TWI759501B - Polymerizable composition, photosensitive composition for black matrix, and photosensitive composition for black column spacer - Google Patents

Abstract

(式中之符號之含義參照說明書)The polymerizable composition of the present invention contains a colorant (A), an alkaline developable compound (B) and a polymerization initiator (C), and the colorant (A) contains an organic colorant (A1) and an inorganic colorant A colorant for agent (A2). Preferably, the organic colorant (A1) and the inorganic colorant (A2) are an organic black pigment and an inorganic black pigment, respectively. Moreover, it is also preferable that the alkali-developable compound (B) is an alkali-developable compound represented by the following general formula (I).

(For the meaning of the symbols in the formula, please refer to the manual)

Description

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

The present invention relates to a polymerizable composition containing a colorant, an alkaline developable compound, and a polymerizable initiator, a photosensitive composition for a black matrix (hereinafter also referred to as "BM"), and a black column spacer (hereinafter also referred to as "BM") It is a photosensitive composition for "BCS") and the hardened|cured material obtained from this polymerizable composition or this photosensitive composition, and the said coloring agent is characterized by containing an inorganic coloring agent and an organic coloring agent together.

In display devices such as liquid crystal display devices and organic EL display devices, spacers are used in order to maintain the distance between the substrates between the upper part and the lower part of the cell.

The spacer is formed by applying a polymerizable composition on a substrate, exposing it through a specific mask, and then developing it. In recent years, a BCS having light-shielding properties by integrating a column spacer and a black matrix into one module has been used.

Patent Document 1 discloses a photosensitive resin composition for a light-shielding film containing an alkali-soluble resin having a perylene skeleton. This document describes that the composition has a spacer function excellent in light-shielding properties, insulating properties, and elastic resilience. Patent Document 2 discloses a photosensitive resin composition containing a black organic pigment (lactamide black) and a black inorganic pigment (carbon black). This document describes that the composition is excellent in dielectric constant, light shielding properties, resolution, and elastic recovery rate. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-072760 [Patent Document 2] International Publication No. 2013/032190

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

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

As a result of earnest research of the present invention, the above objects are achieved by providing the following [1] to [9].

[1] A polymerizable composition containing a colorant (A), an alkaline developable compound (B) and a polymerization initiator (C), wherein the colorant (A) contains an organic colorant A colorant of agent (A1) and inorganic colorant (A2).

[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.

[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);

(式中，R¹ 、R³ 及R⁵ 分別獨立地表示氫原子或甲基， R² 、R⁴ 及R⁶ 分別獨立地表示碳原子數為1～20之烴基或含有雜環之碳原子數為2～20之基， R³ 及R⁴ 複數個存在之情形時，存在相同之情形亦存在不同之情形， Y¹ 、Y² 及Y³ 表示直接鍵、碳原子數為1～20之烴基或含有雜環之碳原子數為2～20之基， 於Y² 複數個存在之情形時，存在相同之情形亦存在不同之情形， Z¹ 、Z² 及Z³ 分別獨立地表示碳原子數為1～20之烴基或含有雜環之碳原子數為2～20之基， 於Z² 複數個存在之情形時，存在相同之情形亦存在不同之情形， 存在R² 、R⁴ 、R⁶ 、Y¹ 、Y² 、Y³ 、Z¹ 、Z² 及Z³ 所表示之基中之氫原子經鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、巰基、異氰酸基或含有雜環之碳原子數為2～20之基取代之情形， 亦存在R² 、R⁴ 、R⁶ 、Y¹ 、Y² 、Y³ 、Z¹ 、Z² 及Z³ 所表示之基中之亞甲基被取代為-O-、-CO-、-COO-、-OCO-、-S-、-SO₂ -、-SCO-或-COS-之情形， m表示0或10以下之正數，a表示0或4以下之正數，b表示0或3以下之正數，c表示0或4以下之正數， 於m為2以上之情形時，b存在相同之情形亦存在不同之情形)。[hua 1]

