having a weight average molecular weight of 200 to 50,000, and a total mass of 100 parts by mass of the component (A) and the component (B). However, 2 to 300 parts by mass may be contained.

  The curable resin composition of the present invention further comprises (E) a photopolymerization initiator in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the components (A) and (D). You may.

  In the present invention, "(meth) acrylate" is a generic term including both acrylate and methacrylate. The terms "(meth) acrylic acid" and "(meth) acryloxy group" are also used as a generic term. Further, in the present invention, “○ ̃ ××” indicating a numerical range is a concept including the lower limit (“「 ”) and the upper limit (“ ×× ”). That is, to be precise, it means "more than or equal to x and less than x". Further, in the present invention, "molecular weight" means weight average molecular weight unless otherwise stated.

  According to the curable resin composition of the present invention, (A) a specific thioether-containing (meth) acrylate derivative as an active ingredient of the adhesion improving action, (B) a polyfunctional epoxy resin of a specific molecular weight, (C) ) Amine compounds of a specific molecular weight are blended in a well-balanced manner. As a result, even if it does not contain other adhesion auxiliaries etc. as in the case of using a conventional silane coupling agent, it has excellent adhesion to the substrate. In particular, the curable resin composition using a conventional polyfunctional thiol compound is insufficient, the adhesion to a substrate in cold conditions is also excellent, 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 (D) component and (E) component.

（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。） <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.

(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 the following formula 3. R ³ is a methyl group or an ethyl group R ⁴ is carbon 1 to 12 hydrocarbon groups.)

(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 carbon number of R ⁴ in the above formula 1 is 1 to 12, straight chain alkyl group, an alkyl group having a side chain, and 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.

  When the thioether-containing (meth) acrylate derivative represented by the above formula 1 is blended in a paint or the like, it has a high adhesion improvement effect to a substrate without an adhesion aid even in a cold environment such as -10 ° C. It exerts and is excellent in the effect of providing flexibility to the obtained coating film. Furthermore, since the thioether containing (meth) acrylate derivative represented by the said Formula 1 has small molecular weight, it is excellent in the solubility with respect to another component. Accordingly, since the thioether-containing (meth) acrylate derivative represented by the above formula 1 has high compatibility with many resins, it can be used for a wide range of paints and has high versatility.

<Multifunctional epoxy resin ((B) component)>
The polyfunctional epoxy resin which is the component (B) is an organic compound having two or more epoxy groups (oxirane ring). 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 regarding adhesion, but the volatility of the polyfunctional epoxy resin becomes high, and the odor tends to become strong. On the other hand, if the weight average molecular weight is larger than 50,000, the solubility in other components may be lowered, and the adhesion to the substrate may be lowered.

  The epoxy equivalent of the multifunctional epoxy resin is 80 to 6000 g / mol, preferably 85 to 5500 g / mol, more preferably 90 to 5000 g / mol. When the epoxy equivalent is smaller than 80 g / mol, the epoxy group per unit volume becomes excessive, and a large amount of the thiol group of the (A) thioether-containing (meth) acrylate derivative and the unreacted epoxy group remain, thereby curing. Toughness of the cured film made of the base resin composition may be lowered, and the adhesion may be lowered. On the other hand, when the epoxy equivalent is larger than 6000 g / mol, the epoxy resin concentration is extremely low, so that the reaction efficiency of the (A) thioether-containing (meth) acrylate derivative with the thiol group is reduced, and it is composed of a curable resin composition. The toughness of the cured film may be reduced, and the adhesion to the substrate may be reduced.

  As a polyfunctional epoxy resin which is the component (B), for example, a double bond of a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or a double bond-containing compound is oxidized with a peroxide The oxidized epoxy resin obtained etc. are mentioned. Among these, glycidyl ether type epoxy resins and glycidyl ester type epoxy resins are preferable because of low reactivity at room temperature and high storage stability. In addition, a polyfunctional epoxy resin can also be used individually by 1 type, and can also be used in mixture of 2 or more types.

