JP2006251536A - Thermosetting composition for protective film, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition with which a protective layer, producing no disconnection of an ITO, being excellent in high stability in the lapse of time, further scarcely producing a residue on a deep portion in the case a protective film is wiped away and so on, and being excellent in an adhesion property with a sealing material, is formed. <P>SOLUTION: The thermosetting composition for the protective film contains an ethylenically unsaturated compound and/or a compound with an epoxy group in the molecule as a thermal cross-linking agent. In the case 0.1 g of the thermosetting composition is dropped on the center of a 10 cm×10 cm glass substrate, and subsequently is applied thereto with spin coating so as to make dry film thickness of the center portion of the glass substrate 2 μm or more, and in the case a taper angle formed with a side face of the applied layer end portion and the substrate surface is represented by (W1) and a taper angle formed with the side face of the same applied layer end portion and the substrate surface after the applied layer has further been subjected to heat treatment at 230°C for 30 minutes is represented by (W2), a following inequality W1/W2≥1.2 is satisfied. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermosetting composition for a protective film. Specifically, the present invention relates to a thermosetting composition for a protective film used for a panel such as a display and a wiring board, a color filter having a protective film formed using the same, and a liquid crystal display device.

Conventionally, in the manufacturing process of a solid-state imaging device, a liquid crystal display device, and a semiconductor integrated circuit device, the functions and purposes are different, but each includes a multi-layering process by stacking devices, so that a technology for flattening an underlying substrate having irregularities is provided. Has become an important technical issue common to each.
For example, in the field of liquid crystal display elements, a colored liquid crystal display device is manufactured by sequentially providing each layer in the order of a color filter layer, a protective film layer, an ITO film, and an alignment film on one transparent substrate. In the case where the color liquid crystal display device has a step, when the liquid crystal compound is sandwiched between the pair of transparent substrates, a distribution (unevenness) occurs in the thickness of the liquid crystal within the pair of substrates. As a result, there has been a problem that a color loss phenomenon due to liquid crystal alignment inhibition or retardation occurs. Therefore, in order to solve this, a curable resin composition containing an epoxy resin and a specific carboxylic acid (anhydride) as a thermal cross-linking agent is used as a protective film that ensures the function of flattening the unevenness of the surface. (Patent Document 1).

  On the other hand, the color filter substrate has a structure in which the flange portions of both substrates are bonded with a sealant so as to be bonded to the TFT substrate with the liquid crystal interposed therebetween. The protective film layer coated on the color filter substrate usually forms a specific protective layer pattern, but an ITO film is formed on the color filter substrate on which the protective film layer is formed with a conventional photosensitive thermosetting composition. If it does, there existed a problem that the ITO film | membrane would hit easily the corner | angular part of the upper surface of the protective layer (edge part), and would be easily disconnected. Further, due to the low hardness of the protective layer, there was a problem that the surface of the protective film layer was wrinkled over time or the ITO film was cracked by the gas generated from the protective film.

Furthermore, in recent years, the number of transflective color filters has increased, and the surface of the image has a more complicated shape. Therefore, the effect of flattening the unevenness has been further demanded.
Japanese Patent No. 3586933

  The present invention is for solving such problems, and forms a protective layer which is excellent in stability over time without disconnection of ITO, and also excellent in adhesiveness and flatness with a sealing agent. It is an object of the present invention to provide a thermosetting composition that can be used.

As a result of intensive studies on the above problems, the present inventor has found that a specific photosensitive composition can achieve the above object, and has completed the present invention. That is, the gist of the present invention is as follows.
(1) A thermosetting composition for a protective film containing an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal crosslinking agent, and 0.1 g of the thermosetting composition is 10 cm. After being dropped on the center of a glass substrate of × 10 cm and then applied by spin coating so that the dry film thickness at the center of the glass substrate is 2 μm or more, the taper angle formed from the side surface of the coating layer end and the substrate plane (W1), and when the taper angle formed from the side surface and the substrate plane of the same coating layer after the coating layer is further heated at 230 ° C. for 30 minutes is defined as (W2): The thermosetting composition for protective films characterized by satisfy | filling.
W1 / W2 ≧ 1.2
(2) A thermosetting composition for a protective film containing an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal crosslinking agent, and further containing a photopolymerization initiator, which is a glass substrate The thermosetting composition was applied to the film with a thickness of 2 μm, irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / cm ² through a mask having a fine line pattern with a line width of 10 mm, and then 23 ° C.
The taper angle formed from the side surface of the fine line image obtained by the shower development process at a water pressure of 0.25 MPa and the substrate plane is (W3), and the side surface of the fine line image obtained by further heating the thin line image at 230 ° C. for 30 minutes. When the taper angle formed from the substrate plane is (W4), the following formula is satisfied: A thermosetting composition for a protective film.
W3 / W4 ≧ 1.2
(3) A thermosetting composition containing an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal cross-linking agent, further containing an alkali-soluble resin, and differentiation of the alkali-soluble resin 10 ^{1/2 of} the molecular weight (M1) corresponding to the maximum peak of the molecular weight distribution curve
The weight content (V2) of an alkali-soluble resin having a molecular weight (M2) twice that of an alkali-soluble resin having a molecular weight (M3) that is ^{10-1 / 2} times the molecular weight (M1) is ^expressed by the following formula: A thermosetting composition for a protective film, characterized by satisfying.
V2 / V3 ≧ 1.3
(4) A color filter having a protective film formed from the thermosetting composition for protective film according to any one of (1) to (3).
(5) A liquid crystal display device having a protective film formed of the thermosetting composition for protective film according to any one of (1) to (3).

  According to the thermosetting composition for a protective film of the present invention, it is possible to form a protective layer which is excellent in aging stability without disconnection of ITO, and also excellent in adhesiveness and flatness with a sealing agent. In addition, the color filter of the present invention is of high quality because a protective film excellent in flatness is used without disconnection of ITO. The liquid crystal display device of the present invention is of high quality because the above-described high quality color filter is used.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of the embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
[1] Thermosetting composition for protective film The thermosetting composition for protective film of the present invention (hereinafter sometimes simply referred to as "thermosetting composition") is an ethylenically unsaturated compound as a thermal crosslinking agent. It is characterized by containing a compound and / or a compound having an epoxy group in the molecule. Moreover, you may contain the hardening | curing agent and other components as needed. For the purpose of increasing the hardness of the protective layer or for the purpose of patterning, if a photoexposure / alkali development step is included before the thermosetting treatment, a photopolymerizable monomer, photopolymerization initiator, alkali-soluble resin, and other components are further included. May be contained. Hereinafter, each component will be described. In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and “total solids” means the total amount of components of the thermosetting composition excluding the solvent. Means.

[1-1] Thermal crosslinking agent [1-1-1] Ethylenically unsaturated compound As the ethylenically unsaturated compound as the thermal crosslinking agent used in the thermosetting composition of the present invention, an ethylenically unsaturated bond is used. Is preferably a compound having two or more ethylenically unsaturated bonds in the molecule from the viewpoint of polymerizability, crosslinkability, etc., and the unsaturated bond thereof. Is more preferably an acrylate compound derived from a (meth) acryloyloxy group.

Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene, etc. Examples of compounds having two or more ethylenically unsaturated bonds in the molecule are typically esters of unsaturated carboxylic acids and polyhydroxy compounds. , (Meth) acryloyloxy group-containing phosphates, urethane (meth) acrylates of hydroxy (meth) acrylate compounds and polyisocyanate compounds, and (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds Epoxy (meth) acrylates, etc. Can be mentioned.

[1-1-1-1] Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound Specific examples of the esters of unsaturated carboxylic acid and polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.

Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol includes the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction products of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.

Specific examples of the esters of the unsaturated carboxylic acid and the polyhydroxy compound are as follows.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , And similar crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  In addition, as esters of unsaturated carboxylic acid and polyhydroxy compound, unsaturated carboxylic acid and aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts These reactants can be mentioned. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, di (meth) acrylate, tri (meth) acrylate, etc. of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.

