JP6510427B2 - Active energy ray-curable resin composition, spacer for display element using the same, and / or color filter protective film - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition, a spacer for a display element, and / or a color filter protective film.

  A resin composition comprising a binder polymer, a photopolymerizable monomer, a photopolymerization initiator and the like has been used as a material for display devices. In recent years, materials for display devices “materials used for LCDs, ELs, PDPs, FEDs (SEDs), rear projection displays, electronic paper, digital cameras, etc., particularly as display elements, materials around display elements”, for example Color liquid crystal displays (LCDs) are rapidly spreading. Generally, in a color liquid crystal display device, a color filter and an electrode substrate such as a TFT substrate are opposed to form a gap of about 1 to 10 μm, a liquid crystal compound is filled in the gap, and the periphery is sealed with a sealing material. I am taking

  The color filter comprises a black matrix layer formed in a predetermined pattern to shield the boundary between pixels on a transparent substrate, and red (R), green (G), usually to form each pixel. It has a structure in which a colored layer in which blue (B) is arranged in a predetermined order, a protective film, and a transparent electrode film are laminated in this order from the side close to the transparent substrate. In addition, an alignment film is provided on the inner surface side of the color filter and the electrode substrate facing the color filter. Furthermore, in order to keep the cell gap between the color filter and the electrode substrate constant and uniform in the gap, a pearl having a constant particle diameter as a spacer is dispersed or a column or stripe having a height corresponding to the cell gap. Shaped spacers are formed. A color image can be obtained by controlling the light transmittance of the liquid crystal layer behind each of the colored pixels. Such color filters are used not only in color liquid crystal display devices but also in other display devices such as EL and rear projection displays.

  The colored layer, the protective film, and the spacer described above can be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each pixel of each color. The protective film is preferably one that can cover only the area on the transparent substrate in which the colored layer is formed, in consideration of the adhesion and sealing properties of the seal portion. In addition, the spacers need to be accurately provided in the formation area of the black matrix layer, that is, in the non-display area. For this reason, the colored layer, the protective film, and the columnar spacer are formed using a curable resin which can easily define the area to be cured by a photomask.

  In addition, if the coating surface of the curable resin is exposed to light and then developed using an organic solvent in order to form a colored layer, a protective film, or a columnar spacer, it is complicated in terms of handling and waste liquid treatment. Since it lacks in properties and stability, a curable resin has been developed in which an acidic group is introduced into the curable resin so that it can be developed with an aqueous alkaline solution after exposure. These applications require high temperatures (200-260 ° C or more) during the formation of the alignment film and the formation of the transparent electrode, so very high heat resistance, and especially heat resistance and color resistance in color resists and spacers. Good things are needed.

  In Patent Document 1, a photosensitive resin obtained by neutralizing an acid-modified epoxy acrylate of cresol novolac epoxy resin with a primary amino compound is used as a polymer component of a photosensitive resin composition for a photo spacer and a color filter. There is. However, a composition containing such a salt of a primary amino compound and water is inferior in coating property and flatness, and it can not be said that the compatibility with an apparatus such as a slit coater is sufficient.

  Moreover, in patent document 2, acid-modified epoxy acrylate of cresol novolac epoxy resin or phenol novolac epoxy resin is used as a polymer component of the photosensitive resin composition for photo spacers. However, there is a problem that the radiation sensitivity and the developability are inferior and the level is not sufficiently satisfactory.

In Patent Document 3, as a polymer film of a protective film of a color filter or a resist ink composition for a flexible printed wiring board, a reaction product in which acrylic acid and dimethylol propionic acid are added to cresol novolac epoxy resin is caprolactone modified and further tetrahydroanhydride A phthalic acid modified active energy ray curable resin is used. The polymer component which is the main component of the composition is excellent in developability and flexibility, but has a problem that it is inferior in elastic recovery rate required as a photo spacer.
Patent Document 4 discloses that a resin composition containing an unsaturated group-containing polycarboxylic acid resin is used as a solder resist, but there is no description at all for a spacer for a display element or a color filter protective film.

Japanese Patent Application Laid-Open No. 2004-109752 Japanese Patent Application Publication No. 2007-010885 Japanese Patent Application Laid-Open No. 2004-300266 Japanese Patent Application Laid-Open No. 4-165358

  The present invention is an active energy ray-curable resin composition which improves the problems of the above-mentioned prior art and is excellent in developability, curability and high-speed coating property, and has heat-resistant transparency, flatness, flexibility and toughness. To provide an excellent display element spacer and color filter protective film.

  MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination, in order to solve the said subject, the present inventors discovered that the resin composition which has a specific compound and a composition solves the said subject, and arrived at this invention.

That is, the present invention
(1) A display element containing a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C), and an organic solvent (D) Spacer active energy ray-curable resin composition for a spacer or color filter protective film,
The reactive polycarboxylic acid compound (A) comprises an epoxy resin (a) having at least two or more epoxy groups in one molecule, and one or more polymerizable ethylenic unsaturated groups in one molecule or more. The compound (b) having a carboxyl group of (1) and, if necessary, a reaction product (E) with a compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule, A reactive polycarboxylic acid compound (A) obtained by reacting an anhydride (d),
The active energy ray-curable resin composition relates to an epoxy resin (a) having at least two or more epoxy groups in one molecule, which is a naphthalene skeleton-containing epoxy resin.
(2) Furthermore, according to the present invention, the reactive polycarboxylic acid compound (A) comprises an epoxy resin (a) having at least two or more epoxy groups in one molecule and one or more polymerizable ethylene in one molecule. A compound (b) having a heterocyclic unsaturated group and one or more carboxyl groups, and a reaction product (E) with a compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule, Furthermore, it is a reactive polycarboxylic acid compound (A) obtained by reacting a polybasic acid anhydride (d), and an epoxy resin (a) having at least two or more epoxy groups in one molecule contains a naphthalene skeleton. A spacer for a display element according to the above (1), which is an epoxy resin, and the epoxy resin (a) having at least two or more epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin It is a color filter protective film for the active energy ray curable resin composition.
(3) Furthermore, in the present invention, the reactive compound (B) is any one or more selected from monofunctional, bifunctional, and trifunctional or higher (meth) acrylates, or the above (1) or The present invention relates to an active energy ray curable resin composition for a spacer for a display element or a color filter protective film described in (2).
(4) Furthermore, in the present invention, the proportion of the reactive compound (B) is 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the reactive polycarboxylic acid compound (A) as a use ratio in the resin composition. It is related with the spacer for display elements in any one of (1)-(3), or the active energy ray curable resin composition for color filter protective films.
(5) The present invention further relates to a spacer for a display element formed from the active energy ray-curable resin composition according to any one of the above (1) to (4).
(6) The present invention further relates to a color filter protective film formed from the active energy ray-curable resin composition according to any one of the above (1) to (4).

  The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention is excellent in developability, has high radiation sensitivity, and is excellent in heat-resistant transparency, flatness, flexibility, and toughness. It is possible to provide a spacer for a display element and a color filter protective film.

Hereinafter, the present invention will be described in detail.
The reactive polycarboxylic acid compound (A) in the present invention comprises an epoxy resin (a) having at least two or more epoxy groups in one molecule and one or more polymerizable ethylenically unsaturated groups in one molecule. A polybasic acid is further added to the reaction product of a compound (b) having one or more carboxyl groups, and, if necessary, a compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule. It is obtained by reacting the anhydride (d).
That is, as the reactive polycarboxylic acid compound (A) in the present invention, the reaction product (E) of the epoxy resin (a) and the compound (b) is reacted with the polybasic acid anhydride (d), or the epoxy resin It can be obtained by reacting the reaction product (E) of (a), compound (b) and compound (c) with polybasic acid anhydride (d).

