JP6357485B2 - Active energy ray curable resin composition, and display element spacer and / or color filter protective film using the same - Google Patents

Description

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

  For display device materials, resin compositions comprising a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and the like have been used. In recent years, materials for display devices such as “LCD, EL, PDP, FED (SED), rear projection display, electronic paper, digital camera, etc., especially display elements, materials around display elements” Color liquid crystal displays (LCDs) are rapidly spreading. In general, a color liquid crystal display device has a structure in which a color filter and an electrode substrate such as a TFT substrate are opposed to each other to provide 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. Have taken.

  The color filter has a black matrix layer formed in a predetermined pattern on the transparent substrate to shield the boundary between pixels, and usually red (R), green (G), A colored layer in which blue (B) is arranged in a predetermined order, a protective film, and a transparent electrode film are stacked in this order from the side close to the transparent substrate. An alignment film is provided on the inner surface side of the color filter and the electrode substrate facing the color filter. Further, in the gap, in order to maintain a uniform and uniform cell gap between the color filter and the electrode substrate, pearls having a constant particle diameter are dispersed as spacers, or columns or stripes having a height corresponding to the cell gap. Shaped spacers are formed. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind each pixel colored in each color. 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 can be formed using a resin. The colored layer needs to be formed in a predetermined pattern for each color pixel. The protective film is preferably one that can cover only the region where the colored layer is formed on the transparent substrate in consideration of the adhesion and sealing property of the seal portion. In addition, the spacer must be accurately provided in the black matrix layer forming region, that is, in the non-display region. For this reason, a colored layer, a protective film, and a columnar spacer have been formed using a curable resin that can easily limit a region to be cured by a photomask.

  In addition, in order to form a colored layer, a protective film, or a columnar spacer, development using an organic solvent after exposing the coated surface of the curable resin is complicated in terms of handling and waste liquid treatment, and economical. Therefore, 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 a high temperature (200-260 ° C. or higher) when forming an alignment film and a transparent electrode, so that they have very high heat resistance, especially heat resisting color resistance in color resists and spacers. There is a need for excellent products.

  In Patent Document 1, a photosensitive resin produced by neutralizing an acid-modified epoxy acrylate of a cresol novolak epoxy resin with a primary amino compound is used as a polymer component of a photosensitive resin composition for a photospacer and a color filter. Yes. However, such a composition containing a salt of a primary amino compound and water has poor applicability and flatness, and cannot be said to be sufficiently compatible with a slit coater or the like.

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

In Patent Document 3, a reaction product obtained by adding acrylic acid or dimethylolpropionic acid to cresol novolac epoxy resin as a polymer component of a protective film for a color filter or a resist ink composition for a flexible printed wiring board is caprolactone-modified, and then tetrahydroanhydride is modified. Active energy ray curable resin modified with phthalic acid is used. The polymer component that is the main component of the composition is excellent in developability and flexibility, but has a problem that it is inferior in the elastic recovery rate required as a photospacer.
Patent Document 4 discloses that a resin composition containing an unsaturated group-containing polycarboxylic acid is suitable for a solder resist, but does not describe a display element spacer or a color filter protective film at all. .

Japanese Unexamined Patent Publication No. 2004-109752 Japanese Unexamined Patent Publication No. 2007-010885 Japanese Laid-Open Patent Publication No. 2004-300026 Japanese Patent No. 2704661

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

  As a result of intensive studies in order to solve the above problems, the present inventors have found that a resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

That is, the present invention
(1) Reactive polycarboxylic acid compound (A), reactive compound (B) other than reactive polycarboxylic acid compound (A), photopolymerization initiator (C), and organic solvent (D) An active energy ray-curable resin composition for a spacer or color filter protective film, wherein the reactive polycarboxylic acid compound (A) is one per molecule with the epoxy resin (a) represented by the general formula (1) The above compound (b) having a polymerizable ethylenically unsaturated group and one or more carboxyl groups, and if necessary, a compound having at least two hydroxyl groups and one or more carboxyl groups in one molecule (c) It is related with this active energy ray hardening-type resin composition which is the reactive polycarboxylic acid compound (A) obtained by making a polybasic acid anhydride (d) react further with the reaction product (E) with this.

(Where n represents a positive number from 0 to 2)
(2) Further, in the present invention, the reactive polycarboxylic acid compound (A) includes an epoxy resin (a) represented by the general formula (1) and one or more polymerizable ethylenically unsaturated groups in one molecule. A polybasic acid anhydride is further added to the reaction product (E) of the compound (b) having one or more carboxyl groups and the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule. The present invention relates to a display element spacer or an active energy ray-curable resin composition for a color filter protective film according to (1), which is a reactive polycarboxylic acid compound (A) obtained by reacting the product (d).
(3) Furthermore, this invention relates to the spacer for display elements formed from the active energy ray hardening-type resin composition as described in said (1) or (2).
(4) The present invention further relates to a color filter protective film formed from the active energy ray-curable resin composition according to (1) or (2).

  The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention has excellent developability, high radiation sensitivity, and excellent heat-resistant transparency, flatness, flexibility, and toughness. The display element spacer and the color filter protective film can be provided.