[1-1-1-2] (Meth) acryloyloxy group-containing phosphates (meth) acryloyloxy group-containing phosphates are not particularly limited as long as they are phosphate compounds containing (meth) acryloyloxy groups. The following general formulas (VIIIa) to (VIIIc) are preferable.

(In the formulas (VIIIa), (VIIIb) and (VIIIc), R ¹⁰ represents a hydrogen atom or a methyl group;
An integer of ˜25, q is 1, 2 or 3. )
Here, p is preferably 1 to 10, particularly 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) Examples thereof include acryloyloxyethylene glycol phosphate, and these may be used alone or as a mixture.

[1-1-1-3] Urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound As urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound, for example, Hydroxy (meth) acrylate compounds such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and fats such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane Polyisocyanate, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate Polyisocyanate compounds such as alicyclic polyisocyanates such as bicycloheptane triisocyanate, aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate And the like. For example, trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd. can be used.

Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly Compound (i-1) obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, Alternatively, as a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, and “Duranate” manufactured by Asahi Kasei Kogyo Co., Ltd. Biuret such as “18H-70B” Compounds having three or more isocyanate groups in one molecule, such as Yup, adduct types such as "Duranate P-301-75E", "Duranate E-402-90T", and "Duranate E-405-80T" 4 or more in one molecule, such as compound (i-2) obtained by polymerizing, or compound (i-3) obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, Preferably, compounds having 6 or more isocyanate groups, such as “Duranate ME20-100” (i) manufactured by Asahi Kasei Kogyo Co., Ltd., pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Such as dipentaerythritol hexaacrylate, 1 or more hydroxyl groups and 2 or more in one molecule, it can preferably be obtained by reacting a compound having three or more (meth) acryloyloxy group (ii).

  Here, the molecular weight of the compound (i) is preferably 500 to 200,000, and particularly preferably 1,000 to 150,000. The molecular weight of the urethane (meth) acrylates as described above is preferably 600 to 150,000. Further, it preferably has 6 or more urethane bonds, particularly preferably 8 or more, more preferably 6 or more (meth) acryloyloxy groups, and particularly preferably 8 or more.

  In addition, such urethane (meth) acrylates include, for example, the compound (i) and the compound (ii) between the former isocyanate group and the latter hydroxyl group in an organic solvent such as toluene or ethyl acetate. It can be produced by a method of reacting at a molar ratio of 1/10 to 10/1 at 10 to 150 ° C. for about 5 minutes to 3 hours using a catalyst such as n-butyltin dilaurate as necessary. it can.

[1-1-1-4] Epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound (meth) acrylic acid or hydroxy (meth) acrylate compound and polyepoxy compound Examples of the epoxy (meth) acrylates include (meth) acrylic acid or a hydroxy (meth) acrylate compound as described above, (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly ) Tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) Aliphatic polyepoxy compounds such as trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, phenol novolac polyepoxy compounds, brominated phenol novolak polyepoxy compounds, (o-, m-) , P-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, aromatic polyepoxy compounds such as bisphenol F polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate And a heterocyclic polyepoxy compound such as a reaction product with a polyepoxy compound such as.

[1-1-1-5] Other ethylenically unsaturated compounds As other ethylenically unsaturated compounds, in addition to the above, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, diallyl phthalate, etc. Thioether bond-containing compounds with improved cross-linking speed by sulfating ether bonds of allyl esters, divinyl phthalate and other vinyl group-containing compounds and ether bond-containing ethylenically unsaturated compounds with phosphorus pentasulfide to thioether bonds. And, for example, polyfunctional (meth) acrylate compounds described in Japanese Patent No. 3164407 and JP-A-9-100111 and silica sols having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (Nissan Chemical Co., Ltd.) "IPA-ST"), methyl ethyl ketone Dispersed organosilica sol (“MEK-ST” manufactured by Nissan Chemical Co., Ltd.), methyl isobutyl ketone dispersed organosilica sol (“MIBK-ST” manufactured by Nissan Chemical Co., Ltd.), etc.] using an isocyanate group or mercapto group-containing silane coupling agent Examples thereof include compounds in which strength and heat resistance as a cured product are improved by reacting and bonding silica sol to an ethylenically unsaturated compound via a silane coupling agent, such as a bonded compound.

As the above ethylenically unsaturated compounds, known compounds described in the detailed description of Japanese Patent Application No. 2004-324666 may be used alone or two or more of them may be used in combination.
In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable. Among the ester (meth) acrylates, ester (meth) acrylates containing 3 or more (meth) acryloyloxy groups such as dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are particularly preferable.

  The content of the ethylenically unsaturated compound in the thermosetting composition of the present invention is usually 1% by weight or more, preferably 2% by weight or more, and usually 60% by weight or less, preferably with respect to the total solid content. 40% by weight or less. If the amount of the ethylenically unsaturated compound is too small, the sensitivity and the development dissolution rate are liable to be lowered, and if too large, the reproducibility of the image cross-sectional shape is liable to be lowered and the resist film is liable to be thin.

[1-1-2] Compound having epoxy group in molecule As an epoxy compound in the molecule used in the present invention, for example, (i) obtained by reacting a monohydroxy compound or a polyhydroxy compound with epichlorohydrin (poly ) A glycidyl ether compound, (ii) a polyglycidyl ester compound obtained by reacting a (poly) carboxylic acid compound and epichlorohydrin, and (iii) a (poly) glycidylamine compound obtained by reacting a (poly) amine compound with epichlorohydrin And compounds ranging from low molecular weight substances to high molecular weight substances.

[1-1-2-1] Polyglycidyl ether compound Examples of the polyglycidyl ether compound include diglycidyl ether type epoxy of polyethylene glycol, diglycidyl ether type epoxy of bis (4-hydroxyphenyl), and bis (3,5 Diglycidyl ether type epoxy of -dimethyl-4-hydroxyphenyl), diglycidyl ether type epoxy of bisphenol F, diglycidyl ether type epoxy of bisphenol A, diglycidyl ether type epoxy of tetramethylbisphenol A, diglycidyl ether type epoxy of ethylene oxide Glycidyl ether type epoxy, dihydroxyoxyfluorene type epoxy, dihydroxyalkyleneoxylfluorene type epoxy, bisphenol A / aldehyde novolak type epoxy Bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, as xy, phenol novolac type epoxy, cresol novolac type epoxy, and polyglycidyl ether resin, Examples thereof include phenol resin type epoxy resins such as a polymerization epoxy resin of phenol and naphthalene.

These (poly) glycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride, a divalent acid compound or the like to introduce a carboxyl group.
[1-1-2-2] Polyglycidyl ester compound Examples of the polyglycidyl ester compound include diglycidyl ester type epoxy of hexahydrophthalic acid, diglycidyl ester type epoxy of phthalic acid, and the like.

[1-1-2-3] Polyglycidylamine compound Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane, triglycidylamine type epoxy of isocyanuric acid, and the like. It is done.
[1-1-2-4] Others As other examples, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (Meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxy A polymer in which (meth) acrylate having an epoxy group such as heptyl is used alone or in combination of two or more, or other comonomer is usually added to a (meth) acrylate structural unit having an epoxy group in an amount of 10 to 70. A polymer containing a mol%, preferably 15-60 mol%, can be mentioned. Among these, as the copolymer, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, (meth) acrylic Esters of (meth) acrylic acid such as phenyl acid, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and styrene And vinyl aromatic compounds such as α-methylstyrene, p-methylstyrene, and vinylnaphthalene. A preferred (meth) acrylate having an epoxy group is glycidyl (meth) acrylate. Preferred copolymers include dicyclopentanyl (meth) acrylate and α-styrene.