As an epoxy resin (a) which has an at least 2 or more epoxy group in 1 molecule in this invention, a naphthalene frame | skeleton containing epoxy resin is mentioned.
As such a naphthalene skeleton-containing epoxy resin, for example, as described in JP-A-4-165358, a phenol obtained by reacting a dimethylol compound such as bis (hydroxymethyl) paracresol with a naphthol under acid catalysis Novolaks of the same kind can be obtained by reacting with an epihalogen compound in the presence of an alkali.
Furthermore, those commercially available as naphthalene skeleton-containing epoxy resins include, for example, NC-7000, NC-7300, NC-7700 (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (Dainippon Ink Chemical Industry Co., Ltd. And the like.

In the present invention, a naphthalene skeleton-containing epoxy resin is used as the epoxy resin (a). However, in some cases, an epoxy resin having at least two or more epoxy groups in one molecule other than the naphthalene skeleton-containing epoxy resin may be used in combination in the reaction.
As another epoxy resin, for example, phenol novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadiene phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin And biphenol type epoxy resin, bisphenol-A novolac type epoxy resin, glyoxal type epoxy resin , alicyclic epoxy resin, heterocyclic epoxy resin and the like.

  Examples of the phenol novolac epoxy resin include Epiclon N-770 (manufactured by Dainippon Ink and Chemicals, Inc.), D.I. E. N438 (made by Dow Chemical Co., Ltd.), Epikote 154 (made by Yuka Shell Epoxy Co., Ltd.), EPPN-201, RE-306 (made by Nippon Kayaku Co., Ltd.) and the like. Examples of cresol novolac epoxy resins include Epiclon N-695 (Dainippon Ink and Chemicals, Inc.), EOCN-102S, EOCN-103S, EOCN-104S (Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Nippon Kayaku Co., Ltd.) Dow Chemical Co., Ltd.), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of trishydroxyphenylmethane type epoxy resins include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epicoat E1032H60 (oiled shell epoxy resin) Manufactured by Co., Ltd., and the like. Examples of dicyclopentadiene phenol type epoxy resins include XD-1000 (manufactured by Nippon Kayaku Co., Ltd.), Epiclon EXA-7200 (manufactured by Dainippon Ink and Chemicals, Inc.), TACTIX-556 (manufactured by Dow Chemical Co.) Etc.

  As bisphenol type epoxy resin, for example, Epicoat 828, Epicoat 1001 (manufactured by oiled shell epoxy), UVR-6410 (manufactured by Dow Chemical Co.), D.I. E. Bisphenol-A type epoxy resin such as R-331 (made by Dow Chemical Co., Ltd.), YD-8125 (made by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (made by Nippon Kayaku Co., Ltd.), UVR-6490 (made by Dow Chemical Co.) Bisphenol-F type epoxy resins, such as Dow Chemical Co., YDF-8170 (made by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

Examples of biphenol type epoxy resins include biphenol type epoxy resins such as NC-3000 and NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), and bixylenol of YX-4000 (manufactured by Yuka Shell Epoxy Co., Ltd.) Type epoxy resin, YL-6121 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like. Examples of the bisphenol A novolac epoxy resin include Epiclon N-880 (manufactured by Dainippon Ink and Chemicals, Inc.) and Epicoat E157S75 (manufactured by Yuka Shell Epoxy Co., Ltd.).
Examples of glyoxal-type epoxy resins that can be obtained from the market include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) and the like. As an alicyclic epoxy resin, EHPE-3150 (made by Corporation | KK Daicel) etc. are mentioned, for example. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.

  In the present invention, the compound (b) having one or more polymerizable ethylenic unsaturated groups and one or more carboxyl groups in one molecule is reacted to impart reactivity to active energy rays. is there. There are no limitations as long as the ethylenically unsaturated group and the carboxyl group are each one or more in the molecule. These include monocarboxylic acid compounds and polycarboxylic acid compounds.

  Examples of monocarboxylic acid compounds having one carboxyl group in one molecule include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated group-containing mono The reaction product with a glycidyl compound is mentioned. In the above, as (meth) acrylic acids, for example, (meth) acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 A half reactant which is an equimolar reactant, a (meth) acrylate derivative having one hydroxyl group in a molecule, and a half reactant which is an equimolar reactant of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative Esters etc. are mentioned.

  Furthermore, as a polycarboxylic acid compound having two or more carboxyl groups in one molecule, a half ester which is an equimolar reactant with a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule, a saturated or unsaturated di-ester Examples thereof include half esters which are equimolar reaction products of a basic acid and a glycidyl (meth) acrylate derivative having a plurality of epoxy groups.

  Among these, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is preferred in terms of sensitivity when used as an active energy ray-curable resin composition. As the compound (b), compounds having no hydroxyl group are preferable.

  The compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule in the present invention is reacted for the purpose of introducing a hydroxyl group into the carboxylate compound.

  Specific examples of the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule, which is optionally used in the present invention, include, for example, dimethylol propionic acid and dimethylol butanoic acid Polyhydroxy-containing monocarboxylic acids such as dimethylol acetic acid, dimethylol butyric acid, dimethylol valeric acid and dimethylol caproic acid can be mentioned. Particularly preferable examples include dimethylol propionic acid and the like.

  Among these, in consideration of the stability of the reaction between the epoxy resin (a) and the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarboxylic acids, and mono Even when a carboxylic acid and a polycarboxylic acid are used in combination, the value represented by the total molar amount of monocarboxylic acid / the total molar amount of polycarboxylic acid is preferably 15 or more.

  As a preparation ratio of the total of carboxylic acid of the epoxy resin (a), the compound (b) and the compound (c) optionally used in this reaction, it should be suitably changed according to a use. That is, when all the epoxy groups are carboxylated, storage stability as a reactive epoxy carboxylate compound is high because unreacted epoxy groups do not remain. In this case, only the reactivity due to the introduced double bond will be utilized.

  On the other hand, by intentionally reducing the charged amount of the carboxylic acid compound and leaving the unreacted residual epoxy group, the reactivity by the introduced unsaturated bond and the reaction by the residual epoxy group, for example, the polymerization reaction by the photo cation catalyst or heat It is also possible to utilize the polymerization reaction in combination. However, in this case, attention should be paid to the storage of the reactive epoxy carboxylate compound (E) and the examination of the production conditions.

  In the case of producing a reactive epoxy carboxylate compound (E) which does not leave an epoxy group, the total of the compound (b) and the compound (c) optionally used is 90 to 90 to 1 equivalent of the epoxy resin (a). It is preferable that it is 120 equivalent%. Within this range, manufacture under relatively stable conditions is possible. If the total preparation amount of the compound (b) and the compound (c) to be used if necessary is larger than this, the excess of the compound (b) and the compound (c) is unfavorably remaining.

  Moreover, when leaving an epoxy group intentionally, it is preferable that the sum total of a compound (b) and a compound (c) is 20-90 equivalent% with respect to 1 equivalent of said epoxy resin (a). If it deviates from this range, the reaction by the additional epoxy group does not proceed sufficiently. In this case, sufficient attention must be paid to the gelation during the reaction and the temporal stability of the reactive epoxy carboxylate compound (E).

