JP2009120683A - Curable resin composition and curing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition having good storage stability, adhesion curing even at a low temperature, giving a slightly discolored cured product, and reducing the amount of energy required for curing, by making use of a photocurable resin composition including a new aminimide-based photobase generator. <P>SOLUTION: The curable resin composition includes, as essential components, (A) 100 pts.wt. of a mixture of a glycidyl (meth)acrylate compound (a1) and an epoxy resin (a2) having at least two glycidyl groups in a molecule and (B) 1-30 pts.wt. of an aminimide compound having one or more structures represented by general formula (I) in a molecule and generating a base upon irradiation with active energy rays. A method for curing the curable resin composition is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

By using an amine imide compound that generates a base upon irradiation with active energy rays, the present invention can be cured with less energy than before, can be reliably cured at low temperatures, and has excellent storage stability. The present invention relates to a curable resin composition.

Photo-curing technology is widely used for adhesives, sealants, coating agents, resist agents, etc., taking advantage of features such as low-temperature curing, process shortening, short-time curing, and microfabrication compared to conventional thermosetting technologies. ing. Curing systems mainly used in photocuring are roughly classified into radical curing and cationic curing. In the case of radical curing, the photo radical generator and (meth) acrylate resin are the main components and are characterized by curing immediately after light irradiation, but generally have low adhesive strength, large curing shrinkage, poor heat resistance, etc. There is a problem. Cationic curing consists of a photoacid generator such as diaryliodonium salt or triarylsulfonium salt and an epoxy resin, oxetane resin, vinyl ether resin or the like having cationic polymerizability, and the photoacid generator generates an acid upon light irradiation. The cationic polymerizable resin is cured. In the case of cationic curing, it has characteristics such as fast curing, high adhesive strength, and low curing shrinkage, but because of the occurrence of poor curing due to moisture or slight basic contamination on the surface of the adherend, and strong acid remains in the system When using an adherend made of a metal or an inorganic material, there is a problem of causing corrosion.

As one means for solving such a problem of cationic curing, research on anion curing using a photobase generator that generates a basic compound by light irradiation has been recently conducted. As such photobase generators, for example, carbamate derivatives and oxime ester derivatives are generally known, and these compounds generate primary or secondary amines upon irradiation with light, and polymerize epoxy resins. It is used for curing (for example, Non-Patent Document 1). The technology for generating a base catalyst by light is already well known in the art, and is widely used in photoresist technology. In narrow line width resists, in order to obtain the dimensional stability of the developed edge, an anionic polymerization type curing form with little termination reaction is often used (for example, Non-Patent Document 2, Patent Documents 1 to 3). In the method of curing an epoxy resin with a photogenerated basic substance, amines are listed as typical basic compounds, and these amines are the most useful photogenerated bases to date. For example, substituted benzyl carbamate derivatives generate primary and secondary amines by light irradiation (for example, Non-Patent Documents 3 to 5).

However, most of these compounds have low generation efficiency, and since the basic compound generated by light irradiation is a primary or secondary amine, the basicity is low, and the catalytic activity for sufficiently curing the epoxy resin is low. There is a problem of not having.

As photobase generators capable of photochemically generating tertiary amines having higher basicity, aromatic amine imide compounds have been reported in Patent Documents 4 and 5, etc., and epoxy resins and polyvalent thiol compounds A case has been reported in which the heat curing start temperature is lowered after light irradiation in an addition curing reaction with the like. Patent Document 5 also reports a combination of an aromatic amine imide compound and a singlet / triplet sensitizer, that is, a hydrogen abstraction type radical generator.

However, these aromatic amine imide compounds have high crystallinity, limited solubility in resins, and heat curing temperatures after light irradiation are not sufficiently low. It is well known that amine imide compounds are decomposed by heating and generate a tertiary amine through the Curtius transition, and bonded to carbonyl carbon as an amine imide compound that decomposes by low temperature heating to generate a tertiary amine. Patent Document 6 reports an amine imide compound having a structure in which a hydroxyl group is bonded to carbon.

