TWI627503B - Active energy ray-curable resin composition, spacer for display element and / or color filter protective film using the same - Google Patents

Abstract

The present invention provides an active energy ray-curable resin composition capable of forming spacers for display elements and color filter protective films that are excellent in heat resistance, transparency, flatness, flexibility, and toughness, and spacers for display elements and color. Filter protective film. The resin composition of the present invention contains a reactive polycarboxylic acid compound (A), a reactive compound (B) other than the compound (A), a photopolymerization initiator (C), and an organic solvent (D), and the compound (A ) Is obtained by further reacting a polybasic acid anhydride (d) with a reactant, which is at least a reactant of the epoxy resin (a) and the compound (b) represented by the following general formula (1), and The compound (b) is a polymer having one or more ethylenically unsaturated groups and one or more carboxyl groups that can be polymerized in one molecule.

(Wherein R ₁ to R ₈ represent a hydrogen atom, etc., and G represents an epoxy group)

Description

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

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.

As a material for a display device, a resin composition including a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and the like has been used. In recent years, materials for display devices have rapidly spread as "materials used in LCDs, ELs, PDPs, FEDs (SEDs), rear projection displays, electronic papers, or digital cameras, especially display elements and materials around display elements." For example, a color liquid crystal display (LCD). Generally, a color liquid crystal display device has a structure in which a color filter is opposed to an electrode substrate such as a TFT substrate, and a gap portion of about 1 to 10 μm is provided. A liquid crystal compound is filled in the gap portion, and the periphery is sealed with a sealing material. .

The color filter has a structure in which a black matrix layer formed in a predetermined pattern in order to shield a boundary portion between pixels is sequentially laminated on a transparent substrate from a near transparent substrate side, and red ( R), green (G), blue (B), a colored layer, a protective film, and a transparent electrode film which are arranged in a predetermined order. An alignment film is provided on the inner surface side of the color filter and the electrode substrate facing the color filter. Furthermore, in the gap portion, in order to connect the color filter and the electrode base The cell gaps between the plates are kept constant and uniform, and ball beads having a certain particle diameter are dispersed as spacers, or columnar or strip-shaped spacers having a height corresponding to the cell gap are formed. Furthermore, a color image is obtained by controlling the light transmittance of the liquid crystal layer located behind each of the pixels colored in each color. The color filters described above are used not only in color liquid crystal display devices, but also in other display devices such as EL and rear projection displays.

The coloring layer, the protective film, and the spacer may be formed using a resin. The colored layer needs to be formed into a predetermined pattern corresponding to pixels of each color. Regarding the protective film, in consideration of the sealability or airtightness of the sealing portion, it is preferable to cover only the area where the colored layer is formed on the transparent substrate. In addition, the spacer needs to be accurately positioned in the black matrix layer formation region, that is, the non-display region. Therefore, a coloring layer, a protective film, and a columnar spacer are formed using a curable resin that can be easily restricted by a photomask to a region to be cured.

In addition, if the coating surface of the curable resin is exposed to develop 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, and lacks economy and stability. Therefore, a curable resin has been developed in which an acidic group is introduced into the curable resin and development can be performed using an alkaline aqueous solution after exposure. In these applications, a high temperature (200-260 ° C. or higher) is applied when forming an alignment film and forming a transparent electrode. Therefore, those who have very high heat resistance are sought, and especially those with excellent color heat resistance and color photoresist and spacers.

In Patent Document 1, as a polymer component of a photosensitive resin composition for a photoresist spacer and a color filter, an acid-modified epoxy acrylate of a cresol novolac epoxy resin is used with a primary amine compound. A photosensitive resin obtained by neutralization. However, such a composition containing a salt or water of a primary amine compound is inferior in coatability and flatness, and has insufficient adaptability to a device such as a slit coater.

In Patent Document 2, as a polymer component of the photosensitive resin composition for a photoresist spacer, a cresol novolac epoxy resin or an acid-modified epoxy acrylate of a phenol novolac epoxy resin is used. However, there is a problem that the radiation sensitivity and the developability are not satisfactory and are not satisfactory.

In Patent Document 3, as a polymer component of a protective film of a color filter or a photoresist ink composition for a flexible printed wiring board, an active energy ray-curable resin obtained by the following method is used: p-cresol novolac The varnish epoxy resin was added with acrylic acid and dimethylolpropionic acid to obtain a reactant, and the reactant was subjected to caprolactone modification, and further to tetrahydrophthalic anhydride modification. The polymer component, which is the main component of the composition, is excellent in developability and flexibility, but has a problem that the elastic recovery rate required as a photoresist spacer is poor.

Patent Document 4 discloses a case where a resin composition containing an epoxy carboxylic acid ester compound is used for an optical material, but there is no description about a spacer for a display element or a protective film for a color filter.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-109752

Patent Document 2: Japanese Patent Application Laid-Open No. 2007-010885

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-300266

Patent Document 4: International Publication No. 2008/004630

An object of the present invention is to improve the problems of the above-mentioned prior art, and to provide an active energy ray-curable resin composition with good developability, hardenability, and high-speed coating properties. A spacer for a display element and a color filter protective film.

The present inventors have conducted diligent research in order to solve the above-mentioned problems, and as a result, have found that a resin composition having a specific compound and composition can solve the above-mentioned problems and complete the present invention.

That is, the present invention relates to the following:

(1) A spacer for a display element or an active energy ray-curable resin composition for a color filter protective film, which contains a resin other than the reactive polycarboxylic acid compound (A) and the reactive polycarboxylic acid compound (A). Reactive compound (B), photopolymerization initiator (C), and organic solvent (D), and the reactive polycarboxylic acid compound (A) further reacts the polybasic acid anhydride (d) with the reactant (E) Whereas, the above-mentioned reactant (E) is a reactant of the epoxy resin (a), the compound (b), and optionally the compound (c) represented by the general formula (1), and the above-mentioned compound (b) is a Those having one or more ethylenically unsaturated groups and one or more carboxyl groups that can be polymerized in the molecule, and the compound (c) are those having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule.

(Wherein R ₁ to R ₈ may be the same or different, and represent a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom; G represents an epoxypropyl group)

(2) Further, the present invention relates to an active energy ray-curable resin composition for a spacer for a display element or an active energy ray-curable resin composition for a color filter protective film according to (1), wherein the reactive polycarboxylic acid compound (A) is further a polybasic acid anhydride (d) a product obtained by reacting a reactant (E), the reactant (E) being a reactant of the epoxy resin (a), the compound (b), and the compound (c) represented by the general formula (1); The compound (b) is a polymer having one or more ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) is a polymer having at least two hydroxyl groups and one or more carboxyl groups in one molecule. By.

