KR20130125788A - Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition - Google Patents

Abstract

INDUSTRIAL APPLICATION This invention is a compound which can be used for the photoinitiator which is hard to generate | occur | produce outgas suitable for sealing agents, such as an electronic component, especially liquid crystal sealing agent, and has photocurability in a visible region, the photoinitiator containing this compound, and photocurable It is to provide a resin composition. (1) A compound obtained by reacting an organic acid compound and / or a hydroxy compound with a compound containing at least two epoxy groups in a molecule, wherein the compound is a compound A or the hydroxy compound wherein the organic acid compound is dimethylaminobenzoic acid It is a compound which is the compound B which is oxythioxanthone. (2) A photoinitiator comprising a photoinitiating compound and a visible light sensitizing compound, wherein the photoinitiating compound is Compound A and the visible light sensitizing compound is Compound B. (3) It is a photocurable resin composition containing a photopolymerizable monomer or oligomer, and the photoinitiator of the said (2) description.

Description

COMPOUND SUITABLE FOR PHOTOPOLYMERIZATION INITIATOR, PHOTOPOLYMERIZATION INITIATOR, AND PHOTOCURABLE RESIN COMPOSITION

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, a photoinitiator using the compound, and a photocurable resin composition.

In recent years, a large number of liquid crystal display panels having characteristics of light weight, high precision, and low power consumption have been produced by the liquid crystal dropping method as display panels of various devices such as large liquid crystal televisions and mobile phones.

With a liquid crystal dropping method, after apply | coating the curable liquid crystal sealing agent for light and heat combinations on the board | substrate with which the electrode pattern and the orientation film were apply | coated, and also dropping a liquid crystal to the board | substrate with which the liquid crystal sealing agent was apply | coated, or a paired board | substrate, an opposing board | substrate To fasten the substrate, i.e., to form a cell gap by performing photocuring by ultraviolet irradiation or the like as a first step, and to completely cure the sealing agent by thermosetting with a pressure jig-free as a second step to manufacture a liquid crystal display panel. That's how.

In such a liquid crystal dropping method, photocuring and thermosetting reactions proceed in a state where an uncured sealing agent is in contact with a liquid crystal. Thus, the liquid crystal sealing agent is a liquid crystal seal during a curing process, that is, before and after photocuring and before and after thermosetting. Reduction of contamination with respect to the liquid crystal derived from the agent is desired.

Similarly, the sealing agent, such as the airtight sealing agent of an electronic component, is also required to reduce the contamination to the electronic component derived from the sealing agent in the hardening process.

Moreover, with the recent performance improvement of the liquid crystal panel, the characteristic may change by the influence of ultraviolet light in an orientation direction, a kind of alignment film, and a liquid crystal material, and the sealing agent which can harden | cure in the visible light region with small energy is calculated | required. have.

As a photocurable resin composition used in electronic material fields, such as a liquid-crystal sealing agent, Photosensitive agent which is a diamino benzophenone derivative of the number average molecular weights 400-3000 in patent document 1, and hydrogen emission of the number average molecular weights 350-3000 A photocurable resin composition containing a fluorescent radical polymerization initiator and a specific monomer and / or monomer is disclosed.

As a self-polymerization type photoinitiator for hardening coating coating or printing ink, the reaction product of the epoxy compound and thioxanthone carboxylic acid which were specified in patent document 2 is disclosed.

Japanese Patent Laid-Open No. 2005-263987 Japanese Patent Laid-Open No. 2004-224993

However, although the diaminobenzophenone derivative of the specific number molecular weight which is a photosensitizer disclosed by the reference document 1 is photosensitivity in a visible light range, it is hard to generate | occur | produce outgas, but storage stability is unstable in that a functional group is an amino group derived from a primary amine. There is a problem.

In addition, the main uses of the self-polymerizing photopolymerization initiator disclosed in Reference Document 2 are paints and printing inks, and outgas to be a problem has an odor, and has no effect on outgass and liquid crystals that affect high-speed response such as liquid crystal seals. It was not possible to cope with the contamination level by dissolution, bleeding, or the like.

The subject of this invention is a compound which can hardly generate | occur | produce outgas suitable for sealing agents, such as an electronic component, especially a liquid crystal sealing agent, and can be used for the photoinitiator which has photocurability in a visible region, and the photoinitiator containing this compound. And a photocurable resin composition.

The present invention has the following configuration.

(1) A compound obtained by reacting an organic acid compound and / or a hydroxy compound with a compound containing at least two epoxy groups in a molecule, wherein the compound is

Compound A, wherein the organic acid compound is dimethylaminobenzoic acid, or

The compound of said compound B whose said hydroxy compound is hydroxy thioxanthone.

(2) A photoinitiator containing a photoinitiating compound and a visible light sensitizing compound,

The photoinitiating compound is Compound A,

The photoinitiator whose said visible light sensitizing compound is the said compound B.

(3) Photocurable resin composition containing a photopolymerizable monomer or oligomer, and the photoinitiator of the said (2) description.

According to this invention, the compound suitable for sealing agents, such as an electronic component, especially a liquid crystal sealing agent, which is hard to generate | occur | produce outgas, can be used for the photoinitiator which has photocurability in a visible region, and the photoinitiator containing this compound. And a photocurable resin composition.

