Polymerizable composition, photosensitive composition for black matrix, and photosensitive composition for black columnar spacer

Abstract

The polymerizable composition of the present invention is a polymerizable composition containing a colorant (A), an alkali-developable compound (B) and a polymerization initiator (C), wherein the colorant (A) is a colorant containing an organic colorant (A1) and an inorganic colorant (A2). The organic colorant (A1) and the inorganic colorant (A2) are preferably an organic black pigment and an inorganic black pigment, respectively. In addition, the alkali-developable compound (B) is also preferably an alkali-developable compound represented by the following general formula (I). (The meaning of the symbols in the formula is referred to the specification.)

Description

Technical Field

[0001] The present invention relates to a colorant containing both an inorganic colorant and an organic colorant, a polymerizable composition containing an alkali-developable compound and a polymerization initiator, a photosensitive composition for a black matrix (hereinafter also referred to as BM) and a photosensitive composition for a black columnar spacer (hereinafter also referred to as BCS), and a cured product obtained from the polymerizable composition or the photosensitive composition. Background Art

[0002] In display devices such as liquid crystal display devices and organic EL display devices, spacers are used to maintain a distance between upper and lower substrates of a cell.

[0003] The spacer is formed by applying a polymerizable composition on a substrate, exposing it to light through a predetermined mask, and then developing it. In recent years, BCS has been used, which integrates a columnar spacer and a black matrix into one module to give it light-shielding properties.

[0004] Patent Document 1 discloses a photosensitive resin composition for a light-shielding film containing an alkali-soluble resin having a fluorene skeleton. In the document, it is described that the composition has a spacer function with excellent light-shielding properties, insulation properties, and elastic recovery rate. Patent Document 2 discloses a photosensitive resin composition containing a black organic pigment (lactam black) and a black inorganic pigment (carbon black). In the document, it is described that the composition has excellent dielectric constant, light-shielding properties, resolution, and elastic recovery rate.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2017-072760

[0008] Patent Document 2: International Publication No. 2013 / 032190 Summary of the invention

[0009] The problem to be solved by the present invention is that there is no cured product (particularly BCS) having excellent light-shielding properties, elastic recovery, chemical resistance, low dielectric constant, and good electrical properties.

[0010] Therefore, the object of the present invention is to provide a polymerizable composition and a photosensitive composition for BCS that can obtain BCS having excellent light-shielding properties, elastic recovery, chemical resistance, low dielectric constant and good electrical properties, a cured product obtained from the polymerizable composition, the photosensitive composition for BM and the photosensitive composition for BCS, a display device containing the cured product, and a method for manufacturing the cured product.

[0011] The present invention has been studied intensively and has achieved the above-mentioned object by providing the following [1] to [9].

[0012] [1] A polymerizable composition comprising a colorant (A), an alkali-developable compound (B), and a polymerization initiator (C), wherein the colorant (A) comprises an organic colorant (A1) and an inorganic colorant (A2).

[0013] [2] The polymerizable composition according to [1], wherein the organic colorant (A1) and the inorganic colorant (A2) are an organic black pigment and an inorganic black pigment, respectively.

[0014] [3] The polymerizable composition according to [1] or [2], wherein the alkali-developable compound (B) is an alkali-developable compound represented by the following general formula (I).

[0015] [Chemical formula 1]

[0016]

[0017] (Where R 1 , R 3 and R 5 each independently represents a hydrogen atom or a methyl group,

[0018] R 2 , R 4 and R 6 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0019] R 3 and R 4 When there are multiple, there are the same cases and there are different cases.

[0020] Y 1 , Y 2 and Y 3 represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0021] Y 2 When there are multiple, there are the same cases and there are different cases.

[0022] Z 1 , Z 2 and Z 3 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0023] Z 2 When there are multiple, there are the same cases and there are different cases.

[0024] R 2 , R 4 , R 6 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 The hydrogen atoms in the groups represented may be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, mercapto groups, isocyanate groups or groups having 2 to 20 carbon atoms and containing heterocyclic rings.

[0025] R 2 , R 4 , R 6 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 The methylene group in the represented group is sometimes substituted by -O-, -CO-, -COO-, -OCO-, -S-, -SO2-, -SCO- or -COS-.

[0026] m represents a positive number less than 0 or 10, a represents a positive number less than 0 or 4, b represents a positive number less than 0 or 3, and c represents a positive number less than 0 or 4.

[0027] When m is 2 or more, b may be the same or different.)

[0028] [4] The polymerizable composition according to any one of [1] to [3], wherein the polymerization initiator (C) is a polymerization initiator having a group represented by the following general formula (II).

[0029] [Chemical formula 2]

[0030]

[0031] (Where R 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R 11 and R 12 The hydrogen atoms in the group represented by may be substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a group having 2 to 20 carbon atoms and containing a heterocyclic ring. 11 and R 12The methylene group in the group represented by may also be referred to as -O-, -CO-, -COO-, -OCO-, -NR 13 -、-NR 13 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or CSO-substituted,

[0032] R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0033] n represents 0 or 1,

[0034] The * in the formula represents the bonding site. )

[0035] [5] A photosensitive composition for a black matrix, comprising the polymerizable composition according to any one of [1] to [4].

[0036] [6] A photosensitive composition for a black column spacer, comprising the polymerizable composition according to any one of [1] to [4].

[0037] [7] A method of producing a cured product by using the polymerizable composition described in any one of [1] to [4], the photosensitive composition for a black matrix described in [5], or the photosensitive composition for a black columnar spacer described in [6], by light irradiation or heating.

[0038] [8] A cured product, which is a cured product of the polymerizable composition according to any one of [1] to [4], the photosensitive composition for a black matrix according to [5], or the photosensitive composition for a black columnar spacer according to [6].

[0039] [9] A display device comprising the cured product described in [8]. DETAILED DESCRIPTION

[0040] Hereinafter, the polymerizable composition of the present invention will be described in detail based on preferred embodiments.

[0041] The polymerizable composition of the present invention contains a colorant characterized by containing both an inorganic colorant and an organic colorant, an alkali-developable compound, and a polymerization initiator.

[0042] <Colorant (A)>

[0043] The colorant (A) used in the polymerizable composition of the present invention contains an organic colorant (A1) and an inorganic colorant (A2), and a known pigment or dye can be mixed and used. Here, the so-called pigment refers to a colorant insoluble in the solvent described below, and the inorganic or organic colorant also includes a colorant insoluble in the solvent or a colorant obtained by laking an inorganic or organic dye.

[0044] Examples of the organic colorant (A1) include organic pigments and organic dyes.

[0045] Examples of the organic pigment include aniline black, lactam black, perylene black (also referred to as perylene black), Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, and organic pigments represented by zirconium, barium, or aluminum lakes.

[0046] Among the above, organic black pigments represented by aniline black, lactam black, and perylene black are preferred because of their excellent light-shielding properties.

[0047] Examples of the organic dye include anthraquinones such as astaxanthin and alizarin, anthocyanidins, β-carotene, carotenal, capsanthin, chalcone, safflower, quercetin, crocin, chlorophyll, curcumin, cochineal, naphthoquinones such as shikonin, bixin, flavonoids, β-cyanidin, henna dye, heme, lycopene, riboflavin, natural pigments / dyes such as rutin, auto-oxidizing dyes such as indoline, dihydroxyacetone, nitroso compounds, nitro Compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindolinone compounds, quinacridone compounds, anthraquinone compounds, perinone compounds, perylene compounds, pyrrolopyrroledione compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, etc.

[0048] Examples of the inorganic colorant (A2) include inorganic pigments and inorganic dyes.

[0049] Examples of the inorganic pigments include inorganic white pigments such as titanium dioxide and zinc oxide; nitro dyes such as mine, HCBlue 2, and Basic Blue 26; disperse dyes; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (red iron) and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and loess; inorganic black pigments such as black iron oxide and low-valent titanium oxide; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide, and cobalt titanate; inorganic blue pigments such as ultramarine and Prussian blue; pearl pigments such as titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, and bismuth oxychloride foil; metal powder pigments such as aluminum powder, copper powder, and gold; surface-treated inorganic and metal powder pigments; carbon black obtained by a furnace process, a tank process, or a thermal decomposition process, or acetylene black, ketjen black Carbon black such as lamp black, a substance obtained by adjusting or coating the above carbon black with an epoxy resin, a substance obtained by pre-dispersing the above carbon black in a resin in a solvent and coating it with 20 to 200 mg / g of the resin, a substance obtained by subjecting the above carbon black to an acidic or alkaline surface treatment, a carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen content per 100 m calculated from CO and CO2 in the volatile components at 950°C 2 Inorganic black pigments represented by carbon black, graphitized carbon black, pigment black 7, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, titanium black, etc. having a surface area of ​​9 mg or more.

[0050] Among the above-mentioned pigments, black pigments are preferably used because of their high light-shielding properties.

[0051] Examples of the inorganic dyes include dyes containing metals (transition metals, etc.), such as vanadium dyes (vanadium compounds, the same below), chromium dyes, molybdenum dyes, manganese dyes, iron dyes (ferrous oxalate, etc.), etc. It should be noted that the inorganic dyes also include inorganic components that are colored in the resin particles [for example, components that are colored by interaction (coordination or complex formation, etc.) with the resin having a fluorene skeleton], such as metal ions (for example, cations of transition metals such as vanadium, chromium, manganese, cobalt, nickel, and copper) or compounds containing metal ions.

[0052] As the above-mentioned pigment, commercially available products may be used, and examples thereof include Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, and 184. , 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50, etc.