(3) Further, the present invention relates to an active energy ray-curable resin composition for a spacer for a display element or an active energy ray-curable resin for a color filter protective film, such as (1) or (2), wherein R ₁ to R ₈ is a hydrogen atom.

(4) The present invention further relates to a spacer for a display element, which is formed of the active energy ray-curable resin composition according to any one of (1) to (3) above.

(5) The present invention further relates to a color filter protective film formed of the active energy ray-curable resin composition according to any one of (1) to (3) above.

The active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (A) of the present invention can provide an excellent developability, high radiation sensitivity, and excellent heat transparency, flatness, flexibility, and toughness. 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) of the present invention is obtained by further reacting a polybasic acid anhydride (d) with a reactant, and the reactant is an epoxy resin (a) and a compound ( b), and a reactant of the compound (c) as needed, the compound (b) is a polymer having one or more ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the compound (c) is One molecule has at least two hydroxyl groups and one or more carboxyl groups.

That is, the reactive polycarboxylic acid compound (A) of the present invention can be obtained by reacting a polybasic acid anhydride (d) with the reactant (E) of the epoxy resin (a) and the compound (b), or The reactant (E) of the oxyresin (a), the compound (b), and the compound (c) is obtained by reacting a polybasic acid anhydride (d) with it.

In the present invention, the characteristics of the present invention can be exerted by introducing an ethylenically unsaturated group and a hydroxyl group into a molecular chain by an epoxycarboxylic acid esterification reaction.

In the general formula (1) as the epoxy resin (a), each of R ₁ to R ₈ may be the same or different, and is appropriately selected from a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom. Examples of the C1-C4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tertiary butyl group. Examples of the halogen atom include a chlorine atom. , Bromine atom, iodine atom, etc. In the present invention, R ₁ to R _{8 are} preferably hydrogen atoms.

The epoxy compound (a) for producing the reactive polycarboxylic acid compound (A) of the present invention may contain the general formula (2)

(Wherein R ₁ to R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group of C1 to C4, or a halogen atom)

A phenolic compound of 80 mol% or more of the indicated compound is obtained by epoxidation. For example, Japanese Patent Application Laid-Open No. 2005-200527 describes this manufacturing method, and manufacturing can be performed according to this method. That is, a phenol resin of the general formula (2) is synthesized by a condensation reaction of phenol, C1-C4 alkyl-substituted phenol, or halogen-substituted phenol and glyoxal, and the phenol resin is epoxidized, thereby making it possible to epoxidize the phenol resin. An epoxy resin (a) of the general formula (1) is obtained.

Furthermore, as a commercially available product, GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.) or JER1031S (manufactured by Japan Epoxy Resins), each of which R ₁ to R ₈ in the general formula (1) are hydrogen atoms, can be obtained.

The melting point or softening point of the epoxy compound (a) used in the present invention is 100 ° C or higher. also, Its epoxy equivalent is in the range of 120 to 200 g / eq., And more preferably in the range of 155 to 180 g / eq.

In the present invention, the compound (b) having one or more ethylenically unsaturated groups and one or more carboxyl groups that can be polymerized in one molecule is added to the reactant in order to impart reactivity to active energy rays. There is no restriction as long as there are one or more ethylenically unsaturated groups and carboxyl groups in the molecule. Examples thereof include a monocarboxylic acid compound and a polycarboxylic acid compound.

Examples of the monocarboxylic acid compound having one carboxyl group in a molecule include (meth) acrylic or butenoic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and an unsaturated group Reactant of the monoglycidyl compound. In the above, examples of (meth) acrylics include (meth) acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, (meth) acrylic acid dimer, and saturated or unsaturated dimers. Half-esters of Molar reactants such as (a) acid anhydrides and (meth) acrylic acid ester derivatives having one hydroxyl group in one molecule, as saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylates Derivatives and other semi-esters of Mol reactants.

Further, as the polycarboxylic acid compound having two or more carboxyl groups in one molecule, half-esters such as a mole reactant with a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule, and saturation Or half-esters of Mole reactants such as unsaturated dibasic acids and epoxypropyl (meth) acrylate derivatives having a plurality of epoxy groups.

Among these, in terms of sensitivity when making an active energy ray-curable resin composition, the best examples include (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid . The compound (b) is preferably one which does not have a hydroxyl group in the compound.

In the present invention, the compound (c) having at least two hydroxyl groups and one or more carboxyl groups in one molecule is added to the reactant in order to introduce a hydroxyl group into a carboxylic acid ester compound.

In the present invention, specific examples of the compound (c) having at least two or more hydroxyl groups and one or more carboxyl groups in one molecule used as necessary include, for example, dimethylolpropionic acid and dimethylolbutanoic acid. (butane acid), dimethylolacetic acid, dimethylolbutyric acid, butyric acid, dimethylolvaleric acid, dimethylolhexanoic acid, etc. Particularly preferred examples include dimethylolpropionic acid.

Among these, if the stability of the reaction of the epoxy resin (a) with the compound (b) and the compound (c) is considered, the compound (b) and the compound (c) are preferably monocarboxylic acids. When a monocarboxylic acid and a polycarboxylic acid are used in combination, the value indicated by the total molar amount of the monocarboxylic acid / the total molar amount of the polycarboxylic acid is preferably 15 or more.

In this reaction, the total feed ratio of the carboxylic acid of the epoxy resin (a) to the compound (b) and the compound (c) used as necessary should be appropriately changed depending on the application. That is, when all epoxy groups have been carboxylic acid-esterified, since there is no unreacted epoxy group, the storage stability in the form of a reactive epoxy carboxylate compound is high. In this case, only the reactivity brought by the introduced double bond is used.

On the other hand, by deliberately reducing the feed amount of the carboxylic acid compound so that the unreacted residual epoxy group remains, the reactivity of the introduced unsaturated bond can be used in combination with the reaction using the remaining epoxy group, for example Polymerization reaction or thermal polymerization reaction using photo-cation catalyst. However, in this case, attention should be paid to the study of storage and manufacturing conditions of the reactive epoxy carboxylic acid ester compound (E).

In the case of producing a reactive epoxy carboxylic acid ester compound (E) that does not have an epoxy group remaining, the total of the compound (b) and the compound (c) used as necessary is preferably relative to the above-mentioned epoxy resin (a ) 1 equivalent is 90 ~ 120 equivalent%. If it is within this range, then Manufacturing. When the total feeding amount of the compound (b) and the compound (c) used as necessary is larger than the above, excess compound (b) and compound (c) will remain, which is not preferable.