1 is a contaminant of Example 1
2 is the contaminant of Example 2
3 is a contaminant of Example 3
4 is a contaminant of Comparative Example 1
5 is a contaminant of Comparative Example 2
6 is a contaminant of Comparative Example 3
7 is a wiring section in which orientation is tested. The line (wiring part) / space (liquid part) is 200 µm / 200 µm.
8 is an orientation of a wiring part of Example 4
9 is an orientation of the wiring portion of Reference Example 1

[compound]

The compound of the present invention is a compound obtained by reacting an organic acid compound and / or a hydroxy compound with a compound containing at least two epoxy groups in the molecule (hereinafter also referred to as an epoxy group-containing compound),

Compound A, wherein the organic acid compound is dimethylaminobenzoic acid, or

The hydroxy compound is Compound B, which is hydroxythioxanthone,

The carboxyl group of dimethylaminobenzoic acid and the hydroxyl group of hydroxy thioxanthone react with the epoxy group of the epoxy group-containing compound to form a hydroxyl group.

The compound of the present invention is a photopolymerization initiator for sealing agents such as liquid crystal sealing agents,

Compound A acts as a photoinitiating compound which is photoexcited by the visible light sensitizing compound,

Compound B acts as a visible light sensitizing compound.

Here, the visible light sensitizing compound refers to a compound having a wavelength of 380 nm or more, preferably 400 nm or more, more preferably 420 nm or more visible light. The photoinitiating compound does not have light absorption in the visible light, but is ultraviolet light. It refers to a compound having an absorption with respect to and generating a radical.

Compounds A and B, when acting as a photoinitiating compound or a visible light sensitizing compound in the photocuring reaction, do not volatilize the decomposition products due to the fact that the compounds themselves do not cleave, and do not generate liquid crystal contamination. Since the molecular weight is large and it is difficult to volatilize, liquid crystal contamination by the volatilization of the compound itself is also unlikely to occur. Moreover, since the residue derived from diamino benzoic acid which comprises compound A has an amino group derived from tertiary amine, and acts as a catalyst in photocuring reaction, it is excellent in stability.

Compound B is a so-called hydrogen-releasing type photoradical polymerization initiator compound, which absorbs an active energy ray, and the radical photopolymerization initiator in a triplet excited state forms a hydrogen donor and a complex in an excited state, that is, an exciplex, and a hydrogen donor Since the radical atom is released from the hydrogen atoms and the active radicals are generated to initiate radical polymerization, there are few decomposition products and little outgas component is generated.

Further, Compounds A and B have OH groups in their molecules and are high in polarity, and therefore, are excellent in compatibility with high polar photopolymerizable oligomers which are usually used in photocurable resin compositions, and have different polarities with liquid crystal materials. Since the solubility with respect to is low, it is thought that the contamination inhibitory property of a liquid crystal is excellent.

Compound A can be manufactured by making diamino benzoic acid which is an organic acid compound, and an epoxy group containing compound react.

Compound B can be manufactured by making hydroxy thioxanthone which is a hydroxy compound, and an epoxy group containing compound react.

Specifically, diaminobenzoic acid or hydroxy thioxanthone and an epoxy group-containing compound are used in terms of a basic catalyst and reactivity, preferably with respect to 1 equivalent of an epoxy group in the presence of a trivalent organic phosphoric acid compound and / or an amine compound as described later. 100 equivalent% of diaminobenzoic acid or hydroxythioxanthone is reacted. The reaction product is then purified by removing the basic catalyst by treatment such as filtration or centrifugation or washing with water.

As an epoxy-group-containing compound used when manufacturing compounds A and B, at least 2 from a viewpoint of ensuring photoinitiation photoexcitation by compound A by a visible light sensitizing compound, and a viewpoint that compound B ensures visible light sensibility It is a polyfunctional epoxy resin containing two or more epoxy groups, Preferably it is an aliphatic or aromatic bifunctional epoxy resin.

Examples of the polyfunctional epoxy resin include trimethylolpropanepolyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, phenol novolak type glycidyl ether, and cresol novolac type glyc Cydyl ether, tetraglycidyl diamino diphenylmethane, triglycidyl aminophenol, etc. are mentioned, As an aliphatic bifunctional epoxy resin, polyethyleneglycol diglycidyl ether, diethylene glycol diglycidyl ether, tri Ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hexanediol diglycidyl ether, etc. are preferable, and bisphenol A type diglycidyl ether and bisphenol F type diglyl as aromatic bifunctional epoxy resins are preferable. Cylyl ether, bisphenol AD diglycidyl ether, biphenyl diglycidyl ether, resorcinol diglycidyl ether, and the like Be given to, and, among them to be diethylene glycol diglycidyl ether, and more preferably, to a bisphenol A diglycidyl ether represented by the formula (6) represented by the formula (5).

From the viewpoint of stably securing the photoinitiation photo-excited by the visible light sensitizing compound,

Compound A is obtained by reacting diaminobenzoic acid with diethylene glycol diglycidyl ether.

Compound A1 represented by

Formula (2) obtained by reacting diaminobenzoic acid with bisphenol A diglycidyl ether:

Compound A2 represented by is more preferable.

From the point of view of ensuring stable visible light sensitivity,

Compound B is obtained by reacting hydroxythioxanthone with diethylene glycol diglycidyl ether.

Compound B1 represented by

Formula (4) obtained by reacting hydroxythioxanthone and bisphenol A diglycidyl ether:

Compound B2 represented by is more preferable.

[Photopolymerization initiator]

The photoinitiator of the present invention is a photoinitiator containing a photoinitiator compound and a visible light sensitizing compound, wherein the photoinitiating compound is Compound A and / or the visible light sensitizing compound is Compound B.

As described above, the photopolymerization initiator of the present invention is suitable for the sealing agent because the outgas can be reduced compared to the conventional photopolymerization initiator by using the compound A or the compound B in at least either the photoinitiating compound and the visible light sensitizing compound. A photocurable resin composition can be comprised. Preferred compounds A and B in the photopolymerization initiator of the present invention include those described above for the compounds A and B.