  When the epoxy compound is a resin, the preferred molecular weight is not particularly limited as long as the solution of the protective film material of the present invention can be uniformly applied, and depends on the thickness of the coating film to be formed, application conditions, purpose, etc. The polystyrene-converted weight average molecular weight measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) is usually preferably in the range of 2,000 to 300,000. Preferably it is 3,000-100,000, More preferably, it is 4,000-50,000.

The epoxy group used in the epoxy compound or epoxy resin used in the present invention is usually 1,2 epoxy group, but 1,3 epoxy is used for the purpose of improving stability over time or imparting flexibility. A group (oxetane) or a 4,3-epoxycyclohexyl group can also be used.
The content of the epoxy compound in the thermosetting composition of the present invention is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 98% by weight with respect to the total solid content. % Or less, preferably 95% by weight or less. If the amount of the epoxy compound is too small, adhesion to the support, reduction in hardness, thermogravimetric change, and increase in the contact angle on the side surface of the thermosetting film are likely to occur.

[1-2] Curing Agent In the present invention, a curing agent can be further added to shorten the time under curing conditions or change the set temperature, and different curing conditions can be appropriately selected depending on the manufacturing process of each element. .
The curing agent used in the present invention is not particularly limited as long as it does not impair the required function, but is usually a heavy benzoic acid compound, a polyvalent carboxylic acid (anhydride), a heavy carboxylic acid (anhydride) containing polyvalent carboxylic acid. Examples thereof include coalescence, thermal acid generator, amine compound, polyamine compound, and block carboxylic acid.

[1-2-1] Benzoic acid compounds.
Examples of benzoic acid compounds include benzoic acid, hydroxyl groups, halogen groups, alkyl groups, acyl groups, acyloxyl groups, alkoxyl groups, aryl groups, allyl groups, and the like at positions 2 to 6 on the benzene ring of benzoic acid. Among these, those having a hydroxyl group having a high curing ability with respect to epoxy are preferable, particularly those having two or more hydroxyl groups, such as 3,4,5-trihydroxybenzoic acid. 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid and the like.

[1-2-2] Polycarboxylic acid (anhydride)
Examples of the polyvalent carboxylic acid (anhydride) include alicyclic polycarboxylic acids such as methyl hymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, etc. (Anhydrides), phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tricarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, etc., succinic acid, trimellitic acid, malein Examples include acids, cycloaliphatic acid anhydrides such as cyclopentanetetracarboxylic acid, and hydrolysates of aromatic acid anhydrides. Among these, trimellitic acid (anhydride) and phthalic anhydride are preferable.

[1-2-3] Polymer containing polyvalent carboxylic acid (anhydride) The polymer containing polyvalent carboxylic acid (anhydride) includes (anhydrous) polyvalent carboxylic acid such as maleic anhydride. And, for example, (meth) acrylic acid and its alkyl esters, (meth) acrylonitrile, (meth) acrylamide, styrene, (poly) alkyleneoxy, alkylene having an anchoring group such as alkyl, etc. A polymer containing a polyvalent carboxylic acid (anhydride) such as a polymer with a compound having one or more compounds therein, and a partial half ester modified polymer of the polyvalent carboxylic acid (anhydride) portion in the polymer, etc. Can be mentioned. Among these, a copolymer of maleic anhydride and an alkylene having a positioning group such as (poly) alkyleneoxy or alkyl is preferable.

[1-2-4] Thermal acid generator Examples of the thermal acid generator include various onium salt compounds such as aromatic diazonium salts, diaryliodonium salts, triallylsulfonium salts, triallyl selenium salts, and sulfonate esters. And halogen compounds.
Specific examples of the aromatic diazonium salt include chlorobenzenediazonium hexafluorophosphate, dimethylaminobenzenediazonium hexafluoroantimonate, naphthyldiazonium hexafluorophosphate, dimethylaminonaphthyldiazonium tetrafluoroborate and the like. Diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium triflate, 4,4′-di-t-butyl-diphenyliodonium triflate, 4 4,4′-di-t-butyl-diphenyliodonium tetrafluoroborate, 4,4′-di-t-butyl-diphenyliodonium hexafluorophosphate, and the like.

  Monophenylsulfonium salts include benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimonate, Examples thereof include benzyl-p-hydroxyphenylmethylsulfonium hexafluoroantimonate, monophenylsulfonium salt types such as compounds represented by the following general formula (1), and benzylphenylsulfonium salt types.

(In the formula, Z represents a phenyl group.)
Triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tri (p-chlorophenyl) sulfonium tetrafluoroborate, Examples include tri (p-chlorophenyl) sulfonium hexafluorophosphate, tri (p-chlorophenyl) sulfonium hexafluoroantimonate, 4-t-butyltriphenylsulfonium hexafluorophosphate, and the like.

  Triallyl selenium salts include triallyl selenium tetrafluoroborate, triallyl selenium hexafluorophosphate, triallyl selenium hexafluoroantimonate, di (chlorophenyl) phenyl selenium tetrafluoroborate, di (chlorophenyl) phenyl selenium hexafluoro Examples thereof include phosphate, di (chlorophenyl) phenyl selenium hexafluoroantimonate, and the like.

Examples of sulfonic acid esters include benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, and 2,4-dinitrobenzyl tosylate. Etc.
Examples of the halogen compound include 2-chloro-2-phenylacetophenone, 2,2 ′, 4′-trichloroacetophenone, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, bis-2- (4-chlorophenyl) -1,1,1-trichloroethane Bis-1- (4-
Chlorophenyl) -2,2,2-trichloroethanol, bis-2- (4-methoxyphenyl) -1,1,1-trichloroethane and the like.

Among these thermal acid generators, the monophenylsulfonium salt type or the benzylphenylsulfonium salt type is preferable.
[1-2-5] Examples of the amine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, piperidine, pyrrolidine, triethylenediamine, and trimethyl. Hexamethylenediamine, dimethylcyclohexylamine, tetramethylguanidine, triethanol
Aliphatic amines such as ruamine, N, N′-dimethylpiperazine, dicyanamide or derivatives thereof, DBU (1,8-diazabiscyclo (5,4,0) undecene-1), DBU tetraphenylborate salts (first, first 2, 3),
Metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, benzyldimethylamine, dimethylamino-p-cresol, 2- (dimethylaminejomethyl) phenol, 2,4,6-tris (dimethylamino) Methyl) phenol, pyridine, picoline, DBU (1,8-diazabiscyclo (5,4,0) undecene-1), 2,4,6-tris (dimethylaminomethyl) phenol tri-2-ethylhexyl Aromatic amines such as acid salts (first, second, third),
2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)]-Ethyl-S-triazine, 2,4-diamino-6- [2-ethylimidazolyl- (1)]-ethyl-S- Triazine, 2,4-diamino-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4- Imidazole compounds such as methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, diethylenetriamine, iminobispropylamine, bis (hexamethylene) A triamine etc. are mentioned. Of these, dicyanamide and DBU tetraphenylborate salts are preferred.

[1-2-6] Polyamine compound Examples of the polyamine compound include triethyltetramine, tetraethylenepentamine, pentaethylenehexamine, dimethylaminopropylamine, diethylaminopropylamine, N-aminoethylpiperazine, mensendiamine, isofluorodiamine, Aliphatic polyamines such as bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylamine, N, N-dimethylcyclohexylamine, m-xylenediamine, xylylenediamine, xylylenediamine derivatives, xylylenediamine trimers And aromatic polyamines such as Of these, N, N-dimethylcyclohexylamine is preferred.

[1-2-7] Block Carboxylic Acid Examples of the block carboxylic acid include, for example, the above-mentioned (polyvalent) carboxylic acids and carboxylic acids of polymers containing them, as disclosed in JP-A-4-218561 and JP-A-2003-66223. Examples thereof include block carboxylic acids to which vinyl ether is added by the methods described in JP-A-2004-339332, JP-A-2004-339333, and the like.

