TW201237048A - Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition - Google Patents

Abstract

To provide: a compound, which is suitable for a sealing agent for electronic components or the like, especially suitable for a liquid crystal sealing agent and does not easily generate out gas, and which can be used for a photopolymerization initiator that is photocurable within a visible range; a photopolymerization initiator which contains the compound; and a photocurable resin composition. (1) A compound, which is obtained by having an organic acid compound and/or a hydroxy compound react with a compound that contains at least two epoxy groups in each molecule, said compound being a compound A that is obtained using dimethyl amino benzoic acid as the organic acid compound or being a compound B that is obtained using hydroxythioxanthone as the hydroxy compound. (2) A photopolymerization initiator, which is composed of a photoinitiating compound and a visible light sensitizing compound, and wherein the photoinitiating compound is the compound A and the visible light sensitizing compound is the compound B. (3) A photocurable resin composition which contains a photopolymerizable monomer or oligomer and a photopolymerization initiator set forth in (2).

Description

201237048 VI. Description of the Invention: [Technical Field] The present invention relates to a compound obtained by reacting a specific organic acid compound and/or a hydroxy compound with an epoxy group-containing compound, and a photopolymerization initiator using the compound (photo polymerization initiator) and photohardening resin composite. [Prior Art] In recent years, liquid crystal display panels, which are lightweight, high-definition, and low-power, are widely used as large LCD TVs, mobile phones, and display panels for various devices. Produced by liquid crystal dispensing technique. The liquid crystal dropping technique is applied to a substrate to which an electrode pattern and an orientation film are applied, by applying a photo and thermal use hardening type liquid crystal sealant. Further, the substrate coated with the liquid crystal sealing agent or the liquid crystal is dropped on the pair of substrates, and the opposite substrate is bonded to the substrate, and the substrate is subjected to photo-deuteration by ultraviolet irradiation or the like as a first stage. The rapid fixation, that is, liquid crystal cell formation, is used as a second stage by thermal hardening using a moldless jig to completely harden the sealant, thereby manufacturing a liquid crystal display panel. Due to such a liquid crystal dropping technique, the uncured sealant is photohardened and thermally cured in contact with the liquid crystal in the state of -5 to 201237048, and the liquid crystal sealing agent is required to be hardened, that is, The reduction of contamination of the liquid crystal by the liquid crystal sealing agent before and after photohardening and before and after thermal hardening. Similarly, for a sealant such as a hermetic sealant for electronic parts, it is also required to achieve a reduction in contamination of the electronic parts by the sealant during the hardening process. Moreover, with the improvement of the performance of the liquid crystal panel in recent years, in the orientation direction, the type of the alignment film, and the liquid crystal material, the characteristics may change due to the influence of the ultraviolet light, and therefore it is desirable to have a small energy. a hardenable sealant in the visible light region. As a photocurable resin composition used in the field of electronic materials such as a liquid crystal sealing agent, Patent Document 1 discloses a photosensitive film containing a diaminobenzophenone derivative having a number average molecular weight of 400 to 3,000. Photo sensitizer, and a photoradical polymerization initiator having a number average molecular weight of 350 to 3000, and a specific monomer and/or monomer Photocurable resin composition. As a self-polymerization photopolymerizaton initiator for curing a coating or a printing ink, Patent Document 2 discloses a specific epoxy compound and thioxanthone. (thio xanthone) a reaction product formed by a carboxylic acid. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2004-224993 [Patent Document 2] JP-A-2004-224993 [Problems to be Solved by the Invention] However, the diaminobenzophenone derivative having a specific number of molecular weights as a photosensitizer disclosed in Document 1 has photosensitivity and degassing in the visible light region (out-gas) It is also difficult to occur, but since the functional group is derived from the amine group of the primary amine, storage stability may become unstable. Further, the main use of the self-polymerized photopolymerization initiator disclosed in Document 2 is a paint or a printing ink, and the degassing as a problem lies in an odor, and does not correspond to a liquid crystal seal. The high speed response affects the degree of contamination caused by degassing, dissolution of liquid crystals, and bleed of residual liquid. An object of the present invention is to provide a compound which is suitable for a sealing agent for an electronic component or the like, particularly a liquid crystal sealing agent, which is difficult to be degassed and which can be used as a photopolymerization initiator having photocurability in a visible light region, and contains the same. A photopolymerization initiator of the compound and a photocurable resin composition. [Means for Solving the Problem] The present invention has the following constitution. (1) A compound obtained by reacting an organic acid compound and/or a hydroxy compound with a compound having at least two epoxy groups in a molecule, wherein the compound is a compound, and the organic acid compound is a genus 201237048 The compound A of dimethylamino benzoic acid or the aforementioned hydroxy compound is a compound of the compound B belonging to the hydroxythioxanthone. (2) A photopolymerization initiator, which is a photopolymerization initiator formed from a photoinitiating compound and a visible light sensitization compound, and is characterized by: The compound is the compound A, and the visible light sensitizing compound is the compound B described above. (3) A photocurable resin composition comprising a photopolymerizable monomer or an oligomer and an optical polymerization initiator according to the above (2). [Effects of the Invention] According to the present invention, it is possible to provide a compound suitable for a sealing agent for an electronic component or the like, particularly a liquid crystal sealing agent, which is difficult to generate degassing and has a photocurable initiator in the visible light region. A photopolymerization initiator containing the compound and a photocurable resin composition. [Best Mode for the Invention] [Compound] The compound of the present invention is an organic acid compound and/or a hydroxy compound and a compound having at least two epoxy groups in the molecule (hereinafter, abbreviated as an epoxy group-containing compound). The compound obtained by the reaction is characterized by:

The organic acid compound is dimethylamino benzoic acid compound A -8 - 201237048, or the hydroxy compound is hydroxy thioxanthone compound B, and dimethylamino benzoic acid carboxyl group and hydroxy thioxanthone The hydroxyl group is reacted with an epoxy group of the epoxy group-containing compound to form a hydroxyl group. The compound of the present invention is a photopolymerization initiator for a sealant such as a liquid crystal sealing agent, and the compound A functions as a photoinitiating compound which is photoexcitation by a visible light sensitizing compound, and the compound B It functions as a visible light sensitizing compound. Here, the visible light sensitizing compound means a compound having a light absorption of visible light having a wavelength of 380 nm or more, preferably 400 nm or more, more preferably 420 nm or more, and a photoinitiating compound. It refers to a compound which does not have light absorption to the aforementioned visible light, but has a light absorption for ultraviolet light and a radical generating. Since the compounds A and B act as a photoinitiating compound or a visible light sensitizing compound in a photohardening reaction, the compound itself does not cleavate, and liquid crystal contamination does not occur due to volatilization of the decomposition product ( Liguid crystal contamination) Moreover, since the molecular weight of the compound itself is large and difficult to volatilize, liquid crystal contamination caused by the volatilization of the compound itself is also difficult to occur. Further, since the residue derived from the diamine benzoic acid constituting the compound A has an amine group derived from a tertiary amine and functions as a catalyst in a photocuring reaction, it is excellent in stability. Since compound B' is a so-called hydrogen-removing reaction type photoradical polymerization initiation 201237048 compound 'when absorbing active energy ray, the photo-radical polymerization initiator in the triplet excitation state will be A hydrogen donor forms a complex of an excited state, that is, an exciplex, and a hydrogen atom is taken from a hydrogen donor to form an active radical to initiate radical polymerization, and is decomposed into a hydrogen donor. There are few substances, and there is no degassing component. In addition, since the compounds A and B have an OH group in the molecule and have high polarity, they are usually in a phase with a photopolymerizable oligomer having a high polarity which is used for the photocurable resin composition. When the solubility is excellent, the solubility in the liquid crystal is low because of the difference in polarity of the liquid crystal material, and it is presumed that the liquid crystal has excellent contaminant properties. Compound A can be produced by reacting a diamine benzoic acid which is an organic acid compound itself with an epoxy group-containing compound, and Compound B, such as a hydroxy thioxanthone which is itself a hydroxy compound, and an epoxy group-containing compound The compound can be produced by carrying out a reaction. Specifically, the diamino benzoic acid or the hydroxythioxanthone and the epoxy group-containing compound are preferably in the presence of a basic catalyst from the viewpoint of reactivity, preferably 3 yuan as described later. In the presence of an organophosphorus compound and/or an amine compound, 1 equivalent of the epoxy group is reacted with 1 〇〇 equivalent % of the diamino benzoic acid or the hydroxy thioxanthone. Next, the reaction product is treated by filtration or centrifugation or water washing to remove the basic catalyst for purification. In the epoxy group-containing compound used in the production of the compounds A and B, the compound A can ensure the light-excited by the visible light sensitizing compound - 10, 201237048, and the visible light can be ensured from the compound B. In view of sensitization, it is a polyfunctional cyclic ester which contains at least two or more epoxy groups, and is preferably an aliphatic or aromatic bifunctional epoxy resin. The polyfunctional epoxy resin may be exemplified by trimethylolpropane polyglyceryl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether sorbitol polyglycidyl ether, and phenolic glycerol type glycerol Ether, phenolic glycidyl ether, tetraglycidyldiaminophenyltriglycidylaminophenol, etc., aliphatic bifunctional epoxy resin is polyethylene glycol diglycid, diethylene An alcohol diglycidyl ether, a triethylene glycol diglycidyl ether, a diol diglycidyl ether, a hexanediol diglycidyl ether or the like is preferred. The aromatic bifunctional epoxy resin is preferably exemplified by A-type diglycidyl ether, bisphenol F-glycidol, bisphenol AD glycidyl ether, and bisphenol-type diglycidyl ether. Among them, diethylene glycol diglycidyl ether represented by the following formula (5) and bisphenol A diglycidyl ether represented by the following formula (6) are more preferable. Viewpoint Oxygen tree shrinkage, cresylphenol, oil ether, polypropylene, bisphenol, diglycerol,

(5)

(6) 201237048 Compound A is more preferably a reaction of diamine benzoic acid with diethylene glycol diglycidyl ether from the viewpoint of stably ensuring the photoinitiation of light excited by a visible light sensitizing compound. The obtained formula can be expressed by the following formula (1): [Chemical 2]

The compound A1 represented by or the reaction of diamine benzoic acid with bisphenol A diglycidyl ether can be obtained by the following formula (2):

Represents compound A2. From the viewpoint of stably ensuring visible light sensitivity, the compound B, more preferably the reaction of the hydroxythioxanthone with the diethylene glycol diglycidyl ether, can be obtained by the following formula (3): -12- 201237048 4]

The compound B1 represented by the reaction, or the reaction of the hydroxythioxanthone with the bisphenol A diglycidyl ether, can be obtained by the following formula (4) = [Chemical 5]