  When the compound (b) and the compound (c) are used, the molar ratio of the compound (b) to the compound (c) is 95: 5 to 5:95, and further 95: 5 to 40: A range of 60 is preferred. Within this range, the sensitivity to active energy rays is good, and sufficient hydroxyl groups can be introduced for reacting the reactive epoxy carboxylate compound (E) with the polybasic acid anhydride (d).

  The carboxylation reaction can also be reacted without solvent or diluted with solvent and reacted. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.

  The preferred amount of the solvent to be used is suitably adjusted according to the viscosity and use of the resin to be obtained, preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight with respect to 100 parts by weight of the solid content. Used to be.

  Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and petroleum ether which is a mixture thereof, white Examples thereof include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents and the like.

  As ester solvents, alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene Mono or polyalkylene glycol monoalkyl ether monoacetates such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as And the like.

  As ether solvents, alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and the like Ethers, cyclic ethers such as tetrahydrofuran and the like can be mentioned.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and the like.

Besides this, it can be carried out in a single or mixed organic solvent such as other reactive compound (B) described later. In this case, when it is used as a curable composition, it is preferable because it can be used directly as a composition.

  At the time of reaction, it is preferable to use a catalyst to accelerate the reaction, and the amount of the catalyst used is a reactant, ie, an epoxy resin (a), a carboxylic acid compound (b), and a compound optionally used (c And 0.1 to 10 parts by weight, based on 100 parts by weight of the reaction product, to which the solvent and the like are optionally added. The reaction temperature at that time is usually 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, chromium octanoate, octane Known basic catalysts such as zirconium acid can be mentioned.

Further, as the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di -tert- butyl - to use a 4-hydroxycarboxylic toluene are preferred.

  In this reaction, the end point is a point when the acid value of the sample becomes 5 mg KOH / g or less, preferably 3 mg KOH / g or less, while sampling appropriately.

  As a preferable molecular weight range of the reactive epoxy carboxylate compound (E) obtained in this way, the polystyrene conversion weight average molecular weight in GPC is a range of 500 to 50,000, and more preferably 1,000 to 30,000. .

  When the molecular weight is smaller than this molecular weight, the toughness of the cured product is not sufficiently exhibited. When the molecular weight is larger than this, the viscosity becomes high and coating and the like become difficult.

  Next, the acid addition step will be described in detail. The acid addition step is carried out for the purpose of introducing a carboxyl group into the reactive epoxy carboxylate compound (E) obtained in the previous step to obtain a reactive polycarboxylic acid compound (A). That is, by adding polybasic acid anhydride (d) to the hydroxyl group generated by the carboxylation reaction, a carboxyl group is introduced via an ester bond.

  As a specific example of polybasic acid anhydride (d), for example, any compound having an acid anhydride structure in the molecule can be used, but it is excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance, etc. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride, or maleic anhydride Is particularly preferred.

  The reaction of adding the polybasic acid anhydride (d) can be carried out by adding the polybasic acid anhydride (d) to the above-mentioned carboxylation reaction solution. The addition amount should be suitably changed according to a use.

  For example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali-developable resist, the addition amount of the polybasic acid anhydride (d) is not limited to the final value of the polybasic acid anhydride (d). The solid content acid value (based on JIS K 5601-2-1: 1999) of the reactive polycarboxylic acid compound (A) obtained in a static manner is 40 to 120 mg.KOH / g, more preferably 60 to 120 mg.KOH / g, It is preferable to charge the calculated value. When the solid content acid value at this time is in this range, the aqueous alkaline solution developability of the photosensitive resin composition of the present invention exhibits good developability. That is, good patternability and control over over development are also wide, and excess acid anhydride does not remain.

  At the time of reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reactant, ie, an epoxy compound (a), a carboxylic acid compound (b), and a compound optionally used (c And 0.1 to 10 parts by weight with respect to the total of 100 parts by weight of the reactive epoxy carboxylate compound (E) obtained from the above and the reaction product including the polybasic acid anhydride (d) and optionally the solvent and the like. It is. The reaction temperature at that time is usually 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibin, methyltriphenylstibin, chromium octanoate, octane Acid zirconium and the like.

  The present acid addition reaction can be reacted without a solvent or can be diluted with a solvent and reacted. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. Also, in the case of using a solvent in the previous step of the carboxylation reaction, it is also possible to directly provide for the next step, acid addition reaction, without removing the solvent, on the condition that it is an inert for both reactions. it can. The solvents which may be used may be the same as those which may be used in the carboxylation reaction.

  The preferred amount of the solvent to be used is suitably adjusted according to the viscosity and use of the resin to be obtained, preferably 90 to 30 parts by weight, more preferably 80 to 50 parts by weight with respect to 100 parts by weight of the solid content. It is used to be

In addition to this, it can be carried out in a single or mixed organic solvent such as a reactive compound (B) described later. In this case, when it is used as a curable composition, it is preferable because it can be used directly as a composition.

  Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor etc.

  This reaction is terminated as the point where the acid value of the reaction product is in the range of plus or minus 10% of the set acid value while sampling appropriately.

As a preferable molecular weight range of a reactive polycarboxylic acid compound (A), the polystyrene conversion weight average molecular weight in GPC is a range of 500 to 50,000, and more preferably 1,000 to 30,000.
The proportion of the reactive polycarboxylic acid compound (A) in the resin composition is about 5 to 69% by weight, preferably about 8 to 59% by weight.

  Examples of the reactive compound (B) usable in the present invention include so-called reactive oligomers such as radical reactive acrylates, cationic reactive other epoxy compounds, vinyl compounds sensitive to both of them.

  Examples of the radical reactive acrylates include monofunctional (meth) acrylates, bifunctional (meth) acrylates, trifunctional or higher (meth) acrylates, polyester (meth) acrylates, urethane (meth) acrylate oligomers, polyesters (meth Acrylate oligomers, epoxy (meth) acrylate oligomers and the like can be mentioned.

  As monofunctional (meth) acrylates, for example, acryloyl morpholine; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; cyclohexane -1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl ( Aliphatic (meth) acrylates such as meta) acrylate, phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumyl phenoxyethyl (meth) acrylate, Libromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenylphenol epoxy (meth) acrylate And aromatic (meth) acrylates.

  As a bifunctional (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, bisphenol A (poly) ethoxy di (meth) acrylate, bisphenol A (poly) propoxy di (meth) acrylate, bisphenol F (poly) ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene Glycol di (meth) acrylate di- (meth) acrylate of ε-caprolactone adduct of neopentyl glycol neohydroxyl glycol (eg, Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620 etc.) etc. But it can.

The trifunctional or higher polyfunctional (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane octane tri (meth) acrylate, trimethylolpropane propane (poly) d Tokishitori ( meth) acrylate, trimethylolpropane (poly) Puropokishitori (meth) acrylate, methylol such as trimethylolpropane (poly) ethoxy (poly) Puropokishitori (meth) acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol Le (poly) d Tokishitetora (meth) acrylate, pentaerythritol (poly) propoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, Jipentaerisuri Rutetora (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentae Risuritoru such as dipentaerythritol hexa (meth) acrylate; tris [(meth) acryloyloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloyloxy Ethyl] isocyanurate and the like; succinic acid-modified pentaerythritol triacrylate and succinic acid-modified dipentaerythritol pentaacrylate can be mentioned.

The (poly) ester (meth) acrylate oligomer, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly) d Ji glycol, (poly) propylene glycol Etc., 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1 Linear or branched alkyl diols such as 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dioxane Alicyclic alkyl radicals such as methanol (Poly) ester diol which is a reaction product of a diol compound such as bisphenol A (poly) ethoxy diol or bisphenol A (poly) propoxy diol with the above dibasic acid or its anhydride, (meth) acrylic The reaction product with an acid etc. are mentioned.