Among the curing agents, a polymer containing a polyvalent carboxylic acid (anhydride), an onium salt compound, a block carboxylic acid compound, and a benzoic acid compound have a low contact angle between the thermosetting layer and the support, and It is preferable in that the activity of the curing reaction is good and high hardness and adhesion to the support can be obtained. Specific examples include the following compounds.
(I) maleic anhydride and (ii) ethylene, butylene, or propylene compound containing an alkyl group having 1 to 20 carbon atoms, a polypropyleneoxypropylene group having 1 to 15 carbon atoms, or a polyethyleneoxypropylene group having 1 to 15 carbon atoms , A polyvalent carboxylic acid copolymer with at least one ethylene compound selected from styrene;
Block carboxylic acid compound consisting of adduct of trimellitic acid or maleic acid and ethyl vinyl ether;
Benzyl-p-hydroxyphenylmethylsulfonium hexafluorophosphate, p-hydroxyphenyldimethylsulfonium hexafluoroantimonate, p-acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-p-hydroxyphenylmethylsulfo Monophenylsulfonium salts such as nium hexafluoroantimonate, monophenylsulfonium salt types such as compounds represented by the following general formula (1), or benzylphenylsulfonium salt types;

(In the formula, Z represents a phenyl group.)
Examples include benzoic compounds such as 2,5-dihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid.
Among these, polyvalent carboxylic acid copolymers and benzoic acid compounds are excellent in improving the adhesion to the support, and monosulfonium salts are excellent in improving the hardness.

Benzoic acid compounds are particularly preferable because they are excellent in thermosetting and heat melting properties (change in taper angle), give high flatness, have high light transmittance, and are less affected by color change due to heat.
The content of the curing agent in the thermosetting composition of the present invention is usually 0.05% by weight or more, preferably 0.1% by weight or more, and usually 30% by weight or less, preferably with respect to the total solid content. Is 20% by weight or less. If the amount of the curing agent is too small, the adhesion to the support and the hardness are liable to decrease. On the other hand, if the amount is too large, the thermal weight loss is likely to increase.

[1-3] Photopolymerizable monomer When the photopolymerizable monomer used in the thermosetting composition of the present invention includes a patterning step by photoexposure / development before the thermosetting treatment, an exposed portion and a non-exposed portion associated therewith. It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule from the viewpoint that the difference in developer solubility can be expanded, and the unsaturated bond is derived from a (meth) acryloyloxy group. The acrylate compound is preferably a photopolymerizable and low molecular weight compound that can be polymerized, and is not particularly limited, but is preferably a polyfunctional monomer having a functional group, and an ethylenic double bond. More preferred is an addition-polymerizable compound having at least one. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  The above “compound capable of addition polymerization having at least one ethylenic double bond” means that when the coloring composition for color filter of the present invention is irradiated with actinic rays, it acts by the action of a photopolymerization initiator described later. It is a compound having an ethylenic double bond that undergoes addition polymerization and cures. Examples of such a compound include the ethylenically unsaturated compounds described in the section [1-1-1], and the same compounds as the thermal cross-linking agent can be used. It is preferable to use an alkali-soluble material that can be easily developed.

  Specific examples of preferable photopolymerization monomers include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexaacrylate are more preferable.

[1-4] Photopolymerization initiator Any known photopolymerization initiator used in the thermosetting composition of the present invention can be used, and an ethylenically unsaturated group is polymerized from ultraviolet to visible light. And a compound that generates a compound capable of generating a radical to be generated.
Specific examples of the polymerization initiator that can be used in the present invention are listed below.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( Halomethylated triazine derivatives such as 4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine ,
Halomethylated oxadiazole derivative, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenylimidazole dimer, benzoin such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoin alkyl ethers,
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone,
Benzanthrone derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2, -dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1, -trichloromethyl- (p-butylpheny ) Acetophenone derivatives such as ketones, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone ,
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate,
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine,
Phenazine derivatives such as 9,10-dimethylbenzphenazine,
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl,
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethyl Aminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino ) Α-Aminoalkylphenone compounds such as chalcone.

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyloxime), etc., described in JP-A 2000-80068, JP-A 2001-233842, JP-A 2001-235858, and WO 02/00903 Examples thereof include oxime derivatives represented by the compounds described above.

These photopolymerization initiators are used alone or in combination. Examples of combinations include, for example, Japanese Patent Publication No. 53-12802, Japanese Patent Laid-Open No. 1-279903,
2-48664 publication, Unexamined-Japanese-Patent No. 4-164902, or Unexamined-Japanese-Patent No. 6-75373 etc. The combination of the initiator is mentioned.
The content of the photopolymerization initiator in the thermosetting composition of the present invention is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less, based on the total solid content. It is preferably 30% by weight or less. If the amount of the ethylenically unsaturated compound is too small, the sensitivity tends to decrease, and if it is too large, the background stain (development solubility) tends to decrease.
[1-4] Alkali-soluble resin The alkali-soluble resin used in the thermosetting composition of the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include the following compounds. (Meth) acrylic acid, (meth) acrylic acid ester, maleic acid, vinyl acetate, maleimide, etc., unsaturated group and carboxyl group-containing epoxy resin, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (Meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide and the like, a hydroxyl group or carboxyl group-containing vinyl resin containing a hydroxyl group or a carboxyl group, and polyamide, polyester, polyether, polyurethane, polyvinyl butyral, Polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose and the like can be mentioned. Of these, unsaturated group and carboxyl group-containing epoxy resins and carboxyl group-containing vinyl resins are preferred from the viewpoints of alkali developability and image formability.

[1-4-1] Unsaturated Group and Carboxy Group-Containing Epoxy Resin As the unsaturated group and carboxyl group-containing epoxy resin according to the present invention, an α, β-unsaturated group-containing carboxylic acid adduct of an epoxy resin may be used. Unsaturated group and carboxyl group-containing epoxy resin to which a monovalent carboxylic acid and / or anhydride thereof is added, that is, (ii) carboxyl group of α, β-unsaturated monocarboxylic acid to epoxy group of epoxy resin An ethylenically unsaturated bond is added via an ester bond (—COO—) formed by ring-opening addition of (3), and (iii) a carboxyl of polyvalent carboxylic acid or anhydride thereof is formed on the resulting hydroxyl group. The thing to which group was added is mentioned. Hereinafter, the constituent components of the unsaturated group- and carboxyl group-containing epoxy resin will be described in detail.
[1-4-1-1] The epoxy resin used for the unsaturated group and carboxyl group-containing epoxy resin can be appropriately selected from the epoxy compounds introduced above, for example, bisphenol A epoxy. Resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, trisphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentane, etc., among which phenol novolac epoxy resin, or A cresol novolac epoxy resin, a polymerized epoxy resin of phenol and dicyclopentadiene, a copolymer of glycidyl methacrylate and an alkyl (meth) acrylate, and the like are preferable.

[1-4-1-2] α, β-unsaturated monocarboxylic acid Examples of α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, Citraconic acid, etc., and pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol Examples include penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth) acrylic acid and ε-caprolactone, (Meth) acrylic acid is preferred.

[1-4-1-3] Polyvalent carboxylic acid or anhydride thereof Examples of the polyvalent carboxylic acid or anhydride thereof include oxalic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, and 3-methyltetrahydro. Phthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydro Examples include phthalic acid, 4-ethylhexahydrophthalic acid, and anhydrides thereof. Among them, maleic acid anhydride, tetrahydrophthalic acid anhydride, or hexahydrophthalic acid anhydride is preferable, and tetrahydrophthalic acid anhydride is preferable. Is more preferable.