When compound A is used as a photoinitiator in the photoinitiator of this invention, as a visible light sensitizer, alkyldiamino benzophenone, diamino benzophenone, an alkylamino benzoic acid ester, anthracene, thioxanthone, coumarin, kere Tokumarin, cyanine, phthalocyanine, naphthalocyanine, etc. can be used, Preferably it is a benzophenone skeleton and / or a thioxanthone skeleton from a viewpoint of the efficiency of reactivity by energy transfer, More preferably, it is a thioxanthone skeleton, More preferably, it is compound B.

When compound B is used as a visible light sensitizing compound in the photoinitiator of this invention, as a photoinitiation compound, a self-cleaving benzoin type compound, acetophenones, hydroxyacetophenones, (alpha)-amino acetophenones, (alpha) Acyl oxime esters, acyl phosphine oxide compounds, azo compounds and the like can be used, and hydrogen-releasing benzophenones, benzoin ethers, benzyl ketals, dibenzosuberones, anthraquinones and xanthones , Thioxanthones, halogenoacetophenones, dialkoxyacetophenones, hydroxyacetophenones, halogenobisimidazoles, halogenotriazines and the like can be used.

From the viewpoint of suppressing liquid crystal contamination by the outgas, the photoinitiating compound is preferably a hydrogen emission type, among which benzophenones, anthraquinones and thioxanthones are more preferable, and thioxanthones are further preferred. It is preferable that these number average molecular weights are 500-3000. More preferably, compound A is used as a photoinitiating compound.

In the photoinitiator of the present invention, the molar ratio of the photoinitiating compound to the visible light sensitizing compound (photoinitiating compound / visible light sensitizing compound) is preferably 1/5 to 1 / from the viewpoint of supplying a stable and sufficient radical. 1, more preferably 1/3 to 1/1, still more preferably 1/2 to 1/1.

[Photocurable resin composition]

The photocurable resin composition of this invention contains a photopolymerizable monomer or oligomer, and the photoinitiator of this invention.

Although a photopolymerizable monomer or oligomer can use a well-known material, from a viewpoint of suppressing the contamination by dissolution to a liquid crystal, a (meth) acrylic acid ester monomer and / or these oligomers and bisphenol-A epoxy resin and (meth) acrylic acid The partial (meth) acrylic epoxy resin obtained by reacting is preferable, and the partial (meth) acrylic epoxy resin obtained by reacting bisphenol-A epoxy resin and (meth) acrylic acid is more preferable.

As the (meth) acrylic acid ester monomer and / or the oligomer thereof, 2-hydroxyethyl (meth) acrylate, di, tri or tetraethylene glycol di (meth) acrylate, epoxy modified di (meth) acrylate, It is urethane modified di (meth) acrylate, More preferably, it is epoxy modified di (meth) acrylate, urethane modified di (meth) acrylate, More preferably, it is epoxy modified di (meth) acrylate.

The partial (meth) acrylated epoxy resin obtained by reacting a bisphenol-A epoxy resin and (meth) acrylic acid is obtained as follows.

First, the bisphenol A type epoxy resin and (meth) acrylic acid are reacted with 10 to 90 equivalent% of (meth) acrylic acid with respect to 1 equivalent of epoxy group in the presence of a basic catalyst, preferably a trivalent organic phosphoric acid compound and / or an amine compound. . The reaction product is then purified by removing the basic catalyst by treatment such as filtration, centrifugation and / or washing with water.

As a basic catalyst, the well-known basic catalyst used by reaction of an epoxy resin and (meth) acrylic acid can be used. Moreover, the polymer supported basic catalyst which carried the basic catalyst on the polymer can also be used.

Examples of the trivalent organophosphorus compound include alkylphosphines such as triethylphosphine, tri-n-propylphosphine and tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine and tris- Aryl phosphines such as (2,6-dimethoxyphenyl) phosphine and salts thereof; phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite, tris (nonylphenyl) phosphite and salts thereof; have. As a salt of a trivalent organophosphorus compound, a triphenyl phosphine ethyl bromide, a triphenyl phosphine butyl bromide, a triphenyl phosphine octyl bromide, a triphenyl phosphine decyl bromide, a triphenyl phosphine isobutyl bromide, and a triphenyl phosphine ethyl bromide Phenyl phosphine propyl chloride, triphenyl phosphine pentyl chloride, triphenyl phosphine hexyl bromide, etc. are mentioned. Especially, triphenyl phosphine is preferable.

As the amine compound, tertiary amines such as diethanolamine, triethylamine, triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-tria Xavicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (Me-TBD), 1,8-dia Xavicyclo [5.4.0] undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [ 4.3.0] strong basic amines, such as non-5-ene (DBN) and 1,1,3,3- tetramethylguanidine, and its salt can be mentioned. Especially, 1,5,7-triazabicyclo [4.4.0] deck-5-ene (TBD) is preferable. Benzyltrimethylammonium chloride and benzyl triethylammonium chloride are mentioned as a salt of an amine compound.

In view of ease of handling of the resin composition, that is, viscosity suitable for defoaming, coating property, and printability, the content of the photopolymerizable monomer or oligomer in the photocurable resin composition of the present invention is preferably 50 to 90% by weight, more preferably. Preferably from 60 to 80% by weight, more preferably from 70 to 80% by weight.

To 100 parts by weight of the photopolymerizable monomer or oligomer from the viewpoint of reducing the residual of uncured component of the photopolymerizable monomer or oligomer to suppress the contamination of the liquid crystal and also the influence on the contamination by elution of the photoinitiator component to the liquid crystal. The photopolymerization initiator of the present invention is preferably 0.5 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight.