When the epoxy group is intentionally left, the total of the compound (b) and the compound (c) is preferably 20 to 90 equivalent% based on 1 equivalent of the epoxy resin (a). When it is out of this range, further epoxy group reaction does not proceed sufficiently. In this case, great attention needs to be paid to gelation during the reaction and the stability of the reactive epoxy carboxylic acid ester compound (E) over time.

When using the compound (b) and the compound (c), the molar ratio of the compound (b) to the carboxylic acid is used. The compound (b): the compound (c) is preferably 95: 5 to 5:95, and more preferably The range is from 95: 5 to 40:60. Within this range, the sensitivity to the active energy ray is good, and a sufficient amount of hydroxyl groups can be introduced in order to react the polybasic acid anhydride (d) with the reactive epoxy carboxylic acid ester compound (E).

The carboxylic acid esterification reaction may be performed without a solvent, or may be diluted and reacted with a solvent. The solvent that can be used here is not particularly limited as long as it is a solvent inert to the carboxylic acid esterification reaction.

The preferred amount of the solvent to be used is appropriately adjusted according to the viscosity or use of the obtained resin, and it is used in a manner of preferably 90 to 30 parts by weight and more preferably 80 to 50 parts by weight relative to 100 parts by weight of the solid content.

Specific examples include 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 gasoline, solvent naphtha, etc., ester solvents, ether solvents, ketone solvents, and the like.

Examples of the ester-based solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, and diethylene glycol. Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate , Mono- or polyalkylene glycol monoalkyl ether monoacetates such as butanediol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Polycarboxylic acid alkyl esters and the like.

Examples of the ether-based solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol di Glycol ethers such as ethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; and cyclic ethers such as tetrahydrofuran.

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

In addition, it can be performed in the single or mixed organic solvent of other reactive compounds (B) etc. mentioned later. In this case, when it is used as a hardening composition, it can be used as a composition as it is, and it is preferable.

During the reaction, it is preferable to use a catalyst in order to promote the reaction. The amount of the catalyst used is relative to the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b), and the compound (c) used as required. The total amount of 100 parts by weight of the solvent and other reactants added according to circumstances is usually 0.1 to 10 parts by weight. The reaction temperature at this time is usually 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octoate, zirconium octoate, etc. Media, etc.

In addition, as the thermal polymerization inhibitor, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrin, diphenylamine, 3,5-di -Tertiary butyl-4-hydroxytoluene and the like.

In this reaction system, appropriate sampling is performed, and the time point at which the acid value of the sample becomes 5 mgKOH / g or less, preferably 3 mgKOH / g or less is set as the end point.

As a preferable molecular weight range of the reactive epoxy carboxylic acid ester compound (E) obtained in the above manner, a polystyrene equivalent weight average molecular weight obtained from GPC is in a range of 500 to 50,000, more preferably 1,000 to 30,000.

When the molecular weight is smaller than the above molecular weight, the toughness of the hardened material cannot be sufficiently exhibited, and when the molecular weight is excessively larger than the above value, the viscosity becomes high and application is 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 epoxy carboxylic acid ester compound (E) obtained in the previous step. That is, the polybasic acid anhydride (d) is added to a carboxyl group via an ester bond by performing an addition reaction on a hydroxyl group generated by a carboxylic acid esterification 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. Particularly preferred are succinic anhydride and orthobenzene which are excellent in alkali aqueous solution developability, heat resistance and hydrolysis resistance. Dicarboxylic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Trimellitic anhydride or maleic anhydride.

The reaction for adding the polybasic acid anhydride (d) can be performed by adding the polybasic acid anhydride (d) to the carboxylic acid esterification reaction solution. The addition amount should be appropriately changed according to the application.

Regarding the addition amount of the polybasic acid anhydride (d), for example, when the reactive polycarboxylic acid compound (A) of the present invention is to be used as an alkaline developing type resist, it is preferable to use the reaction obtained finally. The acid value (based on JISK 5601-2-1: 1999) of the solid content of the polycarboxylic acid compound (A) is 40 ~ 120mg‧KOH / g, more preferably 60 ~ 120mg‧KOH / g. Acid anhydride (d). In the case where the acid value of the solid component is in this range, the developability of the alkaline aqueous solution of the photosensitive resin composition of the present invention shows good developability. That is, the patterning property is good, and the management range for over-development is wide, and there is no excess acid anhydride remaining.

During the reaction, in order to promote the reaction, it is preferable to use a catalyst. The amount of the catalyst used is added to the reactant by an epoxy compound (a), a carboxylic acid compound (b), and a compound (c) used as necessary. The total amount of the obtained reactive epoxy carboxylic acid ester compound (E), the polybasic acid anhydride (d), the solvent used according to the situation, and other reactants is 100 parts by weight, usually 0.1 to 10 parts by weight. The reaction temperature at this time is usually 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours. Specific examples of usable catalysts include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octoate, zirconium octoate, etc.

The present acid addition reaction may be carried out without a solvent, or may be carried out by dilution with a solvent. The solvent that can be used here is not particularly limited as long as it is a solvent that is inert to the acid addition reaction. In the case where the solvent is used for the carboxylic acid esterification reaction in the previous step, the two reactions may be inert, and the solvent may be directly submitted to the next step, the acid addition reaction, without removing the solvent. The solvent that can be used can be the same as the user in the carboxylic acid esterification reaction.

The amount of the preferred solvent should be appropriate according to the viscosity or use of the resin obtained. When adjusted, it is preferably used in a range of 90 to 30 parts by weight, more preferably 80 to 50 parts by weight, based on 100 parts by weight of the solid component.

In addition, it can also be performed in the single or mixed organic solvent of the reactive compound (B) etc. mentioned later. In this case, it is preferable to use the composition as a composition when it is used as a curable composition.

The thermal polymerization inhibitor and the like are preferably the same as those exemplified in the carboxylic acid esterification reaction.

In this reaction, appropriate sampling is performed, and the end point is when the acid value of the reactant becomes a range of plus or minus 10% of the set acid value.

As a preferable molecular weight range of the reactive polycarboxylic acid compound (A), a polystyrene equivalent weight average molecular weight obtained from GPC is in a range of 500 to 50,000, and more preferably 1,000 to 30,000.

The use ratio of the reactive polycarboxylic acid compound (A) in the resin composition is usually 5 to 69% by weight, and preferably about 8 to 59% by weight.

Examples of the reactive compound (B) that can be used in the present invention include so-called reactivity such as radical-reactive acrylates, cation-reactive other epoxy compounds, and ethylene-based compounds that react to both. Oligomers.