Examples of urethane (meth) acrylate oligomers include diol compounds (eg, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1, 6 Hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5- Pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropyl ester Diols etc.) or a reaction product of these diol compounds with dibasic acids or their anhydrides (eg, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or their anhydrides) Polyester diol and organic polyisocyanate (for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, linear saturated hydrocarbon isocyanate such as 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate , Norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diiso Aneto, cyclic saturated hydrocarbon isocyanates such hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p- phenylene diisocyanate, 3,3'-dimethyl-4,4 '- biphenylene diisocyanate The reaction product etc. which made it react, aromatic polyisocyanates, such as 6-isopropyl- 1, 3- phenyl diisocyanate and 1, 5- naphthalene diisocyanate, and then added hydroxyl group-containing (meth) acrylate, etc. are mentioned.

  The epoxy (meth) acrylate oligomer is a carboxylate compound of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, trishydroxyphenylmethane epoxy (meth) acrylate, dicyclopentadiene phenol epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol-A novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy Examples include (meth) acrylates and the like.

  Vinyl compounds include vinyl ethers, styrenes and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene and ethylstyrene. Other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate and the like.

  Moreover, as a cation reaction type monomer, if it is a compound which generally has an epoxy group, there will be no limitation in particular. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Union Carbide Corporation) "Silacure UVR-6110" etc., 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ("ELR-4206" produced by Union Carbide Co., Ltd.), limonene dioxide (Daicel Chemical Co., Ltd.) Manufactured by Kogyo Co., Ltd. “Celloxide 3000”, etc., allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy) Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate ("Syracure UVR-6128" manufactured by Union Carbide Co., Ltd.), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Among these, as the reactive compound (B), monofunctional, bifunctional, trifunctional or more trifunctional (meth) acrylates and the like are most preferable from the viewpoint that the polymerizability is good and the strength of the obtained spacer etc. is improved. .

  The reactive compound (B) of the present invention may be used alone or in combination of two or more. The use ratio of the reactive compound (B) in the composition is preferably 30 parts by weight to 250 parts by weight, and 50 parts by weight to 200 parts by weight with respect to 100 parts by weight of the reactive polycarboxylic acid compound (A). More preferable. When the amount of the reactive compound (B) to be used is 30 parts by weight to 250 parts by weight, the sensitivity of the composition, the heat resistance such as the spacer for display element obtained, and the elastic properties become better.

  The photopolymerization initiator (C) of the present invention reacts with active energy rays to polymerize the reactive polycarboxylic acid compound (A) and the reactive compound (B) other than the reactive polycarboxylic acid compound (A). Is a component that produces an active species that can initiate As such a photoinitiator (C), an O-acyl oxime compound, an acetophenone compound, a biimidazole compound etc. are mentioned.

  As an O-acyl oxime compound, for example, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9- Ethyl-6-benzoyl-9H-carbazol-3-yl] -octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1 -[9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 And-(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Among these, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6 -(2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4-] (2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred. These O-acyl oxime compounds may be used alone or in combination of two or more.

  As an acetophenone compound, an alpha-amino ketone compound and an alpha-hydroxy ketone compound are mentioned, for example.

  Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4). And -morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.

  Examples of the α-hydroxy ketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.

  Among these acetophenone compounds, α-amino ketone compounds are preferred, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-dimethylamino-2- (4-methylbenzyl) More preferred is -1- (4-morpholin-4-yl-phenyl) -butan-1-one.

  As a biimidazole compound, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ Bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5, 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi An imidazole etc. are mentioned. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole is preferred, and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole is more preferred.

Further, the photopolymerization initiator as the (C) may be a commercially available product, such as 2-methyl-1- (4-methylthiophenyl a phenyl) - 2-morpholinopropan-1-one (Irgacure 907), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (IRGACURE 379), ethanone-1- [9-ethyl-6- (2-) Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE OXE 02) (all from Ciba Specialty Chemicals) and the like.

  In the active energy ray-curable resin composition of the present invention, the amount of the component (C) used is usually 1% by weight or more and 10% by weight or less when the solid content of the resin composition of the present invention is 100% by weight. Preferably, it is 1% by weight or more and 7% by weight or less.

Moreover, said photoinitiator (C) can also be used together with a hardening accelerator (F). As a curing accelerator which can be used in combination, for example, triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamyl ester, amines such as EPA, 2-mercapto And hydrogen donors such as benzothiazole. The amount of these curing accelerators used is usually 0% by weight or more and 5% by weight or less, when the solid content of the resin composition of the present invention is 100% by weight.

  As the organic solvent (D), one which dissolves or disperses each constituent uniformly and does not react with each constituent is suitably used. As such organic solvents (D), the above-mentioned aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof, such as petroleum ether, white gasoline, solvent naphtha, etc., ester solvents, ether solvents In addition to ketone solvents, for example, alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene Glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, ketones and the like can be mentioned. These may be used alone or in combination of two or more.

  Specific examples of the organic solvent (D) include alcohols such as benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether; propylene Propylene glycol monoalkyl ethers such as glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monomethyl ether acetate Diethylene Diethylene glycol monoalkyl ether acetates such as recall monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate etc Methyl acetate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate, etc. lactate esters such as ethyl hydroxyacetate, 2-hydroxy-2-methyl Ethyl propionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl Acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Aliphatic carboxylic acids such as Terides: Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and the like; Ketones such as N-methylpyrrolidone, γ-butyrolactone and the like. These may be used alone or in combination of two or more.

  The solid content concentration in the composition is usually 10% by weight or more and 40% by weight or less, preferably 15% by weight or more and 35% by weight or less. By making solid content concentration of the said composition into the said range, the improvement of a coating property, the improvement of a film thickness uniformity, and generation | occurrence | production of a coating nonuniformity can be suppressed effectively.

  The viscosity of the composition at 25 ° C. is usually 1.0 mPa · s or more and 1,000 mPa · s or less. Preferably, it is 2.0 mPa · s or more and 100 mPa · s or less. By setting the viscosity of the composition in the above range, it is possible to achieve a well-balanced viscosity that can be leveled spontaneously even if coating unevenness occurs while maintaining the uniformity of the film thickness.

  The alkali-soluble resin (G) used as necessary in the active energy ray-curable resin composition of the present invention includes, for example, a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, and a carboxyl group. Copolymerizing a monomer, a monomer having an epoxy group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, another monomer, and the above-mentioned monofunctional (meth) acrylate It can be manufactured by

  Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5- Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono ( Meta) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) Acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide.

  As specific examples of the acid anhydride having an ethylenic double bond, maleic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, 3-methyl phthalic anhydride, methyl 5-norbornene-2,3-dicarboxylic anhydride Examples thereof include acids, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-ylsuccinic anhydride and the like.

  Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or salts thereof.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl methyl acrylate.

  As a monomer which has phenolic hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene etc. are mentioned. In addition, one or more hydrogen atoms of these benzene rings are alkyl groups such as methyl group, ethyl group and n-butyl group; alkoxy groups such as methoxy group, ethoxy group and n-butoxy group; halogen atoms; Examples include a haloalkyl group in which one or more hydrogen atoms are substituted by a halogen atom; a nitro group; a cyano group; a monomer substituted by an amide group or the like.

  As a monomer having a sulfonic acid group, vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (meth) allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl And (meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropane sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid and the like.