[0053] In the polymerizable composition of the present invention, the content of the colorant (A) is not particularly limited, but is preferably 5 to 10 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 20 to 60 parts by mass, relative to 100 parts by mass of the alkali-developable compound (B) described below. When the content of the colorant (A) is within the above range, the polymerizable composition is a composition having excellent storage stability without aggregation of the colorant, and the light-shielding property of the cured product of the polymerizable composition becomes high, so it is preferred.

[0054] For example, when forming a cured product with a thickness of 1 to 3 μm, the content of the colorant (A) is not particularly limited, but is preferably 5 to 10 parts by mass, more preferably 10 to 80 parts by mass, and further preferably 20 to 60 parts by mass, relative to 100 parts by mass of the alkali-developable compound (B).

[0055] In addition, from the viewpoint of high transmittance at 780 nm, the amount of the inorganic colorant (A2) in the polymer composition is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the organic colorant (A1). On the other hand, from the viewpoint of high light-shielding properties, the amount of the inorganic colorant (A2) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the organic colorant (A1).

[0056] <Alkali-Developable Compound (B)>

[0057] The alkali-developable compound (B) according to the present invention is a compound having a hydrophilic group and exhibiting alkali-developability. In the present invention, as the alkali-developable compound (B), any compound conventionally used can be used as long as the above-mentioned conditions are satisfied.

[0058] Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfone group, an amino group, an amide group, or a salt thereof. A hydroxyl group and a carboxyl group are preferred because the alkali-developable compound (B) has high alkali developability.

[0059] The preferred functional group equivalent (mass of the polymer compound containing 1 equivalent of the hydrophilic group) of the hydrophilic group in the alkali-developable compound (B) is 50 to 10,000.

[0060] When the functional group equivalent of the hydrophilic group is in the above range, the alkali developability is excellent, which is preferred.

[0061] The preferred molecular weight of the alkali-developable compound (B) is 2000 to 10000, particularly preferably 3000 to 6000, as a weight average molecular weight. The number average molecular weight is 1000 to 8000, particularly 2000 to 5000. When the molecular weight of the alkali-developable compound (B) is within the above range, a cured product having excellent developability and excellent chemical resistance can be obtained, which is preferred.

[0062] The acid value of the alkali-developable compound (B) is preferably 10 to 200 mg / KOH, and more preferably 30 to 150 mg / KOH. When the acid value is 10 mg / KOH or more, alkali developability can be easily obtained, and when the acid value is 200 mg / KOH or less, the production of the polymer compound can be easily made. Here, the acid value is a value measured according to JIS K 0050 and JIS K 0211.

[0063] As the alkali-developable compound (B), specifically, copolymers of compounds represented by the above-mentioned general formula (I) and acrylates can be used; linear phenolic varnish and / or resol phenolic varnish epoxy resins; polyphenylmethane-type epoxy resins having a multifunctional epoxy group; epoxy acrylate resins; epoxy addition compounds having a structure obtained by addition of an unsaturated monobasic acid to an epoxy compound represented by the following general formula (III); resins (unsaturated compounds) having a structure obtained by esterification reaction of an epoxy addition compound having a structure obtained by addition of an unsaturated monobasic acid to an epoxy compound represented by the following general formula (III) with a polyacid anhydride, etc.

[0064] [Chemical formula 3]

[0065]

[0066] (wherein, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, or a substituent selected from the group represented by the following formula (a), (b), (c) or (d),

[0067] The hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with halogen atoms. 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 (hereinafter, also referred to as R 21 ~R 28 ) each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, k is a number from 0 to 10, and when k ≥ 1, a plurality of R 21 ~R 28 and M may be the same or different.)

[0068] [Chemical formula 4]

[0069]

[0070] (Where R 29 represents a hydrocarbon group having 1 to 20 carbon atoms,

[0071] R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 (hereinafter, also referred to as R 30 ~R 58 ) each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom,

[0072] R 31 ~R 38 and R 40 ~R 68 The methylene group in the group represented may be substituted with an unsaturated bond, -O- or -S-.

[0073] R 30 With R 31 、R3 1 With R 32 , R 32 With R 33 , R 33 With R 34 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 43 With R 44 , R 44 With R 45 , R 45 With R 46 , R 51 With R 52 , R 52 With R 53 , R 53 With R 54 , R 55 With R 56 , R 56 With R 57 and R 57With R 58 Sometimes they are bonded to form rings,

[0074] In the groups represented by (a), (b), (c) and (d), * indicates a bonding site. )

[0075] By using the alkali-developable compound represented by the above general formula (I), a cured product obtained from the polymerizable composition is excellent in chemical resistance, which is preferred.

[0076] It is preferred to use an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the above general formula (III); or to use a reaction product obtained by an esterification reaction between an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the above general formula (III) and a polyacid anhydride, because the sensitivity of the polymerizable composition becomes high and the elastic recovery rate of the cured product obtained from the polymerizable composition is excellent.

[0077] From the perspective of improving the dispersibility of the colorant (A) and improving heat resistance, the alkali-developable compound (B) is preferably an epoxy compound represented by the general formula (III); an epoxy compound having the following structure [(e)] obtained by adding an unsaturated monobasic acid to the epoxy compound represented by the general formula (III); or an unsaturated compound having the following structure [(f)] obtained by an esterification reaction of such an unsaturated compound with a polyacid anhydride.

[0078] [Chemical formula 5]

[0079]

[0080] (In the formula, Y 7 represents the residue of an unsaturated monobasic acid, Y 8 Indicates the residue of a polyacid anhydride, and * indicates the bonding site. )

[0081] Among the alkali-developable compounds represented by the general formula (III), when M is a group represented by (b) or (c), it is particularly preferred because the solvent resistance of a cured product obtained from the polymerizable composition becomes good.

[0082] In the above general formula (I), R 2 , R 4 , R 6 , Y 1 ~Y 3 and Z 1 ~Z 3The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, but preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. In view of good sensitivity when used as a polymerization initiator (C), an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms are more preferred.

[0083] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, and isodecyl.

[0084] Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl and 4,8,12-tetradecatrienylallyl. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl and 4-decenyl.

[0085] The cycloalkyl group having 3 to 20 carbon atoms is a saturated monocyclic or polycyclic alkyl group having 3 to 20 carbon atoms. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentyl, and tetradecahydroanthracenyl. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentyl.

[0086] The cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. Examples thereof include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl and decahydronaphthylpropyl. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl and 4-cyclohexylbutyl.

[0087] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, and the like; phenyl, biphenyl, naphthyl, anthryl, and the like substituted with one or more of the above-mentioned alkyl groups, the above-mentioned alkenyl groups, or carboxyl groups, halogen atoms, and the like; for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like; phenyl, biphenyl, naphthyl, anthryl, and the like substituted with one or more of the above-mentioned alkyl groups, the above-mentioned alkenyl groups, or carboxyl groups, halogen atoms, and the like; for example, 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like.

[0088] The aralkyl group having 7 to 20 carbon atoms is a group having 7 to 20 carbon atoms obtained by replacing the hydrogen atom of the alkyl group with an aryl group having 6 to 19 carbon atoms among the aryl groups having 6 to 20 carbon atoms. Examples thereof include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl. The aralkyl group having 7 to 10 carbon atoms is a group having 7 to 10 carbon atoms obtained by replacing the hydrogen atom of the alkyl group with an aryl group having 6 to 9 carbon atoms among the aryl groups having 6 to 10 carbon atoms. Examples thereof include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0089] In the above general formula (I), R 2 , R 4 and R 6 , Y 1 ~Y 3 and Z 1 ~Z 3 The group having 2 to 20 carbon atoms and containing a heterocyclic ring is not particularly limited, but examples thereof include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, pyridazinyl, piperazinyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thiophene. Phenyl, phenylthio, benzophenylthio, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxyoxazolidin-3-yl, etc., when specifically described including substituents, groups having the following structures can be mentioned.

[0090] [Chemical formula 6]

[0091]

[0092] (In the above formulae, R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. It should be noted that * in the formulae means that the groups represented by these formulae have the * portion as a bonding site.)

[0093] Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include groups having 1 to 6 carbon atoms among the groups exemplified as the above alkyl group having 1 to 20 carbon atoms.

[0094] Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include straight-chain or branched alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, and hexylene.

[0095] As sometimes R 2 , R 4 , R 6 , Y 1 ~Y 3 and Z 1 ~Z 3 Examples of the halogen atom substituted for a hydrogen atom in the group represented by include fluorine, chlorine, bromine and iodine.

[0096] As sometimes replace R 2 , R 4 , R 6 , Y 1 ~Y 3 and Z 1 ~Z 3 Examples of the unsaturated bond of the methylene group in the group represented by include -C=C- and -C≡C-.

[0097] As M and R in the above general formula (III), 21 ~R 58 Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same groups as those mentioned above for the hydrocarbon group having 1 to 20 carbon atoms.

[0098] As R in the above general formula (III) 30 ~R 58 Examples of the heterocyclic ring-containing group having 1 to 20 carbon atoms include the same groups as those described above for the heterocyclic ring-containing group having 1 to 20 carbon atoms.

[0099] As the halogen atom which replaces the hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (III), and R 21 ~R 28 and R 30 ~R 58 Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0100] As R in the above general formula (III) 30 With R 31 , R 31 With R 32 , R 32 With R33 , R 33 and R34 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 43 With R 44 , R 44 With R 45 , R 45 With R 46 , R 51 With R 52 , R 52 With R 53 , R 53 With R 54 , R 55 With R 56 , R 56 With R 57 and R 57 With R 58 Examples of the ring formed by bonding include cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, 5- to 7-membered rings such as lactone rings and lactam rings, and condensed rings such as naphthalene and anthracene.

[0101] The unsaturated monobasic acid refers to an acid having an unsaturated bond in its structure and having one hydrogen atom per molecule that can be ionized to form a hydrogen ion.