Examples of the radically reactive acrylates include monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher (meth) acrylate, and polyester (meth) acrylate , (Meth) acrylate oligomer, polyester (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, and the like.

Examples of the monofunctional (meth) acrylate include acrylfluorenyl Porphyrin; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and other (meth) acrylates containing cyclohexyl; cyclohexyl Alkane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) acrylic acid Aliphatic (meth) acrylates such as dicyclopentenyl ester, dicyclopentenyloxyethyl (meth) acrylate; phenoxyethyl (meth) acrylate, phenyl (meth) acrylate (poly ) Ethoxyester, p-cumylphenoxyethyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, ( Aromatic (meth) groups such as 2-hydroxy-3-phenoxypropyl methacrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenylphenol epoxy (meth) acrylate, etc. )Acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol Di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, bisphenol A (poly) ethoxydi (meth) acrylate, bisphenol A (poly) propoxybis (methyl) Base) acrylate, bisphenol F (poly) ethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, hydroxytrimethyl Di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol acetate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.) and the like.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include bis (trimethylolpropane) tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylol Octane tri (meth) acrylate, trimethylolpropane (poly) ethoxytri (meth) acrylate, trimethylolpropane (poly) propoxytri (meth) acrylate, trihydroxy Methyl propyl Hydroxymethyls such as alkane (poly) ethoxy (poly) propoxytri (meth) acrylate; neopentaerythritol tri (meth) acrylate, neopentaerythritol (poly) ethoxytetra ( (Meth) acrylate, neopentaerythritol (poly) propoxytetra (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol tetra (meth) acrylate, di Neopentaerythritol such as neopentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate; tris [(meth) acryloxyethyl] isocyanurate, Caprolactone modified tri [(meth) acryloxyethyl] isocyanurate, etc .; Succinic acid modified neopentaerythritol triacrylate, Succinic acid modified dipentaerythritol pentaacrylate Esters.

Examples of the (poly) ester (meth) acrylate oligomer include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, and (poly) ethylene Glycols, (poly) propylene glycols, and other diols, 1,4-butanediol, 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 -Linear or branched alkyl glycols such as propylene glycol, alicyclic alkyl glycols such as cyclohexane-1,4-dimethanol, bisphenol A (poly) ethoxydiol or bisphenol A ( A reactant of a diol compound such as poly) propoxydiol and the above-mentioned dibasic acid or its anhydride, that is, a reactant of (poly) ester diol and (meth) acrylic acid, and the like.

Examples of the (meth) acrylate oligomer include a diol compound (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butane Alcohol, 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 polypropyleneoxy glycol, etc.) or these diol compounds and dibasic acids or their anhydrides (e.g., succinic acid, adipic acid Acid, azelaic acid, dimer acid, isophthalic acid, The reactants of terephthalic acid, phthalic acid, or their anhydrides are polyester diols, and organic polyisocyanates (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4 -Chain saturated hydrocarbon isocyanates such as trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane Cyclic saturated hydrocarbon isocyanates such as diisocyanate, methylenebis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, 2,4-toluene diisocyanate, 1, 3-Benzyldimethyl diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate Isocyanates, aromatic polyisocyanates such as 1,5-naphthalene diisocyanate), and reactants obtained by adding a hydroxyl group-containing (meth) acrylate.

The epoxy (meth) acrylate oligomer is a compound having an epoxy group and a carboxylic acid ester compound of (meth) acrylic acid. Examples include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, trihydroxyphenylmethane epoxy (meth) acrylate, dicyclopentyl Diene phenol epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, biphenol epoxy (meth) acrylate Bisphenol A novolac epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal epoxy (meth) acrylate, heterocyclic epoxy (meth) ) Acrylate, etc.

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

The cation-reactive monomer is generally not particularly limited as long as it is a compound having an epoxy group. Examples include: glycidyl (meth) acrylate, methylglycidyl ether, ethylglycidyl ether, butylglycidyl ether, bisphenol A diglycidyl ether, 3,4-cyclo Oxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Cyracure UVR-6110 manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxy ring Hexane carboxylate, vinyl cyclohexene dioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonene dioxide ("Celloxide 3000" manufactured by Daicel Chemical Industries, etc.), allyl cyclohexene dioxide 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Kanji Alkane, bis (3,4-epoxycyclohexyl) adipate (Cyracure UVR-6128 manufactured by Union Carbide, etc.), 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, difunctional, trifunctional or higher (meth) acrylates, etc. are preferred from the viewpoint of good polymerizability and improvement in the strength of the obtained spacers and the like. .

The reactive compound (B) of the present invention may be used alone or as a mixture of two or more. In this composition, the use ratio of the reactive compound (B) is preferably 30 to 250 parts by weight, and more preferably 50 to 200 parts by weight relative to 100 parts by weight of the reactive polycarboxylic acid compound (A). . When the amount of the reactive compound (B) used is 30 parts by weight to 250 parts by weight, the sensitivity of the composition, the heat resistance of the obtained spacer for display elements, and the like are better.

As the photopolymerization initiator (C) of the present invention, a reactive compound (B) other than the reactive polycarboxylic acid compound (A) can be produced in order to react with the active energy ray to react ) Ingredients of the active species to start polymerization. Examples of the photopolymerization initiator (C) include an O-fluorenyl oxime compound, an acetophenone compound, and a biimidazole compound.

Examples of the O-fluorenyl oxime compound include ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O -Ethynyloxime), 1- [9-ethyl-6-benzylidene-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate, 1- [9 -Ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -ethane-1-oneoxime-O-benzoate, 1- [9-n-butyl -6- (2-ethylbenzyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethyl ketone-1- [9-ethyl- 6- (2-methyl-4-tetrahydrofurylbenzyl) -9H-carbazol-3-yl] -1- (O-ethylamidoxime), ethyl ketone-1- [9-ethyl- 6- (2-methyl-4-tetrahydropyranylbenzyl) -9H-carbazol-3-yl] -1- (O-ethylamidoxime), ethyl ketone-1- [9- Ethyl-6- (2-methyl-5-tetrahydrofurylbenzyl) -9H-carbazol-3-yl] -1- (O-ethylamidoxime), ethyl ketone-1- [9- Ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolane) methoxybenzyl} -9H-carbazol-3-yl] -1- (O-acetylamoxime) and the like. Among these, ethyl ketone-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] -1- (O-acetamidine Oxime), ethyl ketone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl] -1- (O -Ethynyloxime) or ethyl ketone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxy Benzamidine} -9H-carbazol-3-yl] -1- (O-ethylamidoxime). These O-fluorenyl oxime compounds may be used alone or as a mixture of two or more.