ここで、Ｒ１は、Ｈまたは官能基を有していても良いアルキル基または／およびアリール基を示す。Ｒ２、Ｒ３およびＲ４は、それぞれ独立に、官能基を有していても良いアルキル基または／およびアリール基を示す。 By the way, it is known that the amine imide compound which has the following general formula (I) structure has photoactivity, and these heat decomposition temperatures become low.

Here, R1 represents H or an alkyl group or / and an aryl group which may have a functional group. R2, R3 and R4 each independently represents an alkyl group or / and an aryl group which may have a functional group.

In the invention filed prior to the present application (Japanese Patent Application No. 2006-175008), the present inventors have disclosed a curability containing an amine imide compound having the above structure as a photobase generator and an epoxy / thiol resin as a curable resin. It has been found that by using a resin composition, the irradiation amount of active energy rays can be reduced without lowering the curability. On the other hand, when an epoxy / thiol resin is used, the storage stability of the curable resin composition is disadvantageously deteriorated. For this reason, development of the resin composition which can reduce the irradiation amount of an active energy ray while maintaining the storage stability of resin is calculated | required.

: European Patent No. 599571 : European Patent No. 555749 : JP-A-4-330444 : International Patent Publication WO2002 / 051905 : JP 2003-26772 A : JP 2000-229927 A : Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Ed. by G. Bradley, John Wiley and Sons Ltd. (1998, p479-p545) : Pure and Appl. Chem. , 64, 1239 (1992) : J. Org. Chem. , 55, 5919 (1990) : Polym. Mat. SciEng. 64, 55 (1991) : Macromol. , 28, 365 (1995)

The object of the present invention is that the photocurable resin composition containing the novel amine imide photobase generator has good storage stability, can be adhesively cured even at low temperatures, has little coloration of the cured product, and is necessary for curing. An object of the present invention is to provide a curable composition that can reduce the amount of energy.

ここで、Ｒ１は、Ｈまたは官能基を有していても良いアルキル基または／およびアリール基を示す。Ｒ２、Ｒ３およびＲ４は、それぞれ独立に、官能基を有していても良いアルキル基または／およびアリール基を示す。 The present invention relates to 100 parts by weight of a mixture of (A) a glycidyl (meth) acrylate compound (a1) and an epoxy resin (a2) having at least two glycidyl groups in the molecule, (B) the following general formula (I) A curable resin composition having 1 to 30 parts by weight of an amine imide compound having one or more structures shown in the molecule and generating a base by irradiation with active energy rays as an essential component, and a method for curing the curable resin composition .

Here, R1 represents H or an alkyl group or / and an aryl group which may have a functional group. R2, R3 and R4 each independently represents an alkyl group or / and an aryl group which may have a functional group.

The glycidyl (meth) acrylate compound (a1) as the component (A) used in the present invention is used for the purpose of improving the active energy ray reactivity while maintaining the cured product properties of the curable resin composition. Here, the glycidyl (meth) acrylate compound is a compound having a glycidyl group and a (meth) acryloyl group in one molecule. Here, the (meth) acryloyl group refers to either an acryloyl group or a methacryloyl group as conventionally used.

The glycidyl (meth) acrylate compound that can be used in the present invention is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, A compound in which at least one glycidyl group of a compound having one or more glycidyl groups is (meth) acryloylated is preferably used. Among these, glycidyl acrylate having a phenol novolac type structure is particularly preferable from the viewpoint of reactivity and weather resistance of the cured product. Examples of commercially available glycidyl (meth) acrylate compounds having a phenol novolac type structure include trade names: SPS-600 (manufactured by Showa Polymer Co., Ltd.), EB3603 (manufactured by Daicel-Cytec).

The epoxy resin (a2) having at least two glycidyl groups in the molecule of the component (A) used in the present invention gives adhesiveness to the curable resin composition, and further adjusts curability by irradiation with active energy rays. It is used for the purpose.