Hereinafter, the present invention will be described in detail.
The reactive polycarboxylic acid compound (A) in the present invention comprises an epoxy resin (a) represented by the general formula (1), one or more polymerizable ethylenically unsaturated groups and one or more carboxyls in one molecule. A compound (b) having a group, and, if necessary, a reaction product (E) of a compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule; Obtained by reacting (d).

That is, the reactive polycarboxylic acid compound (A) in the present invention is obtained by reacting the reaction product (E) of the epoxy resin (a) with the compound (b) with the polybasic acid anhydride (d), or It is obtained by reacting a polybasic acid anhydride (d) with a reaction product (E) of (a), a compound (b) and a compound (c).
In the present invention, the characteristics of the present invention are exhibited by introducing an ethylenically unsaturated group and a hydroxyl group into the molecular chain by an epoxy carboxylation reaction.

  The epoxy resin (a) represented by the general formula (1) in the present invention is (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) α, α-dimethylbenzyl) phenol) (hereinafter referred to as phenol). Compound (PA1)) and epihalohydrin are obtained. This epoxy resin is shown as the following representative structure.

(Where n represents a positive number from 0 to 2)

Although this epoxy resin is generally available as TECMOREVG 3101L (printintech), NC-6300C (manufactured by Nippon Kayaku), NC-6300H (manufactured by Nippon Kayaku), etc., it can also be obtained by the following production method. it can.
The epoxy resin (a) used in the present invention is more preferably a solid at normal temperature. In the present invention, an epoxy resin (a) having a softening point of 50 to 100 ° C. or a melting point of 50 to 190 ° C. is usually used, but the softening point is 60 to 100 ° C. or the melting point of 60 to 190 ° C. Those are preferred. Moreover, epoxy equivalent is 130-500 g / eq. Can be usually used in the present invention, but preferably 150 to 400 g / eq. More preferably, 170-300 g / eq. It is. If the epoxy equivalent is too small, it tends to be hard and fragile, and if the epoxy equivalent is too large, it may be difficult to obtain hardness and the glass transition point may be lowered.

  Examples of the epihalohydrin used in the reaction between the phenol compound (PA1) and epihalohydrin include epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, and the like, which are easily available industrially in the present invention. Epichlorohydrin is preferred. The usage-amount of epihalohydrin is 2-15 mol normally with respect to 1 mol of hydroxyl groups of a phenol compound (PA1), Preferably it is 4-10 mol. If too much epihalohydrin is used, not only the productivity is poor, but also the softening point of the epoxy resin to be produced is lowered, and there are cases where the tackiness and the like when a prepreg is made are not affected. In addition, when the amount of epihalohydrin is 2 mol or less, the value of n may increase and gelation may easily occur during production.

  In the epoxidation reaction, an alkali metal hydroxide is preferably used. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be used as a solid or an aqueous solution thereof. For example, when alkali metal hydroxide is used as an aqueous solution, an aqueous solution of alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or normal pressure. Then, liquid separation is performed to remove water, and the epoxidation reaction can be carried out by continuously returning the epihalohydrin to the reaction system. Moreover, when using solid, it is preferable to use a flaky thing from problems, such as the ease of handling and solubility. The usage-amount of an alkali metal hydroxide is 0.90-1.5 mol normally with respect to 1 mol of hydroxyl groups of a phenol compound (PA1), Preferably it is 1.01-1.25 mol, More preferably 1.01-1.15 mol.

In the epoxidation reaction, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylphosphonium chloride, tetramethylphosphonium bromide, trimethylbenzylphosphonium chloride, triphenyl benzyl phosphonium chloride, quaternary phosphonium salts such as triphenyl ethyl phosphonium bromide may be added as a catalyst. The usage-amount of these quaternary salts is 0.1-15g normally with respect to 1 mol of hydroxyl groups of a phenol compound (PA1), Preferably it is 0.2-10g.

  In the epoxidation reaction, an alcohol such as methanol, ethanol and isopropyl alcohol, an ether such as tetrahydrofuran and dioxane, an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, and dimethylimidazolidinone are added to react. It is preferable to carry out the reaction, and in the present invention, alcohols and / or ethers are particularly preferred from the viewpoint of optical properties.

  When using the said alcohols and ethers, the usage-amount is 2-50 weight% normally with respect to the usage-amount of an epihalohydrin, Preferably it is 4-20 weight%. On the other hand, when the aprotic polar solvent is used, the amount used is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used.

  In the epoxidation reaction, the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. On the other hand, reaction time is 0.5 to 10 hours normally, Preferably it is 1 to 8 hours. This reaction may be carried out at normal pressure or under reduced pressure, and the reaction may be carried out under azeotropic dehydration conditions of water-epihalohydrin under reduced pressure conditions. The reaction product of these epoxidation reactions can be purified by removing epihalohydrin, a solvent, or the like under heating and reduced pressure after washing with water or without washing with water. In addition, in order to make an epoxy resin with less hydrolyzable halogen, the recovered reaction product is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. In addition, it is preferable to perform a ring-closing reaction of the by-product to ensure the ring-closing of the halohydrin which is a by-product.

  In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of the phenol compound (PA1) used for epoxidation, Preferably it is 0.05-0. 2 moles. Moreover, reaction temperature is 50-120 degreeC normally, and reaction time is 0.5 to 2 hours normally.