When the photocurable resin composition containing the photoinitiator of this invention is used as a sealing agent, especially a liquid crystal sealing agent, it can harden | cure a photocurable resin also by the visible light which does not damage a liquid crystal or an alignment film well while reducing significantly outgas. have.

On the other hand, in recent years, the following problems arise in the liquid crystal field | area which ODF method is employ | adopted especially by the high density of wiring of an electronic component.

The ODF method is a method in which a liquid crystal panel can be manufactured by directly dropping, bonding, and vacuum-opening a liquid crystal in a closed loop of a sealing agent under vacuum, and a method of reducing the amount of liquid crystal used compared to a conventional injection method. There are many advantages, such as shortening of the injection time to the panel of a liquid crystal, and it is the construction method which is mainstream as a manufacturing method of the liquid crystal panel using the present large sized board | substrate.

The liquid crystal substrate produced by the ODF method is composed of a resin having a (meth) acrylic group, which is a photocurable functional group, and an epoxy group, which is a thermosetting functional group. The liquid crystal substrate is bonded after the dropping of the liquid crystal, irradiated with ultraviolet rays, and temporarily cured.

At this time, if the reaction of the (meth) acryl group by ultraviolet irradiation is insufficient or the ultraviolet rays are not touched by shadows such as wiring, the liquid crystal sealing agent component leaks to the liquid crystal during thermosetting, and as a result, the cause of display defects is caused. do.

In recent years, as mentioned above, photocuring by visible light, which is weaker than ultraviolet light, has been increasingly introduced, and since the high density of wiring tends to make the ultraviolet light hard to reach, the new problem described above becomes more remarkable. have.

Since the photocurable resin composition of this invention contains the photoinitiator of this invention, it hardens | cures not only visible light but also a low dose of ultraviolet-ray about the above-mentioned subject, and it hardens also in a shadow part, and contributes to the solution of the said subject. Can be.

It is preferable that the photocurable resin composition of this invention contains a thermosetting agent further in order to solve the above-mentioned new subject at a high level.

The thermosetting agent is composed of a mixed hydrazide compound, an organic acid dihydrazide compound, an imidazole and its derivatives, a dicyandiamide, an aromatic amine, an aliphatic amine and a derivative thereof from the viewpoint of fast curing speed and good viscosity stability even at low temperatures. At least one compound selected from the group is preferable, a hydrazide mixed crystal compound and / or an organic acid dihydrazide compound are more preferable, and a hydrazide based mixed crystal compound is more preferable.

The hydrazide-based mixed crystal compound refers to a compound that satisfies the following requirements (I) and (II).

(I) A compound obtained by heating and melting two or more kinds of crystalline hydrazide compounds having at least one hydrazide group in one molecule to a melting point or more to obtain a heating melt, and then cooling and solidifying the heating melt. .

(II) A compound having a diffraction peak peculiar to a mixed crystal at 5.5 to 7.5 degrees of the Bragg angle (2θ ± 0.2 degrees) in an X-ray diffraction spectrum by CuKα rays of the compound.

The hydrazide compound having a hydrazide group in the compound preferably contains 5 to 70% by weight, more preferably 5 to 50% by weight, still more preferably 5 to 30% by weight, still more preferably 10 to 20% by weight. do.

The hydrazide-based mixed crystal compound can be produced by a method including a step of heating and melting two or more kinds of crystalline hydrazide compounds at a melting point or more and a step of cooling and solidifying the mixture.

In the present invention, from the viewpoint of melting point, thermal reactivity, and storage stability, as the crystalline hydrazide compound as a raw material, the general formula (1):

Wherein, R represents a hydrogen atom, an alkyl group, or an aryl group which may have a substituent; and a monohydrazide compound represented by Formula (2):

In the formula, A represents at least two compounds selected from the group consisting of dihydrazide compounds represented by alkylene groups which may have substituents, arylene groups which may have substituents or oxo groups. Preference is given to the hydrazide compounds disclosed in -143872, paragraphs 0020 and 0021.

In the present invention, as the crystalline hydrazide compound used as a raw material of the hydrazide-based mixed crystal compound, at least one dihydrazide dibasic acid having two or more hydrazide groups is preferable from the viewpoint of melting point, thermal reactivity, and storage stability. The hydrazide compound in combination with the dibasic dihydrazide may be a polyfunctional hydrazide compound such as a monohydrazide compound and / or a tribasic trihydrazide, but all the hydrazide compounds have two or more hydrazide groups. It is more preferable that it is dibasic dihydrazide.

The dibasic acid dihydrazide is preferably oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, fimel acid dihydrazide, subersandihydrazide, azelasan dihydrazide, sebacsandihydrazide , Dodencanic acid dihydrazide, hexadecane diacid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, carbohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide Zide, Malic acid hydrazide, 2,6-naphthoic acid hydrazide, 1,4-naphthoic acid hydrazide, 4,4'-bisbenzene dihydrazide, hydroquinone diglycolic acid hydrazide, resorcinol diglycolic acid di Hydrazide, catechol diglycolic acid dihydrazide, 4,4'-ethylidene bisphenol-diglycolic acid dihydrazide, 4,4'-vinylidene bisphenol-diglycolic acid dihydride It is 1 or more types of compounds chosen from the group which consists of a jide, More preferably, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, submeric acid dihydrazide, azela It is 1 or more types of compounds chosen from the group which consists of a sand hydrazide, a sebacic acid hydrazide, a dodecane diacid hydrazide, a hexadecane diacid hydrazide, an isophthalic acid dihydrazide, and a terephthalic acid dihydrazide.