[0102] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, and dicyclopentadiene maleate.

[0103] In addition, examples of the polybasic acid anhydride that is reacted after the unsaturated monobasic acid is reacted include biphenyltetracarboxylic anhydride, tetrahydrophthalic anhydride, succinic anhydride, diphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol ditrimellitic anhydride, glycerol trimellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylnadic anhydride.

[0104] The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably set as follows.

[0105] That is, the epoxy addition compound is preferably added in a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid to one epoxy group of the epoxy compound, and the ethylenically unsaturated compound is preferably added in a ratio of 0.1 to 1.0 anhydride structures of the polyacid anhydride to one hydroxyl group of the epoxy addition product.

[0106] The reaction of the epoxy compound represented by the general formula (III), the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

[0107] In order to adjust the acid value and improve the developability of the polymerizable composition, the photosensitive composition for BM and the photosensitive composition for BCS of the present invention, a monofunctional or polyfunctional epoxy compound may be further reacted with the alkali-developable compound (B). The alkali-developable compound (B) preferably has an acid value of 5 to 120 mgKOH / g in solid content, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so as to satisfy the above acid value.

[0108] Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, amyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, Oily ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, butyric acid glycidyl ester, vinyl cyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinane oxide, methyl styrene oxide, cyclohexane oxide, propylene oxide, the following epoxy compounds No.E1, No.E2, etc.

[0109] [Chemical formula 7]

[0110] Epoxy Compound No.E1

[0111]

[0112] [Chemical formula 8]

[0113] Epoxy Compound No.E2

[0114]

[0115] As the polyfunctional epoxy compound, it is preferred to use one or more compounds selected from the group consisting of bisphenol epoxy compounds and glycidyl ethers, because a polymerizable composition having better properties can be obtained.

[0116] As the bisphenol-type epoxy compound, in addition to the epoxy compound represented by the general formula (III), for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can be used.

[0117] Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris(glycidyloxymethyl)propane, 1,1,1-tris(glycidyloxymethyl)ethane, 1,1,1-tris(glycidyloxymethyl)methane, and 1,1,1,1-tetra(glycidyloxymethyl)methane.

[0118] In addition, novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, and dicyclopentadiene novolac epoxy compounds can also be used; alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid Glycidyl esters such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N,N-diglycidyl aniline, etc.; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds, etc.

[0119] As the alkali-developable compound (B), a commercially available item can also be used appropriately.

[0120] Examples of the commercially available products include SPC1000, SPC-2000, SPC-3000, SPRR-1X, SPRR-2X, SPRR-3X, SPRR-5X, SPRR-6X, SPRR-7X, SPRR-8X, SPRR-9X, SPRR-10X, SPRR-11X, SPRR-12X, SPRR-13X, SPRR-14X, SPRR-15X, SPRR-16X, SPRR-17X, SPRR-18X, SPRR-19X, SPRR-20X, and SPRR-21X (all manufactured by Showa Denko K.K.), JET2000, AGOR1060, AGOR3060, ORGA1060, and ORGA2060 (all manufactured by Osaka Organic Chemical Co., Ltd.), and CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.).

[0121] In the polymerizable composition of the present invention, the content of the alkali-developable compound (B) is not particularly limited, but is preferably 10 to 95 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 30 to 80 parts by mass, relative to 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B), and the polymerization initiator (C). When the content of the alkali-developable compound (B) is within the above range, the alkali developability of the polymerizable composition is good, so it is preferred.

[0122] For example, when a cured film having a thickness of 2 to 5 μm is formed, the content of the alkali-developable compound (B) is not particularly limited, but is preferably 10 to 95 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 30 to 80 parts by mass, relative to 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B) and the polymerization initiator (C).

[0123] When the alkali-developable compound (B) contains a compound represented by the general formula (I), the content of the compound represented by the general formula (I) is preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass, based on 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B) and the polymerization initiator (C). When the alkali-developable compound (B) contains an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to the compound represented by the general formula (III) or a reaction product obtained by an esterification reaction of the epoxy addition compound with a polybasic acid anhydride, the content of the epoxy addition compound and the reaction product obtained by an esterification reaction of the epoxy addition compound with a polybasic acid anhydride is preferably 5 to 80 parts by mass, and more preferably 5 to 40 parts by mass, based on 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B) and the polymerization initiator (C). The content of the epoxy addition compound and the reaction product obtained by the esterification reaction of the epoxy addition compound and the polybasic acid anhydride refers to the amount when only one of the epoxy addition compound and the reaction product is contained, and refers to the total amount when both are contained.

[0124] <Polymerization Initiator (C)>

[0125] As the polymerization initiator (C) used in the polymerizable composition of the present invention, a conventionally known radical polymerization initiator can be used.

[0126] The radical polymerization initiator is a photoradical polymerization initiator or a thermal radical polymerization initiator. From the viewpoint of high reactivity, a photoradical polymerization initiator is more preferred.

[0127] The photoradical polymerization initiator is not particularly limited as long as it is a substance that generates radicals by light irradiation, and conventionally known compounds can be used. For example, preferred substances include oxime ester compounds, acetophenone compounds, benzil compounds, benzophenone compounds, and thioxanthone compounds.

[0128] Examples of the oxime ester compounds include compounds having a group represented by the general formula (II). Among the photoradical polymerization initiators, oxime ester compounds can be preferably used in the polymerizable composition of the present invention because of their good sensitivity.

[0129] In the above general formula (II), R 11 ~R 13 The hydrocarbon group having 1 to 20 carbon atoms represented by 2 , R 4 , R 6 , Y 1 ~Y 3 and Z 1 ~Z 3The hydrocarbon groups represented are the same.

[0130] Sometimes, R in the above general formula (II) 11 and R 12 and R 11 or R 12 The group containing a heterocyclic ring with 2 to 20 carbon atoms and the above R 2 , R 4 , R 6 , Z 1 ~Z 3 The heterocyclic ring-containing groups having 2 to 20 carbon atoms are the same.

[0131] Among the compounds having a group represented by the above general formula (II), the compound represented by the following general formula (IV) is preferably used in the polymerizable composition of the present invention because of its particularly high sensitivity.

[0132] [Chemical formula 9]

[0133]

[0134] (Where R 11 , R 12 and n are respectively the same as R in the general formula (II) 11 , R 12 and n are the same,

[0135] R 61 and R 62 each independently represents a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0136] X 1 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 63 R 64 、CO、NR 65 or PR 66 ,

[0137] X 2 represents no bond, direct bond, hydrocarbon group with 1 to 20 carbon atoms, CO, R 63 ~R 66 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R 61 ~R 66 The hydrogen atoms in the groups represented may also be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups or heterocyclic groups.

[0138] R 61 ~R66 The methylene group in the represented group may also be replaced by -O- under the condition that the oxygen is not adjacent.

[0139] R 61 ~R 66 Sometimes, they each independently form a ring with any adjacent benzene ring.

[0140] g represents a number from 0 to 4,

[0141] h represents a number from 0 to 3. )

[0142] In the above general formula (IV), R 61 ~R 66 The hydrocarbon groups having 1 to 20 carbon atoms represented by 2 , R 4 , R 6 , Y 1 ~Y 3 and Z 1 ~Z 3 The hydrocarbon groups having 1 to 20 carbon atoms represented are the same.

[0143] In the above general formula (IV), R 61 ~R 66 The group having 2 to 20 carbon atoms and the above R 2 , R 4 , R 6 and Z 1 ~Z 3 The heterocyclic ring-containing groups having 2 to 20 carbon atoms are the same.

[0144] Examples of preferred oxime ester compounds as the polymerization initiator (C) include compounds No. C1-1 to No. C1-14 shown below. However, the polymerization initiator (C) used in the present invention is not limited to the following compounds.

[0145] [Chemical formula 10]

[0146]

[0147] [Chemical formula 11]

[0148]

[0149] In the general formula (IV), X 1 is a sulfur atom, and X 2 In the case of having no bond, an oxime ester compound having a diphenylsulfide skeleton as exemplified in the above-mentioned compound Nos. C1-1 to C1-7 is preferred from the viewpoint of obtaining a polymerizable composition having good sensitivity by using it in combination as a polymerization initiator.

[0150] In the general formula (IV), X 1 NR 65 , and X 2 In the case of direct bonding, an oxime ester compound having a carbazole skeleton as exemplified in the above-mentioned compound Nos. C1-8 to C1-14 is particularly preferred from the viewpoint of obtaining a polymerizable composition having good sensitivity.

[0151] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, etc.

[0152] Among the above acetophenone compounds, it is preferred to use an α-aminoacetophenone compound having a hydroxyl group as a polymerization initiator because the resulting cured product has less liquid crystal contamination. Preferred α-aminoacetophenone compounds having a hydroxyl group include compounds represented by the following general formula (V).

[0153] [Chemical formula 12]

[0154]

[0155] (wherein, Xr represents a structure represented by the following general formula (i), (ii) or (iii),

[0156] Xs represents a sulfur atom or NR 100 ,

[0157] R 100 , R 101 , R 102 , R 103 and R 104each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, wherein the alkyl group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, or a nitro group, and the phenyl group and the aralkyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, or a nitro group,

[0158] R 101 With R 102 Sometimes, they are connected to form a 3- to 6-membered heterocyclic ring, and sometimes R is bonded to the nitrogen atom in the heterocyclic ring. 99 ,

[0159] R 103 With R 104 They can also be linked to form 3- to 6-membered rings.