The component (a2) that can be used in the present invention includes so-called epi-bis such as diglycidyl ether derived from bisphenol A and epichlorohydrin and derivatives thereof, diglycidyl ether derived from bisphenol F and epichlorohydrin, and derivatives thereof. Liquid epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, glycidyl ether derived from aliphatic / aromatic alcohol and epichlorohydrin, derived from polybasic acid and epichlorohydrin Glycidyl esters and derivatives thereof, glycidyl ethers derived from hydrogenated (hydrogenated) bisphenol A and epichlorohydrin, 3,4-epoxy-6-methylcyclo Aliphatic cyclic epoxy such as xylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and derivatives thereof, 5,5′-dimethylhydantoin type epoxy Examples thereof include substituted epoxy resins derived from resins, triglycidyl isocyanate and isobutylene, and phenol novolac type epoxy resins are particularly preferred from the viewpoint of compatibility with component (a1) and adhesiveness. Examples of commercially available phenol novolac type epoxy resins include, but are not limited to, trade names: jER152, jER154 (both manufactured by JER). In addition, these (a2) components may be used independently or may be used in mixture of 2 or more types.

The weight ratio of the component (a1) and the component (a2) is 75:25 to 25:75, and more preferably 60:40 to 40:60. If the weight ratio of the component (a1) in the component (A) is less than 25%, the adhesive strength of the cured product is inferior, and if it exceeds 75%, delayed curing cannot be imparted, and the solid form at room temperature cannot be obtained. It becomes difficult to keep.

The component (B) amine imide compound used in the present invention generates a base upon irradiation with energy rays and is used as a photoactive catalyst and a retarder for the curable resin composition of the present invention in which the reaction rate is changed by a basic catalyst. can do.

A well-known method can be used for the synthesis | combination of the compound which has the component (B) amine imide structure used by this invention. See, for example, Encyclopedia of Polymer Science and Engineering, John Wiley & Sons Ltd. (1985), Volume 1, p. 740, obtained from the reaction of the corresponding carboxylic acid ester with a halogenated hydrazine and sodium alkoxide or the reaction of the carboxylic acid ester with hydrazine and an epoxy compound. I can do it.

The method for synthesizing the amine imide compound as the (B) photobase generator used in the present invention is not particularly limited. However, in view of the simplicity and safety of the synthesis, from the carboxylic acid ester, hydrazine and epoxy compound. A synthetic method is preferred. In this case, the synthesis temperature and time are not particularly limited, but in general, the compound having the target amine imide structure can be obtained by stirring at a temperature of 0 to 100 ° C. for 30 minutes to 7 days. Preferably, the amine imide compound of the present invention has a characteristic that the thermal decomposition temperature is lower than that of an aromatic amine imide or the like conventionally known as a photobase generator, so that side reactions and thermal decomposition of the generated amine imide are suppressed. It is preferable to adjust the temperature at the initial stage of the synthesis reaction within the range of 0 to 25 ° C. and the temperature at the final stage to 60 ° C. or less.

The carboxylic acid ester as a raw material of the amine imide compound of the present invention used in this synthesis method may be a monofunctional or polyfunctional carboxylic acid ester compound having a —CH (OH) COO— structure in the molecule. Examples include methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-n-ethyl butyrate, 2-hydroxy-n-ethyl caproate, ethyl mandelate, ethyl glycolate, methyl glycolate, isopropyl leucine, dimethyl tartrate, and the like. This is not the case. When a polyfunctional carboxylic acid ester compound is used, an amine imide compound having a plurality of amine imide structures in the molecule can be obtained. The hydrazine compound is not particularly limited, but 1,1-dimethylhydrazine is preferable from the viewpoint of easy availability of raw materials and the high basicity of the generated photobasic substance. Moreover, the epoxy compound which is another raw material should just be a compound which has one or more epoxy groups in a molecule | numerator. For example, in addition to monofunctional epoxy compounds such as propylene oxide, glycylol, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tertiary butylphenol glycidyl ether, resorcinol diglycidyl ether, neopentyl diglycidyl ether, glycerol polyglycidyl ether, So-called epi-bis type liquid epoxy resins such as diglycidyl ether derived from bisphenol A and epichlorohydrin, polyglycidyl ether derived from aliphatic / aromatic alcohol and epichlorohydrin, polyglycidyl ester derived from polybasic acid and epichlorohydrin , Polyfunctional epoxidation such as polyglycidyl ether derived from hydrogenated bisphenol A and epichlorohydrin Things can also be used. When a polyfunctional epoxy resin is used, an amine imide compound having a plurality of amine imide structures in the molecule can be obtained.