Examples of the acetophenone compound include an α-amino ketone compound and an α-hydroxy ketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenyl-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2- Phenylpropane-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, and the like.

Among these acetophenone compounds, an α-amino ketone compound is preferable, and 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butane-1-one or 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenolin-4-yl-phenyl) -butane-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'-biimidazole and the like. 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'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5 5'-tetraphenyl-1,2'-biimidazole.

As the photopolymerization initiator (C), a commercially available product may be used, and examples thereof include 2-methyl-1- (4-methylthiophenyl) -2- Isoline propane-1-one (Irgacure 907), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4- (Phenylphenyl) -butane-1-one (Irgacure 379), ethyl ketone-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] -1- (O-acetylamoxime) (Irgacure OXE02) (above, Ciba Specialty Chemicals) and the like.

In the photosensitive resin composition of the present invention, when the amount of the component (C) used is 100% by weight, the solid content of the resin composition of the present invention is usually 1% by weight or more and 10% by weight. % Or less, preferably 1% to 7% by weight.

The photopolymerization initiator (C) may be used in combination with a hardening accelerator (F). Examples of the curing accelerator that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, and p-dimethylamine. Hydrogen donors such as isoamyl benzoate, amines such as EPA, and 2-mercaptobenzothiazole. About the usage-amount of such a hardening accelerator, when the solid content of the resin composition of this invention is 100 weight%, it is 0 to 5 weight% normally.

As the organic solvent (D), those which dissolve or disperse each constituent component uniformly and do not react with each constituent component can be preferably used. As the organic solvent (D), in addition to the above-mentioned aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and mixtures thereof, namely petroleum ether, white gasoline, solvent naphtha, etc., ester solvents, ether solvents, and ketone solvents Examples include alcohols, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ether acetates, and dipropylene glycol. Monoalkyl ethers, dipropylene glycol monoalkyl ether acetates, lactates, aliphatic carboxylic acid esters, amidines, ketones, and the like. These can be used alone or 2 More than one species is used.

Specifically, examples of the organic solvent (D) include alcohols such as benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Alcohol monoalkyl ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and other propylene glycol monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like Glycol monoalkyl ethers; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate And other diethylene glycol monoalkyl ether acetates; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and other dipropylene glycol monoalkyl ethers; dipropylene glycol monomethyl ether ethyl Esters, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate and other dipropylene glycol monoalkyl ether acetates; methyl lactate, ethyl lactate, n-propyl lactate Esters, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate and other lactates; Ethyl acetate, ethyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-3-methylbutanoate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methyl Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl ethyl acetate, ethyl ethyl acetate, pyruvate Aliphatic carboxylic acid esters such as methyl ester and ethyl pyruvate; N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylethyl Ammonamines such as ammonium; ketones such as N-methylpyrrolidone and γ-butyrolactone. These can 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, and preferably 15% by weight or more and 35% by weight or less. By solidifying the composition The shape component concentration is in the above range, which can improve coating properties, improve film thickness uniformity, and effectively suppress the occurrence of 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. It is preferably 2.0 mPa · s or more and 100 mPa · s or less. By setting the viscosity of the composition to the above-mentioned range, it is possible to achieve a viscosity in such a manner that the uniformity of the film thickness is maintained, and the degree of uniformity by itself can be achieved even if coating unevenness occurs.

In the photosensitive resin composition of the present invention, the alkali-soluble resin (G) used as needed may be, for example, a monomer having a hydroxyl group, an acid anhydride having an ethylenic double bond, a monomer having a carboxyl group, It is produced by copolymerizing a monomer having an epoxy group, a monomer having a phenolic hydroxyl group, a monomer having a sulfonic acid group, other monomers, and the above-mentioned monofunctional (meth) acrylate.

Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) 4-hydroxybutyl acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (methyl) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monoethylene Ether, 2-hydroxyethylallyl ether, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) acrylamide, and the like.

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

Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinylacetic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or the like salt.

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

Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Examples of the benzene ring include one or more hydrogen atoms via alkyl groups such as methyl, ethyl, and n-butyl; alkoxy groups such as methoxy, ethoxy, and n-butoxy; halogen atoms; A halogenated alkyl group in which one or more hydrogen atoms are replaced by a halogen atom; a nitro group; a cyano group;

Examples of the monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy-3- (methyl) allyloxypropanesulfonic acid, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) propenyloxypropanesulfonic acid, 2- (meth) acrylic acid Amine-2-methylpropanesulfonic acid and the like.

Examples of other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylates, ( (Meth) acrylamidines, aromatic vinyl compounds, chloroolefins, and conjugated diene. These compounds may contain a functional group, and examples of the functional group include a carbonyl group and an alkoxy group. In particular, since the partition wall formed of the composition is excellent in heat resistance, (meth) acrylates and (meth) acrylamides are preferred.

When the basic soluble resin (G) is produced by copolymerization, it can be produced by radically polymerizing an unsaturated compound in the presence of a polymerization initiator in a solvent. You can use the above solvent Agents can be used alone or as a mixture of two or more.

As a polymerization initiator used for the polymerization reaction for producing the alkali-soluble resin (G), generally known as a radical polymerization initiator. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2, 2'-Azobis- (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzamidine peroxide, lauryl peroxide, tert-butyl peroxypivalate, Organic peroxides such as 1,1'-bis- (tertiary butyl peroxide) cyclohexane and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a peroxide may be used together with a reducing agent as a redox-type initiator.

In the polymerization reaction for producing the basic soluble resin (G), a molecular weight adjuster can be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, sulfur Thiols such as glycolic acid; xanthates such as dimethyl xanthate disulfide and diisopropyl xanthate disulfide; terpineolene, α-methylstyrene polymers, etc.

Reactive with the above-mentioned monomers having a hydroxyl group, anhydrides having an ethylenic double bond, monomers having a carboxyl group, monomers having an epoxy group, etc., monomers having a phenolic hydroxyl group, monomers having a sulfonic acid group, and the like As the monomer (e) of the group, as the compound (f) having a functional group and an ethylenic double bond which can be bonded to the reactive group, the following combinations are exemplified.