  In the above, in the present invention, the epoxy resin is a phenol novolac epoxy resin, a bisphenol epoxy resin, a hydroxyfluorene epoxy (resin), or the like from the viewpoints of sensitivity, resolution, adhesion to a substrate, and the like as a thermosetting composition. It is a cresol novolac epoxy resin, preferably α, β-unsaturated monocarboxylic acid is (meth) acrylic acid, and polyvalent carboxylic acid or anhydride thereof is tetrahydrophthalic anhydride. Moreover, what has an acid value of 20-200 mg-KOH / g is preferable, and what is 30-180 mg-KOH / g is still more preferable. Further, the weight average molecular weight in terms of polystyrene by GPC measurement is usually 1,000 or more, preferably 1,500 or more, usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less. .

  In the present invention, the unsaturated group- and carboxyl group-containing epoxy resin is dissolved in an organic solvent such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, or propylene glycol monomethyl ether acetate by a conventionally known method. Tertiary amines such as triethylamine, benzyldimethylamine, tribenzylamine, or quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride In the presence of a catalyst such as a phosphorus compound such as triphenylphosphine, or a stibine such as triphenylstibine, In the presence of a thermal polymerization inhibitor such as idroquinone, hydroquinone monomethyl ether and methyl hydroquinone, the α, β-unsaturated monocarboxylic acid is usually added in an amount of 0.7 to 1. 3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents are added, and an addition reaction is usually performed at a temperature of 60 to 150 ° C., preferably 80 to 120 ° C., followed by polyvalent carboxylic acid or an anhydride thereof. Is usually added in an amount of 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group generated in the reaction, and the reaction is carried out under the above conditions. It can be manufactured by a method such as continuing.

  Specific examples of the structural repeating unit of the above unsaturated group and carboxyl group-containing epoxy resin are shown below.

[1-4-2] Carboxyl group-containing vinyl resin As the carboxyl group-containing vinyl resin according to the present invention, for example, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, Unsaturated carboxylic acid such as citraconic acid, styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl Examples thereof include copolymers with vinyl compounds such as (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, and vinyl acetate. Among them, dicyclopentanyl (meth) acrylate has a large rate of change in contact angle due to post-heating, stably forms a liquid crystal protective layer with a low contact angle, and gives a wide latitude against development time and developer deterioration. As the dicyclopentanyl (meth) acrylate, for example, compounds described in JP-A-2001-89533, for example, dicyclopentadiene skeleton, dicyclopentanyl skeleton, dicyclopentenyl skeleton, dicyclopentenyloxyalkyl skeleton (Meth) acrylate and the like.

  Among the above copolymers, a styrene- (meth) acrylate- (meth) acrylic acid copolymer is preferable, and 3-30 mol% styrene, 10-70 mol% (meth) acrylate, 10 (meth) acrylic acid. A copolymer composed of ˜60 mol% is more preferred, and a copolymer composed of 5-25 mol% styrene, 20-60 mol% (meth) acrylate, and 15-55 mol% (meth) acrylic acid is particularly preferred. These carboxyl group-containing vinyl resins have an acid value of 30 to 250 mg-KOH / g, preferably 50 to 200 mg-KOH / g, and more preferably 70 to 150 mg-KOH / g. The weight average molecular weight Mw by GPC measurement is usually 1,000 or more, preferably 1500 or more, more preferably 2000 or more, usually 100,000 or less, preferably 50,000,000 or less, more preferably 20,000 or less, particularly Preferably it is 10,000 or less. When the carboxyl group-containing vinyl resin in the above range is contained, the deformation of the thermosetting composition upon heating is large (the change in the contact angle is large), which is preferable.

  Furthermore, as the carboxyl group-containing vinyl resin, those having an ethylenically unsaturated bond in the side chain are suitable. For example, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl is added to the carboxyl group-containing polymer. (Meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester, etc. Saturated compound, or 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2.1.0] dec-2 Yl] An alicyclic epoxy group-containing unsaturated compound such as oxymethyl (meth) acrylate is obtained by reacting 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing polymer. Reaction products and allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl A compound having two or more unsaturated groups such as (meth) acrylamide, or vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate , Vinyl crotonate, vinyl (meth) acrylamide The ratio of the compound having two or more kinds of unsaturated groups such as, and unsaturated carboxylic acid such as (meth) acrylic acid, or further unsaturated carboxylic acid ester to the whole compound having the former unsaturated group Examples include reaction products obtained by copolymerization so as to be about 10 to 90 mol%, preferably about 30 to 80 mol%.

  The content of the alkali-soluble resin in the thermosetting composition of the present invention is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight based on the total solid content. % Or less. If the amount of the alkali-soluble resin is too small, the reproducibility of the image cross-sectional shape is poor and the heat resistance is lowered, and if it is too much, the sensitivity is lowered and the development dissolution rate is lowered.

The thermosetting composition of the present invention needs to increase the deformation of the resist image during heating, and the content of the alkali-soluble resin and the content of the photopolymerizable monomer are preferably in a specific ratio. Specifically, the content ratio of alkali-soluble resin / photopolymerizable monomer is usually less than 1.3, preferably 1.1 or less.
Furthermore, the alkali-soluble resin used in the thermosetting resin of the present invention is a differential molecular weight distribution curve of a resin obtained by GPC (weight content of the alkali-soluble resin corresponding to each molecular weight contained in the alkali-soluble resin). The weight content (V2) of an alkali-soluble resin having a molecular weight (M2) 10 ^1/2 times the molecular weight (M1) corresponding to the maximum peak of the molecular weight and a molecular weight (M3) 10 ^−1/2 times the molecular weight (M1) V2 / V3 obtained from the weight content (V3) of the alkali-soluble resin is usually 1.3 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 1000 or less, preferably 500 or less, more preferably 200 or less. By using an alkali-soluble resin having a low molecular weight component and a low molecular weight distribution in this way, image forming properties are improved, the protective film strength is improved, and the generation of crack defects in the ITO film on the protective layer is suppressed. Can do.

  The above-mentioned alkali-soluble resin having a specific molecular weight distribution is, for example, a resin solution obtained by dissolving a normally obtained alkali-soluble resin in an organic solvent such as isopropylene glycol monomethyl ether acetate described later in [1-6]. Thereafter, it is mixed with a poor solvent of an alkali-soluble resin such as methanol to precipitate the resin, followed by filtration of the precipitated resin and, for example, air drying under reduced pressure at 40 ° C. for 12 hours.

[1-5] Other components [1-5-1] Adhesion aid The composition of the present invention may contain an adhesion aid for the purpose of improving adhesion to the substrate. Examples of the adhesion assistant include a silane coupling agent.
Specifically, trimethoxysilyl benzoic acid, γ-methylacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. These silane coupling agents may be used alone or in combination of two or more.

The compounding quantity of the adhesion promoter in the composition of this invention exists in the range of 0.1-30 weight part normally per 100 weight part of resin containing an epoxy group.
[1-5-2] Surfactant In addition to the components described above, the thermosetting composition of the present invention further improves coating properties as a coating liquid for the composition and developability of the thermosetting composition layer. For the purpose, nonionic, anionic, cationic, amphoteric, and fluorine based surfactants may be contained.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.

  Further, fluorine-based and silicone-based ones can be preferably used. As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain, and side chain is preferable. Specifically, 1,1,2,2-tetra Fluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, Hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1 , 2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1, 2,2,3,3-hexafluorodecane and the like can be mentioned. These commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafac F142D”, “Same F172”, “Same F173”, “Same” manufactured by Dainippon Ink and Chemicals, Inc. F183 "," F470 "," FC430 "manufactured by Sumitomo 3M Corporation," DFX-18 "manufactured by Neos Corporation, and the like.

  Examples of silicone-based surfactants include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Short SH30PA” manufactured by Torre Silicone Co., Ltd. "SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-444 (4) (5) (6) (7) 6", "TSF" manufactured by Toshiba Silicone Co., Ltd. Commercial products such as “-4460”, “TSF-4452”, “KP341” manufactured by Silicone Co., Ltd., “BYK323”, “BYK330” manufactured by Big Chemie.