（式中のｄは２〜３０の整数であり、Ｒ⁶は炭素数２〜２００の炭化水素基（β１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β２）、イソシアヌレート環（β３）、又はイソシアヌレート環と炭化水素基のみからなる基（β４）である。）
上記式４で表される化合物の中でも、ｄが２〜２０であり、且つＲ⁶が炭素数２〜１５０の炭化水素基である化合物（β１−１）、又はｄが２〜２０であり、且つＲ⁶が炭素数２〜１５０の炭化水素基とエーテル酸素（−Ｏ−）のみからなる基である化合物（β２−１）が、他の成分との溶解性が高いという理由で好ましい。（β１−１）としては、例えば炭素数２〜１０のアルキレンジオール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、フェノールノボラック、ビスフェノールＡ等が挙げられる。（β２−１）としては、例えばポリエチレングリコール、ポリプロピレングリコール、又はジペンタエリスリトール等が挙げられる。 <Glycidyl ether type epoxy resin>
As a glycidyl ether type epoxy resin, the reaction product of epichlorohydrin and the compound represented by following formula 4 is preferable.

(In the formula, d is an integer of 2 to 30, and R ⁶ is only composed of a hydrocarbon group having 2 to 200 carbon atoms (β1), an ether oxygen (—O—) having 2 to 300 carbon atoms, and a hydrocarbon group A group (β2), an isocyanurate ring (β3), or a group consisting only of an isocyanurate ring and a hydrocarbon group (β4).
Among the compounds represented by Formula 4 above, compounds (β1-1) in which d is 2 to 20 and R ⁶ is a hydrocarbon group having 2 to 150 carbon atoms, or d is 2 to 20, In addition, a compound (β2-1) in which R ⁶ is a group consisting of only a hydrocarbon group having 2 to 150 carbon atoms and ether oxygen (—O—) is preferable because of high solubility with other components. As ((beta) 1-1), a C2-C10 alkylene diol, glycerol, pentaerythritol, trimethylolpropane, a phenol novolak, bisphenol A etc. are mentioned, for example. Examples of (β2-1) include polyethylene glycol, polypropylene glycol, and dipentaerythritol.

  By reacting epichlorohydrin with the compound represented by the above formula 4, the chlorohydrin is obtained by the addition reaction of epichlorohydrin with the hydroxyl group of the compound represented by the above formula 4, and the obtained chlorohydrin Can be closed with a base such as sodium oxide to obtain an epoxy resin. The glycidyl ether type epoxy resin may be an epoxy resin obtained by ring-opening polymerization of part of the epoxy groups of the epoxy resin obtained after the above-mentioned ring closure reaction.

（式中のｄは２〜３０の整数であり、Ｒ⁶は炭素数２〜２００の炭化水素基（β１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β２）、イソシアヌレート環（β３）、又はイソシアヌレート環と炭化水素基のみからなる基（β４）である。） The reaction product of epichlorohydrin and the compound represented by the above formula 4 has a structure of the following formula 5.

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

（式中のｅは２〜８の整数であり、Ｒ⁷は炭素数２〜２０の炭化水素基（β５）、炭素数２〜３０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β６）、イソシアヌレート環（β７）、又はイソシアヌレート環と炭化水素基のみからなる基（β８）である。） [Glycidyl ester type epoxy resin]
A glycidyl ester type epoxy resin is a polymer having a weight average molecular weight of 3000 to 20000 obtained by copolymerizing an epoxy group-containing monomer such as glycidyl (meth) acrylate with an alkyl (meth) acrylate having 4 to 25 carbon atoms alone or It is a reaction product of chlorohydrin and a compound represented by the following formula 6, and the like.

(In the formula, e is an integer of 2 to 8; R ⁷ is composed only of a hydrocarbon group having 2 to 20 carbon atoms (β 5), an ether oxygen (—O—) having 2 to 30 carbon atoms and a hydrocarbon group A group (β6), an isocyanurate ring (β7), or a group consisting only of an isocyanurate ring and a hydrocarbon group (β8).