  As other monomers, hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatics Examples thereof include vinyl compounds, chloroolefins and conjugated dienes. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, (meth) acrylic esters and (meth) acrylamides are preferable because the heat resistance of partition walls formed from the composition is excellent.

When copolymerizing alkali-soluble resin (G), it can manufacture by radically polymerizing an unsaturated compound in presence of a polymerization initiator in a solvent . The above-mentioned solvents can be used, may be used alone, or two or more may be mixed and used.

As a polymerization initiator used for the polymerization reaction for manufacturing alkali-soluble resin (G), what is generally known as a radical polymerization initiator can be used. As the radical polymerization initiator, such as 2,2'-azobisisobutyronitrile (AIBN), 2,2' Azobi scan (2,4-dimethylvaleronitrile), 2,2' Azobi scan (4 - methoxy-2,4-dimethylvaleronitrile) azo compounds such as; benzoyl peroxide, lauroyl peroxide, t- butyl peroxypivalate, organic peroxides such as 1,1'-bi scan (t-butylperoxy) cyclohexane and over Hydrogen oxide is mentioned. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent as a redox type initiator.

In the polymerization reaction for producing the alkali-soluble resin (G), a molecular weight modifier can be used to adjust the molecular weight. Examples of molecular weight modifiers include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; dimethyl Kisantoge Njisu Rufido, xanthates such as diisopropyl xanthogen disulfide; terpinolene, alpha-methyl styrene dimer and the like.

The monomer having a hydroxyl group, the acid anhydride having an ethylenic double bond, the monomer having a carboxyl group, the monomer having an epoxy group, the monomer having a phenolic hydroxyl group, the sulfonic acid group As a compound (f) having a functional group capable of binding to the reactive group and an ethylenic double bond, for the monomer (e) having a reactive group such as a monomer having, for example, the following combinations may be mentioned: Be
(1) An acid anhydride (f) having an ethylenic double bond with respect to a monomer (e) having a hydroxyl group
(2) a compound (f) having an isocyanate group and an ethylenic double bond relative to the monomer (e) having a hydroxyl group,
(3) a compound (f) having an acyl chloride group and an ethylenic double bond, relative to the monomer (e) having a hydroxyl group
(4) a compound (f) having a hydroxyl group and an ethylenic double bond with respect to the acid anhydride (e) having an ethylenic double bond,
(5) a compound (f) having an epoxy group and an ethylenic double bond with respect to a monomer (e) having a carboxyl group
(6) The compound (f) which has a carboxyl group and an ethylenic double bond with respect to the monomer (e) which has an epoxy group.

  Specific examples of the acid anhydride having an ethylenic double bond include the examples described above.

  Specific examples of the compound having an isocyanate group and an ethylenic double bond include 2- (meth) acryloyloxyethyl isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate and the like.

  Specific examples of the compound having an acyl chloride group and an ethylenic double bond include (meth) acryloyl chloride.

  As a specific example of a compound which has a hydroxyl group and an ethylenic double bond, the example of the monomer which has the above-mentioned hydroxyl group is mentioned.

  As a specific example of a compound which has an epoxy group and an ethylenic double bond, the example of the monomer which has an above-mentioned epoxy group is mentioned.

  As a specific example of a compound which has a carboxyl group and an ethylenic double bond, the example of the monomer which has the above-mentioned carboxyl group is mentioned.

When the copolymer (f) is reacted with a compound (f) having a functional group capable of binding to a reactive group and an ethylenic double bond, the solvent used for the reaction may be the solvent exemplified in the synthesis of the above copolymer. Can be used.

  Moreover, it is preferable to mix | blend a polymerization inhibitor. As the polymerization inhibitor, known and commonly used polymerization inhibitors can be used, and specific examples include 2,6-di-t-butyl-p-cresol.

  In addition, a catalyst or a neutralizing agent may be added. For example, when a copolymer having a hydroxyl group is reacted with a compound having an isocyanate group and an ethylenic double bond, a tin compound or the like can be used. Examples of the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), dibutyltin diacetate and the like.

  When a monomer having a hydroxyl group is reacted with a compound having an acyl chloride group and an ethylenic double bond, a basic catalyst can be used. Examples of the basic catalyst include triethylamine, pyridine, dimethylaniline, tetramethylurea and the like.

As Mw of alkali-soluble resin (G), 2 * 10 < ³ > -1 * 10 < ⁵ > is preferable and 5 * 10 < ³ > -5 * 10 < ⁴ > is more preferable. By setting the Mw of the alkali-soluble resin (G) to 2 × 10 ³ to 1 × 10 ⁵ , the radiation sensitivity and the developability (the characteristics for accurately forming a desired pattern shape) of the composition can be enhanced.

  Furthermore, in the active energy ray-curable resin composition of the present invention, if necessary, a surfactant, a leveling agent, an antifoamer, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, It is also possible to add a crosslinking agent, an adhesion assistant, a pigment, a dye and the like to impart desired functionality. Fluoride compounds, silicone compounds, acrylic compounds etc. as leveling agents and antifoaming agents, benzotriazole compounds, benzophenone compounds, triazine compounds etc. as ultraviolet light absorbers, hindered amines as light stabilizers Compounds, benzoate compounds and the like, phenol compounds as antioxidants, methoquinone, methyl hydroquinone, hydroquinone and the like as polymerization inhibitors, and the above-mentioned polyisocyanates, melamine compounds and the like as crosslinking agents.

  Besides, as resins (so-called inert polymers) which do not show reactivity to active energy rays, for example, other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, Styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. It is preferable to use these in the range of up to 40 parts by weight in the resin composition.

  The active energy ray-curable resin composition of the present invention comprises usually 5 to 69% by weight, preferably 8 to 59% by weight of the reactive polycarboxylic acid compound (A) in the composition, and the other reactive compound (B). Usually 3 to 64 wt%, preferably 5 to 59 wt%, usually 1 to 10 wt% of the photopolymerization initiator (C), preferably 1 to 7 wt%, usually 60 to 90 wt% of the organic solvent (D) , Preferably 65 to 85% by weight. You may contain 0-80 weight% of another component as needed.

<Method for forming spacer for display element and color filter protective film>
The display element spacer formed from the active energy ray curable resin composition is preferably included in the present invention. The formation method of the said spacer for display elements is
(1) a step of applying the composition onto a substrate to form a coating,
(2) irradiating at least a part of the coating film with radiation;
(3) The process of developing the coating film irradiated with the said radiation, And (4) The process of heating the said developed coating film is passed.
A color filter protective film formed from the active energy ray curable resin composition is preferably included in the present invention. The method for forming the color filter protective film is carried out by appropriately adjusting the viscosity of the resin composition to obtain a coating solution, and applying it to the surface of the color filter on which the colored layer is formed.

A method of forming a photo spacer and / or a color filter protective film by a photolithography method using the active energy ray-curable resin composition of the present invention will be described.
The active energy ray-curable resin composition of the present invention is uniformly coated on a substrate by a known method such as roll coating, spin coating, spray coating or slit coating, and dried to form a photosensitive resin composition layer. . As a coating apparatus, a well-known coating apparatus can be used, for example, a spin coater, an air knife coater, a roll coater, a bar coater, a curtain coater, a gravure coater, a comma coater, etc. are mentioned.
If necessary, apply heat to dry (prebake). As a drying temperature, 50 degreeC or more is preferable, More preferably, it is 70 degreeC or more, Moreover, less than 150 degreeC is preferable, More preferably, it is 120 degrees C or less. The drying time is preferably 30 seconds or more, more preferably 1 minute or more, and preferably 20 minutes or less, more preferably 10 minutes or less.