Represents compound B2. [Photopolymerization initiator] The photopolymerization initiator of the present invention is a photopolymerization initiator containing a photoinitiating compound and a visible light sensitizing compound, characterized in that the photoinitiating compound is Compound A, and / Or the visible light sensitizing compound is Compound B. Thus, since the photopolymerization initiator of the present invention is a result of using either Compound A or Compound B as at least one of a photoinitiating compound and a visible light sensitizing compound, it can be reduced compared with the existing photopolymerization initiator. Degassing-13 - 201237048 Therefore, a suitable photocurable resin composition can be formed as a sealant. Among the photopolymerization initiators of the present invention, preferred compounds A and B are preferred from the above-mentioned compounds A and B. In the photopolymerization initiator of the present invention, when Compound A is used as a photoinitiating compound, as the visible light sensitizing compound, an alkyldiamine benzophenone or a diamine group can be used. Benzophenone, alkylamine benzoate, bacteria, thioxanthone, coumerin, ketocoumarin, cyanine, phthalocyanine, naphthalocyanine From the viewpoint of the efficiency of the reactivity by energy transfer, the benzophenone skeleton and/or the thioxanthone skeleton are preferred, and the thioxanthone skeleton is more preferred, and the compound B is preferably used. In the photopolymerization initiator of the present invention, as the visible light sensitizing compound, when the compound B is used, as the photoinitiating compound, a self-cleavage benzoin can be used. (benzoin) compound, acetophenone benzene, hydroxyacetamidine benzene, α-aminoethyl benzene benzene, α-mercapto oxime ester, fluorenyl phosphine oxide compound, azo group, etc., hydrogen abstraction Benzophenones, benzoin ethers, benzyl ketals Classes, dibenzocycloheptanones, onion ketones, xanthones, thioxanthones, halogenated acetophenones, dialkoxybenzenes, hydroxyacetamidines, halogenated bisimidazoles Class, halogen triterpenoids, etc. The photoinitiating compound is preferably a hydrogen absorbing type from the viewpoint of controlling liquid crystal contamination due to degassing, and more preferably benzophenone-14-201237048, onion ketone, thiophene The ketones are preferably thioxanthone, and the number average molecular weight is preferably from 50,000 to 3,000. Further preferably, Compound A is used as a photoinitiating compound. In the photopolymerization initiator of the present invention, the molar ratio (photoinitiating compound/visible sensitizing compound) of the photoinitiating compound to the visible light sensitizing compound is from the viewpoint of being stable and supplying sufficient radicals. In view of the above, it is preferably from 1/5 to 1/1, more preferably from 1/3 to 1/1, still more preferably from 1/2 to 1/1 [Photocurable resin composition] Photocurable resin of the present invention The composition contains a photopolymerizable monomer or oligomer and a photopolymerization initiator of the present invention. As the photopolymerizable monomer or oligomer, a known material can be used, but from the viewpoint of suppressing the contamination caused by the dissolution of the liquid crystal, it is preferred to use a (meth) acrylate monomer and/or the like. The oligomer and a part of the (meth)acrylylated epoxy resin obtained by reacting the bisphenol A type epoxy resin with (meth)acrylic acid, more preferably: the bisphenol A type epoxy resin and the (methyl group) A part of the (meth)acrylylated epoxy resin obtained by the reaction of acrylic acid. The (meth) acrylate monomer and/or the oligomers are preferably 2-hydroxyethyl (meth) acrylate, di, tri or tetraethylene glycol di(methyl) decene. Acid ester, epoxy-modified di(meth)acrylate, urethane-modified di(meth)acrylate, more preferably: epoxy-modified di(meth)acrylate, amine group Formate-15-201237048 Modified di(meth)acrylate, again preferably: epoxy-modified di(meth)acrylate. A part of the (meth)acrylylated epoxy resin obtained by reacting a bisphenol A type epoxy resin with (meth)acrylic acid can be obtained by the following method. First, a bisphenol A type epoxy resin is used. (Meth)acrylic acid, in the presence of a basic catalyst, preferably in the presence of a 3-membered organic phosphoric acid compound and/or an amine compound, 1 equivalent to an epoxy group, and 10 to 90 (meth)acrylic acid The equivalent % is reacted. Then, the reaction product is refined by filtration, centrifugation, and/or washing to remove the basic catalyst. As the basic catalyst, a well-known basic catalyst used for the reaction of an epoxy resin with (meth)acrylic acid can be used. Further, a basic catalyst supported on a polymer which is supported by a basic catalyst in a polymer may also be used. The trivalent organic phosphorus compound may, for example, be an alkylphosphine such as trimethylphosphine, tri-n-propylphosphine or tri-n-butylphosphine, or a salt thereof, such as triphenylphosphine or n-tolylylene. Arylphosphines such as phosphine, ginseng (2,6-dimethoxyphenyl)phosphine, and salts thereof, such as triphenylphosphite, triethylphosphite, and decylphenylphosphite Examples of the salts of the tribasic organic compound such as a phosphite triester or a salt thereof include triphenylphosphine ethyl bromide, triphenylphosphine butyl bromide, and triphenylphosphine. , octyl bromide, triphenylphosphine decyl bromide, triphenylphosphine isobutyl bromide, triphenylphosphine propyl chloride, triphenylphosphine pentyl chloride, triphenyl Phosphine·hexyl bromide and the like. Among them, triphenylphosphine is preferred. -16- 201237048 The amine compound may, for example, be a secondary amine such as diethanolamine, such as triethylamine, triethanolamine, dimethylbenzylamine, dimethylaminomethylphenol, or the like. a tertiary amine such as ethylaminomethylphenol, such as 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD), 7-methyl·1,5,7-three Azabicyclo[4.4.0]non-5-ene (1\^-78〇), 1,8-diazabicyclo[5.4.0]undecyl-7-ene (DBU), 6-diyl Amino-1,8-diazabicyclo[5.4.0]undecyl-7-ene, 1,5-diazabicyclo[4.3.0]nonyl-5-ene (DBN), 1,1, Strongly basic amines such as 3,3_tetramethylguanidine and salts thereof. Among them, preferred is 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD). The salt of the amine compound may, for example, be benzyltrimethylammonium chloride or benzyltriethylammonium chloride. The photopolymerizable monomer or the photocurable resin composition of the present invention is low in the ease of handling of the resin composition, that is, the viscosity of the defoaming property, the coating property, and the printability. The content of the polymer is preferably from 50 to 90% by weight, more preferably from 60 to 80% by weight, still more preferably from 70 to 80% by weight. The light of the present invention is obtained from the viewpoint of reducing the residual of the uncured portion of the photopolymerizable monomer or the oligomer to suppress the contamination of the liquid crystal, and also the influence of the contamination caused by the dissolution of the photoinitiator component of the liquid crystal. The polymerization initiator is used in an amount of preferably 0.5 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, per 100 parts by weight of the photopolymerizable monomer or oligomer. When the photocurable resin composition containing the photopolymerization initiator of the present invention is used as a sealant, particularly a liquid crystal sealing agent, it is possible to greatly reduce the devitrification, even if it is difficult to damage the liquid crystal or the alignment film. The photocurable resin can still be cured. -17-201237048 On the other hand, in recent years, the "densification of wiring of electronic components" has occurred in particular in the field of liquid crystals using 〇 DF (liquid crystal dropping) technology. The ODF technique refers to the technique of fabricating a liquid crystal panel by directly performing direct dropping, laminating, and vacuum opening of a liquid crystal in a closed loop of a sealant under vacuum, and adopting an injection method in use. In the manufacturing method, there are many advantages such as a decrease in the amount of use of the liquid crystal and a shortening of the injection time of the liquid crystal to the panel, and it is a technique that is mainly used as a method of manufacturing a liquid crystal panel using a large-sized substrate. The liquid crystal substrate produced by the 0DF technique is composed of a resin which simultaneously holds a (meth)acryl group which is a photocurable functional group and an epoxy group which is a thermosetting functional group, and is bonded after the liquid crystal is dropped. And irradiate ultraviolet rays to make them pseudo-hardened, and then heat-harden them. In this case, when the reaction of the (meth)acryl group by ultraviolet irradiation is insufficient, or the shadow of wiring or the like is not applied to the ultraviolet ray, the liquid crystal sealing agent component flows out of the liquid crystal during thermal curing, and as a result, It becomes the cause of display failure. In recent years, as described above, in the case of increasing the light hardening using visible light having a weaker ultraviolet light, the higher the density of the wiring, the more difficult the ultraviolet light is to be irradiated, and the above-mentioned new subject Gradually become more prominent. Since the photocurable resin composition of the present invention contains the photopolymerization initiator of the present invention, even if it is the above-mentioned problem, it can be cured not only in visible light but also in low-intensity ultraviolet rays. The shadow part -18- 201237048 points will still harden, and the page can be solved for the above problems. In the photocurable resin composition of the present invention, in order to solve the above-mentioned new problems at a high level, it is preferred to further contain a thermosetting agent. The thermal hardener is preferably selected from a mixed crystal hydrazide compound or an organic acid diterpene compound from the viewpoint of rapid curing speed and good viscosity stability even at a low temperature. At least one compound, preferably a ruthenium mixed crystal compound and/or an organic acid group, in which imidazole and its derivatives, dicy and i amide, aromatic amine, aliphatic amine and derivatives thereof are grouped. The ruthenium compound is preferably a ruthenium mixed crystal compound. The lanthanide mixed crystal compound means a compound which can meet the following requirements (I) and (Π). (I) It is necessary to heat-melt two or more kinds of crystalline cerium compounds having at least one fluorenyl group in one molecule to obtain a heated melt, and then to cool the molten melt to solidify it. And the compound obtained. (Π) Needed for the use of the above compound CuK (potassium ketone) 〇: X-ray diffraction spectrum of the line, at the Bleuger angle (8^§丫31^1〇(20 ±〇.20.) 5.5° to 7.5°, having a diffraction peak characteristic of a mixed crystal. Among the above compounds, the ruthenium compound having a mercapto group preferably contains 5 to 70% by weight, more preferably It is preferably from 5 to 50% by weight, more preferably from 5 to 30% by weight, still more preferably from 10 to 20% by weight. The lanthanide mixed crystal compound can be composed of a -19 compound containing a crystalline ruthenium compound. - 201237048 Two or more processes of heating and melting above the melting point and mixing, and a process of cooling the mixture to solidify it. In the present invention, from the viewpoints of melting point, thermal reactivity, and storage stability, The crystalline ruthenium compound to be a raw material is preferably selected from the general formula (1):