  By reacting epichlorohydrin with the compound represented by the above-mentioned formula 6, epichlorohydrin and the carboxyl group of the above-mentioned compound of the above-mentioned formula 6 are subjected to an addition reaction to obtain chlorohydrin. A glycidyl ester type epoxy resin can be obtained by ring closure with a base such as sodium oxide. Moreover, the epoxy resin which carried out the ring-opening polymerization of a part of epoxy group of glycidyl-ester type epoxy resin can also be used.

Among the compounds represented by the above-mentioned formula 6, a compound (β5-1) in which e is 2 to 4 and R ⁷ is a hydrocarbon group having 2 to 10 carbon atoms, e is 2 to 6, and compound wherein R ⁷ is a group which consists of only hydrocarbon radical with oxygen ethers having 2 to 30 carbon atoms (-O-) (β6-1), or e is 3, and R ⁷ is an isocyanurate ring hydrocarbon The compound (β8-1) which is a group consisting only of groups is preferably mentioned because of its high solubility.

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

（式中のｅは２〜８の整数であり、Ｒ^７は炭素数２〜２０の炭化水素基（β５）、炭素数２〜３０のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（β６）、イソシアヌレート環（β７）、又はイソシアヌレート環と炭化水素基のみからなる基（β８）である。） The reaction product of epichlorohydrin and the compound represented by the above formula 6 has a structure of the following formula 7.

(In the formula, e is an integer of 2 to 8; R ⁷ is composed only of a hydrocarbon group having 2 to 20 carbon atoms (β 5), an ether oxygen (—O—) having 2 to 30 carbon atoms and a hydrocarbon group A group (β6), an isocyanurate ring (β7), or a group consisting only of an isocyanurate ring and a hydrocarbon group (β8).

<Amine compound ((C) component)>
The amine compound which is the component (C) promotes (catalyses) the reaction between the thiol group and the epoxy group. Examples of the amine compound which is 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. When the weight average molecular weight of the amine compound is less than 90, the volatility of the amine compound is high, which not only causes odor or voids, but also the amine concentration at the time of heat curing becomes low, so the crosslinking reaction hardly progresses and adhesion Tends to decrease. When the weight average molecular weight of the amine compound exceeds 700, the water resistance is lowered and the adhesion is likely to be lowered.

  Examples of monofunctional amines include primary amines, secondary amines, and tertiary amines. Examples of polyamines include primary amines, secondary amines, tertiary amines and composite amines. The composite 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 can also be used in mixture of 2 or more types.

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

（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。） [Imidazole compound]
Among the amine compounds, imidazole compounds are most suitable for achieving both storage stability and curing in a short time under low temperature conditions. In addition, an imidazole compound coated with a phenol resin or the like can also be used. The imidazole compound is a compound represented by the following formula 8.

(R ⁹ represents 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 And R ⁸ , R ¹⁰ and R ^{11 each} represent 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 combine to form a ring When it is, it is a hydrocarbon group having 2 to 8 carbon atoms.)

  Specific examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 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-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-hydroxymethyl imidazole is mentioned.

<Multifunctional (Meth) Acrylate ((D) Component)>
The curable resin composition of the present invention containing (A) a thioether-containing (meth) acrylate derivative, (B) a polyfunctional epoxy resin, and (C) an amine compound can be cured by heating. By further adding (D) a polyfunctional (meth) acrylate to the curable resin composition, photocuring or photothermal two-step curing can be imparted.

  Among the many double bond-containing compounds, as an advantage of using a polyfunctional (meth) acrylate as the component (D), it reacts with the (A) thioether-containing (meth) acrylate derivative in the curable resin composition of the present invention at room temperature (A) to form a tough cured product upon reaction with a thioether-containing (meth) acrylate derivative, (A) to form a tough cured product, (A) thioether-containing (meth) acrylate The reaction of the derivative with (D) polyfunctional (meth) acrylate is hardly catalyzed by (C) an amine compound, (B) non-reacted with the polyfunctional epoxy resin, and the like.

（式中のｆは２〜３０の整数であり、Ｒ^１２は炭素数２〜２００の炭化水素基（ε１）、炭素数２〜３００のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基（ε２）、イソシアヌレート環（ε３）、又はイソシアヌレート環と炭化水素基のみからなる基（ε４）であり、Ｒ^１３は水素原子またはメチル基である。） The compound represented by following formula 9 is mentioned as a preferable example of such polyfunctional (meth) acrylate. In addition, the polyfunctional (meth) acrylate which is (D) component can also be used individually by 1 type, and can also be used in mixture of 2 or more types.