The monohydrazide compound is preferably acetohydrazide, propionic acid hydrazide, pentanic acid hydrazide, lauric acid hydrazide, cyclohexanecarbohydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide At least one compound selected from the group consisting of, more preferably selected from the group consisting of acetohydrazide, propionic acid hydrazide, pentanic acid hydrazide, lauric acid hydrazide, cyclohexanecarbohydrazide, salicylic acid hydrazide At least one compound.

Especially, as a combination of dibasic dihydrazide, the combination of adipic acid dihydrazide, sebacic acid dihydrazide, adipic acid dihydrazide, decandiodihydrazide, sebacic acid dihydrazide, and decandidiohydrazide is preferable.

In the photocurable resin composition of the present invention, the content of the thermosetting agent is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the photopolymerizable monomer or oligomer from the viewpoint of having sufficient thermal reactivity and maintaining storage stability. It is more preferable that it is 30 weight part.

It is preferable that the photocurable resin composition of this invention contains coupling agents, such as filler particle | grains and a silane coupling agent, from the viewpoint mentioned later, and hardening | curing agents other than the photopolymerizable monomer or oligomer which were suitable in this invention as needed as needed. And additives such as initiators, elastomers, chain transfer agents, ion trapping agents, ion exchangers, leveling agents, pigments, dyes, plasticizers, antifoaming agents and the like other than the photopolymerization initiators which are suitable in the present invention.

The particle | grains for fillers are added for the purpose of improving the adhesive reliability of a curable composition by controlling the viscosity of a curable composition, the strength improvement of the hardened | cured material which hardened the curable composition, or suppressing linear expansion. The filler inorganic particles and / or the filler organic resin particles can be preferably used as the filler particles, but the filler inorganic particles are preferred from the viewpoint of low coefficient of linear expansion and reduction of the cure shrinkage rate for the development of adhesive strength.

Calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, At least one inorganic particle selected from the group consisting of glass beads, mica active clay, bentonite, aluminum nitride, and silicon nitride is preferred, and at least one inorganic particle selected from the group consisting of silicon dioxide, talc, alumina, bentonite. Is more preferable, silicon dioxide and / or talc are more preferable, and silicon dioxide is more preferable.

From the viewpoint of expressing the addition effect as the adhesive strength by stress relaxation at the time of curing as the organic resin particles for the filler, a copolymer obtained by copolymerizing polymethyl methacrylate, polystyrene, monomers constituting these and other monomers, polyester fine particles, At least one organic resin selected from the group consisting of core shell type fine particles comprising a shell comprising polyurethane fine particles, rubber fine particles, and a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature Particles are preferred, the group consisting of core shell type fine particles consisting of a core comprising polyester fine particles, polyurethane fine particles, rubber fine particles, and a copolymer having a high glass transition temperature and a core having a low glass transition temperature. At least one organic selected from Resin particles are more preferred, and core shell type fine particles composed of a shell comprising a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature are more preferable. In the core shell type fine particles, it is preferable that the copolymer having a high glass transition temperature is polymethacrylic acid and the copolymer having a low glass transition temperature is butyl acrylate.

In the photocurable resin composition of the present invention, the content of the inorganic particles for the filler is preferably 2 to 40 parts by weight based on 100 parts by weight of the photopolymerizable monomer or oligomer from the viewpoint of improving the adhesiveness due to the stress dispersion effect and the improvement of the linear expansion coefficient. And it is more preferable that it is 5-30 weight part.

When the thermosetting resin composition of this invention is used as a liquid crystal sealing agent, a silane coupling agent is preferable as an adhesion | attachment adjuvant for adhere | attaching a liquid crystal sealing agent and a liquid crystal display panel favorably.

1 selected from the group consisting of (gamma) -aminopropyl trimethoxy silane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, and (gamma) -isocyanate propyl trimethoxysilane. Compounds of species or more are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

In the photocurable resin composition of the present invention, the content of the coupling agent is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 2 parts by weight based on 100 parts by weight of the photopolymerizable monomer or oligomer from the viewpoint of maintaining the adhesive strength, especially the moisture resistance. More preferred.

<Examples>

Example 1 Synthesis of Compound A1

Denacol EX-850L (diethylene glycol diglycidyl ether, manufactured by Nagase Chemtex Co., Ltd.) 13.7 g, 4-dimethylaminobenzoic acid 14.8 g, PS-PPh ₃ (polyphenyl (PS) in triphenylphosphine ( 900 mg of toluene, a basic catalyst carrying PPh ₃ ), and 200 ml of toluene were mixed and stirred at 110 ° C. for 48 hours. The reaction mixture was cooled to room temperature and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure to obtain an amine adduct of Denacol EX-850L. Identification was carried out by HPLC to confirm that 70% or more of the target component was contained.

Example 2 Synthesis of Compound A2

Epiclonal EXA-850CRP (bisphenol A diglycidyl ether, manufactured by DIC Corporation) 1.70 g, 4-dimethylaminobenzoic acid 1.57 g, PS-PPh ₃ (manufactured by Biotaji Co., Ltd.) 50 mg, 20 ml of toluene were mixed and 110 ° C. Stir at 48 h. The reaction mixture was cooled to room temperature and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure to obtain an amine adduct of Epiclone EXA-850CRP. Identification was carried out by HPLC to confirm that 70% or more of the target component was contained.