The amount of component (B) added to 100 parts by weight of component (A) is preferably 1 to 30 parts by weight, more preferably 5 to 15 parts by weight. If it is less than 1 part by weight, the active energy ray curability of the curable resin composition is insufficient, and if it exceeds 30 parts by weight, the cured product properties such as heat resistance and strength of the cured product are deteriorated.

In the present invention, the component (C) photoradical generator can be further used for the purpose of suppressing the coloring of the cured product of the curable resin composition of the present invention and enhancing the activity against active energy rays. As the (C) photoradical generator, a commonly known hydrogen abstraction type radical generator and / or cleavage type radical generator can be used.

Examples of the hydrogen abstraction type radical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-Iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, naphthalene derivatives such as 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene, Anthracene derivatives such as 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, pyrene derivatives, carbazole, 9- Tylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H -Carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole, 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-ethyl-3,6-dinitro -9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9-allylcarba , 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl)- 9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, etc. Carbazole derivatives, benzophenone, 4-phenylbenzophenone, 4,4′-bis (dimethoxy) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-benzoylbenzoic acid Methyl ester, 2-methyl ester Benzophenone derivatives such as nzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, aromatic carbonyl compounds, [4- (4-methylphenyl Thio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1-chloro Examples thereof include thioxanthone derivatives such as -4-propoxythioxanthone and coumarin derivatives.

A cleavage-type radical generator is a type of radical generator that generates radicals by cleavage of the compound when irradiated with active energy rays. Specific examples thereof include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, Examples include, but are not limited to, oxime ketones, acylphosphine oxides, thiobenzoic acid S-phenyls, titanocenes, and derivatives obtained by increasing the molecular weight thereof. Commercially available cleavage type radical generators include 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl- 1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloyloxyethoxy) -benzoyl] -1-hydroxy-1 -Methylethane, diphenylketone, phenyl-1-hydroxy-cyclohexylketone, benzyldimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η6-isopropylbenzene)- (Η5-cyclopentadienyl) -iron (II) hexafur Orophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4 -Dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4- (methylthiobenzoyl) -1- Examples thereof include, but are not limited to, methyl-1-morpholinoethane.

The component (C) photo radical generator used in the present invention, that is, a hydrogen abstraction type or a cleavage type radical generator can be used alone or in combination. A combination of one or more cleavage radical generators is more preferable in terms of stability of the agent alone and curability of the composition in the present invention. A high molecular weight type in which a structure of a cleavage type radical generator is introduced into a polymer oligomer / polymer is more preferable because outgas at the time of curing and after curing is small.

By the way, depending on the type of the (C) photo radical generator, there may be a difference in the effect depending on the structure of the (B) amine imide compound to be combined. Since this is considered to be affected by the combination of wavelengths of the absorption energy lines of the amine imide compound and the radical generator, the optimal combination of (B) the amine imide compound and (C) the photo radical generator may be arbitrarily selected. . Moreover, when the weight ratio of (C) component with respect to (B) component becomes large too much, photocurability will fall, but the coloring property with respect to hardened | cured material will fall. In the curable resin composition of the present invention, the compounding amount of the component (C) with respect to 100 parts by weight of the resin is preferably 0.01 to 10 parts by weight, and more preferably 1 to 5 parts by weight. If it is less than 0.01 part by weight, a sufficient photoactivity improving effect cannot be obtained, and if it exceeds 10 parts by weight, the basic catalytic action is inhibited.