(1) an acid anhydride having an ethylenic double bond (f) to a monomer (e) having a hydroxyl group, (2) a compound having an isocyanate group and an ethylenic double bond (f) to a monomer (e) having a hydroxyl group, ( 3) A compound having a fluorenyl group and an ethylenic double bond (f) to a monomer (e) having a hydroxyl group, (4) A compound having a hydroxyl and an ethylenic double bond (f) to an acid anhydride having an ethylenic double bond (e), (5) Compound having epoxy group and ethylenic double bond (f) vs. monomer having carboxyl group (e), (6) Compound having carboxyl group and ethylenic double bond (f) vs. monomer having epoxy group (e).

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

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

Specific examples of the compound having a fluorenyl chloride group and an ethylenic double bond include (meth) acrylic fluorenyl chloride.

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

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

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

When reacting a copolymer with a compound (f) having a functional group capable of bonding with a reactive group and an ethylenic double bond, as the solvent used for the reaction, the solvents exemplified in the synthesis of the above copolymer can be used.

Moreover, it is preferable to mix | blend a polymerization inhibitor. As a polymerization inhibitor, a well-known public polymerization inhibitor can be used, Specifically, 2,6-di-tert-butyl p-cresol is mentioned.

A catalyst or a neutralizing agent may be added. For example, when reacting a copolymer having a hydroxyl group 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, dibutyltindi (cis-butenedi) Acid monoesters), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), dibutyltin diacetate, and the like.

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

The Mw of the basic soluble resin (G) is preferably 2 × 10 ³ to 1 × 10 ⁵ , and more preferably 5 × 10 ³ to 5 × 10 ⁴ . By setting the Mw of the alkaline soluble resin (G) to 2 × 10 ³ to 1 × 10 ⁵ , the radiation sensitivity and developability of the composition can be improved (characteristics of accurately forming a desired pattern shape).

Furthermore, a surfactant, a leveling agent, a defoaming agent, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a cross-linking agent, and an adhesion agent may be added to the photosensitive resin composition of the present invention as necessary. Additives, pigments, dyes, and the like to impart functionality to each target. Examples of the leveling agent and defoaming agent include fluorine-based compounds, polysiloxane-based compounds, and acrylic compounds. Examples of the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, and three Examples of light stabilizers include hindered amine compounds and benzoate compounds. Examples of antioxidants include phenol compounds. Examples of polymerization inhibitors include p-methoxyphenol. , Methylhydroquinone, hydroquinone, and the like; examples of the crosslinking agent include the above-mentioned polyisocyanates and melamine compounds.

In addition, as the resins (so-called inert polymers) that do not show reactivity to active energy rays, for example, other epoxy resins, phenol resins, amine ester resins, polyester resins, ketone-formaldehyde resins, cresol resins, Xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and others Modified matter. These are preferably used in the resin composition in a range of up to 40 parts by weight.

The active energy ray-curable resin composition system composition of the present invention usually contains 5 to 69% by weight of the reactive polycarboxylic acid compound (A), preferably 8 to 59% by weight, and usually contains other reactive compounds (B). 3 to 64% by weight, preferably 5 to 59% by weight, usually containing 1 to 10% by weight of the photopolymerization initiator (C), preferably 1 to 7% by weight, usually containing 60 to 90% of the organic solvent (D) % By weight, preferably 65 to 85% by weight. If necessary, it may also contain 0 to 80% by weight of other ingredients.

<Formation method of display spacer and color filter protective film>

The spacer for a display element formed from this composition is preferably included in the present invention. The method for forming a spacer for a display element includes (1) a step of coating the composition on a substrate to form a coating film, (2) a step of irradiating at least a part of the coating film with radiation, and (3) applying the radiation A step of developing the irradiated coating film, and (4) a step of heating the developed coating film.

A method for forming a photoresist 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 briefly 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, and slit coating, and dried to form a photosensitive resin composition layer. . As the coating device, a known coating device 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 Notch wheel coater and so on. Here, an example formed on a transparent common electrode provided on the colored layer will be described.

If necessary, heat to dry (pre-bake). The drying temperature is preferably 50 ° C or higher, more preferably 70 ° C or higher, and still preferably less than 150 ° C, and still more preferably 120 ° C or lower. The drying time is preferably 30 seconds or more, more preferably 1 minute or more, still more preferably 20 minutes or less, and still more preferably 10 minutes or less.

Then, exposure of the photosensitive resin composition layer is performed using active energy rays through a predetermined photomask. According to the photosensitive resin composition of the present invention, even if it is a mask opening having a diameter of about 5 to 10 μm (area of about 20 to 100 μm ² ), the diameter can be accurately set to 6 to 12 μm (area of 30 to 120 μm ^2). ).

The active energy ray used for exposure is not particularly limited as long as the photosensitive resin composition of the present invention can be cured. The active energy ray-curable resin composition of the present invention is easily hardened by the active energy ray. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, γ-rays, and laser rays, and particle beams such as α-rays, β-rays, and electron beams. Considering the preferred use of the present invention, among them, ultraviolet rays, laser rays, visible rays, or electron beams are preferred. The exposure amount is not particularly limited, but is preferably 20 to 1,000 mJ / cm ² .

Then, the unexposed part is removed by a developing solution, and development is performed. Here, an organic solvent may be used as a developing solution for development, and an alkaline aqueous solution is preferably used. Examples of the alkaline aqueous solution usable as a developing solution include aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; hydroxytetramethylammonium, hydroxytetraethylammonium Other organic alkali aqueous solution. These can be used singly or in combination of two or more kinds, and an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a water-soluble agent such as methanol or ethanol can be added. Organic solvents. Concentration of alkali in alkaline aqueous solution From the viewpoint of obtaining a suitable developability, the degree is preferably 0.1 to 5% by weight. As the developing method, there are an immersion method and a spray method, an overflow method, and a vibration immersion method, and a spray method is preferable. Regarding the temperature of the developer, it is preferably used at 25 to 40 ° C. The development time is appropriately determined according to the film thickness or the solubility of the photoresist.

In order to harden more reliably, you may heat (bake) as needed. In the case of baking, the baking temperature is preferably 120 to 250 ° C. The baking time varies depending on the type of heating machine. For example, when the heating step is performed on a hot plate, it can be set to 5 to 30 minutes. When the heating step is performed in an oven, it can be set to 30 minutes. ~ 90 minutes. A stepwise baking method in which the heating step is performed twice or more can also be used.

The film thickness of the spacer formed in the above manner is preferably from 0.1 μm to 8 μm, more preferably from 0.1 μm to 6 μm, and even more preferably from 0.1 μm to 4 μm.

The spacer system formed in this forming method has no uneven coating, has a high degree of flatness, is soft and has low plastic deformation. It can be preferably used for display elements such as a liquid crystal display element and an organic EL display element.

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

Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the examples, "part" means parts by weight and "%" means% by weight unless otherwise specified.