Example 3 Synthesis of Compound B1

13.7 g of Denacol EX-850L (diethylene glycol diglycidyl ether, manufactured by Nagase Chemtex Co., Ltd.), 14.8 g of hydroxythioxanthone, PS-PPh ₃ (manufactured by Biotaji Co., Ltd.) 900 mg, 200 ml of toluene The mixture was stirred at 110 ° C. for 48 hours. The reaction mixture was cooled to room temperature and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure to obtain an amine adduct of Denacol EX-850L. Identification was carried out by HPLC to confirm that the target component was contained at least 60%.

Example 4 Synthesis of Compound B2

Epiclone EXA-850CRP (bisphenol A diglycidyl ether, manufactured by DIC Corporation) 1.70 g, 2-hydroxythioxanthene-10-one 2.17 g, PS-PPh ₃ (manufactured by Biotaji Co., Ltd.) 100 mg, PS -TBD (a solid catalyst carrying 1,5,7-triazabicyclo [4.4.0] dec-5-ene on PS), 100 mg of basic catalyst, manufactured by Biotage, 20 ml of toluene were mixed and 48 at 110 ° C. Stirred for time. The reaction mixture was cooled to room temperature and the catalyst was removed by filtration. The solvent was distilled off under reduced pressure to obtain a thioxanthone adduct of EXA-850CRP. Identification was carried out by HPLC to confirm that the target component was contained at least 60%.

(a) Synthesis of photopolymerizable oligomer (PR850CRP: partially methacrylated epoxy resin of bisphenol A epoxy resin)

100 ° C by mixing 320.2 g of bisphenol A epoxy resin (EXA850CRP, manufactured by DIC Corporation), 90.4 g of methacrylic acid (manufactured by Tokyo Kasei Co., Ltd.), 1.5 g of PS-PPh ₃ (manufactured by Biotaji Co., Ltd.), and 100 mg of BHT. Stirred for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain a partially methacrylated epoxy resin.

(b) photopolymerization initiator

Decomposition type (visible light curing type): Irgacure, I-369 (made by BASF Japan)

Decomposition type (reactive group-containing type): EY resin, KR-2 (manufactured by KSM Co., Ltd.)

(c) Thermosetting agent (hydrazide-based mixed crystal compound)

ADH: Adipic acid hydrazide (manufactured by Otsuka Chemical Co., Ltd.)

C3: mixed crystal thermosetting agent (manufactured by Kyoritsu Chemical Co., Ltd.)

VDH: Dihydrazide (made by Ajinomoto Fine Techno Co., Ltd.) of isopropyl hydantoin skeleton

(d) Resin filler: Metablene, J-5800 (made by Mitsubishi Rayon)

(e) Inorganic filler: Silica (Shihostar, KE-C50HG, manufactured by Nippon Shokubai, 0.5 μm)

(f) Coupling agent: KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Example 5]

In 100 weight part (100 g) of photopolymerizable oligomer PR-850CRP, the photoinitiator containing 1 weight part of photoinitiating compound A1 and 1 weight part of visible light sensitizing compound B1 was dissolved.

Thereafter, 1 part by weight of the coupling agent, 10 parts by weight of the inorganic filler, and 15 parts by weight of the thermosetting agent were mixed, using a triaxial roll mill (roll size, φ 121 × 250 mm, manufactured by Inoue Seisakusho Co., Ltd.) at a pressure of 5 MPa and two passes. It knead | mixed and the curable resin composition was obtained.

[Examples 6 and 7 and Comparative Examples 1 to 3]

After mixing in the compounding composition of Examples 6 and 7 and Comparative Examples 1-3 which were shown in Table 1 on the same conditions as Example 5, it knead | mixed sufficiently using the triaxial roll and obtained each resin composition.

In Comparative Example 3, EHA (Product Name: Darocure EHA), Component Name: 2-ethylhexyl-4- (dimethylamino) benzoate, manufactured by BASF, Inc. was used as the photosensitive compound, and DETX (Product Name). : Photocure DETX (Photocure DETX), a component name: 2, 4- diethyl thioxanthone, the EUTEC CHEMICAL company make) were used.

[Example 8]

In 100 weight part (100 g) of photopolymerizable oligomer PR-850CRP, the photoinitiator containing 1 weight part of photoinitiating compound A1 and 1 weight part of visible light sensitizing compound B1 was dissolved.

Then, 1 weight part of coupling agents, 10 weight part of organic fillers, 5 weight part of inorganic fillers, and 15 weight part of thermosetting agents are mixed, and it pressurizes using a triaxial roll mill (roll dimension, φ121 * 250mm, Inoue Seisakusho company make). The mixture was sufficiently kneaded in 5 MPa and 2 passes to obtain a curable resin composition.

[Examples 9 to 12 and Reference Example 1]

After mixing with the compounding composition of Examples 9-12 and Reference Example 1 shown in Table 2 on the same conditions as Example 8, it knead | mixed sufficiently using the triaxial roll and obtained each photocurable resin composition.

[Evaluation condition]

(1) heating loss

Each photoinitiator weighed using differential thermal balance (TG-DTA, product name: Thermoplus TG8120, manufactured by Rigaku Co., Ltd.) was placed in an aluminum pan, and the weight loss ratio when the temperature was raised to 300 ° C at a heating rate of 10 ° C / min was measured. It was. The larger reduction amount tends to volatilize as the outgas, and the larger the volatilization amount is, the liquid crystal is contaminated and consequently leads to poor display.

(2) reaction rate

The photocurable resin composition was sandwiched so that the thickness of the photocurable resin composition was 0.5 mm by using a glass for LCD having a thickness of 25 mm x 25 mm 0.7 mm and a PET film having a thickness of 25 mm x 25 mm 0.1 mm on the other. device (UVX-01224S1, Ushio electric Co.) in irradiation with light energy of about 200 to 3000mJ / cm ² with an ultraviolet irradiation intensity of 100mW / cm ² was performed by measuring the sample for curing.