  In the epoxidation reaction, after the completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain an epoxy resin that can be used in the present invention. The epoxy resin thus obtained includes a part of the epoxy resin added with the solvent and water, and a part of the epoxy resin in which halogen cannot be closed.

The epoxy resin (a), which is a reaction product of the phenol compound (PA1) and epihalohydrin thus obtained, is excellent in productivity and handleability, and further provides high mechanical strength to the cured product. Those satisfying the conditions are preferred.
1. The epoxy equivalent is preferably 195 to 245 g / eq. , More preferably 200 to 240 g / eq. It is.
2. In gel permeation chromatography, two phenolic compounds (PA1) connected by epihalohydrin are 30 area% or less, three connected are 20 area% or less, more preferably two are connected by 25 area%. In the following, three connected elements are 15 area% or less. The remainder corresponds to the monomer of the epoxy resin (a).

The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule in the present invention is reacted in order to impart reactivity to active energy rays. is there. There is no limitation as long as one or more ethylenically unsaturated groups and carboxyl groups are present 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 saturated or unsaturated dibasic acid and unsaturated group-containing monocarboxylic acid compounds. The reaction material with a glycidyl compound is mentioned. In the above, (meth) acrylic acids include, for example, (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 A half-reaction product of a (meth) acrylate derivative having one hydroxyl group in the molecule and a half-ester reaction product, a half-ester reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl (meth) acrylate derivative. Examples include esters.

Further, polycarboxylic acid compounds having two or more carboxyl groups in one molecule include (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters which are equimolar reactants, saturated or unsaturated dicarboxylic acids. And half-esters which are equimolar reactants of a basic acid and a glycidyl (meth) acrylate derivative having a plurality of epoxy groups.
Of these, most preferable are (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when an active energy ray-curable resin composition is used. As the compound (b), those having no hydroxyl group in the compound are preferable.

The compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule, which is used as necessary in the present invention, is reacted for the purpose of introducing hydroxyl groups into the carboxylate compound. It is.
Specific examples of the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule in the present invention include, for example, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolacetic acid, dimethylolbutyric acid, and dimethylol. Examples thereof include polyhydroxy-containing monocarboxylic acids such as valeric acid and dimethylol caproic acid. Particularly preferable examples include dimethylolpropionic acid and the like.

Among these, considering the stability of the reaction of the epoxy resin (a) with the compound (b) and the compound (c), the compound (b) and the compound (c) are preferably monocarboxylic acids. Even when carboxylic acid and 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.
The charge ratio of the total amount of carboxylic acids of the epoxy resin (a) and the compound (b) and the compound (c) used as necessary in this reaction should be appropriately changed according to the use. That is, when all epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as a reactive epoxy carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

  On the other hand, by deliberately reducing the charged amount of the carboxylic acid compound and leaving an unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, a polymerization reaction or heat caused by a photocationic catalyst, It is also possible to use the polymerization reaction in combination. However, in this case, attention should be paid to storage of the reactive epoxycarboxylate compound (E) and examination of production conditions.

  When producing the reactive epoxycarboxylate compound (E) which does not leave an epoxy group, the total of the compound (b) and the compound (c) used as needed is 90-90 per 1 equivalent of the epoxy resin (a). It is preferable that it is 120 equivalent%. Within this range, it is possible to manufacture under relatively stable conditions. If the total amount of compound (b) and compound (c) used as needed is larger than this, excess compound (b) and compound (c) will remain, such being undesirable.

  Moreover, when leaving an epoxy group intentionally, the sum total of a compound (b) and the compound (c) used as needed is 20-90 equivalent% with respect to 1 equivalent of the said epoxy resin (a). Is preferred. When deviating from this range, the reaction by the further epoxy group does not proceed sufficiently. In this case, sufficient attention must be paid to gelation during the reaction and stability over time of the reactive epoxycarboxylate compound (E).

  When using the compound (b) and the compound (c), 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 to react the reactive epoxycarboxylate compound (E) with the polybasic acid anhydride (d).

  Carboxylation reaction can also be made to react without solvent, or can be diluted with a solvent. 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 solvent used should be adjusted as appropriate according to the viscosity and intended use of the resulting resin, 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 mixtures thereof, petroleum ether, white Examples include gasoline, solvent naphtha, ester solvents, ether solvents, ketone solvents, and the like.

  Examples of ester solvents include 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, and triethylene. Mono, such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, or polyalkylene glycol monoalkyl ether monoacetates, dialkyl glutarate, dialkyl succinate, dialkyl adipate Polycarboxylic acid alkyl esters such as And the like.

  Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Examples include ethers and cyclic ethers such as tetrahydrofuran.

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

  In addition, the reaction can be performed in a single or mixed organic solvent such as other reactive compounds (B) described later. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  In the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is the reaction product, that is, the epoxy resin (a), the carboxylic acid compound (b), and the compound (c) used as necessary. ) And optionally 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the reaction product added with a solvent or the like. 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 catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples thereof include known general basic catalysts such as zirconium acid.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling appropriately.

  A preferred molecular weight range of the reactive epoxycarboxylate compound (E) thus obtained is a polystyrene-reduced weight average molecular weight in GPC in the range of 1,000 to 50,000, more preferably 2,000 to 30,000. It is.

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

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

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

  The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the carboxylation reaction solution. The amount added should be changed as appropriate according to the application.