The softening point, epoxy equivalent, and acid value were measured under the following conditions.

1) Epoxy equivalent: It was measured by the method based on 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 ~ 1-3 [Preparation of reactive polycarboxylic acid compound (A)]

GTR-1800 (manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent of 170 g / eq) was added as the epoxy resin (a) in the amount described in Table 1, and acrylic acid (abbreviated AA, Mw = 72) as the compound (b) The amount described is the amount described in Table 1 as dimethylolpropionic acid (abbreviated as DMPA, Mw = 134) as the compound (c). Add 3 g of triphenylphosphine as a catalyst, and add propylene glycol monomethyl ether monoacetate as a solvent so that the solid content becomes 80% by weight of the reaction solution, and react at 100 ° C for 24 hours to obtain a reactive epoxy. A solution of a carboxylic acid ester compound (E). The solid content component acid value (AV: mgKOH / g) 5 or less was set as the reaction end point, and it progressed to the next reaction. The acid value is measured using a reaction solution and converted into an acid value in the form of a solid component.

Next, to the solution of the reactive epoxy carboxylic acid ester compound (E), tetrahydrophthalic anhydride (abbreviated as THPA) as the polybasic acid anhydride (d) was added in an amount as shown in Table 1, and 100 parts by weight relative to the solid content. Propylene glycol monomethyl ether monoacetate was added as a solvent in an amount of 65 parts by weight, and after heating to 100 ° C, an acid addition reaction was performed to obtain a reactive polycarboxylic acid compound (A) solution. The solid content component acid value (AV: mgKOH / g) is described in Table 1.

Comparative Examples 1-1, 1-2 [Preparation of a comparative reactive polycarboxylic acid compound]

Add the cresol novolac epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200g / eq) as the amount shown in Table 1, the amount shown in Table 1 as the acrylic acid compound (b), and Dimethylolpropionic acid (abbreviated as DMPA, Mw = 134). add Add 3 g of triphenylphosphine as a catalyst, and add propylene glycol monomethyl ether monoacetate as a solvent so that the solid content becomes 80% by weight of the reaction solution, and react at 100 ° C for 24 hours to obtain a carboxylic acid ester compound. Solution. The solid component content acid value (AV: mgKOH / g) is 5 mgKOH / g or less as the end point of the reaction, and the process proceeds to the next reaction.

Next, tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride was added to the reactive epoxy carboxylic acid ester compound solution in the amount described in Table 1, and it was set to 65 parts by weight based on 100 parts by weight of the solid component. As a solvent, propylene glycol monomethyl ether monoacetate was added, and after heating to 100 ° C, an acid addition reaction was performed to obtain a comparative reactive polycarboxylic acid compound solution. The solid content component acid value (AV: mgKOH / g) is described in Table 1.

Comparative Example 1-3 [Comparative Preparation of Reactive Caprolactone Modified Polycarboxylic Acid Compounds]

Add 200g of cresol novolac epoxy resin EOCN-103S (manufactured by Nippon Kayaku, epoxy equivalent 200g / eq), 58g of acrylic acid, 40g of dimethylolpropionic acid, and 3g of triphenylphosphine as catalyst. Propylene glycol monomethyl ether monoacetate was added as a solvent so that the solid content became 80% by weight of the reaction solution, and the mixture was reacted at 100 ° C for 24 hours. Furthermore, 68 g of ε-caprolactone was added and reacted for 8 hours. Then, 91 g of tetrahydrophthalic anhydride (abbreviated as THPA) as a polybasic acid anhydride was added, and propylene glycol monomethyl ether monoacetate was added as a solvent so that 100 parts by weight of the solid content became 65 parts by weight. After heating to 100 ° C, an acid addition reaction was performed to obtain a comparative reactive caprolactone modified polycarboxylic acid compound solution. The acid value (AV: mgKOH / g) of the solid content was 70 mgKOH / g.

The unit of the numerical values in Table 1 is g (gram).

The details of each component used in the examples and comparative examples are shown below.

<Reactive Compound (B)>

B-1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)

<Photopolymerization initiator (C)>

C-1: Ethyl ketone-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamidooxime) (Irgacure (OXE02, manufactured by BASF)

<Organic solvent (D)>

PGMEA: propylene glycol monomethyl ether acetate

DEGDM: Diethylene glycol dimethyl ether

<Other optional ingredients> <Surfactant (H)>

H-1: Polysiloxane surfactant (manufactured by Dow Corning Toray Silicones, SH8400FLUID)

<Preparation of the composition> Example 2-1

To a solution containing an amount equivalent to 100 parts by weight (solid content) of the reactant obtained in Example 1-1 as a reactive polycarboxylic acid compound (A), (B) as a reactive compound (B) was added -1) 100 parts by weight, (C-1) 10 parts by weight as a photopolymerization initiator (C), PGMEA and DEGDM as organic solvents are added so as to have a desired solid content concentration, and mixed as an interface This composition (S-1) was prepared by filtering 0.3 parts by weight of (H-1) of the active agent (H) 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 the mass ratio of PGMEA to DEGDM.

Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2-3

Except that the types and blending amounts of each component were as described in Table 2, the same operations as in Example 2-1 were performed to prepare Examples 2-2 to 2-3 and Comparative Examples 2-1 to 2- Composition of 3. In addition, the numerical value of the organic solvent in Table 2 is the mass ratio of PGMEA to DEGDM.

<Evaluation>

The compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 and the spacers formed from these coating films were evaluated as described below. The evaluation results are shown in Table 3.

(Viscosity)

Using an E-type viscosity meter (manufactured by Toki Sangyo Co., Ltd., TV-200), the viscosity (mPa‧s) of each composition at 25 ° C was measured.

(Solid matter concentration)

Accurately weigh 0.3g of the composition and put it in an alumina dish, add about 1g of diethylene glycol dimethyl ether, and then dry it on a hot plate at 175 ° C for 60 minutes. Determine the solid form of the composition according to the weight before and after drying Concentration (mass%) of the substance.

(Appearance of coating film)

This composition was applied to a 100 × 100 mm chromium film-forming glass using a slit die coater (manufactured by Technomachine Co., Ltd., and a physical and chemical mold), and the pressure was reduced to 0.5 Torr to dry. Pre-bake at 2 ° C for 2 minutes to form a coating film, and then perform exposure at an exposure amount of 200 mJ / cm ² to form a film having a thickness of 4 μm from the upper surface of the chromium film-forming glass. The appearance of the coating film was observed with the naked eye under a sodium lamp. At this time, the stripe spots (one or a plurality of linear spots formed in the coating direction or the direction intersecting the coating direction), haze spots (cloud-like spots), and trail spots (substrate) Support the appearance of punctate spots on the tip). A case where these spots are hardly visible is judged as "○ (good)", a part of which is slightly permissible is judged as "△ (slightly bad)", and a case where it is clearly visible is judged as "x (bad)".