At this time, ultraviolet-ray and visible light of (i) wavelength 340nm-450nm and (ii) wavelength 420nm-450nm were irradiated using the ultraviolet-ray cut filter.

The measurement of the curing rate was measured using FT-IR (Spectrum One, manufactured by Perkin Elma Co., Ltd.), and the reaction rate (conversion rate) of the (meth) acryl group from the peak area of the (meth) acryl group of the obtained IR spectrum. Was calculated.

The calculation of the reaction rate was calculated by the reduction of the area of the (meth) acrylic group absorption 1630cm ^-1 (or 945cm ^-1) on the basis of the area of 1500cm ^-1 absorption of a benzene ring double bond.

(3) Out gas amount

The outgas in 120 degreeC x 60 minutes was measured using the apparatus of TG-DTA (made by Rigaku Corporation), the volatile component amount is compared when the volatile component amount is 1.5% or less, and the volatile component amount is carried out. The case where this was 1.5% or more was made into "x".

(4) pollutant

Dispensing the photocurable resin composition onto an ITO glass substrate (60 mm × 70 mm × 0.7 mmt) with an alignment film (Sun Ever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) subjected to a rubbing treatment with a cross-sectional area of 4000 μm ² using a seal dispenser. It was.

Then, the liquid crystal (TN liquid crystal, MLC-11900-080, Merck make) was dripped on the board | substrate, the upper and lower boards were bonded by the liquid crystal dropping method (ODF method), and the test liquid crystal cell was produced.

UV test liquid crystal cell is cured by irradiating (UV irradiator: UVX-01224S1, Ushio den Fuki manufacture, roughness:: 200mJ 2 seconds to 100mW / cm ² / 365nm) and, after 1 hour column in a hot-air oven at 120 ℃ It hardened | cured and the test hardening liquid crystal cell for orientation tests was produced.

About the obtained cured liquid crystal cell, the orientation state of the liquid crystal at the time of sealing was confirmed.

Confirmation was carried out by an optical microscope, and the polarizing plate was observed by transmission through a test cell in the state of cross nicol.

Micrographs which show the orientation state of the corner part of the hardened liquid crystal cell for a test are shown in FIGS. 1-6 is the scale of 900 micrometers in height x 1200 micrometers in width.

The evaluation criteria of the orientation of a liquid crystal were judged by the presence or absence of the orientation disturbance at the time of sealing.

"○" and the case where there existed more orientation disturbance were made into "x" the case where orientation disorder is 50 micrometers or less at the time of sealing.

(5) stability

The viscosity change at room temperature (25 degreeC) of the photocurable resin composition was measured, and when the viscosity change after 5 days was 20% or less, "(circle)" and the case where the viscosity change after 5 days was 20% or more were judged as "x". .

The viscosity was measured by incubating the photocurable resin composition at 25 ° C., attaching a 3 ° × R7.7 cone rotor to a RE-105U type viscometer (manufactured by Toki Sangyo Co., Ltd.), and applying 0.15 ml of the target resin composition to a cone. It set in the chamber and the viscosity of the photocurable resin composition of 25 degreeC was measured at 2.5 rpm.

The photocurable resin composition immediately after preparation made into a measurement object was left still at 25 degreeC for 5 days, the viscosity of this photocurable resin composition after 5 days was measured by the said method, and the viscosity immediately after preparation of a photocurable resin composition was made into the initial viscosity. And the change rate from the initial viscosity was computed and it was set as evaluation of stability.

When the measurement range was exceeded, measurement was not possible. In addition, the reference | standard of a measurement range over is 1,200,000 mPa * s.

(6) thermosetting

When the viscosity by the rotary rheometer (Leo Stress 300, the Haake company) of the photocurable resin composition made into the measurement reaches to saturation viscosity within 60 minutes after a thermosetting start, "◎", 120 minutes "(Circle)" and the case where it did not reach | attain to saturated viscosity even 120 minutes were judged as "x" when reaching | attaining the saturation viscosity within.

The measurement of the viscosity measured the viscosity change in 120 degreeC for the photocurable resin composition made into the measurement object using the rotary rheometer (Leo Stress 300, Hake make).

Using a parallel plate, in a sample amount of 0.6 g, a gap of 1 mm, and a deformation control mode, the temperature conditions were raised from room temperature to 120 ° C. at 20 ° C./min, and measurement was performed for 120 minutes while maintaining 120 ° C. The time at which the viscosity change (saturated viscosity) was reached was measured.

(7) electrical characteristics

Ampoule test was performed by the sealing compound, and voltage retention (VHR) and ion density (ID) were measured and evaluated.

[Preparation of Sample for Measurement]

0.1g of photocurable resin compositions mix | blended with the ampoule bottle are put, and 1g of TN liquid crystals (MLC-11900-080, Merck make) are added. This ampoule bottle was put into a 120 degreeC oven for 1 hour, and after standing still at room temperature and returning to room temperature (25 degreeC), the liquid crystal part was taken out and filtered by the 0.2 micrometer filter, and it was set as the liquid crystal sample for electrical property evaluation.