X

R NHNH2 [wherein R represents a hydrogen atom, an alkyl group, or an aryl group which may have a substituent]. The monoterpene compound represented by the formula (2): [Chemical Formula 7] h2nhn nhnh2 (2) [wherein A ' represents an alkylene group which may have a substituent, an aryl group or an oxy group which may have a substituent]. The two or more compounds represented by the diterpenoid compounds are preferably the anthracene compounds disclosed in paragraphs 0020 and 002 of JP-A-2010-143872. In the present invention, 'the crystalline ruthenium compound used as a raw material of the lanthanoid mixed crystal compound' is preferably at least one type from the viewpoint of melting point, thermal reactivity, and storage stability. The bismuth dibasic acid diterpene, and the bismuth compound combined with the binary diterpene, -20-201237048 is a polyfunctional hydrazine such as a monoterpene and/or a tribasic acid triterpene. The hydrazine compound is more preferably a dibasic acid diterpenoid having two or more hydrazine compounds. The dibasic acid dioxime is preferably selected from the group consisting of dioxonium oxalate, diammonium malonate, diterpene succinate, diammonium adipate, diammonium pimelate, and suberic acid. Bismuth, bismuth azelaic acid, bismuth azelaic acid, bismuth laurate, hexadecandioic acid diterpene, bismuth citrate, diterpene bismuth, carben Carbo hydrazide), diterpene maleate, diammonium fumarate, diammonium diglycolate, diterpenic tartrate, diterpene malate, diammonium 2,6-naphthoic acid, 1,4 - Di-naphthoic acid, 4,4'-bisbenzodiazepine, hydroquinone diglycolate diterpene, resorcinol diglycol diacetate, catechol diglycolate II醯肼, 4,4'-ethylene bisphenol-diglycolic acid diterpene, 4,4' vinylidene bisphenol-diglycolic acid diterpene in a group of more than one compound, Preferably, it is selected from the group consisting of dioxonium oxalate, diammonium malonate, diterpene succinate, diammonium adipate, diupoleic acid, diterpene dipicate, diterpene sebacate, Diterpene sebacate, diammonium laurate, dihexadecane diacetate, hydrazine Acyl hydrazine two, or more kinds of terephthalic acid compound acyl groups of the hydrazine. The monoterpene compound is preferably selected from the group consisting of acetamidine, bismuth propionate, bismuth valerate, lauric acid laurate, cyclohexane hydrazine, hydrazine salicylate, hydrazine hydroxybenzoate, More than one compound of the group consisting of cerium naphthoate > more preferably selected from the group consisting of acetamidine, strontium propionate, bismuth valerate, bismuth laurate-21 - 201237048 hydrazine, cyclohexane carbaryl, water Among the compounds of the above-mentioned group, the combination of dibasic acid diterpene is preferably diammonium adipate and diterpene sebacate, diammonium adipate. A combination with an oxadione dioxime, azelaic acid dioxime and an oxadione dioxime. In the photocurable resin composition of the present invention, the content of the thermosetting agent is such that the photopolymerizable monomer or oligomer is one from the viewpoint of having sufficient thermal reactivity and maintaining storage stability. The parts by weight are preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight. The photocurable resin composition of the present invention preferably contains a coupling agent such as a filler particle or a silan coupling agent from the viewpoint of the latter, and may contain the present invention as needed. Suitable photopolymerizable monomers or oligomers, hardeners other than thermosetting agents, initiators other than photopolymerization initiators suitable for use in the present invention, elastomers, chain transfer agents An agent, an ion trap agent, an ion exchanger, a leveling agent, an additive for a pigment, a dye, a plasticizer, an antifoaming agent, and the like. The binder particles are added for the purpose of controlling the viscosity of the curable composition, improving the strength of the cured product which hardens the hardenable composition, or suppressing the linear expansion property to improve the adhesion reliability of the curable composition. . The particle for the coating material is preferably used as the inorganic particle for the coating and/or the organic resin particle for the coating, but the linear expansion coefficient is small, and the adhesion strength is lowered to lower the curing shrinkage ratio. Inorganic particles are used. -22-201237048 The inorganic particles for use as a raw material are preferably selected from the group consisting of calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum niobate, and titanium oxide from the viewpoint of easily obtaining a particle size suitable for use as a sealant. At least one of a group of alumina, zinc oxide, cerium oxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and tantalum nitride The above inorganic particles are more preferably at least one inorganic particle selected from the group consisting of ceria, talc, alumina, and bentonite, more preferably ceria and/or talc, and even more preferably dioxide. Hey. The organic resin particles for dip is preferably selected from the group consisting of polymethacrylate and polystyrene from the viewpoint of the effect of adding adhesive strength due to stress relaxation during curing. a copolymer obtained by copolymerizing monomers constituting these monomers with other monomers, polyester fine particles, polyurethane fine particles, rubber fine particles, and an outer shell containing a copolymer having a high glass transition temperature At least one or more kinds of organic resin particles of a core-shell type fine particle composed of a core having a copolymer having a low glass transition temperature, more preferably selected from the group consisting of polyester particles and polyamines At least one of a group of fine particles composed of a urethane fine particle, a rubber fine particle, and a core-shaped fine particle composed of a core containing a copolymer having a high glass transition temperature and a core having a low glass transition temperature The above organic resin particles are more preferably core-shaped fine particles composed of a core body containing a copolymer having a copolymer having a high glass transition temperature and a core having a copolymer having a low glass transition temperature. Further, the core-shell type fine particles are preferably a copolymer-based polymethacrylic acid having a high glass transition temperature and a copolymer-based butyl acrylate having a low glass transition temperature. In the photocurable resin composition of the present invention, the content of the inorganic particles for the coating is improved from the improvement in the adhesion by the stress dispersion effect and the improvement in the linear expansion ratio. It is preferably from 2 to 40 parts by weight, more preferably from 5 to 30 parts by weight, per 100 parts by weight of the photopolymerizable monomer or oligomer. When the thermosetting resin composition of the present invention is used as a liquid crystal sealing agent, the decane coupling agent is suitable as an adhesion promoter for adhering a liquid crystal sealing agent to a liquid crystal display panel. The decane coupling agent is preferably selected from the group consisting of (7-aminopropyltrimethoxysilane, r-mercaptopropyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, r-isocyanatepropyltrimethyl) More preferably, one or more compounds of the group consisting of oxoxane are r-glycidoxypropyltrimethoxy decane. In the photocurable resin composition of the present invention, the content of the coupling agent is from the adhesion strength 'especially From the viewpoint of maintaining moisture proof strength, 100 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 2 parts by weight, of the photopolymerizable monomer or oligomer. [Examples] [Example 1] Synthesis of Compound A1 was synthesized by Naikel EX-8 50 L (diethylene glycol diglycidyl ether, manufactured by Nagase Chemical Technology Co., Ltd.) 13.7 g, 4-di Methylamino benzoic acid i4 8g, PS-PPh3 (polystyrene (PS) containing triphenylphosphine (pph3) base-24-201237048 sexual catalyst, biotechnology Taji company) 9〇〇 Mg, toluene 200 ml, and stirred at 110 ° C for 48 hours. After cooling the reaction mixture to room temperature, the catalyst was removed by filtration. After the solvent was distilled off under reduced pressure, the amine-added product of the product was obtained by HPLC (high-performance liquid chromatography), and it was confirmed that the content of the target component was 70% or more. Example 2] Synthesis of Compound A2 Mixed eppylon EXA- 85 0CRP (bisphenol A diglycidic acid, DIC (manufactured by DIC)) 1.70 g, 4-dimethylamino benzoic acid 1.57 g, PS-PPh3 (raw 50 mg of toluene and 20 ml of toluene were stirred at 11 ° C for 48 hours. After cooling the reaction mixture to room temperature, the catalyst was removed by filtration. The solvent was distilled off under reduced pressure to obtain a solvent. The amine adduct of EBClEX EXC-8 50CRP. The result of the identification by HPLC was confirmed to contain the fact that the target component was 70% or more. [Example 3] Synthesis of compound b 1 was synthesized to obtain Nikel EX-8 5 0L (diethylene glycol diglycidyl ether, Changchun Chemical Technology Co., Ltd.) 13.7g, thiol-containing bacteria _ 14.8g, -25- 201237048 ?8-?? 113 (made by Biotech Taji) 90〇1^, toluene 200ml' and stirred at 110 ° C for 48 hours. After cooling the reaction mixture to room temperature, the catalyst was removed by filtration. After the solvent was distilled off under reduced pressure, the amine adduct of the product was obtained by HPLC. The result of the identification by HPLC was confirmed to contain the fact that the target component was 60% or more. [Example 4] Compound B2 Synthetic mixed eppylon EXA-850CRP (bisphenol A diglycidyl ether, DIC (manufactured by DIC)) 1.70 g, 2-hydroxythiazolin-10-one 2.17 g, PS-PPh3 (manufactured by Biotech Taji) ) 100mg, ?5-butyl 8〇 (?5 uploading 1,5,7-triazabicyclo[4.4.0]癸-5-ene solid catalyst for alkaline catalyst, biotechnology Taji 100 mg of toluene, 20 ml of toluene, and stirred at 110 ° C for 48 hours. After the reaction mixture was cooled to room temperature, the catalyst was removed by filtration. After the solvent was distilled off under reduced pressure, a thioglycol adduct of EXA-8 50 CRP was obtained. The result of the identification by HPLC was confirmed to contain the target component of 60 ° /. The above facts. (a) Synthesis of a photopolymerizable oligomer (PR85 0CRP: a partially methacrylylated epoxy resin of a bisphenol A type epoxy resin) mixed with a bisphenol A type epoxy resin (EXA850CRP, DIC) -26-201237048 ) 320.2 g, 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.5 g of PS-PPh3 (manufactured by Biotech Taji), and 100 mg of BHT, and stirred at 100 ° C for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain a partially methylenylated epoxy resin. (b) Photopolymerization initiator decomposition type (visible light curing type): Igya, I-369 (manufactured by BASF Japan) Decomposition type (type containing reactive group): EY resin, KR-2 (iC. (c) Thermosetting agent (anthraquinone mixed crystal compound) ADH: Diterpene adipate (manufactured by Otsuka Chemical Co., Ltd.) C3: Mixed crystal heat curing agent (manufactured by Kyoritsu Chemical Industry Co., Ltd.) VDH: Diisopropyl acetoin skeleton (manufactured by Ajinomoto Precision Technology Co., Ltd.) (d) Resin pigment: Meribrion, J-5800 (manufactured by Mitsubishi Rayon Co., Ltd.) (e) Inorganic beverage : cerium oxide (Western Star, KE-C50HG, manufactured by Nippon Shokubai Co., Ltd., 〇.5μηι) (f) Coupling agent: ΚΒΜ403 (manufactured by Shin-Etsu Chemical Co., Ltd.) [Example 5] Photopolymerizable oligomer PR-8 5 0 CRP 100 parts by weight (10 μg), photopolymerization obtained by dissolving 1 part by weight of the photoinitiating compound A 1 and 1 part by weight of visible light sensitizing -27-201237048 B1 Starting agent. Then, 1 part by weight of the mixed coupling agent, 1 part by weight of the inorganic material, and 15 parts by weight of the heat curing agent were used, and a three-roll mill (lepton size: Φ 121 x 250 mm 'manufactured by Inoue Co., Ltd.) was used. The kneaded resin composition was obtained by sufficiently kneading in a manner of a pressure of 5 M Pa (megapascal) or 2 passes. [Examples 6, 7 and Comparative Examples 1 to 3] According to the same conditions as in Example 5, and mixing according to the blending compositions of Examples 6, 7 and Comparative Examples 1 to 3 shown in Table 1, a three-roll type was used. After the mill was sufficiently kneaded, each resin composition was obtained.