Next, exposure of the photosensitive resin composition layer is performed by active energy rays through a predetermined photomask. With the active energy ray-curable resin composition of the present invention, even if the mask opening has a diameter of about 5 to 10 μm (area of about ²⁰ to 100 μm ² ), the diameter is 6 to 12 μm (area of 30 to 120 μm) with high accuracy. It can be formed in the range of ² ).

The active energy ray used for exposure is not particularly limited as long as the resin composition of the present invention can be cured. The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Here, specific examples of the active energy ray include ultraviolet rays, visible rays, infrared rays, electromagnetic waves such as X rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet light, laser light, visible light or electron beam is preferred, in view of the preferred applications of the present invention. The exposure dose is not particularly limited, but is preferably 20 to 1,000 mJ / cm ² .

Subsequently, the unexposed area is removed with a developer and development is performed. Although the developing solution used for development here may use an organic solvent, it is preferable to use aqueous alkali solution. Examples of alkaline aqueous solutions that can be used as a developer include aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and the like; organic bases such as hydroxytetramethylammonium and hydroxytetraethylammonium Aqueous solution of These can be used alone or in combination of two or more, and surfactants such as anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, and water-soluble organic solvents such as methanol and ethanol Can also be used. The concentration of alkali in the aqueous alkali solution is preferably 0.1 to 5% by weight from the viewpoint of obtaining appropriate developability. As a developing method, there are a dip method, a shower method, a liquid deposition method, and a vibration immersion method, but a shower method is preferable. The temperature of the developer is preferably 25 to 40 ° C. The development time is appropriately determined in accordance with the film thickness and the solubility of the resist.

  Heating (baking) may be performed as necessary to further ensure curing. When baking is performed, the baking temperature is preferably 120 to 250 ° C. The baking time may vary depending on the type of heating device, but may be, for example, 5 minutes to 30 minutes when the heating step is performed on a hot plate, or 30 minutes to 90 minutes when the heating step is performed in an oven. A step bake method or the like in which heating is performed twice or more can also be used.

The film thickness of the formed spacer is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.
The spacer formed in the formation method is a spacer that is flexible and has a small plastic deformation, with no unevenness in application and high flatness. It can be suitably used for display devices such as liquid crystal display devices and organic EL display devices.

  Moreover, as a color filter protective film, 0.5 micrometer-100 micrometers are preferable, and 1 micrometer-10 micrometers are more preferable. When the film thickness is too small, it is difficult to obtain the performance required for the protective film such as barrier property and flatness, and when it is too large, the performance such as transparency may be deteriorated.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In the examples, "parts" indicates parts by weight and "%" indicates% by weight unless otherwise noted.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured according to JIS K 7236: 2001.
2) Softening point: It measured by the method according to JISK7234: 1986.
3) Acid value: measured by a method according to JIS K 0070: 1992

Synthesis Example 1-1
In a glass container equipped with a thermometer, a reflux condenser, and a stirrer, 168 parts (1.0 mole) of 2,6-bis (hydroxymethyl) paracresol and 1008 parts (7.0 moles) of α-naphthol are charged. As a solvent , 1500 mL of methyl isobutyl ketone was added and stirred at room temperature under nitrogen atmosphere. 1.7 parts by weight of p-toluensulfonic acid (1.0% by weight with respect to the para-cresol dimethylol compound) was noted for heat generation, and was gradually added so that the liquid temperature did not exceed 50 ° C. After the addition, the mixture was heated to 50 ° C. on an oil bath and reacted for 2 hours, 500 mL of methyl isobutyl ketone was added, and the mixture was transferred to a separatory funnel and washed with water. After washing with water until the wash water showed neutrality, the organic layer was concentrated under reduced pressure to obtain 370 parts by weight of a pale yellow viscous material. The softening temperature (JIS K 2425 ring and ball method) was 112 ° C., and the hydroxyl equivalent (g / mol) was 138.
Subsequently, 138 parts by weight of the light yellow viscous substance (hydroxyl equivalent (g / mol) 138) and 460 parts by weight of epichlorohydrin are charged in a 1 liter reactor equipped with a thermometer, a stirrer, a dropping funnel and a product water separation unit. Nitrogen substitution was performed. Then, 85 parts by weight of a 48% by weight aqueous solution of sodium hydroxide was added dropwise over 5 hours. During the dropping, the reaction mixture was continuously removed from the reaction system by azeotropy of generated water and aqueous solution of sodium hydroxide with epichlorohydrin under the conditions of a reaction temperature of 60 ° C. and a pressure of 100 to 150 mmHg, and the epichlorohydrin was returned to the system. Then, excess unreacted epichlorohydrin was recovered under reduced pressure, 500 mL of methyl isobutyl ketone was added, and the mixture was washed until the aqueous layer of 100 mL of water showed neutrality. The methyl isobutyl ketone layer was concentrated under reduced pressure to obtain 170 parts by weight of a pale yellow solid epoxy resin product (EP1).
This product had an epoxy equivalent (g / mol) of 213 at a softening temperature (JIS K 2425) of 75 ° C. Further, when the product was subjected to GPC analysis, the composition amount of the epoxy resin of the formula (1) was 57% by weight. The epoxy resin product was confirmed to have M ⁺ 588 by mass spectrum (FAB-MS), and it was confirmed that the component having the following structure was the main component.

Synthesis Example 1-2
In a glass container equipped with a thermometer, a reflux condenser, and a stirrer, 168 parts by weight (1.0 mole) of 2,6-bis (hydroxymethyl) paracresol and 1008 parts by weight (7.0 mole) of β-naphthol are charged. As a solvent , 1500 mL of methyl isobutyl ketone was added and stirred at room temperature under a nitrogen atmosphere. 1.7 parts by weight of p-toluensulfonic acid (1.0% by weight with respect to the para-cresol dimethylol compound) was noted for heat generation, and was gradually added so that the liquid temperature did not exceed 50 ° C. After the addition, the mixture was heated to 80 ° C. on an oil bath and reacted for 2 hours, 500 mL of methyl isobutyl ketone was added, and the mixture was transferred to a separatory funnel and washed with water. After washing with water until the wash water showed neutrality, the organic layer was concentrated under reduced pressure to obtain 371 parts by weight of a yellow solid. The softening temperature (JISK2425 ring and ball method) was 113 ° C., and the hydroxyl equivalent (g / mol) was 138.
Subsequently, 138 parts by weight of the above yellow solid (hydroxyl equivalent (g / mol) 138) and 460 parts by weight of epichlorohydrin are charged into a 1 liter reactor equipped with a thermometer, a stirrer, a dropping funnel and a product water separation unit, and nitrogen substitution is carried out. After the addition, 85 parts by weight of a 48% by weight aqueous solution of sodium hydroxide was added dropwise over 5 hours. During the dropping, the reaction mixture was continuously removed from the reaction system by azeotropy of generated water and aqueous solution of sodium hydroxide with epichlorohydrin under the conditions of a reaction temperature of 60 ° C. and a pressure of 100 to 150 mmHg and the epichlorohydrin was returned to the system. Then, excess unreacted epichlorohydrin was recovered under reduced pressure, 500 mL of methyl isobutyl ketone was added, and the mixture was washed until the aqueous layer of 100 mL of water showed neutrality. The methyl isobutyl ketone layer was concentrated under reduced pressure to obtain 169 parts by weight of a pale yellow solid epoxy resin product (EP2). The product had a softening temperature of 76 ° C. and an epoxy equivalent (g / mol) of 214. Further, the composition amount of the epoxy resin of the formula (1) in the product was 55% by weight, and the mass spectrum (FAB-MS) was M ⁺ 588.