  The addition amount of the polybasic acid anhydride (d) is, for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkali development type resist, the polybasic acid anhydride (d) is finally added. The solid content acid value (based on JISK5601-2-1: 1999) of the reactive polycarboxylic acid compound (A) thus obtained is 40 to 120 mg · KOH / g, more preferably 60 to 120 mg · KOH / g. It is preferable to charge the calculated value as follows. When the solid content acid value at this time is within this range, the aqueous alkaline resin developability of the photosensitive resin composition of the present invention exhibits good developability. That is, good patternability and a wide control range for over-development are possible, and no excess acid anhydride remains.

  In the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is the reaction product, that is, the epoxy compound (a), the carboxylic acid compound (b), and the compound (c) used as necessary. 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the reaction product obtained by adding the reactive epoxycarboxylate compound (E) and polybasic acid anhydride (d) obtained from 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 catalysts that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, octane. Examples include zirconium acid.

  This acid addition reaction can be reacted with no solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. In addition, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can. The solvent that can be used may be the same as that used in the carboxylation reaction.

  The preferred amount of solvent used should be adjusted as appropriate according to the viscosity and intended use of the resulting resin, 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

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

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

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

As a preferable molecular weight range of the reactive polycarboxylic acid compound (A), the polystyrene-equivalent weight average molecular weight in GPC is in the range of 1,000 to 50,000, more preferably 2,000 to 30,000.
The use ratio of the reactive polycarboxylic acid compound (A) in the resin composition is usually 5 to 69% by weight, preferably about 8 to 59% by weight.

  Examples of the reactive compound (B) that can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, cationic reaction type other epoxy compounds, and vinyl compounds sensitive to both.

  Examples of radical reaction type acrylates include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, epoxy ( And (meth) acrylate oligomers.

  Monofunctional (meth) acrylates include, for example, acryloylmorpholine; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; cyclohexane -1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Aliphatic (meth) acrylates such as (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (poly) ethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, Libromophenyloxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenylphenol epoxy (meth) acrylate Aromatic (meth) acrylates such as

  As 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 Di (meth) acrylate of ε-caprolactone adduct of glycol di (meth) acrylate hydroxybivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.) But it can.

As trifunctional or more polyfunctional (meth) acrylates, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, trimethylolpropane (poly) ethoxytri (meth) Methylols such as acrylate, trimethylolpropane (poly) propoxytri (meth) acrylate, trimethylolpropane (poly) ethoxy (poly) propoxytri (meth) acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol (poly) ethoxy Tetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Rutetora (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol 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 pentaacrylates.

Examples of the (poly) ester (meth) acrylate oligomer include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, (poly) ethylene glycol, (poly) propylene glycol, Glycols such as 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-dimethanol Alicyclic alkyldioses such as (Poly) ester diol, which is a reaction product of diol compounds such as bisphenol A (poly) ethoxydiol, or bisphenol A (poly) propoxydiol, and the dibasic acid or anhydride thereof, and (meth) acrylic Examples include a reaction product with an acid.

Examples of the urethane (meth) acrylate oligomer include diol compounds (for example, 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 polypropoxy Diol etc.) or a reaction product of these diol compounds and dibasic acid or anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or anhydride thereof) Polyester diol and organic polyisocyanate (eg, chain saturated hydrocarbon isocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate) , Norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), 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, 6-isopropyl-1,3-phenyl diisocyanate, aromatic polyisocyanate such as 1,5-naphthalene diisocyanate), and then a reaction product obtained by adding a hydroxyl group-containing (meth) acrylate.

  The epoxy (meth) acrylate oligomer is a carboxylate compound of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate Bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol-A novolak type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (Meth) acrylate etc. are mentioned.

  Examples of 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, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene 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 (such as “Syracure UVR-6128” manufactured by Union Carbide), 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, the reactive compound (B) is most preferably monofunctional, bifunctional, trifunctional or higher (meth) acrylate, etc., from the viewpoints of good polymerizability and improved strength of the resulting spacer and the like. .

  The reactive compound (B) of the present invention may be used alone or in combination of two or more. The proportion of the reactive compound (B) used 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 preferred. When the usage-amount of a reactive compound (B) is 30 weight part-250 weight part, the heat resistance of the said composition, the heat resistance of the spacer for display elements obtained, and an elastic characteristic become more favorable.

  As the photopolymerization initiator (C) of the present invention, the reactive polycarboxylic acid compound (A) and a reactive compound (B) other than the reactive polycarboxylic acid compound (A) are polymerized in response to active energy rays. Is an ingredient that produces an active species that can initiate Examples of such photopolymerization initiator (C) include O-acyloxime compounds, acetophenone compounds, biimidazole compounds and the like.

  Examples of the O-acyloxime compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9- Ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-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] -ethane-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 -(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Of 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-acyloxime compounds may be used alone or in combination of two or more.

  Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound.

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

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 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.

  Of these acetophenone compounds, α-aminoketone 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.

  Examples of the biimidazole compound include 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 Examples include imidazole. 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.

  A commercial item may be used for said photoinitiator (C), for example, 2-methyl-1- (4-methylthiophenyl))-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-methyl) Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02) (above, Ciba Specialty Chemicals).