[0160] R 105 , R 106 , R 107 and R 108 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group or an alkyl group having 1 to 12 carbon atoms, wherein the alkyl group may be substituted with a halogen atom, a carboxyl group, a cyano group, a nitro group or a hydroxyl group,

[0161] R 99 It represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. The alkyl group is sometimes substituted by a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and the phenyl group and the aralkyl group are sometimes substituted by an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

[0162] The methylene groups in the above-mentioned alkyl groups and aralkyl groups may be replaced by -O-, -S-, -NR- 117 -, -CO-, -CO-O-, -O-CO- or -O-CO-O- substitution.

[0163] R 117 It represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an aralkyl group having 7 to 20 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. The alkyl group is sometimes substituted by a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and the phenyl group and the aralkyl group are sometimes substituted by an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group.

[0164] Wherein, the compound represented by formula (V) has at least one hydroxyl group in the molecule.

[0165] [Chemical formula 13]

[0166]

[0167] (Where R 109 and R 110 Each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an alkyl group having 1 to 4 carbon atoms. When p is 2 or more, they may be the same or different.

[0168] The methylene group in the structure represented by the following (i-1) in the formula may be replaced by -O-, -S-, -NR 117 , -CO-, -CO-O-, -O-CO- or -O-CO-O- substituted,

[0169] [Chemical formula 14]

[0170]

[0171] R 111 represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group or a phenyl group, the phenyl group may be substituted by an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and p represents a number of 1 to 12.

[0172] [Chemical formula 15]

[0173]

[0174] (Where R 112 , R 113 , R 114 , R 115 and R 116 Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group or an alkyl group having 1 to 12 carbon atoms, the alkyl group may be substituted with a halogen atom, a cyano group, a nitro group or a hydroxyl group, and the methylene group in the alkyl group may be replaced with -O-, -S-, -NR 117 , -CO-, -CO-O-, -O-CO- or -O-CO-O- substituted,

[0175] R 106 or R 107 Sometimes with R 112 or R 116 bonded to form a ring.)

[0176] [Chemical formula 16]

[0177]

[0178] (Where R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R108 Same as the above general formula (V), R 109 , R 110 and p is the same as in the above general formula (i).

[0179] As the alkyl groups having 1 to 12 carbon atoms described above in the explanation of the general formula (V), for example, examples of the hydrocarbon groups having 1 to 20 carbon atoms in the general formula (I), that is, alkyl groups having 1 to 12 carbon atoms among the alkyl groups having 1 to 20 carbon atoms, can be cited.

[0180] As the alkyl groups having 1 to 4 carbon atoms described above in accordance with the general formula (V), examples of the hydrocarbon groups having 1 to 20 carbon atoms in the general formula (I) above, i.e., alkyl groups having 1 to 20 carbon atoms and alkyl groups having 1 to 4 carbon atoms in the alkyl groups described above can be cited.

[0181] Examples of the aralkyl groups having 7 to 20 carbon atoms described above with reference to the general formula (V) include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0182] Examples of the alkenyl groups having 2 to 12 carbon atoms described above with reference to the general formula (V) include vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-octenyl, and 1-decenyl.

[0183] As R in the general formula (V) 101 With R 102 Preferred examples of the heterocyclic ring which may be connected to form a 3- to 6-membered ring include a piperidine ring, a piperazine ring, a morpholine ring, and a lactam ring.

[0184] As R in the general formula (V) 103 With R 104 Preferred examples of the 3- to 6-membered ring that can be connected to form include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a lactone ring, and a lactam ring.

[0185] As R in the general formula (V) 106 or R 107 With R 112 or R 116 Examples of the ring formed by bonding include a carbazole ring, a thianthracene ring, and a dibenzothiophene ring as a structure after combining with the benzene rings adjacent to the left and right of Xs.

[0186] Examples of the halogen atoms described above in the explanation of the general formula (V) include fluorine, chlorine, bromine and iodine.

[0187] Specific examples of the α-aminoacetophenone-based compound having a hydroxyl group include the following Compound No. C2-1 to Compound No. C2-11.

[0188] [Chemical formula 17]

[0189]

[0190]

[0191] Examples of the benzil-based compound include benzil and the like.

[0192] Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide.

[0193] Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0194] Examples of other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and titanocene compounds such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)]titanium and the like.

[0195] Commercially available free radical initiators include Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, NCI-930 (all manufactured by ADEKA Corporation); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (all manufactured by TRONLY);

[0196] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo compounds, peroxides, and persulfates are exemplified as preferred compounds.

[0197] Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis(methyl isobutyrate), 2,2′-azobis-2,4-dimethylvaleronitrile, and 1,1′-azobis(1-acetoxy-1-phenylethane).

[0198] Examples of the peroxide include benzoyl peroxide, di-tert-butylbenzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0199] Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0200] Among the above-mentioned polymerization initiators (C), a polymerization initiator having a hydroxyl group is particularly preferred because it can provide a display device having low liquid crystal contamination and excellent electrical characteristics.

[0201] The polymerization initiator (C) described above may be used alone or in combination of two or more.

[0202] In the polymerizable composition of the present invention, the content of the polymerization initiator (C) is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the alkali-developable compound (B) from the perspective of good curability. When the content of the polymerization initiator (C) is within the above range, a polymerizable composition having good curability and excellent storage stability without precipitation of the polymerization initiator can be obtained, so it is preferred.

[0203] For example, when a cured film having a thickness of 2 to 5 μm is formed, the content of the polymerization initiator (C) is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B) and the polymerization initiator (C).

[0204] An ethylenically unsaturated compound may be further added to the polymerizable composition of the present invention. Adding an ethylenically unsaturated compound is preferred because the sensitivity and chemical resistance are improved. The ethylenically unsaturated compound is a compound having an ethylenically unsaturated bond and is not the alkali-developable compound (B). Examples of the ethylenically unsaturated compound include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends such as (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate, and ω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasic acids such as hydroxyethyl(meth)acrylate·maleate, hydroxypropyl(meth)acrylate·maleate, dicyclopentadiene·maleate, or polyfunctional(meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups;2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following acrylic compounds No. 1 to No. 4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Esters of unsaturated monobasic acids and polyols or polyphenols such as acrylates, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dihydroxymethyl di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trioxane anhydrides of unsaturated polybasic acids such as 1,2-dihydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylnadic anhydride; amides of unsaturated monobasic acids and polyamines such as (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, benzyldimethylbis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene dicyanide, and allyl nitrile;Unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated Saturated imides; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain such as polystyrene, poly(methyl)acrylate, poly(n-butyl)(meth)acrylate, polysiloxane, etc.; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and vinyl carbamate compounds of polyisocyanate compounds, vinyl monomers containing hydroxyl groups and vinyl epoxy compounds of polyepoxide compounds. ;

[0205] The above-mentioned ethylenically unsaturated compounds may be used alone or in combination of two or more.

[0206] As the above-mentioned ethylenically unsaturated compound, commercially available products may also be used. Examples of such commercially available products include KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215 and M-350 (all manufactured by Toagosei Co., Ltd.); NK ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG, and HD-N (all manufactured by Shin-Nakamura Chemical Co., Ltd.); SPC-1000 and SPC-3000 (all manufactured by Showa Denko K.K.); NK OLIGO U-4HA, U-4H, U-6HA, U-15HA, U-108A, U-1084A, U-200AX, U-122A, U-340A, U-324A, UA-53H, UA-100, AH-600 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.), ArtResin UN-9200A, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, SH-380G, SH-500, SH-9832, UN-901T, UN-904, UN-905, UN-906, UN-906S, UN-907, UN-952, UN-953, UN-954, H-91, H-135 (all manufactured by Negami Industries), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (all manufactured by Sartomer), EBECRYL8810 (manufactured by Daicel), etc.

[0207] [Chemical formula 18]

[0208] Acrylic Compound No.1

[0209]

[0210] [Chemical formula 19]

[0211] Acrylic Compound No.2

[0212]

[0213] [Chemical formula 20]

[0214] Acrylic Compound No.3

[0215]

[0216] [Chemical formula 21]

[0217] Acrylic Compound No.4

[0218]

[0219] In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total of the colorant (A), the alkali-developable compound (B), the polymerization initiator (C), and the ethylenically unsaturated compound. When the content of the ethylenically unsaturated compound is within the above range, the obtained cured product has excellent curability and light-shielding properties, so it is preferred.

[0220] For example, in the case of forming a cured film having a thickness of 1 to 3 μm, the content of the ethylenically unsaturated compound is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total of the polymerization initiator (C), the colorant (A), the alkali-developable compound (B) and the ethylenically unsaturated compound.

[0221] A solvent may be further added to the polymerizable composition of the present invention. As the solvent, a solvent that can dissolve or disperse the above-mentioned components (colorant (A), alkali-developable compound (B), polymerization initiator (C) and ethylenically unsaturated compound, etc.) can be generally used as needed. Examples thereof include ketone solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, amber Ester solvents such as dimethyl ether and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dimethicone Ether ester solvents such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene and pinene; mineral spirits, SWAZOL #310 (all manufactured by COSMO Matsuyama Oil Co., Ltd.); and SOLVESSO #100 (all manufactured by Exxon Chemical Co., Ltd. halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and water, etc. These solvents can be used alone or as a mixed solvent of two or more.

[0222] Among them, ketone solvents, ester solvents, ether ester solvents, and the like, particularly cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate, and PGMEA are preferred because they have good compatibility with the resist and the polymerization initiator in the polymerizable composition.

[0223] It is preferred to use PGMEA, 3-methoxybutyl acetate and dimethyl succinate in combination because a uniform coating surface can be obtained. It is particularly preferred that the mass ratio of the solvents (PGMEA:3-methoxybutyl acetate:dimethyl succinate) is 15 to 25:2 to 5:1.