Synthesis Example 1-3
Naphthol-cresol novolak resin (when naphthol and cresol are reacted with aldehyde, the naphthol content in naphthol and cresol is 70% by weight, while the nitrogen purge is applied to a glass container equipped with a thermometer, reflux condenser, and stirrer. Add 160 parts by weight of resin obtained by reaction with 5% by weight of α-naphthol in naphthol, softening point of 110 ° C., 370 parts by weight of epichlorohydrin (4 molar equivalents to phenol resin), and 37 parts by weight of dimethyl sulfoxide, It melt | dissolved under stirring and heated up to 40-45 degreeC. Next, 41 parts by weight of flake-like sodium hydroxide was added in portions over 90 minutes, and then reaction was further performed at 40 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, the reaction product was washed with 500 parts by weight of water, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure using a rotary evaporator. To the residue was added 500 parts by weight of methyl isobutyl ketone, and the temperature was raised to 70.degree. Under stirring, 10 parts by weight of a 30% by weight aqueous solution of sodium hydroxide is added, and the reaction is carried out for 1 hour, and then the oil layer is washed with water until the wash water becomes neutral. From the solution obtained, using a rotary evaporator The methyl isobutyl ketone and the like were distilled off under reduced pressure to obtain 196 parts by weight of an epoxy resin product (EP3).
The product had a softening temperature of 93 ° C., an epoxy equivalent (g / mol) of 233, and a melt viscosity at 150 ° C. (ICI melt viscosity cone # 1) of 1.3 Pa · s. In 13 C-NMR, the ratio of the total peak area of 74 to 76 ppm to the total peak area of 68 to 71 ppm was 64: 36.

Examples 1-1 to 1-6
[Preparation of Reactive Polycarboxylic Acid Compound (A)]
The epoxy resin obtained in Synthesis Example 1-1 to 1-3 as the epoxy resin (a) is described in Table 1; the acrylic acid (abbr. AA, Mw = 72) is described in Table 1 as the compound (b), As a compound (c), dimethylol propionic acid (abbreviated as DMPA, Mw = 134) was added in the amount described in Table 1. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction solution, and reacted at 100 ° C. for 24 hours to react with a reactive epoxy carboxylate compound (E) solution I got The reaction proceeded to the next reaction, with a solid content acid value (AV: mg KOH / g) or less as the reaction end point. The acid value was measured in the reaction solution and converted to the acid value as a solid content.
Then, the reactive epoxy carboxylate compound (E) was added polybasic acid anhydride (d), tetrahydrophthalic anhydride (abbreviated THPA) Table 1 wherein the amount, and so that the solid content would be 65 by weight% as a solvent Propylene glycol monomethyl ether monoacetate was added, and after heating to 100 ° C., acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound (A) solution. The solid content acid value (AV: mg KOH / g) is described in Table 1.

Comparative Examples 1-1 and 1-2: Preparation of Reactive Polycarboxylic Acid Compound for Comparison Biphenol-type Epoxy Resin NC-3000H (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288 g / eq), Cresol novolac epoxy resin EOCN-103S (Japan) The amount described in Table 1 was added to Kayaku, epoxy equivalent 200 g / eq), and the amount described in Table 1 was added to acrylic acid as compound (b). 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction liquid, and reacted at 100 ° C. for 24 hours to obtain a carboxylate compound solution. The reaction was terminated with a solid content acid value (AV: mg KOH / g) of 5 mg KOH / g or less, and the reaction proceeded to the next reaction.
Then, as the polybasic acid anhydride to reactive epoxy carboxylate compound solution, tetrahydrophthalic anhydride (abbreviated THPA) Table 1 wherein the amount, and propylene glycol monomethyl ether monoacetate so as to have a solid content would be 65 by weight% as a solvent The reaction mixture was heated to 100 ° C., and acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound solution for comparison. The solid content acid value (AV: mg KOH / g) is described in Table 1.

Comparative Example 1-3 Preparation of a reactive caprolactone modified polycarboxylic acid compound for comparison 200 g of cresol novolac epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 g / eq), 58 g of acrylic acid 40 g of methylol propionic acid, 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content became 80% by weight of the reaction liquid, and reacted at 100 ° C. for 24 hours. Further, 68 g of ε-caprolactone was added and reacted for 8 hours. Then, the multi as polybasic acid anhydride was heated tetrahydrophthalic anhydride (abbreviated THPA) 91g, and the propylene glycol monomethyl ether monoacetate so as to have a solid content would be 65 by weight% as a solvent, to 100 ° C., acid Addition reaction was carried out to obtain a comparative reactive caprolactone modified polycarboxylic acid compound solution. The solid content acid value (AV: mg KOH / g) was 70 mg KOH / g.

In addition, the unit of the numerical value of each component in Table 1 is g (gram).
Moreover, the detail of each component used by the composition of an Example and a comparative example is shown below.
<Reactive Compound (B)>
B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
<Photoinitiator (C)>
C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (IRGACURE OXE02, manufactured by BASF AG)
<Organic solvent (D)>
PGMEA: propylene glycol monomethyl ether acetate DEGDM: diethylene glycol dimethyl ether

<Other optional components>
<Surfactant (H)>
H-1: silicone surfactant (Dow Corning Silicone Co., Ltd., SH8400FLUID)

<Preparation of the composition>
Example 2-1
(B-1) as a reactive compound (B) in a solution containing an amount corresponding to 100 parts by weight (solid content) of the reactant obtained in Example 1-1 as the reactive polycarboxylic acid compound (A) 100 parts by weight, 10 parts by weight of (C-1) as a photopolymerization initiator (C), PGMEA and DEGDM as an organic solvent so as to obtain a desired solid concentration, and (H-) as a surfactant (H) 1) The composition (S-1) was prepared by mixing 0.2 parts by weight and filtering through a membrane filter having a pore size of 0.2 μm. In addition, the numerical value of the organic solvent in Table 2 is a weight ratio of PGMEA and DEGDM.

Examples 2-2 to 2-6 and comparative examples 2-1 to 2-3
The same procedures as in Example 2-1 were followed, except that the types and blending amounts (parts by weight) of the respective components were as described in Table 2, to obtain Examples 2-2 to 2-6 and Comparative Example 2-1. The composition of 2-3 was prepared. In addition, the numerical value of the organic solvent in Table 2 is a weight ratio of PGMEA and DEGDM.

<Evaluation>
The following evaluation was performed about the composition formed of Example 2-1 to 2-6 and comparative example 2-1 to 2-3, and the spacer formed from the coating film. The evaluation results are shown in Table 3.

(viscosity)
The viscosity (mPa · s) of each composition at 25 ° C. was measured using an E-type viscometer (TV-200, manufactured by Toki Sangyo Co., Ltd.).

(Solid content concentration)
0.3 g of the composition is finely divided in an aluminum dish, and after adding about 1 g of diethylene glycol dimethyl ether, it is dried on a hot plate at 175 ° C. for 60 minutes, and the solid content in the composition The concentration (% by weight) was determined.