In Comparative Example 3, Baye II was used as a photoinitiating compound, and EHA (product name: DAR0CURE EHA 'component name: 2-ethylhexyl-4-(dimethylamino) benzoate, manufactured by BASF Corporation) was used. As the photosensitive compound, DETX (product name: photo cure DETX, component name: 2,4-diethylthiaxanthone, manufactured by EUTEC Chemical Co., Ltd.) was used. [Example 8] In 100 parts by weight (1 g) of the photopolymerizable oligomer PR-850CRP, 1 part by weight of the photoinitiating compound A1 and 1 part by weight of the visible light sensitizing compound B1 were dissolved. The photopolymerization initiator ^ is then mixed with 1 part by weight of the coupling agent, 1 part by weight of the organic material, 5 parts by weight of the -28-201237048 inorganic material, and 15 parts by weight of the heat curing agent, using a three-roll mill ( Roller size: Φ 1 2 1 X 250 mm, manufactured by Inoue Co., Ltd.), and kneaded with a pressure of 5 MPa and 2 passes, and a curable resin composition was obtained. [Examples 9 to 12 and Reference Example 1] The same conditions as in Example 8 were carried out, and according to the mixing compositions of Examples 9 to 12 and Table 1 shown in Table 2, a three-roll mill was used. After sufficiently kneading, each photocurable resin composition was obtained. [Evaluation conditions] (1) Weight loss on heating Using differential solar 1 (therma 1 ba I auce) (T G-DTA, product name: thermo plas TG8120, manufactured by Rigaku Corporation The weighted photoinitiator was placed in an aluminum pan and the ratio of the amount of decrease was raised to 300 ° C at a heating rate of 10 ° C / min. A larger amount of reduction means that it is easy to be volatilized and volatilized. If the amount of volatilization is large, the liquid crystal will be contaminated, and as a result, the display may be poor. (2) Reaction rate The photocurable resin composition is as follows: - using a glass of 25 mm x 25 mm thickness 〇 7 mm for LCD (liquid crystal display), and the other side using 25 mm x 25 mm thickness of 0.1 mm PET (polyparaphenyl -29-201237048 II) The film of the ethylene glycol formate film, the thickness of the photocurable resin composition can be clamped in a manner of 〇5 mm, using an ultraviolet irradiation device (UVX-0 1 224S 1, Wuxi Ou electric mechanism), according to l〇〇mW/ The ultraviolet illuminance of cm2 is irradiated with light energy of 200 to 3000 mJ/cm 2 as a sample for measurement of curability. At this time, ultraviolet rays and a heat-ray cutting filter are used to irradiate (i) ultraviolet light and visible light having a wavelength of 340 nm to 450 nm and a wavelength of 420 nm to 450 nm. The measurement of the hardening rate was carried out by FT-IR (Fourier Transform Infrared Spectrometer) (Spectrum One, manufactured by Goldman Co., Ltd.), and the peak area of the (meth)acryl group of the obtained IR (infrared) spectrum was calculated. Reaction rate (conversion ratio) of (meth) propylene group. The calculation of the reaction rate is based on the decrease in the area of the (meth)acryl-based absorption of 1GSOcnr1 (or 945 cm-), and the calculation of the area of the double bond of the benzene ring of 1,500 CHT1. (3) The amount of degassing was measured by a TG-DTA (thermogravimetric analysis-differential thermal analysis method) (manufactured by Rigaku Corporation) to measure the amount of degassing at 120 ° C for x 60 minutes and to carry out the amount of volatile components from the sealant. In the case of the case where the amount of the volatile component is 1.5% or less, "X" is obtained when the amount of the volatile component is 1.5% or more. -30- 201237048 (4) Contaminant photocurable resin composition, with a sealant dispenser, attached to the rubbing treatment with a cross-sectional area of 4000 μm 2 (canibing treatment) A dispensing coating was applied to an ITO (Golden Tin Oxide) glass substrate (60 mm x 70 mm x 0.7 mm thick) of SE-7940 and manufactured by Nissan Chemical Industries, Ltd.). Then, liquid crystal (TN (twisted nematic) liquid crystal, MLC-1 1 900-080, manufactured by Melco) was dropped on the substrate, and the upper and lower substrates were bonded together by a liquid crystal dropping technique (ODF technique) to prepare a test. Use a liquid crystal film. The test liquid crystal cell was irradiated with ultraviolet rays (UV irradiation device: UVX-0 1 224 S1, manufactured by Wuxiou Electric Co., Ltd., illuminance: 200 mJ: 100 mW/cm 2 / 2 sec at 3 65 nm) to harden it, and then, 12 (The hot air oven of TC was thermally hardened for 1 hour to prepare a test cured liquid crystal sheet for the orientation test. The obtained cured liquid crystal sheet for test was used to confirm the orientation state of the liquid crystal during sealing. The confirmation operation was performed using an optical microscope, and the polarizing plate was sandwiched between test cells according to the state of Cross Nicol, and observed by transmission. The orientation state of the corner portion of the test cured sheet was indicated. The photomicrograph 'is shown in Figs. 1 to 6. Fig. 1 to Fig. 6 are the dimensions of the longitudinal direction of 900 μm χ lateral direction of 1 00 μm. The evaluation criteria of the directionality of the liquid crystal are based on the orientation at the time of sealing. Preface -31 - 201237048 If there is any judgment, the orientation disorder will be less than 50μηι, and it will be made into "〇". If there is more than the above orientation disorder, create "X". (5) Stability Determination When the viscosity of the curable resin composition changes at room temperature (25 ° C), the viscosity after 5 days is changed to 20% or less, and the viscosity after 5 曰 is changed to 20% or more. It is judged by the "X". The viscosity is measured by thermostatically treating the photocurable resin composition to 25 t, and attaching it to the RE-105 U-type viscometer (Dongji Industry Machinery Co., Ltd.). The xR7.7 cone rotor was placed in a conical rotor to measure the viscosity of the photocurable resin composition at 25 ° C at 2.5 rpm. The photocurable resin composition immediately after the measurement was allowed to stand at 25 ° C for 5 days, and the viscosity of the photocurable resin composition after 5 days was measured by the above method. The viscosity immediately after the composition is prepared as the initial viscosity -32 - 201237048. The rate of change from the initial viscosity is calculated, and if the evaluation