The curable resin composition of the present invention can also be used as a curable resin composition in a solid state that does not have fluidity at room temperature. Applications that have been difficult to use with a fluid paste-like curable resin composition by making it into a solid form, for example, areas where protrusion of the curable resin composition is problematic, areas where air bubbles are problematic, coating films Application to a portion where it is difficult to adjust the thickness is remarkably improved. In order to obtain a solid form at room temperature, an additive component that does not affect the reaction of the curable resin composition of the present invention, for example, a non-flowable reactive bisphenol A type phenoxy resin or bisphenol F type as a shape retention component. It can be realized by a method of adding a phenoxy resin, a urethane acrylate oligomer, a polyester acrylate oligomer, or a mixture thereof as a raw material component and molding the curable resin composition into a solid form at room temperature.

The curable resin composition formed into a solid shape at room temperature by the above method can be softened or melted by heating to 50 ° C. to 100 ° C., preferably 70 ° C. to 90 ° C. to be in a liquefied fluid state. Here, the liquefied flow state can be represented by the ratio of G ′ (storage elastic modulus) and G ″ (loss elastic modulus) when the thermal behavior of the sheet composition is measured with a rheometer, Is a state where G ″ / G ′ is a value of 1 or more. The curable resin composition in a liquefied flow state can be photocured by activating the (B) amine imide compound in the curable resin composition by irradiating active energy rays.

In the composition of the present invention, pigments, dyes and other colorants, calcium carbonate, talc, silica, alumina, aluminum hydroxide and other inorganic fillers, silver and other conductive particles, as long as the properties of the present invention are not impaired. Flame retardant, boric acid ester, phosphoric acid ester, preservability improver such as inorganic acid, organic acid, organic filler such as acrylic rubber and silicone rubber, polyimide resin, polyamide resin, bisphenol A type phenoxy resin and bisphenol F type phenoxy Polymers such as resins, bisphenol A / bisphenol F copolymerized phenoxy resins, polymethacrylate resins, polyacrylate resins, polyvinyl butyral resins, SBS resins and their modified epoxy resins, thermoplastic elastomers, plasticizers , Organic solvent, antioxidant, defoamer, cup Ing agents, leveling agents, may be appropriate amount of additives such as rheology control agents. By these additions, a composition excellent in resin strength, adhesive strength, flame retardancy, thermal conductivity, storage stability, workability, and the like, and a cured product thereof can be obtained.

The amine imide compound (B) of the present invention is a photobase generator that generates a base upon activation by irradiation with active energy rays such as ultraviolet rays. The active energy rays used here include gamma rays, electron beams, and ultraviolet rays. It means visible light. The irradiation amount is an amount necessary to activate the (B) amine imide compound. As an example, a mixture of (a1) phenol novolac glycidyl acrylate and (a2) phenol novolac epoxy resin is used as component (A), and 1,1-dimethyl-1- (2-hydroxy) is used as component (B). The irradiation amount of ultraviolet rays in the case of using (-3-allyloxypropyl) amine lactimide may be ³ J / cm ² or more. Moreover, the composition of this invention can obtain hardened | cured material with a still smaller energy irradiation amount and short time by simultaneously performing heating in addition to irradiation of an active energy ray. In addition, although (B) amine imide compound of this invention can be activated also by heating other than active energy rays, for example, the polymerization hardening is carried out by using active energy ray irradiation together compared with activation only by heating. Can greatly improve the performance. Since a general ultraviolet irradiation device emits heat rays simultaneously with ultraviolet rays, it is extremely useful for polymerizing and curing the curable resin composition of the present invention.

The cured product of the curable resin composition of the present invention has not only excellent properties such as toughness and transparency, but also the curable resin composition of the present invention irradiated with a predetermined amount of active energy rays. By simply leaving it at room temperature, the polymerization reaction proceeds and a cured product can be obtained without any subsequent treatment such as heating. Utilizing this characteristic, it can be used for various applications such as molding of optical parts, adhesion, sealing, casting, painting, coating materials and the like. The curable resin composition in the composition of the present invention can be cured immediately after energy irradiation, or can be cured immediately after energy irradiation, and can be cured by standing at room temperature or heating for a short time. In the latter case, even when the adhesive member does not transmit energy such as light, adhesive curing can be performed by applying and pasting the composition after irradiating the composition with energy.