(Appearance of coating film)
The composition is coated on a 100 x 100 mm chromium film-formed glass using a slit die coater (Rigaku Die, manufactured by Techno Machine Co., Ltd.), dried under a reduced pressure to 0.5 Torr, and then heated to 100 ° C on a hot plate. The film was prebaked for 2 minutes to form a coating film, and the film was exposed at an exposure dose of 200 mJ / cm ² to form a film having a film thickness of 4 μm from the top surface of the chromium film-formed glass. Under the sodium lamp, the appearance of the coating was observed with the naked eye. At this time, uneven streaks (unevenness of one or a plurality of straight lines in the coating direction or in a direction intersecting the same), haze (uneven cloudiness), uneven pin marks (points formed on the substrate support pins) in the entire coating film Appearance status of the When none of these unevenness was seen, it was judged as "○ (good)", when any was seen a little as "を (slightly poor)", and when clearly seen, as "× (bad)".

(Flatness)
The film thickness of the coating film on the chromium film-formed glass prepared as described above was measured using a needle contact type measuring machine (Surfcom, manufactured by Tokyo Seimitsu Co., Ltd.). The film thickness uniformity measured the film thickness in nine measurement points, and was computed from the following formula. Assuming that the minor axis direction of the substrate is X and the major axis direction is Y, nine measurement points (X [mm], Y [mm]) are (50, 10), (50, 20), (50, 30). (50, 40), (50, 50), (50, 60), (50, 70), (50, 80), (50, 90). When the film thickness uniformity is 2% or less, it can be judged that the film thickness uniformity is good.
Film thickness uniformity (%) = {FT (X, Y) max-FT (X, Y) min} x 100 / {2 x FT (X, Y) avg. }
In the above equation, FT (X, Y) max is the maximum value among the film thicknesses at nine measurement points, FT (X, Y) min is the minimum value among the film thicknesses at nine measurement points, FT (X, Y) Y) avg. Is an average value in the film thickness at nine measurement points.

(High speed application)
The coating solution is applied from a nozzle on a 100 mm × 100 mm non-alkali glass substrate using a slit coater as coating conditions such that the distance between the base and the nozzle is 150 μm and the film thickness after exposure is 2.5 μm. The moving speed of the nozzle is 120 mm / sec. 200 mm / sec. The maximum velocity at which no streaky unevenness due to fluid breakage occurs was determined. At this time, 180 mm / sec. If streaky unevenness does not occur even at the above speeds, it can be determined that high-speed application is possible.

(Radiation sensitivity)
The composition is applied onto a 100 mm × 100 mm ITO sputtered glass substrate by spin coating, and then prebaked on a 90 ° C. hot plate for 3 minutes to form a coating film of 3.5 μm thickness. did. Subsequently, it exposed to the obtained coating film using the ultraviolet exposure device (Oak Manufacturing Co., Ltd. model HMW-680GW) through the photomask in which the circular pattern with a diameter of 12 micrometers was formed as an opening part. Then, it is developed with a 0.05% by mass aqueous potassium hydroxide solution at 25 ° C. for 60 seconds, then washed with pure water for 1 minute, and post-baked in an oven at 230 ° C. for 30 minutes to form a patterned film A spacer was formed. At this time, the minimum exposure amount at which the residual film ratio after post-baking (film thickness of film after post-baking x 100 / film thickness after exposure (before post-baking)) is 90% or more is examined. did. When this value is 55 mJ / cm ² or less, it can be said that the sensitivity is good.
(Development residue)
In addition, the upper surface of the substrate was visually observed to confirm the presence or absence of a residue. Evaluation criteria are as follows.
○ ... no residue △ ... slight residue × ... much residue

(Compression performance)
A spacer having a cylindrical pattern was formed on the substrate in the same manner as in the radiation sensitivity evaluation, except that the exposure amount was an exposure amount corresponding to the sensitivity determined in the evaluation of the radiation sensitivity. At this time, the diameter of the photomask interposed at the time of exposure was changed so that the diameter of the bottom of the pattern after post-baking would be 20 μm. Using a micro compression tester (Fisher Scope H100C, manufactured by Fisher Instruments Co., Ltd.), a 50 μm square planar indenter was used for this spacer, and a compression test was performed with a load of 50 mN. The change was measured, and the recovery rate (%) was calculated from the amount of displacement under a load of 50 mN and the amount of displacement when a load of 50 mN was removed. At this time, when the recovery rate is 70% or more and the displacement at a load of 50 mN is 0.15 μm or more, it can be said that the spacer has a compression performance provided with both a high recovery rate and flexibility.

(Heat-resistant)
The cured film was measured using TG / DTA (manufactured by SII, TG / DTA6200). The mass change was described after holding at 250 ° C. for 1 hour. The smaller the rate of change, the better the heat resistance.

(Total light transmittance)
A spin coater is applied on a 50 mm × 50 mm non-alkali glass substrate and dried under a reduced pressure to 0.5 Torr, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating, and further 200 mJ / cm By exposing with an exposure amount of ² , a film having a thickness of 4 μm was formed. The evaluation substrate having the cured coating film was measured using a haze meter (TC-H3DPK, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

(Heat resistant transmittance )
The evaluation substrate having the cured coating film was heat-treated at 250 ° C. for 1 hour, and the transmittance of wavelength light of 400 nm and 540 nm was measured by using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.).

As is clear from the above results, the active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) in the present invention of Examples 2-1 to 2-6 is a compound of Comparative Example 2-1. It became clear that developability and curability were good compared with the composition of 2-3, and heat resistance, heat-resistant transparency, flatness, flexibility, and toughness were excellent. Moreover, Example 2-2, Example 2-4, and Example 2-6 which also used DMPA which is a compound (c) for preparation of a reactive polycarboxylic acid compound (A), and Example 2-1. It was found to have better compression performance as compared to Examples 2-3 and 2-5.

Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.
The present application is based on the Japanese Patent Application (Japanese Patent Application No. 2014-015809) filed on January 30, 2014, which is incorporated by reference in its entirety. Also, all references cited herein are taken as a whole.

The active energy ray-curable resin composition of the present invention is excellent in developability, curability and high-speed coating property, and is a spacer for a display element excellent in heat resistance, heat resistance transparency, flatness, flexibility and toughness. A color filter protective film can be formed. Therefore, the composition is suitable as a material for forming a liquid crystal display element, a spacer for a display element such as an organic EL, and a color filter protective film.

Claims (5)

A spacer for a display element comprising a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the reactive polycarboxylic acid compound (A), a photopolymerization initiator (C), and an organic solvent (D) An active energy ray-curable resin composition for a color filter protective film, comprising:
The reactive polycarboxylic acid compound (A) comprises an epoxy resin (a) having at least two or more epoxy groups in one molecule, and one or more polymerizable ethylenic unsaturated groups in one molecule or more. compounds having a carboxyl group (b), a compound having at least two hydroxyl groups and one or more carboxyl groups及beauty in one molecule reaction product of (c) to (E), further polybasic acid anhydride ( a reactive polycarboxylic acid compound (A) obtained by reacting d),
The active energy ray curable resin composition, wherein the epoxy resin (a) having at least two or more epoxy groups in one molecule is a naphthalene skeleton-containing epoxy resin . The display element spacer or color filter according to claim 1, wherein the reactive compound (B) is any one or two or more selected from monofunctional, bifunctional and trifunctional or higher (meth) acrylates. Active energy ray-curable resin composition for protective film. The display according to claim 1 or 2, wherein a proportion of the reactive compound (B) is 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the reactive polycarboxylic acid compound (A) as a use ratio in the resin composition. An active energy ray-curable resin composition for a device spacer or a color filter protective film. The spacer for display elements formed from the active energy ray curable resin composition as described in any one of Claims 1-3 . The color filter protective film formed from the active energy ray curable resin composition as described in any one of Claims 1-3 .