(In the formula, f is an integer of 2 to 30, and R ¹² is composed only of a hydrocarbon group having 2 to 200 carbon atoms (ε1), an ether oxygen (—O—) having 2 to 300 carbon atoms, and a hydrocarbon group A 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.

  Moreover, as (D) polyfunctional (meth) acrylate, the thing of a polymer type can also be used suitably. As polymer type polyfunctional (meth) acrylate, (meth) acrylate having epoxy group such as glycidyl (meth) acrylate or the like has a group which reacts with epoxy group like (meth) acrylic acid in homopolymer or copolymer. A polymer obtained by reacting (meth) acrylate, a hydroxyl group-containing (meth) acrylate homopolymer or copolymer such as hydroxyethyl (meth) acrylate, and a hydroxyl group reaction such as 2-isocyanatoethyl 2-methylpropenoate A polymer obtained by reacting a (meth) acrylate having a group, a (meth) acrylate having a carboxyl group such as (meth) acrylic acid or the like or a copolymer with a carboxyl group such as glycidyl (meth) acrylate (Meth) acrylate having a group to be reacted Resulting Te polymers.

  The weight average molecular weight of the (D) polyfunctional (meth) acrylate is 200 to 50,000, preferably 220 to 40,000, and more preferably 240 to 30,000. (D) There is no problem with adhesion even if the weight average molecular weight of the polyfunctional (meth) acrylate is less than 200, but the volatility tends to be high and the odor tends to be strong. On the other hand, if the weight average molecular weight is more than 50,000, the solubility in other components may be low.

  The (meth) acrylate equivalent of (D) polyfunctional (meth) acrylate is 80 to 6000 g / mol, preferably 80 to 4500 g / mol, and more preferably 85 to 3000 g / mol. When the (meth) acrylate equivalent is smaller than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive, and the (A) thiol ether-containing (meth) acrylate derivative and the unreacted (meth) acryloxy group are By remaining in a large amount, the toughness of the cured film made of the curable resin composition may be reduced, and the adhesion may be reduced. On the other hand, when the (meth) acrylate equivalent is greater than 6000 g / mol, the (meth) acryloxy group concentration is extremely low, so that the reaction efficiency of the (A) thioether-containing (meth) acrylate derivative with the thiol group decreases. Toughness of the cured film made of the base resin composition may be lowered, and the adhesion may be lowered.

<Photoinitiator ((E) component)>
The photopolymerization initiator which is the component (E) is added to promote the reaction between the thiol group and the (meth) acryloxy group. Examples of the photopolymerization initiator include a photo radical initiator, a photo cation initiator, and a photo anion initiator. The photo radical initiator is preferably used to shorten the reaction time, the photo cation initiator is preferably used to reduce the cure shrinkage, and the photo anion initiator is an adhesive in the field of electronic circuits and the like. It is preferable to use when giving a property.

  As the photo radical initiator, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 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- (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. may be mentioned. .

  As a photo cation initiator, for example, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, diphenyliodonium Hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, triphenylsulfonium tetrafluoroborate, tri Phenyl sulfonium bromide, tri-p-tolyl sulfonium hexafluorophosphate, tri-p-tolyl sulfonium trifluoromethane sulfonate and the like can be mentioned.

  As a photoanion initiator, for example, 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-butyl triphenyl borate and the like can be mentioned.

<Composition ratio (blended balance)>
In the curable resin composition of the present invention, the mass ratio ((A) / (B)) of (A) thioether-containing (meth) acrylate derivative to (B) polyfunctional epoxy resin is 0.05 to 30. Mix in 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 determined by the characteristics required for the curable resin composition, (A) thioether-containing (meth) acrylate derivative, (B) multifunctional epoxy resin and optionally added (D 2.) It depends on the structure of polyfunctional (meth) acrylate. The properties after curing of the curable resin composition are strictly the (thiol group number) / (epoxy group number + (meth) acryloxy group number) in the curable resin composition unit weight (hereinafter, thiol / (epoxy + ene) Affected by the value of the ratio). For example, if the ratio of thiol / (epoxy + ene) is in the range of 0.5 to 1.5, it tends to form a dense crosslink and tends to be 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 and sticky cured product can be obtained. When the thiol / (epoxy + ene) ratio is less than 0.1 or more than 2.0, gelation tends to be difficult and adhesion tends to be reduced.