of the stability is exceeded, for example, if the measurement range is exceeded, the measurement cannot be performed. Benchmark, l, 200, (6) Thermosetting property The photocurable resin composition to be measured is a viscosity of a rotary rheometer (flow stress 300, manufactured by Haake Co., Ltd.). After the hardening is started, the saturated viscosity is reached within 60 minutes, and the "0.00" is reached, and the saturated viscosity is reached within 1 to 20 minutes to make "〇", and the saturated viscosity cannot be reached even if it is more than 20 minutes. Judging by the way of making X X. In the photocurable resin composition to be measured, a rotary rheometer (flow stress 300, manufactured by Haake Co., Ltd.) was used to measure the viscosity change at 120 °C. Use parallel plate (Parallel Plate) 'test sample volume 〇.6g' panel gap (gap) lmm, strain control mode, and temperature conditions from room temperature to 120 ° C stop at 20 ° C / min The temperature was raised and the measurement was carried out for 120 minutes while maintaining 12 CTC. The time required to reach the viscosity (saturated viscosity) at which no viscosity changes are reached. (7) Electrical characteristics -33- 201237048 An ampoule test was carried out by means of a sealant to measure and maintain the voltage holding ratio (VHR) and ion density (ID). [Preparation of the sample for measurement] The photocurable resin composition 〇.lg was placed in an ampoule bottle, and TN liquid crystal (MLC-11900-080, manufactured by Milk Co., Ltd.) was added. Place the ampoule in 12 (TC for 1 hour, then let it stand at room temperature. After returning to room temperature (25 °C), take out the liquid crystal part and filter it with a 0.2 μηι filter for electrical evaluation. Liquid crystal sample [Measurement of voltage holding ratio and ion density] A liquid crystal sample for evaluation of electrical characteristics was used to produce a sheet for evaluation of electrical characteristics. The method for producing a sheet was subjected to honing treatment with orientation for liquid crystal. On the ιτο glass substrate (55mm x 60mm x 0.7mmt (thickness)) of the film (Caneifa SE-7492, manufactured by Nissan Chemical Industries, Ltd.), a commercially available sealant (Walterok No. 717, manufactured by Kyoritsu Chemical Industry Co., Ltd.) As a frame sealant, a liquid crystal sample for electrical property evaluation is dropped on a substrate, and is bonded by a liquid crystal dropping technique (0 DF technique), and irradiated with ultraviolet rays (u V irradiation device: UVX-0 1 224S1) Wuxiou Electric Co., Ltd., illuminance and irradiation time: 30 seconds at 3000mJ, 100mW/cm2/365mm) to harden it's then heat-hardened in a hot air oven at 120 °C for 1 hour to make electrical Characteristic evaluation The liquid crystal film for the test was measured by a liquid crystal physical property evaluation device (6254C, manufactured by Toyo Kaikeki Co., Ltd.). The applied voltage was measured at 5 V, 6 Hz (-34 - 201237048 Hz), and 1 The voltage holding ratio at 6 msec (milliseconds) is measured at 50 °c. The evaluation criteria for the voltage characteristics are based on the voltage holding ratio, and the voltage holding ratio is 9 8 %. In the above case, "X" is created in the case where the voltage holding ratio is 98% or less. (8) The orientation of the wiring portion is mixed by the mixing example shown in Table 2, and three rolls are used. A mill (roller size: φ 121 x 2 50 mm, manufactured by Inoue Seisakusho Co., Ltd.) was sufficiently kneaded by a pressure of 5 MPa and 2 rolls to obtain each photocurable resin composition (Examples 8 to 12). And Reference Example 1). The photocurable resin composition thus obtained was subjected to a honing treatment with an orientation film at a cross-sectional area of 4000 μm 2 using a sealant quantitative dispenser (Canei SE-5 662, Nissan Chemical Co., Ltd.) Industrial Co., Ltd.) with wiring pattern (using Cr (chromium) Quantitative distribution coating on a glass substrate (line/space: 200 μm / 200 μm) (60 mm x 70 mm x 0.7 mmt (thickness)). Then, liquid crystal VA (vertical alignment) liquid crystal, MLC-6609, and beauty were dropped on the substrate. The panel gap was set to 4 μm, and the film was bonded by a liquid crystal dropping technique (ODF technique) to prepare a test liquid crystal cell. The test liquid crystal film was irradiated with ultraviolet rays (UV irradiation device: UVX-01 224S1, manufactured by Wusei Electric Co., Ltd., illuminance and irradiation time: 3 000 mJ, 100 mW/cm 2 / 3 65 nm for 10 seconds) to harden it, and then The glass was thermally hardened in a hot air oven at 120 ° C for 1 hour to prepare a test hardened liquid crystal for use in the orientation test -35-201237048. In the obtained cured liquid crystal sheet for test, the orientation state of the liquid crystal at the time of sealing between wirings was confirmed. The confirmation operation was carried out under the optical micromirror, and the polarizing plate was sandwiched between the test pieces in the state of the Nikon, and observed by transmission. A micrograph showing the orientation state of the wiring portion of the hardened liquid crystal cell for test is shown in Figs. 7 to 9. Here, the 7th to 9th drawings are all dimensions of the longitudinal direction 900μηι χ lateral 1200μηι. The evaluation criteria of the directivity of the liquid crystal are judged by the presence or absence of the orientation disorder at the time of sealing. When the sealing disorder is performed under the condition of 20 μηι or less, the result is "^", and the orientation disorder is more than the above, and "X" is created. -36-201237048 [Table 1] % heating loss Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Oligomer (PR-MOCRP) 100 100 100 100 100 100 Photopolymerization initiator Compound A 1 4 1 2 Compound B 1 3 1 2 Photoinitiating compound (D ET X) 35 1 Photosensitive compound (EH A) 81 1 Photopolymerization initiator Compound A 2 3 1 Compound B 2 1 1 Photopolymerization initiation Agent (Bu 369) 25 1 Photopolymerization initiator (KR-2) 28 4 Thermal hardener (ADH) 15 15 15 15 15 15 Inorganic tantalum (cerium oxide) 10 10 10 10 10 10 Coupler (KBM403) 1 1 1 1 1 1 340mm filter reaction rate 200mj 60 70 65 72 38 73 340mni filter reaction rate 2000mj 90 92 87 76 72 90 420_ filter reaction rate 200mj 42 48 43 39 0 45 420_Filter Reactor reaction rate 2000mj 81 85 85 72 0 86 Degassing amount 〇〇〇X 〇X Contaminant 〇〇〇XX 〇-37- 201237048