[Measurement of Voltage Retention and Ion Density]

The cell for electrical property evaluation was produced using the liquid crystal sample for electrical property evaluation. The production method of the cell is a commercially available sealing agent (world lock No.717,) on an ITO glass substrate (55 mm x 60 mm x 0.7 mmt) with a TN liquid crystal alignment film (Sun Ever SE-7492, manufactured by Nissan Chemical Industries, Ltd.) subjected to a rubbing treatment. Kyoritsu Chemical Co., Ltd.) was used as a frame sealing agent, the liquid crystal sample for electric property evaluation was dripped on the board | substrate, the upper and lower boards were bonded by the liquid crystal dropping method (ODF method), and ultraviolet-ray (UV irradiation apparatus: UVX- 01224S1, manufactured by Ushio Denki Co., Ltd., roughness and irradiation time: 3000mJ, 100mW / cm ² / 365nm 30 seconds) was irradiated and cured, and then subjected to heat curing in a hot air oven at 120 ℃ for 1 hour to evaluate the electrical properties A liquid crystal cell was produced.

The measurement of voltage retention was performed using the liquid crystal physical property evaluation apparatus (6254C, the Toyo Technica Corporation make). The voltage retention at the applied voltage of 5 V, 60 Hz, and 16 msec was measured. The measurement was performed at 50 degreeC.

The evaluation criteria of the electrical characteristics were judged from the value of the voltage retention.

"(Circle)" and the case where the value of voltage retention are 98% or less were made into "x" when the value of voltage retention is 98% or more.

(8) orientation of wiring

After mixing in the compounding example shown in Table 2, using a triaxial roll mill (roll size, φ 121 × 250 mm, manufactured by Inoue Seisakusho Co., Ltd.), the mixture was sufficiently kneaded in a pressure of 5 MPa and two passes to form each photocurable resin composition (Examples 8 to 12). And Reference Example 1) were obtained. Wiring pattern (line / space by Cr: 200 micrometers) with the orientation film (Seonever SE-5662, Nissan Chemical Co., Ltd.) which the photocurable resin composition obtained in this way using the seal dispenser was sectional area 4000 micrometer <^2> , and was rubbed. / 200 micrometers) It apply | coated dispensing on the glass substrate (60 mm x 70 mm x 0.7 mmt) with.

Thereafter, a liquid crystal (VA liquid crystal, MLC-6609, manufactured by Merck Co., Ltd.) was added dropwise onto the substrate, the gap was set at 4 µm, and the upper and lower substrates were bonded by the liquid crystal dropping method (ODF method) to produce a test liquid crystal cell. It was.

UV test liquid crystal cell and cured by irradiating the (UV irradiation apparatus:: UVX-01224S1, Ushio den Fuki production, illumination and exposure time 3000mJ, 10 seconds to 100mW / cm ² / 365nm), and then in a hot-air oven at 120 ℃ Heat curing was performed for 1 hour to prepare a test cured liquid crystal cell for orientation test.

About the obtained hardened liquid crystal cell for test, the orientation state of the liquid crystal at the time of sealing between wirings was confirmed. Confirmation was carried out by an optical microscope, and the polarizing plate was observed by transmission through a test cell in the state of cross nicol. The micrograph which shows the orientation state of the wiring part of the hardened liquid crystal cell for a test is shown to FIGS. 7-9. 7 to 9 show a scale of 900 µm in length and 1200 µm in width.

The evaluation criteria of the orientation of a liquid crystal were judged by the presence or absence of the orientation disturbance at the time of sealing.

"○" and the case where there existed more orientation disturbance were made into "x" the case where orientation disorder is 20 micrometers or less at the time of sealing.

When the 340 nm filter was used from the above result (Table 1) (general process conditions), the orientation defect did not generate | occur | produce in either Example 200mj, 2000mj. On the other hand, it turned out that the comparative example 1 and the comparative example 2 produce the orientation defect on either condition.

In addition, when a 420 nm filter is used (the manufacturing conditions of a special liquid crystal panel, and may become mainstream in the future), in the comparative example 2 which is a conventional photoinitiator, hardening of a sealing compound does not advance and there exists a problem in the reliability of a liquid crystal panel. Could know.

As mentioned above, it turns out that the compound A1, A2, B1 and B2 of this invention, the photoinitiator and photocurable resin composition using this compound have high utility as a photoinitiator of the liquid crystal sealing agent for dripping methods.

According to the above results (Table 2), when the thermosetting compound is further added to the compounds A1, A2, B1 and B2 of the present invention, and the thermosetting compound is a hydrazide-based mixed crystal compound, the photopolymerization initiator and the photocurability using these compounds It became clear that a resin composition can be used as a liquid crystal sealing agent useful for manufacture of a high quality liquid crystal panel.

Claims (9)

A compound obtained by reacting an organic acid compound and / or a hydroxy compound with a compound containing at least two epoxy groups in a molecule, wherein the compound is
Compound A, wherein the organic acid compound is dimethylaminobenzoic acid, or
The compound of said compound B whose said hydroxy compound is hydroxy thioxanthone. The compound of claim 1, wherein Compound A is represented by Formula (1):

The compound which is compound A1 represented by. The compound of claim 1, wherein compound A is of the formula (2):

The compound which is compound A2 represented by. The compound of claim 1, wherein compound B is of the formula (3):

A compound which is a compound B1 represented by. The compound of claim 1, wherein compound B is represented by the following formula (4):

The compound which is compound B2 represented by. It is a photoinitiator containing a photoinitiator compound and a visible light sensitizer compound,
The photoinitiating compound is Compound A,
The photoinitiator whose said visible light sensitizing compound is the said compound B. The photocurable resin composition containing a photopolymerizable monomer or oligomer, and the photoinitiator of Claim 6. The photocurable resin composition according to claim 7, further comprising a thermosetting compound. The photocurable resin composition according to claim 8, wherein the thermosetting compound is a hydrazide mixed crystal compound.

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