The present invention can reduce the amount of energy required for curing compared to conventionally known photobase-based curable compositions, has good storage stability, can be cured even at low temperatures, and is less colored in the cured product. It can be used as a curable resin composition.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. Further, the blending ratios in the following table are based on weight unless otherwise specified.

(Irradiation device) As an active energy ray irradiation device, an ultraviolet curing device UVL-4001-N manufactured by Ushio Electric Co., Ltd. was used, and ultraviolet rays having a wavelength of 365 nm were irradiated in a predetermined amount of energy.

(Strength evaluation method) Adhesive strength was measured using a 25 × 100 × 1.6 mm SPCC-SD steel plate as the adherend test specimen, and the tensile shear adhesive strength was measured according to JIS K 6850 under the condition of 10 mm / min. Evaluation was performed.

(Storage stability evaluation method) Storage stability refers to the time until each curable resin composition is sealed in a 10 ml light-shielding bottle and stored in a refrigerator at 5 ° C. until the curable resin composition gels and loses its fluidity. Measurement and evaluation were performed. In addition, about the below-mentioned sheet-shaped curable resin composition, after heating and melting at 80 degreeC, evaluation was performed.

(Evaluation of the appearance of the cured product) The appearance evaluation of the cured product was judged visually, and the appearance of the cured product was evaluated in three stages. The case where coloring was not recognized at all was evaluated as ◎, the case where slight coloring was observed was evaluated as ◯, and the case where coloring was clearly observed was determined as △.

(Synthesis of amine imide compound) Polym. Sci. According to the method disclosed in Part A, 38, 18, 3428 (2000) and JP-A-2000-229927, each amine imide compound from a corresponding carboxylic acid methyl ester or carboxylic acid ethyl ester, dimethylhydrazine and an epoxy compound ( The amine imide compounds A and B of the present invention and the amine imide compound C) not included in the present invention were obtained. The amine imide compound A is usually liquid at room temperature, but when crystallized at the time of preparing the curable resin composition, it was melted at 55 ° C. and then mixed and stirred.

(Test method) The materials shown in Tables 2 and 3 were mixed and stirred in a light-shielding container at room temperature with a planetary mixer to prepare a curable resin composition. In Comparative Examples 1-13 and Examples 1-13, each obtained curable resin composition was apply | coated to the to-be-adhered test body, and the predetermined amount of active energy rays was irradiated. Here, the test specimen for strength evaluation was superimposed on another test specimen and allowed to stand at room temperature for 50 hours, and the curable resin composition was adhesively cured to obtain an adhesive strength test specimen. At the same time, a test specimen immediately after being irradiated with an active energy ray and superposed on the other adherend specimen was heated at 100 ° C. for 60 minutes to prepare an adhesive strength specimen which was adhesively cured. In Examples 15 to 20, a curable resin composition molded into a room temperature solid sheet shape was used, and after this sheet was placed on an adherend test body, it was heated to 80 ° C. to form a liquefied fluid state. Further, a predetermined amount of active energy rays was irradiated to the specimen to prepare a test specimen in the same manner as described above.

* In the table, the term "cured" means that the curable resin composition was applied to one of the test specimens, and it was cured quickly after being irradiated with active energy rays, so it could not be bonded and cured with the other specimen. Indicates.

In addition, the kind of raw material component used in Table 1 is as follows.
Component (a1) SPS-600: Phenol novolac glycidyl acrylate (Showa Polymer Co., Ltd.)
SPS-700: bisphenol type glycidyl acrylate (manufactured by Showa Polymer Co., Ltd.)
* Comparative example BP-4EU: Ethylene oxide adduct diacrylate of bisphenol type epoxy resin (manufactured by Kyoeisha)
M-1230: C12,13 mixed higher alcohol glycidyl ether (manufactured by Kyoeisha)
(A2) component jER807: bisphenol type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.)
・ JER152: Phenol novolac type epoxy resin (made by Japan Epoxy Resin Co., Ltd.)
* Comparative Example / YED-122: Alkylphenol monoglycidyl ether (Japan Epoxy Resin Co., Ltd.)
(B) Component / Amineimide Compounds A to C: Compounds listed in Table 1 (C) Component / Cleavage-type photoradical generator 1: 1-benzoylcyclohexanol (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals)
Cleavage-type photo radical generator 2: Diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (trade name: Lucillin TPO BASF Japan)
-Hydrogen abstraction type photo radical generator: Benzophenone Other components-QX-30: Polythiol compound (Japan Epoxy Resin Co., Ltd.)
1256B40: Phenoxy resin (molecular weight of about 50,000, normal temperature solid shape, manufactured by Japan Epoxy Resin Co., Ltd.)
-TBP-23-1: Urethane acrylate oligomer (molecular weight of about 50,000, normal temperature solid form, manufactured by Negami Kogyo Co., Ltd.)