(In the formula, R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ² , R ⁴ and R ⁶ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a carbon atom containing a heterocyclic ring. A base with a number of 2 to 20, when multiple R ³ and R ⁴ exist, the same situation and different situations exist. Y ¹ , Y ² and Y ³ represent direct bonds, and the number of carbon atoms is 1 to 20. A hydrocarbon group or a group containing a heterocyclic ring with 2 to 20 carbon atoms, when there are multiple Y ² , the same situation and different situations exist, and Z ¹ , Z ² and Z ³ each independently represent a carbon atom The number of hydrocarbon groups of 1 to 20 or the group of carbon atoms of 2 to 20 containing heterocycles, when there are multiple Z ² , there are the same situation and different situations, there are R ² , R ⁴ , R ^6. The hydrogen atoms in the groups represented by Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are replaced by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, In the case of substitution of acrylyl, epoxy, vinyl, mercapto, isocyanato or a group containing a heterocycle with 2 to 20 carbon atoms, there are also R ² , R ⁴ , R ⁶ , Y ¹ , Y ² , the methylene group in the group represented by Y ³ , Z ¹ , Z ² and Z ³ is substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ -, In the case of -SCO- or -COS-, m represents a positive number below 0 or 10, a represents a positive number below 0 or 4, b represents a positive number below 0 or 3, c represents a positive number below 0 or 4, and m is 2 In the above cases, b exists in the same situation and also in different situations).

[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);

(式中，R¹¹ 及R¹² 分別獨立地表示氫原子、鹵素原子、硝基、氰基、碳原子數為1～20之烴基或含有雜環之碳原子數為2～20之基，存在R¹¹ 及R¹² 所表示之基中之氫原子經鹵素原子、硝基、氰基、羥基、胺基、羧基、甲基丙烯醯基、丙烯醯基、環氧基、乙烯基、乙烯醚基、巰基、異氰酸基或含有雜環之碳原子數為2～20之基取代之情形，且亦存在R¹¹ 及R¹² 所表示之基中之亞甲基被取代為-O-、-CO-、-COO-、-OCO-、-NR¹³ -、-NR¹³ CO-、-S-、-CS-、-SO₂ -、-SCO-、-COS-、-OCS-或CSO-之情形， R¹³ 表示氫原子、碳原子數為1～20之烴基， n表示0或1， 式中之＊表示鍵結鍵)。[hua 2]

(in the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms, or a group containing a heterocyclic ring with 2 to 20 carbon atoms, there are The hydrogen atoms in the groups represented by R ¹¹ and R ¹² are via halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryl groups, epoxy groups, vinyl groups, vinyl ether groups , mercapto group, isocyanato group or group containing a heterocyclic ring with 2 to 20 carbon atoms is substituted, and there are also cases where the methylene group in the group represented by R ¹¹ and R ¹² is substituted with -O-, - CO-, -COO-, -OCO-, -NR ¹³ -, -NR ¹³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO- In this case, R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, and * in the formula represents a bond).

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

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

[7] A method for producing a cured product using the polymerizable composition according to any one of [1] to [4], the photosensitive composition for a black matrix according to [5], or the black matrix according to [6] The photosensitive composition for column spacers is a method for producing a cured product by light irradiation or heating.

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

[9] A display device comprising the cured product of [8].

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

The polymerizable composition of the present invention contains a colorant, an alkali developable compound, and a polymerizable initiator, and the colorant is characterized by containing an inorganic colorant and an organic colorant together. Hereinafter, each component will be described in order.

<Colorant (A)> The colorant (A) used in the polymerizable composition of the present invention contains an organic colorant (A1) and an inorganic colorant (A2), and known pigments or dyes can be mixed and used. Here, the term "pigment" refers to a coloring agent that is insoluble in a solvent described later, and also includes an inorganic or organic coloring agent that is insoluble in a solvent, or an inorganic or organic dye that has been laked.

As said organic coloring agent (A1), an organic pigment and an organic dye are mentioned.

Examples of the above-mentioned organic pigments include aniline black, lactamide black, 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 other organic pigments represented by zirconium, barium or aluminum lakes, etc.

Among the above-mentioned organic black pigments represented by aniline black, lactamide black, and perylene black, they are preferred because of their excellent light-shielding properties.