[Table 2] Heat reduction % Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Oligomer (PR-850 CRP) 100 100 100 100 100 100 Photopolymerization initiator compound Α1 4 1 2 1 1 1 Compound Β 1 3 1 2 1 1 1 1 ▲ 呼胡泡1 Compound Α 2 3 1 Compound Β 2 1 1 Photopolymerization initiator (KR-2) 28 Thermal hardener (C3) 15 15 15 Thermal hardener (ADH 15 Thermal Hardener (VDH) 20 Resin Dip (W-5800) 10 10 10 10 10 10 Inorganic (cerium oxide) 5 5 5 5 5 5 Coupler (ΚΒ_3) 1 1 1 1 1 1 Stability〇 〇〇〇X 〇Hot hardening ◎ ◎ ◎ 〇〇X Electrical characteristics UV 〇〇〇〇〇〇 Electrical characteristics UV flawless XXX Wiring orientation 〇〇〇 directionality (no wiring) 0 〇〇〇〇 X From the above results (Table 1), it was found that when a 3 40 nm filter was used (general process conditions), in the examples, no orientation failure occurred at 200 mj (mJ) and 2000 mj. The situation. On the other hand, in Comparative Example 1 and Comparative Example 2, the orientation failure occurred in any of the conditions. It has also been found that when a 42 Onm filter is used (the manufacturing conditions of a special liquid crystal panel are likely to become mainstream in the future), in Comparative Example 2 which is a conventional photoinitiator, the sealant is hardened. The fact that the reliability of the liquid crystal panel is not problemd. From the above facts, the compounds Al, A2, B1 and B2 of the present invention are composed of a photopolymerization initiator and a photocurable resin using the compound. The material 'as a photoinitiator for a liquid crystal sealing agent for dropping techniques has a high usability of -38-201237048. From the above results (Table 2), it is understood that a thermosetting compound is further added to the compounds Ai, A2, B1 and B2 of the present invention, and further, if the thermosetting compound is a lanthanoid mixed compound, The photopolymerization initiator and the photocurable resin composition using such a compound can be used as a liquid crystal sealing agent which is useful for the production of a high-grade liquid crystal panel. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1]: The contamination of Example 1. [Fig. 2] The contamination of Example 2. [Fig. 3]: Contamination of Example 3. [Fig. 4]: Contrast of the comparative example. [Fig. 5]: Contamination of Comparative Example 2. [Fig. 6]: Contamination of Comparative Example 3. [Fig. 7]: The wiring portion of the directing will be tested. In this line (wiring portion) / space (liquid crystal portion) is 200 μπι / 3 00 μπι. [Fig. 8] The directivity of the wiring portion of the fourth embodiment. [Fig. 9]: Orientation of the wiring portion of Reference Example 1. -39-