[0224] In the polymerizable composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, based on 100% by mass of the total amount of the polymerizable composition.

[0225] When the content of the solvent is within the above range, the polymerizable composition has excellent handling properties (viscosity or wettability of the polymerizable composition), reduced unevenness during drying, and liquid stability (no precipitation or sedimentation of components contained in the composition), and when a cured product is obtained, the thickness of the cured product can be appropriately controlled, which is preferred.

[0226] The polymerizable composition of the present invention may further contain conventional additives such as epoxy compounds, alkali developability imparting agents, dispersants, latent additives, organic polymers, inorganic compounds, coupling agents, chain transfer agents, sensitizers, surfactants, and melamine compounds, p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, and phenothiazine, as well as thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; defoamers; leveling agents; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-agglomeration agents; catalysts; effect promoters; crosslinking agents; and thickeners.

[0227] Examples of the epoxy compound include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl-2-methyl glycidyl ether, hexadecyl glycidyl ether, stearyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl ether, and dibromocresyl glycidyl ether. ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetra(glycidyloxyphenyl)ethane and pentaerythritol tetraglycidyl ether and other glycidyl ethers; glycidyl acetate, stearic acid glycidyl esters; 2-(3, 4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,3-dioxane, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene epoxide, 3,4-epoxy-6-methylcyclohexylcarboxylate, α-epoxypinane, styrene oxide, epoxycyclohexane, epoxycyclopentane and other epoxycycloalkyl compounds and N-glycidylphthalimide, etc.

[0228] As the above-mentioned epoxy compound, epoxidized polyolefin can also be used. Epoxidized polyolefin refers to a polyolefin into which an epoxy group is introduced by modifying a polyolefin with an epoxy-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having a carbon number of 3 to 20 with an epoxy-containing monomer and other monomers used as needed by any one of a copolymerization method or a grafting method. Ethylene or an α-olefin having a carbon number of 3 to 20, an epoxy-containing monomer and other monomers can be polymerized separately or with multiple other monomers. In addition, it can also be obtained by epoxidizing the double bonds of non-conjugated polybutadiene having a hydroxyl group at the end by a peracetic acid method, and an epoxy compound having a hydroxyl group in the molecule can also be used. In addition, the hydroxyl group can be urethanized with an isocyanate, and an epoxy compound containing a primary alcohol hydroxyl group is reacted with it to introduce an epoxy group.

[0229] Examples of the ethylene or C3-20 α-olefins include ethylene, propylene, butene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, and isoprene.

[0230] Examples of the epoxy group-containing monomer include glycidyl esters of α,β-unsaturated acids, vinylbenzyl glycidyl ether, and allyl glycidyl ether. Specific examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferred.

[0231] As the epoxy compound, commercially available products may be used. Suitable commercial products include, for example, Epolight 40E, 1500NP, 1600, 80MF, 4000, and 3002 (all manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Glycirol ED-503, ED-503D, ED-503G, ED-523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080, and EP-4085 (all manufactured by ADEKA Co., Ltd.); DENACOL EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, DENACOL EX-111, EX-121, EX-141, EX-142, EX-145, EX-146, EX-147, EX-171, EX-192 and EX-731 (all manufactured by Nagase ChemteX Co., Ltd.); EHPE-3150, Celloxide 2021P, 2081, 2000 and 3000 (all manufactured by Daicel); EPIOL M, EH, L-41, SK, SB, TB and OH (all manufactured by NOF Corporation); Epolight M-1230 and 100MF (all manufactured by Kyoeisha Chemical Co., Ltd.); ARON OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (all manufactured by Toagosei Co., Ltd.); ETERNACOLL OXBP and OXTP (produced by Ube Industries, Ltd.); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (produced by Maruzen Petrochemical Co., Ltd.); DENACOL EX-121, EX-141, EX-142, EX-145, EX-146, EX-147, EX-201, EX-203, EX-711, EX-721, Oncoat EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1010, EX-1011 and 1012 (produced by Nagase ChemteX Co., Ltd.); Ogsol PG-100, EG-200, EG-210 and EG-250 (produced by Osaka Gas Chemicals Co., Ltd.); HP4032, HP4032D and HP4700 (all manufactured by DIC Corporation); ESN-475V (manufactured by Tohto Chemical Co., Ltd.);Marproof G-0105SA and G-0130SP (both are made by NOF Corporation); EPICLON N-665 and HP-7200 (both are made by DIC Corporation); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (all are made by Nippon Kayaku Co., Ltd.), etc.;

[0232] The alkali developability imparting agent is a compound that imparts alkali developability without free radical polymerizability. Such a compound is not particularly limited as long as it is soluble in an alkali aqueous solution due to its acid value, but a representative example thereof is an alkali-soluble novolac resin (hereinafter referred to as "novolac resin"). Novolac resin is obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

[0233] As the phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid esters and gallic acid esters are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A are preferred. These phenols can be used alone or in combination of two or more.

[0234] As the aldehydes, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p-n-butylbenzaldehyde can be used. Among these compounds, formaldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes can be used alone or in combination of two or more. The aldehydes are used in a ratio of preferably 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per 1 mol of the phenols.

[0235] As the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid can be used. The amount of these acid catalysts used is preferably 1×10 -4 ~5×10-1 Mole. In the condensation reaction, water is usually used as the reaction medium, but in the case where the phenols used in the condensation reaction are not dissolved in the aqueous solution of the aldehydes and become a non-uniform system from the initial stage of the reaction, a hydrophilic solvent can also be used as the reaction medium. As these hydrophilic solvents, alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane can be listed. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw materials. The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200°C, preferably 70 to 150°C. After the condensation reaction is completed, in order to remove the unreacted raw materials, acid catalysts and reaction media present in the system, the internal temperature is generally raised to 130 to 230°C, the volatile components are distilled off under reduced pressure, and then the molten novolac resin is cast onto a steel belt or the like and recovered.

[0236] After the condensation reaction is completed, the reaction mixture may be dissolved in the hydrophilic solvent and added to a precipitant such as water, n-hexane or n-heptane to precipitate the novolac resin, and the precipitate may be separated and recovered by heating and drying.

[0237] Examples other than the above-mentioned novolac resins include polyhydroxystyrene or derivatives thereof, styrene-maleic anhydride copolymers, and polyvinyl hydroxybenzoates.

[0238] The dispersant may be any substance as long as it can disperse and stabilize the colorant (B), and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used. Preferably, a polymer dispersant including polyester, polyether, or polyurethane having a basic functional group, a dispersant having a nitrogen atom as a basic functional group and an amine and / or a quaternary ammonium salt thereof having an amine value of 1 to 100 mgKOH / g is used.

[0239] The latent additive is a substance that is inactive at room temperature, in the light exposure process and in the pre-baking process, but is activated by removing the protective group by heating at 100 to 250° C. or at 80 to 200° C. in the presence of an acid / base catalyst. Examples of the effects obtained by activation include anti-oxidation, ultraviolet absorption, antifouling properties, recoatability and adhesion.

[0240] As the latent additive, those described in WO2014 / 021023 pamphlet can be preferably used.

[0241] As the latent additive, a commercially available product can be used, and examples thereof include ADEKA ARKLS GPA-5001.

[0242] Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl ester copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, polyurethane resin, polycarbonate, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin, and the like. Among them, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred.

[0243] By using the above-mentioned organic polymer together with the above-mentioned alkali-developable compound (B), the properties of the cured product can also be improved.

[0244] When an organic polymer is used, the amount of the organic polymer used is preferably 10 to 500 parts by mass based on 100 parts by mass of the alkali-developable compound (B).

[0245] The above-mentioned inorganic compound may be contained. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon dioxide, and aluminum oxide; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper, among which titanium oxide, silicon dioxide, layered clay minerals, and silver are preferred.

[0246] By incorporating an inorganic compound into the polymerizable composition of the present invention, a photosensitive paste composition can be used. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

[0247] In addition, these inorganic compounds are also preferably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

[0248] When an inorganic compound is added to the polymerizable composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the alkali-developable compound (B). These inorganic compounds may be used alone or in combination of two or more.

[0249] As the coupling agent, for example, alkyl-functional alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane, alkenyl-functional alkoxysilanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, 3-methylacryloylsilane, and the like can be used. (Meth)acrylate functional alkoxysilanes such as acyloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 2-methacryloxypropyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane alkyl, epoxy-functional alkoxysilanes such as γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, amino-functional alkoxysilanes such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilanes such as 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, etc. Urea-functional alkoxysilanes such as alkoxysilanes, isocyanurate-functional alkoxysilanes such as tris(trimethoxysilylpropyl)isocyanurate, titanium alkoxides such as titanium tetraisopropoxide and titanium tetra-n-butoxide, titanium chelates such as dioctyloxybis(octanediol)titanium and diisopropoxybis(ethyl acetoacetate)titanium, zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, acylated zirconiums such as zirconium tributoxymonostearate, isocyanate silanes such as methyl triisocyanate silane, and the like.

[0250] Adding a coupling agent is preferred because it improves the adhesion between the cured product and the substrate (particularly glass).

[0251] As the coupling agent, commercially available products can be used, and examples thereof include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE- 9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504 and KF-99 (all manufactured by Shin-Etsu Silicone Co., Ltd.), etc.

[0252] As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropionic acid, and 3-mercaptobutyric acid. sulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionic acid ester) and pentaerythritol tetrakis (3-mercaptopropionate); disulfide compounds obtained by oxidation of the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid and other iodinated alkyl compounds; trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioacetate, ethylene glycol dithioacetate, trimethylolpropane trithioacetate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, the following compound No. C1, Karenz PE1 and NR1 manufactured by Showa Denko K.K., etc.