  In addition, the curable resin composition of the present invention is based on 100 parts by mass of the total mass ((A) + (B)) of the (A) thioether-containing (meth) acrylate derivative and the (B) polyfunctional epoxy resin. C) The amine compound is blended so as to be 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass. If 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)), it takes time for the reaction of the thiol group and the epoxy group to proceed, so curing failure is If it exceeds 50 parts by mass, storage stability may be lowered.

  Moreover, when mix | blending (D) polyfunctional (meth) acrylate with respect to the curable resin composition of this invention, the total mass of (A) thioether containing (meth) acrylate derivative and (B) polyfunctional epoxy resin It mixes so that (D) polyfunctional (meth) acrylate may be 2-300 mass parts, preferably 2-250 mass parts with respect to 100 mass parts of ((A)) + (B). When the compounding amount of the component (D) is less than 2 parts by mass with respect to 100 parts by mass of ((A) + (B)), it is difficult to impart photocurability, and when it exceeds 300 parts by mass, the adhesion is lowered. There is a tendency to

  Moreover, when mix | blending (E) photoinitiator with respect to the curable resin composition of this invention, the total mass of (A) thioether containing (meth) acrylate derivative and (D) polyfunctional (meth) acrylate The photopolymerization initiator (E) is blended in an amount of 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of ((A) + (D)). When the compounding amount of the component (E) is less than 0.01 parts by mass with respect to 100 parts by mass of ((A) + (D)), it is difficult to promote photocuring, and when it exceeds 10 parts by mass, it is unnecessary. It is not preferable because it is large.

<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, as a substrate, a substrate which forms a chemical bond with a thioether group (high chemical affinity), 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 adhesion improvement effect to the inorganic base material, the organic substance which has unsaturated bond (including an aromatic ring), the organic substance which has a hydroxyl group and a carboxyl group, or the organic substance which carried out plasma or UV ozone treatment. Specifically, examples of the inorganic base include glass, silicon, various metals and the like. As organic base materials, polyester resins such as poly (meth) acrylic resins, triacetate cellulose (TAC) resins, polyethylene terephthalate (PET) and polybutylene terephthalate, polycarbonate resins, polyimide resins, and polyolefins such as polyethylene and polypropylene Preferred examples include system resins, polycarbonates, polyimides, ABS resins, polyvinyl alcohols, vinyl chloride resins, and polyacetals. In addition, in the curable resin composition of the present invention, the cured film is excellent in flexibility because the (A) thioether-containing (meth) acrylate derivative has a specific hydrocarbon group. Therefore, the cured film easily follows the substrate even under cold conditions, and the adhesion to the substrate is excellent. Therefore, it can be particularly suitably used for the coating of flexible substrates that can be used 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. Moreover, when curable resin composition contains (D) component, it can also be hardened by irradiating light. Examples of the 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), it can 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 used after diluting it with an organic solvent in order to make the reaction system uniform and to facilitate coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents and ether ester solvents, ketone solvents and phosphoric acid ester solvents. Although it is preferable to suppress these organic solvents to the compounding quantity of less than 10000 mass parts with respect to 100 mass parts of curable resin compositions, since a solvent volatilizes basically at the time of becoming a cured film, a cured film It does not affect the physical properties of However, the compound having a functional group that reacts with a thiol group, an epoxy group, or a (meth) acryloyl group, and an amine compound may impair the effects of the present invention when used as a solvent.

  In addition, the curable resin composition of the present invention may be blended with a viscosity modifier such as silica powder for the purpose of adjusting the viscosity. It is preferable to suppress these viscosity modifiers to the compounding quantity of less than 300 mass parts with respect to 100 mass parts of curable resin compositions. If the blending amount of the viscosity modifier exceeds 300 parts by mass, adhesion may be reduced.