化合物、喹啉化合物、蒽醌化合物、香豆素化合物、花青化合物、酞菁化合物、異吲哚啉酮化合物、異吲哚啉化合物、喹吖啶酮化合物、蒽締蒽酮化合物、芘化合物、苝化合物、吡咯并吡咯二酮化合物、硫靛藍化合物、二㗁𠯤化合物、三苯基甲烷化合物、喹酞酮化合物、萘四羧酸、偶氮染料、花青染料之金屬錯合物化合物等。Examples of the above-mentioned organic dyes include anthraquinones such as astaxanthin and alizarin, anthocyanin, β-carotene, catenal, capsanthin, chalcone, safflower, quercetin, Naphthoquinones such as crocin, chlorophyll, curcumin, cochineal, shikonin, lipophanin, flavonoids, betacyanin, red brown pigment, heme, lycopene, riboflavin, rutin, etc. Natural pigments, dyes, auto-oxidative dyes such as indoline; dihydroxyacetone, nitroso compounds, nitro compounds, azo compounds, diazo compounds, 𠮿

Compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthraquinone compounds, pyrene compounds , perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dithioindigo compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids, azo dyes, metal complex compounds of cyanine dyes, etc. .

As said inorganic coloring agent (A2), an inorganic pigment and an inorganic dye are mentioned.

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; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as iron oxide yellow and ochre; inorganic black pigments such as iron oxide black and subvalent titanium oxide; inorganic black pigments such as manganese violet and cobalt violet Violet pigments; inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate; inorganic blue pigments such as ultramarine blue and iron blue; titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated Talc, colored titanium oxide coated mica, bismuth oxychloride foil and other pearl pigments; aluminum powder, copper powder, gold and other metal powder pigments; surface-treated inorganic and metal powder pigments; obtained by furnace method, tank method or thermal cracking method carbon black, or carbon black such as acetylene black, ketjen black or lamp black, which is prepared by adjusting or coating the above carbon black with epoxy resin, and dispersing the above carbon black in a solvent in advance in the resin For those coated with 20 to 200 mg/g resin, the above carbon black is acid or alkaline surface treated, the average particle size is 8 nm or more and the DBP oil absorption is 90 ml/100 g or less carbon black , the total oxygen content calculated from CO and CO ₂ in the volatile matter at 950 ℃ is carbon black with a surface area of 9 mg or more relative to 100 m ² , with graphitized carbon black, pigment black 7, graphite, activated carbon, carbon fiber Inorganic black pigments represented by carbon nanotubes, carbon micro-coil, carbon nanohorn, carbon aerogel, fullerene, titanium black, etc.

Among the above-mentioned pigments, black pigments are preferably used in view of high light-shielding properties.

Examples of the inorganic dyes include dyes containing metals (transition metals, etc.) such as vanadium-based dyes (vanadium compounds, the same below), chromium-based dyes, molybdenum-based dyes, manganese-based dyes, iron-based dyes (iron oxalate, etc.) Wait. Furthermore, inorganic dyes also include inorganic components that are colored in resin particles [for example, components that are colored by interaction (coordination or complexation, etc.) with resins having a stilbene skeleton], such as metal ions (such as vanadium, chromium, etc.). , manganese, cobalt, nickel, copper and other transition metal cations) or compounds containing metal ions.

As said pigment, a commercial item can also be used, for example: 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, 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 Purple 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50 etc.

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 5 to 10 parts by mass relative to 100 parts by mass of the following alkaline developable compound (B). Preferably it is 10-80 mass parts, More preferably, it is 20-60 mass parts. When the content of the colorant (A) is within the above-mentioned range, the polymerizable composition has excellent storage stability without coagulation of the colorant, and the light-shielding property of the cured product of the polymerizable composition becomes high, which is preferable. . 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 relative to 100 parts by mass of the alkaline developable compound (B). parts, more preferably 10 to 80 parts by mass, still more preferably 20 to 60 parts by mass. Moreover, from the viewpoint of high transmittance at 780 nm, in the polymer composition, the inorganic colorant (A2) is preferably 30 parts by mass or less, more preferably 20 parts by mass relative to 100 parts by mass of the organic colorant (A1). parts by mass or less. On the other hand, from the viewpoint of high light-shielding properties, the inorganic colorant (A2) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the organic colorant (A1).

<Alkaline-Developable Compound (B)> The alkali-developable compound (B) of the present invention is a compound having a hydrophilic group and showing alkali-developability. In this invention, as an alkaline developable compound (B), if the said conditions are satisfied, the compound used previously can be used. Examples of the hydrophilic group include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group or a salt thereof, and the hydroxyl group and the carboxyl group have high developability in an alkali due to the alkaline developable compound (B). and better.