[0253] [Chemical formula 22]

[0254] Compound No.C1

[0255]

[0256] Adding the chain transfer agent and the sensitizer is preferred because the pattern of the obtained cured product becomes high-definition.

[0257] As the above-mentioned surfactant, fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates, cationic surfactants such as higher amine hydrohalides and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides, amphoteric surfactants, and silicone surfactants can be used, and they can also be used in combination.

[0258] As the above-mentioned melamine compound, there can be cited compounds obtained by alkyl-etherifying all or part (at least 2) of the active methylol groups (CH2OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine and (poly) methylol urea. Here, as the alkyl group constituting the alkyl ether, there can be cited methyl, ethyl and butyl groups, which can be the same as or different from each other. In addition, the methylol groups that are not alkyl-etherified can self-condense within one molecule or condense between two molecules, and the result is the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril and tetrabutoxymethyl glycoluril can be used. Among them, alkyl-etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

[0259] In the polymerizable composition of the present invention, the content of the optional components other than the colorant (A), the alkali-developable compound (B), the polymerization initiator (C), the ethylenically unsaturated compound, the solvent and the inorganic compound can be appropriately selected depending on the intended use. There is no particular limitation as long as the effects of the present invention are not impaired. However, the total content is preferably 20 parts by mass or less based on 100 parts by mass of the total of the polymerization initiator (C), the colorant (A), the alkali-developable compound (B) and the ethylenically unsaturated compound.

[0260] The photosensitive composition for BM of the present invention contains a colorant (A), an alkali-developable compound (B) and a polymerization initiator (C) as essential components, has photosensitivity and alkali-developability, and is particularly suitable for forming a BM.

[0261] The photosensitive composition for BCS of the present invention contains a colorant (A), an alkali-developable compound (B) and a polymerization initiator (C) as essential components, has photosensitivity and alkali-developability, and is particularly suitable for forming BCS.

[0262] The polymerizable composition, the photosensitive composition for BM or the photosensitive composition for BCS and the cured product of the present invention can be used for curable coatings, varnishes, curable adhesives, printed circuit boards, display devices (color filters in color display liquid crystal display panels such as color TVs, PC monitors, portable information terminals and digital cameras, color filters for various display purposes, color filters for CCD image sensors, touch panels, electroluminescent display devices (partition wall materials for micro LEDs), plasma display panels, black partition walls for organic EL), powder coatings, printing inks, printing plates, adhesives, gel coatings, photoresists for electronic engineering, plating resists, etching resists, solder resists, insulating films, black matrices, resists for forming structures in the manufacturing process of LCDs, and photoresists for forming structures in the manufacturing process of LCDs. The present invention can be used in various applications, such as compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, screen printing templates, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used in the formation of dielectric layers in the sequential lamination of printed circuit boards, and protective films. The application is not particularly limited. Among the above applications, the present invention can be particularly suitably used in display devices.

[0263] The display device of the present invention has the same configuration as a conventionally known display device except that it includes the cured product of the present invention (particularly BCS), but the BCS is preferably provided between cells.

[0264] When the polymerizable composition of the present invention is used as a black partition wall of an organic EL, it is preferred to use an alkali-developable compound having a weight average molecular weight of 5000 or more, and more preferably an alkali-developable compound having a weight average molecular weight of 7000 to 15000, from the perspective of verticalization of the pattern shape, improvement of development adhesion, and improvement of heat resistance. Furthermore, it is particularly preferred that the alkali-developable compound is an unsaturated compound having a structure obtained by an esterification reaction of an epoxy addition compound and a polybasic acid anhydride, wherein the epoxy addition compound has a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the above general formula (III).

[0265] Hereinafter, a method for producing a cured product using the polymerizable composition, the photosensitive composition for BM, and the photosensitive composition for BCS of the present invention will be described in detail.

[0266] The polymerizable composition, photosensitive composition for BM and photosensitive composition for BCS of the present invention can be applied to a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by a spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping and other known means. In addition, it can be applied to a supporting substrate such as a film once and then transferred to another supporting substrate, and the application method is not limited.

[0267] In addition, as a light source of energy rays used when curing the polymerizable composition, the photosensitive composition for BM and the photosensitive composition for BCS of the present invention, electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., or high energy rays such as electron beams, X-rays, and radiation can be utilized. Preferred examples include ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that emit light with a wavelength of 300 to 450 nm.

[0268] Furthermore, the laser direct drawing method, which forms an image directly from digital information such as a computer without using a mask by using a laser in the exposure light source, is useful because it can not only seek to improve productivity, but also seek to improve clarity or position accuracy, etc. As the laser, light with a wavelength of 340 to 430 nm is suitable, and lasers that emit light in the visible to infrared region such as excimer lasers, nitrogen lasers, argon ion lasers, helium cadmium lasers, helium-neon lasers, krypton ion lasers, various semiconductor lasers, and YAG lasers can also be used. When using these lasers, a sensitizing dye that absorbs the visible to infrared region can be added.

[0269] When curing by heating, pre-baking is performed at 70 to 100°C for 100 seconds, and after the solvent is removed, curing is performed by heating at 150 to 250°C for 30 minutes to 1 hour. If the curing temperature is lower than 150°C, sufficient curing may not occur, and if it is higher than 250°C, coloring or decomposition of the cured film may occur.

[0270] The cured product of the present invention is particularly useful as a BCS. The BCS is preferably formed by the following steps: (1) a step of forming a coating film of the photosensitive composition for BCS of the present invention on a substrate; (2) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape; (3) a baking step after exposure; (4) a step of developing the exposed coating film; and (5) a step of heating the developed coating film.

[0271] As the mask, a multi-tone mask such as a halftone mask or a grayscale mask may be used.

[0272] Example

[0273] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[0274] [Manufacturing Example 1] Preparation of Lactam Black Dispersion A-1

[0275] An organic black pigment (black 582 as lactam black, manufactured by BASF), a dispersant (BYK-167) and a polymer for dispersion (alkali-developable compound PGMEA solution B-2 described later) were mixed in amounts of 16 parts by mass, 3.2 parts by mass and 3.6 parts by mass, and then propylene glycol monomethyl ether acetate (PGMEA) was weighed and added to the mixture so that the solid content concentration became 25% by mass to prepare a mixture.

[0276] After the mixture was premixed by a stirrer, zirconium beads with a diameter of 0.3 mm were added in the same weight as the dispersion (the substance obtained by removing the solvent, i.e., PGMEA, from the mixture), and the dispersion was treated by a paint stirrer at a temperature of 25 to 60° C. for 6 hours, and then the zirconium beads were removed by a filter to obtain a dispersion. PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the mixture was made uniform by a stirrer to obtain a lactam black dispersion A-1.

[0277] [Production Example 2] Preparation of Perylene Black Dispersion A-2

[0278] An organic black pigment [CI Pigment Black 31 (PalIogen Black S0084, manufactured by BASF) as perylene black], a dispersant (BYK-167) and a polymer for dispersion (the alkali-developable compound PGMEA solution B-2 described later) were mixed in 12 parts by mass, 3.6 parts by mass and 8 parts by mass, respectively, and propylene glycol monomethyl ether acetate (PGMEA) was weighed and added to the mixture in such a manner that the solid content concentration became 25% by mass to prepare a mixture.

[0279] After the mixture was premixed by a stirrer, zirconium beads with a diameter of 0.3 mm were added in the same weight as the dispersion (the substance obtained by removing the solvent, i.e., PGMEA, from the mixture), and the dispersion was treated by a paint stirrer at a temperature of 25 to 60° C. for 6 hours, and then the zirconium beads were removed by a filter to obtain a dispersion. PGMEA was added to the obtained dispersion to adjust the dispersion concentration to 20% by mass, and the dispersion was made uniform by a stirrer to obtain a perylene black dispersion A-2.

[0280] [Manufacturing Example 3] Preparation of Carbon Black Dispersion A-3

[0281] 20 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black, 12.5 parts by mass of BYK161 (manufactured by BYK Chemie (BYK)) as a dispersant (solid content concentration is 40% by mass), and 67.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and processed by a bead mill to prepare a carbon black dispersion A-3.

[0282] [Manufacturing Example 4] Preparation of Alkaline-Developable Compound PGMEA Solution B-2

[0283] 184 g of 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indane, 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were added, and stirred at 120° C. for 16 hours. The reaction solution was cooled to room temperature, and 160 g of PGMEA, 59 g of diphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and stirred at 120° C. for 4 hours. Furthermore, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120° C. for 4 hours, 100° C. for 3 hours, 80° C. for 4 hours, 60° C. for 6 hours, and 40° C. for 11 hours, 128 g of PGMEA was added to obtain an alkali-developable compound B-2 (Mw=5000, Mn=2100, acid value (solid content) 92.7 mgKOH / g) in the form of a PGMEA solution. The content of the alkali-developable compound in the alkali-developable compound PGMEA solution B-2 was 45% by mass.

[0284] [Manufacturing Example 5] Manufacture of Alkaline-Developable Compound PGMEA Solution B-3

[0285] 75.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-tert-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA were added, and stirred at 90° C. for 1 hour, 100° C. for 1 hour, 110° C. for 1 hour, and 120° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and stirred at 100° C. for 5 hours. Furthermore, 30.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 0.269 g of 2,6-di-tert-butyl-p-cresol and 1.50 g of PGMEA were added, and after stirring at 90° C. for 90 minutes and at 120° C. for 4 hours, 122.2 g of PGMEA was added to obtain the target alkali-developable compound B-3 (Mw=4190, Mn=2170, acid value (solid content) 52 mg·KOH / g) in the form of a PGMEA solution. The content of the alkali-developable compound in the alkali-developable compound PGMEA solution B-3 was 45% by mass.