  In addition, the curable resin composition of the present invention may be added with various additives used for ordinary paints and adhesives. Examples of such additives include surfactants for smoothing the coated surface and aluminum salts for prolonging the usable time. It is preferable to suppress these additives to a compounding 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, adhesion may be reduced.

（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’−１：多価チオール）

（Ａ’―２：チオエーテル含有アルコキシシラン誘導体）

（Ａ’―３：チオエーテル含有アルコキシシラン誘導体）

（Ａ’―４：チオエーテル含有（メタ）アクリレート誘導体）

Next, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited thereto. The reagents used in the present example and the comparative example are as follows. In addition, Mw shows a weight average molecular weight.
<(A) component>
(A-1: Thioether-Containing (Meth) Acrylate Derivative)

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

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

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

(A'-1: multivalent thiol)

(A′-2: Thioether-Containing Alkoxysilane Derivative)

(A'-3: Thioether-Containing Alkoxysilane Derivative)

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

（Ｂ−２、Ｍｗ：２２０）

（Ｂ−３、Ｍｗ：１８０００）
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（官能基比１：１）の共重合体（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−４、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（官能基比１：１）の共重合体（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） <Multifunctional epoxy resin ((B) component)>
(B-1, Mw: 5500)

(B-2, Mw: 220)

(B-3, Mw: 18000)
Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (functional ratio 1: 1) (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)
(B-4, Mw: 45000)
Copolymer of glycidyl methacrylate and cyclohexyl methacrylate (functional ratio 1: 1) (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)

（Ｃ−２、Ｍｗ：１０２）
Ｎ，Ｎ−ジメチル−１，３−プロパンジアミン
（Ｃ−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） <Amine compound ((C) component)>
(C-1, Mw: 110)

(C-2, Mw: 102)
N, N-Dimethyl-1,3-propanediamine (C-3, Mw: 680)

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

（Ｄ−２、Ｍｗ：２４６）

（Ｄ−３、Ｍｗ：５０００）

（ｎは平均１３）
（Ｄ−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Ｃ−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）
（Ｄ−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Ｃ−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） <Multifunctional (Meth) Acrylate ((D) Component)>
(D-1, Mw: 352)

(D-2, Mw: 246)

(D-3, Mw: 5000)

(N is an average of 13)
(D-4, Mw: 22000)
Polymer of equimolar addition of methacrylic acid catalyzed by C-3 to copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)
(D-5, Mw: 45000)
Polymer of equimolar addition of methacrylic acid catalyzed by C-3 to copolymer of glycidyl methacrylate and cyclohexyl methacrylate (white solid obtained by reprecipitating 50 wt% methyl isobutyl ketone solution with hexane)

<Photoinitiator ((E) component)>
(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-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] dec-5-ene

<Curable resin composition>
The components (A) to (E) were mixed with the compositions and amounts shown in Tables 1 to 4 below, and stirred with a spatula until uniform, to obtain curable resin compositions of the respective examples and comparative examples. . Evaluation of the following Adhesiveness 1 (Adhesiveness at room temperature), Adhesiveness 2 (Adhesiveness in cold regions), Adhesiveness 3 (Photocurable), flexibility and storage stability using the obtained curable resin composition went. The results are shown in Tables 1 to 4.

[Fabrication of evaluation test piece 1]
Test pieces for evaluation of adhesion 1, adhesion 2 and flexibility were obtained as follows. Each curable resin composition is coated on a 25 mm wide PET film with a die coater to a thickness of 100 microns, another PET film is overlaid thereon, and then cured at 150 ° C. for 1 hour for evaluation. Test piece 1 was obtained. In addition, as a PET film, Toray Industries, Ltd. product and Lumirror U46-100 were used.