  In the photosensitive 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 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). The curing accelerator can be used in combination, such as triethanolamine, diethanolamine, N- methyldiethanolamine, 2-methylamino-benzoate, dimethylamino acetophenone, p- dimethylaminobenzoic acid isoamyl ester, amines such as EPA, 2- And hydrogen donors such as mercaptobenzothiazole. The amount of these curing accelerators used is usually 0 wt% or more and 5 wt% or less when the solid content of the resin composition of the present invention is 100 wt%.

  As the organic solvent (D), those that uniformly dissolve or disperse each constituent component and do not react with each constituent component are suitably used. Examples of the organic solvent (D) include the above-described aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, 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 Examples include glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, and ketones. These may be used alone or in admixture of two or more.

  Specifically, examples of the organic solvent (D) include alcohols such as benzyl alcohol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Propylene glycol monoalkyl ethers such as propylene 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, diechi Diethylene glycol monoalkyl ether acetates such as diglycol 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 mono Dipropylene glycol monoalkyl ethers such as butyl 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 Ether acetates; lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; ethyl hydroxyacetate, 2-hydroxy-2-methylpropion Ethyl acetate, 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, etc. Aliphatic carboxylic acids Esters; Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide; Ketones such as N-methylpyrrolidone and γ-butyrolactone. These may be used alone or in admixture of two or more.

  The solid content concentration in the composition is usually from 10% by weight to 40% by weight, and preferably from 15% by weight to 35% by weight. By making the solid content concentration of the composition within the above range, it is possible to effectively suppress the applicability, the film thickness uniformity and the coating unevenness.

  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 spontaneously leveled even when coating unevenness occurs while maintaining film thickness uniformity.

  Examples of the alkali-soluble resin (G) used as necessary in the photosensitive resin composition of the present invention include a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, and a monomer having a carboxyl group. Manufactured by copolymerizing a monomer having a phenolic hydroxyl 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.

  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 ( (Meth) 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.

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

  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-epoxycyclohexylmethyl acrylate.

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

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, and the like.

  Other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatic 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 acid esters and (meth) acrylamides are preferable because the partition walls formed from the composition are excellent in heat resistance.

  When copolymerizing the alkali-soluble resin (G), it can be produced by radical polymerization of an unsaturated compound in the presence of a polymerization initiator in a solvent. The above-mentioned solvent can be used, may be used independently, and may mix and use 2 or more types.

  As the polymerization initiator used in the polymerization reaction for producing the alkali-soluble resin (G), those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4- Azo compounds such as methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane and peroxides Examples include hydrogen oxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox 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 the molecular weight modifier 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; xanthate disulfide, xanthogen such as diisopropyl xanthogen disulfide; terpinolene, alpha-methyl styrene dimer and the like.

Monomers having a phenolic hydroxyl group such as monomers having a hydroxyl group, acid anhydrides having an ethylenic double bond, monomers having a carboxyl group, monomers having an epoxy group, sulfonic acid groups As a compound (f) having a functional group capable of binding to the reactive group and an ethylenic double bond with respect to the monomer (e) having a reactive group such as a monomer having Can be mentioned.
(1) An acid anhydride (f) having an ethylenic double bond with respect to the monomer (e) having a hydroxyl group,
(2) A compound (f) having an isocyanate group and an ethylenic double bond with respect to the monomer (e) having a hydroxyl group,
(3) Compound (f) having an acyl chloride group and an ethylenic double bond with respect to monomer (e) having a hydroxyl group,
(4) For the acid anhydride (e) having an ethylenic double bond, the compound (f) having a hydroxyl group and an ethylenic double bond,
(5) Compound (f) having an epoxy group and an ethylenic double bond with respect to monomer (e) having a carboxyl group,
(6) A compound (f) having a carboxyl group and an ethylenic double bond with respect to the monomer (e) having an epoxy group.

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

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

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

  Specific examples of the compound having a hydroxyl group and an ethylenic double bond include the above-described monomers having a hydroxyl group.

  Specific examples of the compound having an epoxy group and an ethylenic double bond include the above-described monomers having an epoxy group.

  Specific examples of the compound having a carboxyl group and an ethylenic double bond include the above-described examples of the monomer having a carboxyl group.

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

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

  Further, 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), and dibutyltin diacetate.

  For example, 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 developability (characteristic for accurately forming a desired pattern shape) of the composition can be enhanced.

  Furthermore, the photosensitive resin composition of the present invention includes a surfactant, a leveling agent, an antifoaming agent, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a crosslinking agent, if necessary. It is also possible to add adhesion assistants, pigments, dyes and the like to impart the desired functionality. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents and antifoaming agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as ultraviolet absorbers, hindered amines as light stabilizers, etc. Compounds, benzoate compounds, etc., antioxidants such as phenol compounds, polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone and the like, and crosslinking agents include the polyisocyanates and melamine compounds.

  In addition to this, as resins not showing reactivity to active energy rays (so-called inert polymers), 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. These are preferably used in the resin composition in the range of up to 40 parts by weight.

  In the active energy ray-curable resin composition of the present invention, the reactive polycarboxylic acid compound (A) is usually contained in the composition in an amount of 5 to 69% by weight, preferably 8 to 59% by weight, and other reactive compounds (B). Usually 3 to 64% by weight, preferably 5 to 59% by weight, the photopolymerization initiator (C) is usually 1 to 10% by weight, preferably 1 to 7% by weight, and the organic solvent (D) is usually 60 to 90% by weight. , Preferably 65 to 85% by weight. If necessary, other components may usually be contained in an amount of 0 to 80% by weight.