Of these, silicone surfactants are preferred, and polyether-modified silicone surfactants are more preferred.
Examples of the anionic surfactant include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples thereof include polymer surfactants. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of commercially available products include alkyl sulfate salts such as “Emar 10” manufactured by Kao Corporation, and alkyl naphthalene sulfonates such as “Perex NB-L” manufactured by Kao Corporation. “Homogenol L-18”, “Homogenol L-100” manufactured by Kao Corporation and the like can be mentioned.
The cationic surfactants include quaternary ammonium salts, imidazoline derivatives, amine salts, and the like, and the amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids, and the like. Is mentioned. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of commercially available products include “Acetamine 24” manufactured by Kao Corporation for alkylamine salts, and “Cotamine 24P” and “Cotamin 86W” manufactured by Kao Corporation for quaternary ammonium salts.

  Two or more kinds of surfactants may be combined. Silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant Examples include combinations of agents. Of these, silicone surfactants / fluorine surfactants are preferred. In this silicone surfactant / fluorine surfactant combination, for example, “TSF4460” manufactured by GE Toshiba Silicone Co., Ltd. “DFX-18” manufactured by Neos Co., Ltd., “BYK-300” manufactured by BYK Chemie Co., Ltd., “manufactured by Seimi Chemical Co., Ltd.” "S-393", Shin-Etsu Silicone "KP340" / Dainippon Ink "F-478", Toray Silicone "SH7PA" / Daikin "DS-401", Nihon Unicar "L-77" / “FC4430” manufactured by Sumitomo 3M Ltd.

In the thermosetting composition of the present invention, the content of the surfactant is preferably 10% by weight or less, more preferably 1 to 5% by weight, based on the total solid content.
In addition, the thermosetting composition of the present invention mainly has a contact angle θ (degrees) of a droplet of the resin composition with respect to the clean glass surface and a surface tension σ (mN) by appropriately selecting the surfactant. / M) is preferably adjusted so as to satisfy the following formulas (1), (2) and (3). Following formula (1), (2)
By satisfying either of (3) and (3), it is possible to prevent the occurrence of coating unevenness and drying unevenness.

θ ≦ 5 × (σ ₀ −σ) (1)
σ ≦ σ ₀ −1 (2)
θ ≦ 15 (3)
[In the above formula, σ ₀ is the surface tension (mN / m) of the solvent alone used in the resin composition. ]
The thermosetting composition of the present invention preferably satisfies the following formulas (1 ′), (2 ′), and (3 ′), and the following formulas (1 ″), (2 ″), And (3 ″) are more preferable, and it is particularly preferable that the following formulas (1 ′ ″), (2 ′ ″), and (3 ′ ″) are satisfied.

θ ≦ 4 × (σ ₀ −σ) (1 ')
σ ≦ σ ₀ −1.5 (2 ')
θ ≦ 12 (3 ')

θ ≦ 3 × (σ ₀ −σ) (1 '')
σ ≦ σ ₀ -2 (2``)
θ ≦ 9 (3``)

θ ≦ 3 × (σ ₀ −σ) (1 ''')
σ ≦ σ ₀ -2 (2 ''')
θ ≦ 5 (3 ''')

In addition, the thermosetting composition of the present invention has a surface tension σ ′ (mN / m) when diluted until the solvent weight is doubled by the solvent used in the resin composition in terms of leveling properties. The surface tension σ (mN / m) before dilution preferably satisfies the following formula (4), more preferably satisfies the following formula (4 ′), and satisfies the following formula (4 ″): Is particularly preferred.

｜ σ−σ ′ | ≦ 0.4 (4)
｜ σ−σ ′ | ≦ 0.3 (4 ′)
｜ σ−σ ′ | ≦ 0.2 (4 '')

In the present invention, the contact angle and the surface tension are measured by the following methods, respectively, and the dilution method is as follows.

<Contact angle>
After the glass substrate for liquid crystal panel is cleaned with a cleaning agent, it is subjected to light cleaning by UV ozone treatment, and the contact angle with pure water is zero degrees, that is, a clean glass substrate that spreads out completely, and the resin composition for the glass substrate The static contact angle is measured at 23 ° C. using a contact angle measuring device by the droplet method.

<Surface tension>
A platinum plate whose surface is fully red hot with an alcohol lamp or the like and cleaned is prepared, and the static surface tension of the resin composition is measured at 23 ° C. using a surface tension meter by a flat plate method.
<Dilution method>
At room temperature, the same solvent as that used in the resin composition is added dropwise to the resin composition in the beaker while stirring and diluted.

[1-5-3] Other Additives The thermosetting composition of the present invention includes various additives such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p in addition to the above components. -A thermal polymerization inhibitor such as cresol may be contained in an amount of 2% by weight or less based on the total solid content, and a plasticizer such as dioctyl phthalate, didodecyl phthalate, tricresyl phosphate or the like in the same proportion of 40% by weight or less. good.

  Furthermore, in this invention, a polymerization accelerator can also be added as needed. Specifically, for example, an ester of an amino acid such as N-phenylglycine or a dipolar compound thereof, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole Mercapto group-containing compounds such as 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, hexanedithiol , Trifunctional thiol compounds such as trimethylolpropane tristhioglyconate, pentaerythritol tetrakisthiopropionate, N, N-dialkylaminobenzoic acid ester, N-phenylglycine or Examples thereof include derivatives such as salts such as ammonium salts and sodium salts, amino acids having aromatic rings such as phenylalanine, salts such as ammonium and sodium salts, and derivatives such as esters, and derivatives thereof.

In the thermosetting composition of the present invention, the content of the polymerization accelerator is preferably 20% by weight or less, more preferably 1 to 10% by weight, based on the total solid content.
[1-6] Organic solvent Each of the above-described components is usually prepared by using an organic solvent so that the solid content concentration is 5 to 50% by weight, preferably 10 to 40% by weight. Is done.

  The organic solvent is not particularly limited as long as it can dissolve and disperse the above-described components and has good handleability. Specifically, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMAc”), methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, tetrahydrofuran, etc. However, the boiling point is preferably in the range of 100 to 200 ° C, more preferably in the range of 120 to 170 ° C. It is those of.

[1-7] Pattern-forming characteristics of the thermosetting composition for protective film of the present invention The thermosetting composition of the present invention is characterized by pattern-forming characteristics before and after heat treatment. Specifically, When 0.1 g of thermosetting composition is dropped onto the center of a 10 cm × 10 cm glass substrate and then applied by spin coating so that the dry film thickness at the center of the glass substrate is 2 μm or more, or (ii) photopolymerization In the case of containing an initiator, the thermosetting composition is applied to a glass substrate with a film thickness of 2 μm and irradiated with ultraviolet light having a wavelength of 365 nm at 100 mJ / cm ² through a mask having a fine line pattern with a line width of 10 mm. Then, when a thin line image having a line width of 10 mm is formed by performing a shower development process at 23 ° C. and a water pressure of 0.25 MPa, the taper angle formed from the side surface and the substrate plane of each image is W1, 3 and when the taper angles formed from the side surface and the substrate plane in the same part as before heating of the thin line image subjected to heat treatment at 230 ° C. for 30 minutes are W2 and W4, respectively, W1 / W2, W3 / W4 is 1.2 or more. W1 / W2 and W3 / W4 are preferably 1.3 or more, more preferably 1.5 or more, and are usually 10 or less, preferably 8 or less.

Here, the taper angle means the angle between the substrate and the straight line connecting the end of the image in contact with the substrate and the height of the pattern at a position 1 μm from the end (FIG. 1).
In addition, the process of said (i) is a method of measuring the taper angle of the pattern of the thermosetting composition of this invention which does not contain a photoinitiator. That is, when the glass plate is rotated at 100-2000 rpm, a liquid (so-called star-shaped) image is formed by inducing liquid breakage as the thermosetting composition leaves the center of rotation. This makes it easy to measure the taper angles (W1 and W2) formed from the side surface of the image and the substrate plane.