From the results of Examples 1 to 19 and Comparative Examples 1 to 16, in the case where only the glycidyl acrylate compound is used as the curable resin as the component (A), only the surface is sufficiently cured by irradiation with low energy active energy rays. Adhesive strength cannot be obtained, and there is almost no delayed curing. On the other hand, even when only the epoxy resin of the component (a2) is used as the curable resin as the component (A), sufficient adhesive strength cannot be obtained by irradiation with low energy active energy rays, and the delayed curing property is inferior. Met. Similarly, when no glycidyl acrylate is used as the component (a1) or when no epoxy resin having at least two glycidyl groups in the molecule is used as the component (a2), the low energy active energy ray curability is similarly used. Or there is a problem in delayed curing. On the other hand, the curable resin composition of the present invention can give practically sufficient adhesive strength even when cured at low energy, either in a fluid paste form or a solid form at normal temperature, and also has an active energy ray. It is also possible to delay cure by adjusting the amount of heat applied after irradiation. In addition, the storage stability is good, and a cured product with little coloring can be obtained.

By using the curable resin composition of the present invention, it is possible to cure at low energy, and since the storage stability, coloring resistance of the cured product and delayed curing are good, general adhesion and sealing. It can be suitably used not only for stopping, casting, molding, painting and coating, but also for applications where adhesion to a light-shielding substrate and coloring of adhesive are problematic, for example, for bonding optical disks.

Claims (10)

A curable resin composition comprising the following components (A) to (B):
(A) 100 parts by weight of a mixture of a glycidyl (meth) acrylate compound (a1) and an epoxy resin (a2) having at least two glycidyl groups in the molecule, (B) a structure represented by the following general formula (I) 1 to 30 parts by weight of an amine imide compound having one or more in the molecule,

(R1 represents H or an alkyl group which may have a functional group or / and an aryl group. R2, R3 and R4 each independently represents an alkyl group which may have a functional group or / and Represents an aryl group.) The curable resin composition according to claim 1, wherein the (B) amine imide compound generates a base by irradiation with active energy rays and is used as a curing agent in the curable resin composition. The curable resin composition according to claim 1, wherein the curable resin composition further comprises (C) 0.01 to 10 parts by weight of a photoradical generator. The adhesive composition according to any one of claims 1 to 3, wherein the (a1) glycidyl (meth) acrylate compound has a phenol novolac type structure. The curable resin composition according to any one of claims 1 to 4, wherein the epoxy resin (a2) having at least two glycidyl groups in the molecule is a phenol novolac type epoxy resin. The curing according to any one of claims 1 to 5, wherein a mixing ratio of the (a1) glycidyl (meth) acrylate compound and (a2) an epoxy resin having at least two glycidyl groups in the molecule is 75:25 to 25:75. Resin composition The curable resin composition according to any one of claims 1 to 6, wherein the curable resin composition is in a solid form having no fluidity at room temperature and is in a liquefied fluid state at 50 ° C to 100 ° C. A curable resin composition according to claim 7, wherein the curable resin composition is cured by irradiating an active energy ray after heating to a temperature at which the curable resin composition is in a liquefied fluid state. After applying the curable resin composition according to any one of claims 1 to 7 on an adherend, the active energy ray is irradiated, and another adherend is applied on the curable resin composition irradiated with the active energy ray. Adhesion hardening method that overlaps and hardens without adding new energy. The adhesion hardening method whose another to-be-adhered body of the said Claim 9 is a light-shielding member.