<Method for forming display spacer and color filter protective film>
The display element spacer formed from the composition is suitably included in the present invention. The method for forming the display element spacer is as follows:
(1) A step of applying the composition onto a substrate to form a coating film,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and (4) a step of heating the developed coating film.

  A method for forming a photo spacer and / or a color filter protective film by photolithography using the active energy ray-curable resin composition of the present invention will be briefly described. The active energy ray-curable resin composition of the present invention is uniformly applied on a substrate by a known method such as roll coating, spin coating, spray coating, slit coating, and the like, and dried to form a photosensitive resin composition layer. . As the coating apparatus, a known coating apparatus can be used, and examples thereof include a spin coater, an air knife coater, a roll coater, a bar coater, a curtain coater, a gravure coater, and a comma coater. Here, an example of forming on a transparent common electrode further provided on the colored layer is described.

  If necessary, heat to dry (pre-bake). As 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 degreeC or less. The drying time is preferably 30 seconds or longer, more preferably 1 minute or longer, and preferably 20 minutes or shorter, more preferably 10 minutes or shorter.

Next, the photosensitive resin composition layer is exposed with active energy rays through a predetermined photomask. With the photosensitive resin composition of the present invention, even a mask opening having a diameter of about 5 to 10 μm (area of about ²⁰ to 100 μm ² ) has a high accuracy, that is, a diameter of 6 to 12 μm (area of 30 to 120 μm ² ). A range can be formed.

There is no restriction | limiting in particular as an active energy ray used for exposure, if the photosensitive resin composition of this invention can be hardened. The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention. Although it does not specifically limit as an exposure amount, Preferably it is 20-1,000 mJ / cm < ² >.

Subsequently, the unexposed portion is removed with a developer, and development is performed. Here, an organic solvent may be used as the developer used for development, but an alkaline aqueous solution is preferably used. Examples of the alkaline aqueous solution that can be used as the developer include aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; organic bases such as hydroxytetramethylammonium and hydroxytetraethylammonium. An aqueous solution of These can be used singly or in combination of two or more, and surfactants such as anionic surfactant, cationic surfactant, amphoteric surfactant and 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 dipping method, a shower method, a liquid piling method, and a vibration dipping method, but a shower method is preferable. The temperature of the developer is preferably 25 to 40 ° C. The development time is appropriately determined according to the film thickness and the solubility of the resist.

  Heating (baking) may be performed as necessary in order to ensure curing. When baking is performed, the baking temperature is preferably 120 to 250 ° C. Although baking time changes with kinds of heating apparatus, when performing a heating process on a hotplate, for example, when performing a heating process in oven, it can be set to 30 minutes-90 minutes. The step baking method etc. which perform a heating process 2 times or more can also be used.

The thickness of the spacer thus formed 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 forming method is a spacer that has no unevenness in coating, has a high degree of flatness, is flexible, and has a small plastic deformation. It can be suitably used for display elements such as liquid crystal display elements and organic EL display elements.

  The color filter protective film is preferably 0.5 μm to 100 μm, more preferably 1 μm to 10 μm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Further, in the examples, unless otherwise specified, “parts” indicates mass parts and “%” indicates wt%.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.
1) Epoxy equivalent: Measured by a method according to JISK7236: 2001.
2) Softening point: Measured by a method according to JISK7234: 1986.
3) Acid value: measured by a method according to JISK0070: 1992

Examples 1-1 to 1-3
[Preparation of Reactive Polycarboxylic Acid Compound (A)]
As an epoxy resin (a), NC-6300H (manufactured by Nippon Kayaku; n = 0 (64%) of general formula (1), n = 1 (23%), n = 2 or more (13%); epoxy equivalent 230 g / eq) is the amount shown in Table 1, compound (b) is acrylic acid (abbreviation AA, Mw = 72) is the amount shown in Table 1, and compound (c) is dimethylolpropionic acid (abbreviation DMPA, Mw = 134). The amount described in 1 was added. 3 g of triphenylphosphine as a catalyst and propylene glycol monomethyl ether monoacetate as a solvent were added so that the solid content would be 80% by weight of the reaction solution, and reacted at 100 ° C. for 24 hours to obtain a reactive epoxycarboxylate compound (E) solution. Got. The solid end acid value (AV: mgKOH / g) of 5 or less was set as the reaction end point, and the next reaction proceeded. The acid value was measured with a reaction solution and converted into an acid value as a solid content.
Next, tetrahydrophthalic anhydride (abbreviated as THPA) as the polybasic acid anhydride (d) in the reactive epoxycarboxylate compound (E) solution is 65 wt. Propylene glycol monomethyl ether monoacetate was added so as to be part and heated to 100 ° C., followed by acid addition reaction to obtain a reactive polycarboxylic acid compound (A) solution. The solid content acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Examples 1-1 and 1-2
[Preparation of Comparative Reactive Polycarboxylic Acid Compound]
Cresol novolac type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200 g / eq) is listed in Table 1, acrylic acid is listed in Table 1 as compound (b), and dimethylolpropionic acid is used as compound (c) (Abbreviation DMPA, Mw = 134) was added in the amount shown 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 would be 80% by weight of the reaction solution, and reacted at 100 ° C. for 24 hours to obtain a carboxylate compound solution. The solid end acid value (AV: mgKOH / g) was 5 mgKOH / g or less, and the reaction was terminated, and the next reaction proceeded.
Next, as a polybasic acid anhydride in the reactive epoxycarboxylate compound solution, tetrahydrophthalic anhydride (abbreviated as THPA) is listed in Table 1, and propylene glycol as a solvent to be 65 parts by weight with respect to 100 parts by weight of solid content. After adding monomethyl ether monoacetate and heating to 100 ° C., an acid addition reaction was performed to obtain a comparative reactive polycarboxylic acid compound solution. The solid content acid value (AV: mgKOH / g) is shown in Table 1.