By using the thermosetting composition of the present invention, a shape having a small taper angle necessary for the shape of the liquid crystal protective layer is obtained by heating (see FIG. 2). By this shape with a small taper angle, the shape of the ridge portion of the protective film becomes smooth, and disconnection of ITO can be prevented.
[2] Method for Forming Protective Film and Color Filter Next, a method for forming a protective film using the thermosetting composition of the present invention and a color filter having the protective film will be described.

First, a black matrix obtained by a method described in Japanese Patent Application Laid-Open No. 2003-33011 and the like, a red, blue, and green color filter are provided.
Using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray, the thermosetting composition of the present invention described above is usually 0.1 to 2 mm thick on a transparent substrate on which a thick ITO is deposited. Apply. The coating film thickness of the thermosetting composition is usually 0.5 to 5 μm. The coating film made of the thermosetting composition is dried, and if necessary, for example, patterning by light exposure / development is performed before the thermosetting treatment.

  When a patterning step by light exposure / development is included before the thermosetting treatment, a photomask is placed on the dried coating film of the thermosetting composition layer, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel. In general, an image obtained after development is required to have a fine line reproducibility of 1 cm width, and there is a tendency that a finer fine line reproducibility is required due to a demand for a high-quality display. In order to stably reproduce high-definition fine lines, the cross-sectional shape of the fine line image after development is a rectangular shape with a clear contrast between the non-image and the image area, such as development time, developer aging, physical stimulation of the development shower, etc. A wide development margin is preferable.

[2-1] Drying Step For drying the coating film made of the composition of the present invention, vacuum drying, hot plate, IR oven, convection oven or the like can be used. Preferred drying conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes.
[2-2] Exposure / development process When a patterning process by photoexposure / development is included before the thermosetting process, examples of the light source used for the exposure process of the dried coating include xenon lamps, halogen lamps, tungsten lamps, and high-pressure mercury lamps. And lamp light sources such as ultra-high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps and low pressure mercury lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, and the like. When only light of a specific wavelength is used, an optical filter can be used.

The development process is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured portion. However, as described above, from the viewpoint of environmental pollution, harm to the human body, fire risk, etc., the organic solvent Instead, it is preferred to use an alkaline developer.
Examples of such an alkaline developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, triethanol. An aqueous solution containing an organic alkali compound such as amine, tetraalkylammonium hydroxide, and tetramethylammonium hydroxide can be used.

If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.
For example, the surfactant used in the developer includes an anionic surfactant having a sodium naphthalene sulfonate group, a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group. And cationic surfactants.

Although there is no restriction | limiting in particular about the method of development processing, Usually, it is 10-50 degreeC, Preferably it is carried out by methods, such as immersion development, spray development, brush development, ultrasonic development, at 15-45 degreeC.
[2-3] Heat treatment step In the present invention, each image after (i) drying when there is no exposure / development step or after development when (ii) exposure / development step is a cross section close to a rectangular shape It has a shape. In order to obtain a shape having a small taper angle necessary for the shape of the protective film, it is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, usually 300 ° C. or lower, preferably 280 ° C. or lower, and usually Heat treatment for 10 minutes or more, preferably 15 minutes or more, more preferably 20 minutes or more, usually 120 minutes or less, preferably 60 minutes or less, more preferably 40 minutes or less, and the rectangular cross-sectional shape has a small taper angle The shape is deformed to form a protective film having a width of 1 cm and a height of 0.2 to 5 μm.

  As the range of deformation during heating, the thermosetting composition and heating conditions are adjusted as appropriate, and the taper angle formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane (W1 or W3 described above). ) Compares the taper angle (W2 or W4 described above) formed from the side surface of the thin line image after the heat treatment and the substrate plane, W1 / W2 or W3 / W4 is 1.2 or more, preferably 1.3. Above, more preferably 1.5 or more, usually 10 or less, preferably 8 or less. The higher the heating temperature or the longer the heating time, the higher the deformation rate. Conversely, the lower the heating temperature or the shorter the heating time, the lower the deformation rate. Further, as described in the above section [1-4], the content of the alkali-soluble resin / the content of the photopolymerizable monomer, the alkali-soluble resin having a specific weight average molecular weight and a specific molecular weight distribution, and side chains Those having an ethylenic addition polymerizable group are particularly excellent in the deformation effect upon heating, the rectangularity after development, and the gentle side surface formability by heating.

[3] Liquid crystal display device (panel)
Next, a manufacturing method of the liquid crystal display device (panel) according to the present invention will be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on a color filter, and the protective film is formed on the alignment film, and then a liquid crystal cell is formed by bonding to a counter substrate. Liquid crystal is injected into and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed. The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
[1] When patterning is performed by light exposure / development before thermosetting (Examples 1 to 3, Comparative Example 1)
[1-1] Formation of Protective Film A thermosetting resin composition having the composition shown in Table 1 was applied on a glass plate “AN100” for color filter manufactured by Asahi Glass Co., Ltd., and heated to 80 ° C. on a hot plate. And dried for 3 minutes to obtain a coating film having a dry film thickness of 2 μm. Thereafter, image exposure was performed from the coating film side through 3 kW high-pressure mercury through a fine line pattern mask having a line width of 10 mm so that ultraviolet light with a wavelength of 365 nm was 100 mJ / cm ² . Next, using a developer composed of an aqueous solution containing 1% by weight of potassium carbonate and 4% by weight of a nonionic surfactant, after performing shower development at 23 ° C. and a water pressure of 0.25 MPa, development is performed with pure water. Stop and rinse with water spray. The shower development time was adjusted between 10 and 120 seconds, and was twice the time (break time) for dissolving and removing the photosensitive layer. The glass substrate thus imaged was heated at 230 ° C. for 30 minutes to obtain a fine line image deformed to a gentle side surface. The cross-sectional shape of the fine line before and after heating was measured with a scanning electron microscope “S4100” manufactured by Hitachi, Ltd. The contact angle between the measurement, the substrate plane and the side surface of the fine line image was determined, and the change rate of the contact angle before and after heating was evaluated by the following method.

[1-2] Evaluation of rate of change in taper angle by heating The cross-sectional shape of the thin wire before and after heating was measured with a scanning electron microscope “S4100” manufactured by Hitachi, Ltd., the taper angle was obtained, and the side surface and substrate of the thin wire image before heating The taper angle (W3) formed from the plane, the side surface of the thin line image after heating, and the taper angle (W4) formed from the substrate plane are obtained, and the taper angle change rate (W3 / W4) is determined by heating. Changes in the taper angle were evaluated as follows. Table 1 shows the evaluation results of the taper angle.

A: W3 / W4 is 2 or more B: W3 / W4 is 1.5 or more and less than 2 C: W3 / W4 is 1.2 or more and less than 1.5 D: W3 / W4 is less than 1.2 [1-3] Pencil Hardness A coating film was formed by performing exposure, development, and heat treatment similar to the above except that the entire coated surface of the thermosetting composition was exposed at 100 mJ / cm ² without using a mask. Next, the pencil hardness of this coating film was measured according to the measuring method of JIS K-5400. Table 1 shows the measurement results of the pencil height.

[1-4] Image Formability Images obtained by the above exposure and development processes were evaluated as follows.
A: The remaining photosensitive layer on the non-image area of the glass substrate was less than 2% of the total area of the non-image area.
B: The remaining photosensitive layer on the non-image area of the glass substrate was 2% or more and less than 10% of the total area of the non-image area.
C: The remaining photosensitive layer on the non-image area of the glass substrate was 10% or more and less than 30% of the entire non-image area.
D: The remaining photosensitive layer on the non-image area of the glass substrate was 30% or more of the entire non-image area.