[0286] [Examples 1 to 15 and Comparative Examples 1 to 4] Preparation of polymerizable compositions

[0287] The components were mixed according to the formulations shown in Tables 1 to 4 to obtain polymerizable compositions (Examples 1 to 15 and Comparative Examples 1 to 4). The numerical values ​​of the formulations in the tables represent parts by mass.

[0288] In addition, the symbols of each component in the table represent the following components.

[0289] A1-1 Lactam black dispersion A-1

[0290] A1-2 Perylene Black Dispersion A-2

[0291] A2-1 Carbon black dispersion A-3

[0292] B-1 CCR-1171H

[0293] [Alkali-developable compound PGMEA solution represented by general formula (I), solid content 69.5%: manufactured by Nippon Kayaku Co., Ltd.]

[0294] B-2 Alkaline developing compound PGMEA solution B-2

[0295] B-3 Alkaline developing compound PGMEA solution B-3

[0296] C-1 Compound No.C1-1

[0297] C-2 Compound No.C1-8

[0298] C-3 Compound No.C2-1

[0299] D-1 KAYARAD DPHA (ethylenically unsaturated compound: manufactured by Nippon Kayaku Co., Ltd.)

[0300] D-2 UA-306H (urethane acrylate: manufactured by Kyoeisha Chemical Co., Ltd.)

[0301] D-3 M-450 (ethylenically unsaturated compound: manufactured by Toagosei Co., Ltd.)

[0302] E-1 γ-Glycidoxypropyltrimethoxysilane (coupling agent)

[0303] E-2 Karenz PE-1 (thiol compound: manufactured by Showa Denko K.K.)

[0304] F-1 PGMEA

[0305] F-2 3-Methoxybutyl acetate

[0306] F-3 Dimethyl succinate

[0307] [Evaluation of Cured Product Obtained from Polymerizable Composition]

[0308] The cured products obtained from the comparative polymerizable compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were evaluated for elastic recovery, light shielding properties (OD value), relative dielectric constant, low liquid crystal contamination (VHR), chemical resistance, and 780 nm transmittance according to the following procedures. The results are collectively recorded in Tables 1 to 4.

[0309] (Elastic recovery rate)

[0310] The polymerizable compositions of Examples 1 to 15 and the comparative polymerizable compositions of Comparative Examples 1 to 3 were applied to a glass substrate by spin coating (3 μm thickness, 300 rpm×7 seconds), dried, and pre-baked at 90° C. for 100 seconds to remove the solvent. Next, a photomask was used and a high-pressure mercury lamp was used to irradiate the glass substrate with 100 mJ / cm 2 After exposure, the film was developed using a 0.04wt% KOH aqueous solution. After that, it was heated at 230°C for 30 minutes to form a pattern. A load-removal test was performed on a 20μm portion of the obtained pattern using a Shimadzu dynamic microhardness tester DUH-211 with a load of 40mN. The elastic recovery rate (%) was calculated using the following calculation formula.

[0311] Elastic recovery rate (%) = [(recovery distance / compression displacement) × 100]

[0312] A cured product having an elastic recovery rate (%) of 60% or more can be used as BCS, a cured product having an elastic recovery rate (%) of 70% or more can be preferably used as BCS, and a cured product having an elastic recovery rate (%) of 80% or more can be particularly preferably used as BCS.

[0313] (OD value)

[0314] The polymerizable compositions of Examples 1 to 15 and the comparative polymerizable compositions of Comparative Examples 1 to 3 were spin-coated (300 rpm, 7 seconds) on a glass substrate and dried, and then pre-baked at 90° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, a cured product was prepared by baking at 230° C. for 30 minutes. The OD value of the obtained film was measured using a MacBeth transmission densitometer, and the OD value per unit film thickness was calculated by dividing the OD value by the film thickness after post-baking.

[0315] A cured product with an OD value of 1.0 or more per unit film thickness can be used as a general BCS, a cured product with an OD value of 1.5 or more can be used as a high light-shielding BCS due to its high light-shielding property, a cured product with an OD value of 1.75 or more per unit film thickness can be preferably used as a high light-shielding BCS, and a cured product with an OD value of 2.0 or more per unit film thickness can be particularly preferably used as a BCS. A cured product with an OD value of less than 1.0 per unit film thickness cannot be used as a BCS.

[0316] (Relative dielectric constant)

[0317] The polymerizable compositions of Examples 1 to 15 and the comparative polymerizable compositions of Comparative Examples 1 to 3 were spin-coated on a glass substrate (3 μm thick, 300 rpm × 7 seconds), dried, pre-baked at 90° C. for 100 seconds, and heated by a high-pressure mercury lamp at 100 mJ / cm without using a mask. 2 After exposure, the samples were heated at 230° C. for 180 minutes to prepare the evaluation samples. (Evaluation Method) The evaluation samples were measured using an LCR meter, Agilent 4284A, with AC 1V and 1kHz applied.

[0318] A cured product with a relative dielectric constant of less than 5.0 can be used as BCS, a cured product with a relative dielectric constant of 4.5 or less can be preferably used as BCS, and a cured product with a relative dielectric constant of 4.0 or less can be particularly preferably used as BCS. A cured product with a relative dielectric constant of 5.0 or more cannot be used as BCS.

[0319] (VHR)

[0320] The polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were applied onto a glass substrate (100 mm×100 mm) using a spin coater and pre-baked at 90° C. for 100 seconds to form a coating film with a thickness of 3.0 μm. Next, a mirror projection collimator exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used to irradiate the glass substrate without using a mask at an exposure dose of 200 mJ / cm 2 The coating film was irradiated with ultraviolet rays and then post-baked at 230° C. for 30 minutes.

[0321] Mix 1 part by mass of the post-baked coating with 40 parts by mass of liquid crystal "RS-182" manufactured by ADEKA Co., Ltd. and store at 120°C for 1 hour. Take it out to room temperature and let it stand, then collect the supernatant. Measure the VHR (voltage holding ratio) of the collected liquid crystal composition. The detailed evaluation method is as follows. Inject the liquid crystal composition into a TN unit for liquid crystal evaluation (unit thickness is 5μm, electrode area is 8mm×8mm oriented film JALS2096), and use VHR-1A (manufactured by TOYO Corporation) to measure VHR. (Measurement conditions: pulse voltage amplitude is 60μs, frame period is 16.7ms, wave height is ±5V, and measurement temperature is 60°C)

[0322] A cured product with a VHR of 90% or more has low liquid crystal contamination and can be used as BCS, a cured product with a VHR of 95% or more can be preferably used as BCS, and a cured product with a VHR of 98% or more can be particularly preferably used as BCS. A cured product with a VHR of less than 90% cannot be used as BCS.

[0323] (NMP chemical resistance)

[0324] The N-methylpyrrolidone (NMP) dissolution test was performed by the following procedure.

[0325] First, the polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were applied on a glass substrate by a spin coater so that the final film thickness was 3 μm, and then dried under reduced pressure for 1 minute and then dried on a 90° C. hot plate for 120 seconds. 2After exposure, the resist-coated substrate was obtained by heating in an oven at 230°C for 40 minutes after the development process. Two test substrates (25 mm × 35 mm square) were cut from the prepared resist-coated substrate and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). Then, the vial containing the test substrate was placed in a clean oven at 90°C for 60 minutes for NMP dissolution test. After standing for 40 minutes, the vial was taken out from the hot bath, and the NMP dissolution solution was measured for absorbance every 1 nm in the wavelength range of 300 to 800 nm by a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation). For the light source, a halogen lamp and a deuterium lamp (switching wavelength 360 nm) were used, and for the detector, a photomultiplier tube was used, and the slit width was 2 nm as the measurement condition. The sample solution was placed in a quartz cell of 1 cm square for measurement. Absorbance is a dimensionless quantity that indicates the degree to which the intensity of light is attenuated when light passes through a certain object in spectroscopy, and is defined by the following formula.

[0326] A(absorbance)=-log 10 (I / I0) (I: transmitted light intensity, I0: incident light intensity)

[0327] The incident light intensity and the transmitted light intensity in the above formula can be regarded as the light intensity I0 transmitted through the single NMP and the light intensity I transmitted through the sample solution when the light is incident on the sample solution and the single NMP respectively by the same light source. Therefore, (I / I0) in the above formula represents the light transmittance, and the absorbance A becomes the value obtained by logarithmically expressing the reciprocal of the transmittance. The absorbance A is an expression used when calculating the concentration of a substance contained in the sample solution. The case of absorbance A=0 indicates a state in which no light is absorbed at all (transmittance is 100%), and the case of absorbance A=∞ indicates a state in which no light is transmitted at all (transmittance is 0%). That is, the stronger the absorbance, the more the resist coating component is dissolved into the NMP, and the worse the NMP resistance. The spectral area of ​​the absorbance as the evaluation standard can be expressed as the sum of the absorbances at each wavelength, which refers to the sum of the dissolved resist components.

[0328] The spectral area (nm) of the measured absorbance was calculated, and the NMP chemical resistance was evaluated according to the following criteria.

[0329] Evaluation criteria for NMP chemical resistance:

[0330] Determination by the area value of the absorption spectrum of the NMP elution solution (wavelength 300 to 800 nm)

[0331] ○: Less than 20 (nm)

[0332] △: 20 (nm) or more and less than 60 (nm)

[0333] ×: 60 (nm) or more

[0334] The samples with an NMP chemical resistance evaluation of 0 can be particularly preferably used as BCS, the samples with △ can be used as BCS, and the samples with × cannot be used as BCS.