The preferred functional group equivalent of the hydrophilic group in the alkaline developable compound (B) (the mass of the polymer compound containing 1 equivalent of the hydrophilic group) is 50 to 10,000. When the functional group equivalent of a hydrophilic group is in the said range, it is excellent in alkali developability, and it is preferable.

The preferred molecular weight of the alkaline developable compound (B) is a weight average molecular weight of 2,000 to 10,000, particularly preferably 3,000 to 6,000. Moreover, the number average molecular weight is 1000-8000, especially 2000-5000. When the molecular weight of the alkali-developable compound (B) is in the above-mentioned range, a cured product excellent in developability and chemical resistance can be obtained, which is preferable.

The acid value of the above alkaline developable compound (B) is preferably 10 to 200 mg/KOH, more preferably 30 to 150 mg/KOH. When the acid value is 10 mg/KOH or more, it is easy to obtain sufficient alkaline developability, and when it is 200 mg/KOH or less, the production of the polymer compound is easily facilitated. Here, the so-called acid value is based on JIS K 0050 and JIS K 0211.

Specifically, as the alkaline developable compound (B), a compound represented by the above-mentioned general formula (I), a copolymer of an acrylate, a phenolic and/or cresol novolac epoxy resin, and a polyfunctional ring can be used. Oxygen-based polyphenylmethane type epoxy resin; epoxy acrylate resin; epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (III), etc. ; Resins (unsaturated compounds), etc. having a structure obtained by an esterification reaction, the above-mentioned esterification reaction is a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (III) Esterification of epoxy addition compounds with polybasic acid anhydrides.

(式中，M表示選自直接鍵、碳原子數為1～20之烴基、-O-、-S-、-SO₂ -、-SS-、-SO-、-CO-、-OCO-或下述式(a)、(b)、(c)或(d)所表示之群之取代基， 存在M所表示之碳原子數為1～20之烴基中之氫原子經鹵素原子取代之情形，R²¹ 、R²² 、R²³ 、R²⁴ 、R²⁵ 、R²⁶ 、R²⁷ 及R²⁸ (以下亦記載為「R²¹ ～R²⁸ 」)分別獨立地表示氫原子、碳原子數為1～20之烴基、或鹵素原子，k為0～10之數，於k≧1之情形時，複數個存在之R²¹ ～R²⁸ 及M分別存在相同之情形，亦存在不同之情形)[hua 3]

(wherein, M represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO- or Substituents of the group represented by the following formula (a), (b), (c) or (d), there is a case where the hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M is substituted by a halogen atom , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ (hereinafter also referred to as “R ²¹ to R ²⁸ ”) each independently represent a hydrogen atom and the number of carbon atoms is 1 to 1 The hydrocarbon group of 20 or the halogen atom, k is a number from 0 to 10, and when k≧1, the plural R ²¹ to R ²⁸ and M are the same or different respectively)

(式中，R²⁹ 表示碳原子數為1～20之烴基， R³⁰ 、R³¹ 、R³² 、R³³ 、R³⁴ 、R³⁵ 、R³⁶ 、R³⁷ 、R³⁸ 、R³⁹ 、R⁴⁰ 、R⁴¹ 、R⁴² 、R⁴³ 、R⁴⁴ 、R⁴⁵ 、R⁴⁶ 、R⁴⁷ 、R⁴⁸ 、R⁴⁹ 、R⁵⁰ 、R⁵¹ 、R⁵² 、R⁵³ 、R⁵⁴ 、R⁵⁵ 、R⁵⁶ 、R⁵⁷ 及R⁵⁸ (以下亦記載為「R³⁰ ～R⁵⁸ 」)分別獨立地表示氫原子、碳原子數為1～20之烴基、含有雜環之碳原子數為2～20之基、或鹵素原子， 存在R³¹ ～R³⁸ 及R⁴⁰ ～R⁶⁸ 所表示之基中之亞甲基被取代為不飽和鍵、-O-或-S-之情形， 存在R³⁰ 與R³¹ 、R³¹ 與R³² 、R³² 與R³³ 、R³³ 與R³⁴ 、R³⁵ 與R³⁶ 、R³⁶ 與R³⁷ 、R³⁷ 與R³⁸ 、R⁴³ 與R⁴⁴ 、R⁴⁴ 與R⁴⁵ 、R⁴⁵ 與R⁴⁶ 、R⁵¹ 與R⁵² 、R⁵² 與R⁵³ 、R⁵³ 與R⁵⁴ 、R⁵⁵ 與R⁵⁶ 、R⁵⁶ 與R⁵⁷ 及R⁵⁷ 與R⁵⁸ 鍵結而形成環之情形， (a)、(b)、(c)及(d)所表示之基中之＊表示鍵結鍵)[hua 4]