Claims (1)

201237048 VII. Patent Application Range: 1. A compound obtained by reacting an organic acid compound and/or a hydroxy compound with a compound having at least two epoxy groups in a molecule, characterized in that the compound is the aforementioned The organic acid compound is a compound A of dimethylamino benzoic acid or a compound of the compound B in which the hydroxy compound is hydroxythioxanthone. 2. The compound of claim 1, wherein the compound A is the following formula (1): Represents compound A1. 3. The compound of claim 1, wherein the compound A is the following formula (2): Represents compound A2. -40- 201237048 4 · The compound of claim 1 wherein the aforementioned compound B is of the following formula (3): Represents compound B1. 5 _ as claimed in claim 1, wherein the compound B is a compound of the following formula (4): (4) Compound B2 indicated. 6. A photopolymerization initiator which is a photopolymerization initiator derived from a photoinitiating compound and a visible light sensitizing compound, wherein the photoinitiating compound is the compound A and the visible light The sensitizing compound is the aforementioned compound B. A photocurable resin composition comprising a photopolymerizable monomer or oligomer and a photopolymerization initiator according to claim 6 of the patent application. 8. The photocurable resin composition according to item 7 of the patent application, further comprising a thermosetting compound in -41 - 201237048. 9. The photocurable resin composition according to claim 8, wherein the thermosetting compound is a lanthanide mixed crystal compound. -42-