[Fabrication of evaluation test piece 2]
The test piece for evaluation of the adhesiveness 3 was obtained as follows. Each curable resin composition is coated on a PET film of 25 mm in width and 150 mm in length with a die coater to a thickness of 100 microns, another PET film is superposed thereon, and then a high pressure mercury lamp (i-line conversion) light irradiation amount of light: the 500 mJ / cm ² irradiated to a test piece for evaluation 2A, was 3000 mJ / cm ² irradiated to obtain a specimen for evaluation 2B. In addition, as a PET film, Toray Industries, Ltd. product and Lumirror U46-100 were used.

[Adhesion 1 (room temperature adhesion)]
The test specimen for evaluation 1 was allowed to stand at 25 ° 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 (PET film is broken)
:: tensile strength of 5 N / 25 mm or more (PET film is not broken)
X: less than 5 N / 25 mm

[Adhesion 2 (Coldness in cold regions)]
The test specimen 1 for evaluation was allowed to stand at −10 ° 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 (PET film is broken)
:: tensile strength of 5 N / 25 mm or more (PET film is not broken)
X: less than 5 N / 25 mm

[Adhesion 3 (photo-curable)]
In each of the evaluation test pieces 2A and 2B, one PET film is pulled in the width direction while holding the evaluation test piece with both hands, and the relative displacement (displacement in the width direction) with respect to the other PET film is visually observed. Observed and evaluated.
:: no deviation in both of the evaluation test pieces 2A and 2B ○: no deviation only in the evaluation test piece 2B ×: no deviation both in the evaluation test pieces 2A and 2B

[Flexibility]
The test specimen 1 for evaluation was allowed to stand at -10 ° C for 24 hours, and then wound around a rod with a diameter of 8 mm for 1 minute, observed visually, and evaluated as follows.
○: no cracks ×: cracks

Storage stability
About the curable resin composition of each example and comparative example, while measuring the viscosity (viscosity after mixing) at 25 ° C immediately after mixing, after heating at 40 ° C for 12 hours, the viscosity (viscosity after heating) It measured and the viscosity after heating was remove | divided by the viscosity immediately after mixing, the thickening rate was computed, and it evaluated as follows. The viscosity was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd. under the following conditions.
Used rotor: 1 ° 34 '× R24
Measurement range: 0.5183 to 103.7 Pa · s
:: Thickening rate 1.0 to 1.8
○: Thickening rate 1.8 to 10
X: out of the above range

  In the curable resin compositions of Examples 1-1 to 1-17, high adhesion, good flexibility, and excellent storage stability under room temperature and cold conditions are observed. On the other hand, in Comparative Examples 1-5 to 1-8 using a compound that does not correspond to the above-mentioned Formula 1 as the component (A), the adhesion and flexibility under cold conditions are lacking. In Comparative Examples 1-1 and 1-2 in which the amount of the component (A) is too small or too large relative to the component (B), the adhesion is poor not only under cold conditions but also at normal temperature. Among them, in Comparative Example 1-1 in which the amount of the component (A) is too small relative to the component (B), the flexibility is also lacking. Adhesion is lacking in Comparative Example 1-3 in which the component (C) is not blended. In Comparative Example 1-4 in which the component (C) is blended in excess with respect to the component (A) and the component (B), the storage stability is poor. Moreover, it was confirmed that photocurability can be provided by adding (D) component in Examples 2-1 to 2-10. Moreover, in Examples 3-1 to 3-5, it was confirmed that curing can be performed with less light irradiation when the component (E) is added.

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) containing an amine compound having a weight average molecular weight of 90 to 700,
The mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.05 to 30,
Curable resin composition which 0.01-50 mass parts of said (C) components are mix | blended with respect to 100 mass parts of total mass of said (A) component and said (B) component.

(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 the following formula 3. R ³ is a methyl group or an ethyl group R ⁴ is carbon 1 to 12 hydrocarbon groups.)

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

(R ⁵ is a hydrogen atom or a methyl group)   (D) The multifunctional (meth) acrylate having a weight average molecular weight of 200 to 50,000 is compounded in an amount of 2 to 300 parts by mass with respect to 100 parts by mass of the total mass of the component (A) and the component (B). The curable resin composition according to claim 1.   The curability according to claim 2, wherein the photopolymerization initiator (E) is blended in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total mass of the component (A) and the component (D). Resin composition.