[0335] (780nm transmittance)

[0336] The polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were applied onto a glass substrate (100 mm×100 mm) using a spin coater and pre-baked at 90° C. for 100 seconds to form a coating film with a thickness of 3.0 μm. Next, a mirror projection collimator exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.) was used to irradiate the glass substrate without using a mask at an exposure dose of 200 mJ / cm 2 The coating film was irradiated with ultraviolet rays. After that, it was post-baked at 230°C for 30 minutes to prepare a sample. The 780nm transmittance of the obtained sample was measured by an absorptiophotometer. A 780nm transmittance of 80% or more was set as ○, a transmittance of more than 60% and less than 80% was set as △, and a transmittance of less than 60% was set as ×.

[0337] The samples evaluated as ○ or △ can be used as BCS, and the samples evaluated as ○ can be used particularly preferably. The samples evaluated as × cannot be used as BCS.

[0338] Table 1

[0339] Example 1 2 3 4 5 A1-1 35 32 35 35 A1-2 35 A2-1 2 5 2 2 2 B-1 13 13 13 13 13 B-2 11 11 11 11 11 B-3 C-1 0.3 0.3 0.3 0.3 0.15 C-2 C-3 0.15 D-1 1.5 1.5 1.5 1.5 1.5 D-2 1 1 1 1 D-3 1 E-1 0.1 0.1 0.1 0.1 0.1 E-2 0.1 0.1 0.1 0.1 0.1 F-1 24 24 24 24 24 F-2 9 9 9 9 9 F-3 3 3 3 3 3 total 100 100 100 100 100 Elastic recovery rate (%) More than 80% 70％ More than 80% More than 80% More than 80% OD value ( / um) 1.5 1.5 1.5 1.5 1.5 Relative dielectric constant 3.5 3.7 3.5 3.7 3.5 Low liquid crystal contamination (VHR) (%) 99 99 99 98 99 NMP Chemical Resistance ○ △ ○ ○ ○ Transmittance at 780nm ○ △ ○ ○ ○

[0340] Table 2

[0341] Example 6 7 8 9 10 A1-1 35 35 35 35 A1-2 35 A2-1 2 2 2 2 2 B-1 13 B-2 24 24 24 24 B-3 11 C-1 0.15 0.3 0.3 0.3 0.3 C-2 C-3 0.15 D-1 1.5 1.5 1.5 1.5 1.5 D-2 1 1 1 1 D-3 1 E-1 0.1 0.1 0.1 0.1 0.1 E-2 0.1 0.1 0.1 0.1 0.1 F-1 24 24 24 24 24 F-2 9 9 9 9 9 F-3 3 3 3 3 3 total 100 100 100 100 100 Elastic recovery rate (%) More than 80% More than 80% More than 80% More than 80% More than 80% OD value ( / um) 1.5 1.5 1.5 1.5 1.5 Relative dielectric constant 3.5 3.5 3.5 3.7 3.5 Low liquid crystal contamination (VHR) (%) 99 99 98 98 99 NMP Chemical Resistance ○ △ △ △ △ Transmittance at 780nm ○ ○ ○ ○ ○

[0342] Table 3

[0343] Example 11 12 13 14 15 A1-1 35 37 39 39 35 A1-2 A2-1 2 5 9 9 2 B-1 11 8 8 13 B-2 8 5 5 11 B-3 24 C-1 0.3 0.3 0.3 0.3 C-2 0.1 C-3 0.2 D-1 1.5 1.5 1.5 1.5 1.5 D-2 1 1 1 1 1 D-3 E-1 0.1 0.1 0.1 0.1 0.1 E-2 0.1 0.1 0.1 0.1 F-1 24 24 24 24 24 F-2 9 9 9 9 9 F-3 3 3 3 3 3 total 100 100 100 100 99.9 Elastic recovery rate (%) More than 80% 70％ 70％ 70％ More than 80% OD value ( / um) 1.5 1.75 2.0 2.0 1.5 Relative dielectric constant 3.5 4 4.5 4.7 3.5 Low liquid crystal contamination (VHR) (%) 99 95 95 95 99 NMP Chemical Resistance △ ○ ○ ○ ○ Transmittance at 780nm ○ △ △ △ ○

[0344] Table 4

[0345] Comparative Example 1 2 3 A1-1 44 48 A1-2 A2-1 30 B-1 17 8 6 B-2 14 9 7 B-3 C-1 0.3 0.3 0.3 C-2 C-3 D-1 1.5 1.5 1.5 D-2 1 1 1 D-3 E-1 0.1 0.1 0.1 E-2 0.1 0.1 0.1 F-1 24 24 24 F-2 9 9 9 F-3 3 3 3 total 100 100 100 Elastic recovery rate (%) 40％ 70％ 70％ OD value ( / um) 1.5 1.75 2.0 Relative dielectric constant 3.9 4 4 Low liquid crystal contamination (VHR) (%) 99 95 93 NMP Chemical Resistance △ × × Transmittance at 780nm × ○ ○

[0346] As shown in Tables 1 to 4, the cured product obtained from the polymerizable composition of the present invention is useful as a BCS because it satisfies the light-shielding property (OD value), relative dielectric constant, low liquid crystal contamination (VHR), chemical resistance, 780nm transmittance, and has excellent elastic recovery rate at a high level.

[0347] Industrial Applicability

[0348] The cured product obtained from the polymerizable composition, photosensitive composition for BM or photosensitive composition for BCS of the present invention is a cured product (particularly BCS) having excellent light shielding properties, elastic recovery, chemical resistance, low dielectric constant and good electrical properties. The cured product is particularly useful in display devices and the like.

Claims

1. A polymerizable composition comprising a colorant (A), an alkali-developable compound (B) and a polymerization initiator (C), wherein: The colorant (A) is a colorant containing an organic colorant (A1) and an inorganic colorant (A2), The organic colorant (A1) and the inorganic colorant (A2) are respectively an organic black pigment and an inorganic black pigment, The alkali-developable compound (B) is an alkali-developable compound represented by the following general formula (I) and a resin having a structure obtained by an esterification reaction between an epoxy addition compound and a polybasic acid anhydride, wherein the epoxy addition compound has a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (III), The content of the coloring agent (A) is 20 to 60 parts by mass based on 100 parts by mass of the alkali-developable compound (B). In the formula, R 1 , R 3 and R 5 each independently represents a hydrogen atom or a methyl group, R 2 , R 4 and R 6 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, R 3 and R 4 When there are multiple, they are the same or different. Y 1 , Y 2 and Y 3 represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, Y 2 When there are multiple, they are the same or different. Z 1 , Z 2 and Z 3 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, Z 2 When there are multiple, they are the same or different. R 2 , R 4 , R 6 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 The hydrogen atoms in the represented group may be substituted or unsubstituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group or a group having 2 to 20 carbon atoms and containing a heterocyclic ring, R 2 , R 4 , R 6 , Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 The methylene group in the represented group may also be substituted by -O-, -CO-, -COO-, -OCO-, -S-, -SO2-, -SCO- or -COS- or unsubstituted, m represents a positive number less than 0 or 10, a represents a positive number less than 0 or 4, b represents a positive number less than 0 or 3, and c represents a positive number less than 0 or 4. When m is 2 or more, b is the same or different, In the formula, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO2-, -SS-, -SO-, -CO-, -OCO-, or a substituent selected from the group represented by the following formula (a), (b), (c) or (d), The hydrogen atoms in the hydrocarbon group having 1 to 20 carbon atoms represented by M may be substituted with halogen atoms. 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 (hereinafter, also referred to as R 21 ~R 28 ) each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, k is a number from 0 to 10, and when k ≥ 1, a plurality of R 21 ~R 28 and M have the same or different situations. In the formula, R 29 represents a hydrocarbon group having 1 to 20 carbon atoms, R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 (hereinafter, also referred to as R 30 ~R 58 ) each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom, R 31 ~R 38 and R 40 ~R 68 The methylene group in the group represented may be substituted with an unsaturated bond, -O- or -S-. R 30 With R 31 , R 31 With R 32 , R 32 With R 33 , R 33 With R 34 , R 35 With R 36 , R 36 With R 37 , R 37 With R 38 , R 43 With R 44 , R 44 With R 45 , R 45 With R 46 , R 51 With R 52 , R 52 With R 53 , R 53 With R 54 , R 55 With R 56 , R 56 With R 57 and R 57 With R 58 Sometimes they are bonded to form rings, In the groups represented by (a), (b), (c) and (d), * represents a bonding site.

2. The polymerizable composition according to claim 1, wherein The polymerization initiator (C) is a polymerization initiator having a group represented by the following general formula (II), In the formula, R 11 and R 12 Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R 11 and R 12 The hydrogen atoms in the group represented by is substituted or unsubstituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a group having 2 to 20 carbon atoms and containing a heterocyclic ring, 11 and R 12 The methylene groups in the groups represented by are also represented by -O-, -CO-, -COO-, -OCO-, -NR 13 -、-NR 13 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or CSO-substituted or unsubstituted, R 13 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, In the formula, * represents a bonding site. 3 . A photosensitive composition for a black matrix, comprising the polymerizable composition according to claim 1 . 4 . A photosensitive composition for a black columnar spacer, comprising the polymerizable composition according to claim 1 . 5 . A method for producing a cured product by irradiating light or heating the polymerizable composition according to claim 1 or 2 , the photosensitive composition for a black matrix according to claim 3 , or the photosensitive composition for a black columnar spacer according to claim 4 . 6 . A cured product, which is a cured product of the polymerizable composition according to claim 1 or 2 , the photosensitive composition for a black matrix according to claim 3 , or the photosensitive composition for a black columnar spacer according to claim 4 .

7. A display device comprising the cured product according to claim 6.

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