M-1: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate (DPHA)
S-1: “Irgacure 907” manufactured by Ciba Special Chemicals Co., Ltd.
P-1: Addition polymerization of bisphenol and epichlorohydrin Alkali-soluble resin obtained by adding acrylic acid and acid anhydride to epoxy resin (weight average molecular weight 6000, acid value 98)
Here, the differential molecular weight distribution curve of the alkali-soluble resin (P-1) (plot of the weight content value of the alkali-soluble resin corresponding to the molecular weight with respect to the molecular weight of the alkali-soluble resin)
The weight content (V2) of the alkali-soluble resin having a molecular weight (M2) 10 ^1/2 times the molecular weight (M1) corresponding to the maximum peak of the molecular weight (M3) is 10 ^−1/2 times the molecular weight (M3). The value (V2 / V3) divided by the weight content (V3) of the alkali-soluble resin was 1.2.

(In the formula, m represents a natural number.)
P-2: An alkali-soluble resin (P-1) was once dissolved in isopropylene glycol monomethyl ether acetate to form a resin solution having a solid content of 62% by weight, and then the resin was dropped into three times the amount of methanol in the resin solution Precipitated, followed by filtration of the precipitated resin and air drying at 40 ° C. V2 / V3 was 15.
P-3: An alkali-soluble resin (P-1) was once dissolved in isopropylene glycol monomethyl ether acetate to obtain a resin solution having a solid content of 62% by weight, and then 1.5 times the amount of the resin solution. Of methanol was dropped and precipitated, followed by filtration of the precipitated resin and air drying at 40 ° C. V2 / V3 was 5.
Q-1: “Marproof MR0200” manufactured by NOF Corporation (maleic anhydride / styrene / ethylene polymer having an alkyl group)
R-1: glycidyl methacrylate / dicyclopentanyl (molar ratio 2: 1),
6000 weight average molecular weight (Mw) 6000.
R-2: Bisphenol A / aldehyde novolac type epoxy (Japan Epoxy “157S70”)
F-1: Silicone surfactant “BYK323”
SH-1: γ-Guylidoxypropyltrimethoxysilane PGMA: Isopropylene glycol monomethyl ether acetate

According to Table 1 above, Examples 1 and 2 using the thermosetting composition of the present invention have a high hardness of the protective layer and have a gentle side surface shape. An ITO deposition surface was formed.

[2] When patterning by light exposure / development is not performed before thermosetting (Examples 4 to 9)
[2-1] Formation of Protective Film 0.1 g of a thermosetting resin composition having the composition shown in Table 1 was dropped onto the center of a glass plate for color filter “AN100” manufactured by Asahi Glass Co., Ltd. having a size of 10 cm × 10 cm. Then, the glass plate was rotated at 100-2000 rpm, and a radial image was formed by inducing liquid breakage as the test solution moved away from the rotation center. This image was dried on a hot plate at 80 ° C. for 3 minutes to obtain a radial image having a dry film thickness of 2 μm at the center of rotation. This sample was heated at 230 ° C. for 30 minutes to form a radial image deformed on a gentle side surface.

  The cross-sectional shape of the image before and after heating is measured with a scanning electron microscope “S4100” manufactured by Hitachi, Ltd., the taper angle (W1, W2) between the substrate plane and the image side surface is obtained, and the change rate (W1) of the taper angle before and after heating. / W2), pencil height was evaluated and measured in the same manner as in Example 1. The results are shown in Table 2.

The relationship between the symbols other than Q-2 to Q-5 and R-3 below and the respective components is the same as in Table 1. Q-2: “Marialim AKM0531” (maleic anhydride / styrene / polyethyleneoxyl group manufactured by NOF Corporation) Ethylene polymer)
-Q-3: "Sun aid SI-60" monophenylsulfonium salt manufactured by Sanshin Chemical Industry Co., Ltd.-Q-4: trimellitic anhydride-Q-5: garlic acid (3,4,5-trihydroxybenzoic Acid)
-R-3: "Epicoat 4004p" (polyglycidyl ether obtained by reacting bisphenol F and epichlorohydrin) manufactured by Japan Epoxy Resin Co., Ltd.
The evaluation standard of the taper angle change rate (W1 / W2) was based on the taper angle change rate (W3 / W4) of Example 1.
According to the said Table 2, Examples 4-9 using the photosensitive composition of this invention had the high deformation rate of a taper angle, and the favorable ITO vapor deposition surface without a disconnection was formed.

In the present invention, there is no ITO disconnection, excellent stability over time, and there is little residue on the heel part when the protective film is wiped off, and a protective film with excellent adhesion to a sealing agent can be formed. In the field of a thermosetting composition for a protective film and a liquid crystal display device, a film thermosetting composition can be provided, and a high-quality color filter and a liquid crystal display device can thereby be provided. Industrial applicability is extremely high. In addition, the present invention provides printed wiring boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, solder resist films and coverlay films in organic electroluminescence, and insulation of various electronic components. Since it can be used as a thermosetting composition useful for forming a coating layer, and as a thermosetting composition for a color filter, a black matrix, a rib, and a spacer used for a liquid crystal panel such as a liquid crystal display, Industrial applicability is extremely high in this field as well.

It is the schematic diagram explaining the taper angle formed from the side of a coating layer edge part or a thin line image, and a substrate plane. It is explanatory drawing which showed the image formation characteristic before the heating of the thermosetting composition for liquid crystal protective layers, and after a heating.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image 2 Substrate surface 3 Taper angle 4 Substrate 5 Cross section of coating layer end or thin line image before heat treatment 6 Cross section of coating layer end or thin line image after heat treatment 7 Application layer end or thin line image before heat treatment Taper angle (W1 or W3) formed from the side surface and substrate plane
8 Tapered angle (W2 or W4) formed from the edge of the coating layer after heat treatment or the side surface of the fine line image and the substrate plane

Claims (6)

A thermosetting composition for a protective film containing an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal crosslinking agent, wherein 0.1 g of the thermosetting composition is 10 cm × 10 cm When it is dropped onto the center of the glass substrate and then applied by spin coating so that the dry film thickness at the center of the glass substrate is 2 μm or more, the taper angle formed from the side surface of the coating layer end and the substrate plane is set to (W1 ) When the taper angle formed from the side surface of the same coating layer end and the substrate plane after the coating layer is further heated at 230 ° C. for 30 minutes and the taper angle is (W2), the following formula is satisfied: A thermosetting composition for a protective film.
W1 / W2 ≧ 1.2 A thermosetting composition for a protective film, which contains an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal crosslinking agent, and further contains a photopolymerization initiator, The thermosetting composition was applied at a film thickness of 2 μm, irradiated with ultraviolet light with a wavelength of 365 nm at 100 mJ / cm ² through a mask having a thin line pattern with a line width of 10 mm, and then a shower at 23 ° C. and a water pressure of 0.25 MPa. The taper angle formed from the side surface of the fine line image obtained by the development process and the substrate plane is (W3), and the fine line image is further formed from the side surface of the thin line image and the substrate plane after being heated at 230 ° C. for 30 minutes. When the taper angle is (W4), a thermosetting composition for a protective film satisfying the following formula:
W3 / W4 ≧ 1.2 A thermosetting composition containing an ethylenically unsaturated compound and / or a compound having an epoxy group in the molecule as a thermal crosslinking agent, further containing an alkali-soluble resin, and a differential molecular weight distribution curve of the alkali-soluble resin The weight content (V2) of the alkali-soluble resin having a molecular weight (M2) 10 ^1/2 times the molecular weight (M1) corresponding to the maximum peak of the molecular weight (M3) and the molecular weight (M3) 10 ^−1/2 times the molecular weight (M1) A thermosetting composition for a protective film, wherein the weight content (V3) of the alkali-soluble resin satisfies the following formula:
V2 / V3 ≧ 1.3   Furthermore, a photoinitiator is contained, The thermosetting composition for protective films of any one of Claim 1 thru | or 3 characterized by the above-mentioned.   The color filter which has a protective film formed with the thermosetting composition for protective films in any one of Claims 1 thru | or 4.   A liquid crystal display device having a protective film formed from the thermosetting composition for a protective film according to claim 1.

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