Comparative Example 1-3
[Preparation of reactive caprolactone-modified polycarboxylic acid compound for comparison]
200 g of cresol novolac type epoxy resin EOCN-103S (Nippon Kayaku, epoxy equivalent 200 g / eq), 58 g of acrylic acid, 40 g of dimethylolpropionic acid, 3 g of triphenylphosphine as a catalyst, propylene glycol monomethyl ether mono as a solvent Acetate was added so that the solid content would be 80% by weight of the reaction solution, and reacted at 100 ° C. for 24 hours. Further, 68 g of ε-caprolactone was added and reacted for 8 hours. Next, 91 g of tetrahydrophthalic anhydride (abbreviated as THPA) is added as a polybasic acid anhydride, and propylene glycol monomethyl ether monoacetate is added as a solvent to 65 parts by weight with respect to 100 parts by weight of solid content, and heated to 100 ° C. Then, an acid addition reaction was performed to obtain a comparative reactive caprolactone-modified polycarboxylic acid compound solution. The solid content acid value (AV: mgKOH / g) was 70 mgKOH / g.

The unit of numerical values in Table 1 is g (grams).
Moreover, the detail of each component used by the Example and the comparative example is shown below.
<Reactive compound (B)>
B-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)
<Photopolymerization initiator (C)>
C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02, manufactured by BASF)
<Organic solvent (D)>
PGMEA: Propylene glycol monomethyl ether acetate DEGDM: Diethylene glycol dimethyl ether

<Other optional components>
<Surfactant (H)>
H-1: Silicone surfactant (manufactured by Dow Corning Toray, SH8400 FLUID)

<Preparation of the composition>
Example 2-1
As a reactive polycarboxylic acid compound (A), in a solution containing an amount corresponding to 100 parts by weight (solid content) of the reactant obtained in Example 1-1, (B-1) as a reactive compound (B) 100 parts by weight, 10 parts by weight of (C-1) as a photopolymerization initiator (C), PGMEA and DEGDM as organic solvents are added so as to have a desired solid content concentration, and (H- 1) The said composition (S-1) was prepared by mixing 0.3 weight part and filtering with a membrane filter with a hole diameter of 0.2 micrometer. In addition, the numerical value of the organic solvent in Table 2 is a mass ratio of PGMEA and DEGDM.

Examples 2-2 to 2-3 and comparative examples 2-1 to 2-3
Except having changed the kind and compounding quantity of each component as having described in Table 2, it operated similarly to Example 2-1, and of Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-3. A composition was prepared. In addition, the numerical value of the organic solvent in Table 2 is a mass ratio of PGMEA and DEGDM.

<Evaluation>
The following evaluation was performed about the spacer formed from the composition of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3, and 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 (manufactured by Toki Sangyo Co., Ltd., TV-200).

(Solid content concentration)
0.3 g of the composition is precisely grounded on an aluminum dish, about 1 g of diethylene glycol dimethyl ether is added, and then dried on a hot plate at 175 ° C. for 60 minutes, and the solid content in the composition is determined from the weight before and after drying. The concentration (mass%) was determined.

(Appearance of coating film)
The composition is applied onto a 100 × 100 mm chromium film using a slit die coater (manufactured by Techno Machine Co., Ltd., Rika Die), dried under reduced pressure to 0.5 Torr, and then heated to 100 ° C. on a hot plate. The film was pre-baked for 2 minutes to form a coating film, and further exposed at an exposure amount of 200 mJ / cm ² to form a film having a film thickness of 4 μm from the upper surface of the chromium film-forming glass. Under the sodium lamp, the appearance of the coating film was observed with the naked eye. At this time, streak unevenness (one or a plurality of straight line unevenness that can be applied or crossed in the direction of application), haze unevenness (cloudy unevenness), pin mark unevenness (points that can be formed on the substrate support pins) The appearance situation of the unevenness of the shape was investigated. A case where almost none of these unevennesses was visible was judged as “◯ (good)”, a case where any of these unevennesses was seen a little, “△ (somewhat bad)”, and a case where it was clearly visible was judged as “x (bad)”.

(Flatness)
The film thickness of the coating film on the chromium-deposited glass produced as described above was measured using a needle contact type measuring machine (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom). The film thickness uniformity was calculated from the following equation by measuring the film thickness at nine measurement points. The nine measurement points are (X [mm], Y [mm]) are (50, 10), (50, 20), (50, 30), where X is the minor axis direction of the substrate and Y is the major axis direction. ), (50, 40), (50, 50), (50, 60), (50, 70), (50, 80), (50, 90). When the film thickness uniformity is 2% or less, it can be determined that the film thickness uniformity is good.