(Flatness)

Using a pin contact measuring machine (manufactured by Tokyo Precision Co., Ltd., Surfcom), The film thickness of the coating film on the chromium film-forming glass manufactured in the above manner. The film thickness uniformity was obtained by measuring the film thickness at 9 measurement points and calculating it according to the following formula. The nine measurement points are when the short axis direction of the substrate is set to X and the long axis direction is set to Y. (X [mm], Y [mm]) is (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, the film thickness uniformity can be judged to be 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 of the film thickness at 9 measurement points, FT (X, Y) min is the minimum value of the film thickness at 9 measurement points, and FT (X, Y, Y) avg. Is the average of the film thicknesses at 9 measurement points.

(High-speed coating properties)

Use a slit coater to apply on a 100mm × 100mm alkali-free glass substrate. As a coating condition, spray the coating solution from the nozzle so that the distance between the substrate and the nozzle is 150 μm and the film thickness after exposure becomes 2.5 μm. The moving speed of the nozzle was varied within a range of 120 mm / sec. To 200 mm / sec., And the maximum speed at which no streaks caused by the liquid cutoff were generated was obtained. At this time, when no streaks are generated even at a speed of 180 mm / sec. Or more, it can be determined that high-speed coating can be applied.

(Radiation sensitivity)

This composition was coated on a 100 mm × 100 mm ITO sputtered glass substrate by a spin coating method, and thereafter, pre-baked on a hot plate at 90 ° C. for 3 minutes, thereby forming a coating film having a thickness of 3.5 μm. . Next, a UV mask (Oak Manufacturing Co., Ltd., model HMW-680GW) was used to expose the obtained coating film through a mask formed with a circular pattern having a diameter of 12 μm as an opening. Thereafter, it was developed with a 0.05% by mass potassium hydroxide aqueous solution at 25 ° C for 60 seconds, and then washed with pure water for 1 minute, and then baked in an oven at 230 ° C for 30 minutes, thereby forming a space formed by a patterned film. Thing. At this time, the minimum exposure amount after the post-bake residual film rate (film thickness of the post-bake film × 100 / film thickness after exposure (before-bake)) was 90% or more, and this value was used as the sensitivity. . When the value is 55 mJ / cm ² or less, the sensitivity is good.

(Development residue)

In addition, the upper surface of the substrate was visually observed to confirm the presence or absence of residues. The evaluation criteria are as follows.

○ ... No residue.

△ ... Slight residue.

× ... There are many residues.

(Compression performance)

Except that the exposure amount was equivalent to the sensitivity determined in the above-mentioned evaluation of the radiation sensitivity, a spacer formed by a cylindrical pattern was formed on the substrate in the same manner as in the evaluation of the radiation sensitivity. At this time, the diameter of the bottom of the pattern after the baking is changed to 20 μm so that the diameter of the photomask interposed during exposure is changed. The spacer was subjected to a compression test using a micro compression tester (Fischerscope H100C, manufactured by Fischer Instruments Co., Ltd.) using a 50 μm square flat indenter at a load of 50 mN, and the change in the amount of compression displacement corresponding to the load was measured, and the change was made from 50 mN The amount of displacement at the load and the amount of displacement when the 50mN load is removed are used to calculate the recovery rate (%). 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, the spacer can be said to have compressive properties having both a high recovery rate and flexibility.

(Full light transmittance)

It was coated on a 50mm × 50mm alkali-free glass substrate using a spin coater, reduced to 0.5 Torr, and dried, and then pre-baked on a hot plate at 100 ° C for 2 minutes to form a coating film, and then 200 mJ / cm ² The film was exposed at an exposure amount to form a film having a thickness of 4 μm. The evaluation substrate having the cured coating film was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., TC-H3DPK).

(Heat-resistant transparency)

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

From the above results, it is clear that the active energy ray-curable composition containing the reactive polycarboxylic acid compound (A) of the present invention of Examples 2-1 to 2-3 and the composition of Comparative Examples 2-1 to 2-3 In contrast, it has good developability and hardenability, and is excellent in heat-resistant transparency, flatness, flexibility, and toughness. In addition, Example 2-1 and Example 2-2 and Example 2-3 in which DMPA (c) was also used in the preparation of the reactive polycarboxylic acid (A) showed that it had more excellent compression performance.

The present invention is described in detail with reference to specific aspects, but it is clear to practitioners that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Furthermore, this application is based on a Japanese patent application filed on November 28, 2013 (Japanese Patent Application No. 2013-246535), and the entirety thereof is incorporated by reference. Also, all references cited herein are incorporated as a whole.

[Industrial availability]

The active energy ray-curable composition of the present invention has good developability, hardenability, and high-speed coating properties, and can form a spacer for a display element and color filter protection which are excellent in heat resistance transparency, flatness, flexibility, and toughness. membrane. Therefore, this composition is suitable as a material for forming a spacer for a display element such as a liquid crystal display element, an organic EL, and a color filter protective film.

Claims (4)

An active energy ray-curable resin composition for a display element spacer or a color filter protective film, comprising a reactive polycarboxylic acid compound (A) and a reactive compound (B) other than the reactive polycarboxylic acid compound (A) ), A photopolymerization initiator (C) and an organic solvent (D), and a reactive polycarboxylic acid compound (A) is obtained by further reacting a polybasic acid anhydride (d) with a reactant (E), and the reactant ( E) is a reactant of the epoxy resin (a), the compound (b), and the compound (c) represented by the general formula (1), and the compound (b) is one or more ethylene polymers that can be polymerized in one molecule For the unsaturated unsaturated group and one or more carboxyl groups, the compound (c) is one having at least two hydroxyl groups and one or more carboxyl groups in one molecule, (Wherein R ₁ to R ₈ may be the same or different, and each represents a hydrogen atom, an alkyl group of C 1 to C 4, or a halogen atom; G represents an epoxypropyl group). For example, the spacer for a display element or the active energy ray-curable resin composition for a color filter protective film of item 1 of the patent application range, wherein R ₁ to R _{8 in the} general formula (1) are hydrogen atoms. A spacer for a display element, which is formed of an active energy ray-curable resin composition according to item 1 or 2 of the scope of patent application. A color filter protective film is formed of an active energy ray-curable resin composition with the scope of claims 1 or 2.