Film thickness uniformity (%) = {FT (X, Y) max−FT (X, Y) min} × 100 / {2 × FT (X, Y) avg. }

  In the above formula, FT (X, Y) max is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, FT (X, Y, Y) avg. Is an average value in the film thickness at nine measurement points.

(High speed application)
Application is performed on a 100 mm × 100 mm non-alkali glass substrate using a slit coater, and the application conditions are as follows: the coating liquid is discharged from the nozzle so 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 speed at which streaky unevenness due to liquid breakage does not occur was determined. At this time, 180 mm / sec. If streaky unevenness does not occur even at the above speed, 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 using a spin coating method, and then prebaked on a 90 ° C. hot plate for 3 minutes to form a coating film having a thickness of 3.5 μm. did. Next, the obtained coating film was exposed using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW) through a photomask in which a circular pattern having a diameter of 12 μm was formed as an opening. Then, after developing for 60 seconds at 25 ° C. with a 0.05 mass% potassium hydroxide aqueous solution, washing with pure water for 1 minute, and further post-baking in an oven at 230 ° C. for 30 minutes, a pattern film is formed. A spacer was formed. At this time, the minimum exposure amount at which the residual film ratio after post-baking (film thickness after post-baking × 100 / film thickness after exposure (before post-baking)) is 90% or more is examined, and this value is defined as sensitivity. did. When this value is 55 mJ / cm ² or less, it can be said that the sensitivity is good.
(Development residue)
Moreover, the surface on the board | substrate was observed visually and the presence or absence of the residue was confirmed. The evaluation criteria are as follows.
○: No residue.
Δ: There is a slight residue.
×… There are many residues

(Compression performance)
A spacer having a cylindrical pattern was formed on the substrate by operating in the same manner as in the evaluation of radiation sensitivity except that the exposure amount was the exposure amount corresponding to the sensitivity determined in the above-described evaluation of radiation sensitivity. At that time, the diameter of the photomask through which exposure was performed was changed so that the diameter of the bottom of the pattern after post-baking would be 20 μm. This spacer is subjected to a compression test with a load of 50 mN using a micro compression tester (Fischer Scope H100C, manufactured by Fisher Instruments Co., Ltd.) and a 50 μm square flat indenter. The change was measured, and the recovery rate (%) was calculated from the displacement when the load of 50 mN was removed and the displacement when the 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 having both a high recovery rate and flexibility.

(Total light transmittance)
A 50 mm × 50 mm non-alkali glass substrate was applied using a spin coater, dried under reduced pressure to 0.5 Torr, pre-baked on a hot plate at 100 ° C. for 2 minutes to form a coating film, and further 200 mJ / cm By exposing with the exposure amount of ² , the film | membrane with a film thickness of 4 micrometers was formed. The evaluation board | substrate which has the said cured coating film was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, TC-H3DPK).

(Heat resistant transparency)
The evaluation board | substrate which has the said cured coating film was heat-processed at 250 degreeC x 1 hr, and the transmittance | permeability of the wavelength light of 400 nm and 540 nm was measured using the spectrophotometer (Hitachi Ltd. make, U-3310).

  As is clear from the above results, the active energy ray-curable compositions containing the reactive polycarboxylic acid compound (A) in Examples 2-1 to 2-3 of the present invention are Comparative Examples 2-1 to 2-1. It was revealed that the developability and curability were good and excellent in heat-resistant transparency, flatness, flexibility, and toughness as compared with the composition of No.-3. Moreover, Example 2-1 and Example 2-2 which also used DMPA (c) for the preparation of the reactive polycarboxylic acid (A) were more excellent in compression than Example 2-3 which was not used. It has been found to have performance.

Although the invention has been described in detail with reference to specific 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 invention.
In addition, this application is based on the Japan patent application (Japanese Patent Application No. 2013-246535) for which it applied on November 28, 2013, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

  The active energy ray-curable composition of the present invention has good developability, curability, and high-speed coating property, and is excellent in heat-resistant transparency, flatness, flexibility, and toughness. 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 (4)

Reactive polycarboxylic acid compound (A), reactive compound (B) other than reactive polycarboxylic acid compound (A), photopolymerization initiator (C) and display element spacer or color containing organic solvent (D) An active energy ray-curable resin composition for a filter protective film,
The reactive polycarboxylic acid compound (A) has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule with the epoxy resin (a) represented by the general formula (1). A polybasic acid anhydride (d) is further added to the reaction product (E) of the compound (b) and, if necessary, the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule. This active energy ray hardening-type resin composition which is the reactive polycarboxylic acid compound (A) obtained by making this react.

(Where n represents a positive number from 0 to 2)   The reactive polycarboxylic acid compound (A) has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule with the epoxy resin (a) represented by the general formula (1). The polybasic acid anhydride (d) is further reacted with the compound (b) and the reaction product (E) of the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule. The active energy ray-curable resin composition for a display element spacer or color filter protective film according to claim 1, which is the resulting reactive polycarboxylic acid compound (A).   The spacer for display elements formed from the active energy ray hardening-type resin composition of Claim 1 or 2.   A color filter protective film formed from the active energy ray-curable resin composition according to claim 1.