(wherein, 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 to R ⁵⁸ ”) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group containing a heterocyclic ring having 2 to 20 carbon atoms, or a halogen atom , there is a situation in which the methylene group in the groups represented by R ³¹ to R ³⁸ and R ⁴⁰ to R ⁶⁸ is substituted with an unsaturated bond, -O- or -S-, there are R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , and R ⁵⁷ and R ⁵⁸ are bonded to form a ring, (a), (b) , (c) and (d) in the base represented by * represents a bonding bond)

By using the alkali-developable compound represented by the above-mentioned general formula (I), the cured product obtained from the polymerizable composition has excellent chemical resistance, which is preferable.

If an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the above general formula (III) is used; The basic developable compound of the reaction product obtained by adding the epoxy compound represented by the formula (III) to the epoxy compound having the structure of unsaturated monobasic acid and the esterification reaction of polybasic acid anhydride), then the polymerizable combination Since the sensitivity of the material becomes high, and the cured material obtained from the polymerizable composition is excellent in the elastic recovery rate, it is preferable.

Since the dispersibility of the colorant (A) becomes good and the heat resistance is good, the above-mentioned alkaline developable compound (B) is preferably an epoxy compound represented by the above-mentioned general formula (III); in the above-mentioned general formula (III) An epoxy compound having the following structure [(e)] obtained by adding an unsaturated monobasic acid to the indicated epoxy compound; or an epoxy compound having the following structure obtained by esterification of the unsaturated compound with a polybasic acid anhydride Unsaturated compounds of structure [(f)].

(式中，Y⁷ 表示不飽和一元酸之殘基，Y⁸ 表示多元酸酐之殘基， ＊表示鍵結鍵)[hua 5]

(In the formula, Y ⁷ represents the residue of an unsaturated monobasic acid, Y ⁸ represents the residue of a polybasic acid anhydride, and * represents a bond)

In the alkaline developable compound represented by the general formula (III), when M is a group represented by (b) or (c), the solvent resistance of the cured product obtained from the polymerizable composition changes. Good, so excellent.

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

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, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, third octyl, nonyl, isononyl, decyl and isodecyl, etc.

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 Alkenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4,8,12-tetradecenyl Carbotrienyl allyl, etc. 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 Alkenyl etc.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydrocyclopentyl alkene, bicyclo[1.1.1]pentyl and tetradecylhydroanthracenyl, etc. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and adamantyl. Alkyl, decahydronaphthyl, octahydrocyclopentadiene and bicyclo[1.1.1]pentyl, etc.

The above-mentioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2 -Cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecyl ethyl, 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-adamantylpropyl and 3-decahydronaphthylpropyl, etc. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, and cyclooctyl Methyl, 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 Base et al.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, and the like, or one or more of the above-mentioned alkyl groups. , phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted by the above alkenyl or carboxyl, halogen atoms, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methyl Phenyl, 2,4,6-trimethylphenyl, etc. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and the like, or one or more of the above-mentioned alkyl group, the above-mentioned alkenyl group, or a carboxyl group. , halogen atoms, etc. substituted phenyl, biphenyl, naphthyl, anthracenyl, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4 , 6-trimethylphenyl, etc.

The above-mentioned aralkyl group having 7 to 20 carbon atoms means that the hydrogen atom of the alkyl group is substituted by an aryl group having 6 to 19 carbon atoms in the above-mentioned aryl group having 6 to 20 carbon atoms. base of carbon atoms. For example, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a naphthylpropyl group, and the like are mentioned. The above-mentioned aralkyl group having 7 to 10 carbon atoms means that a hydrogen atom of the alkyl group is substituted with an aryl group having 6 to 9 carbon atoms in the above-mentioned aryl group having 6 to 20 carbon atoms and has 7 to 10 carbon atoms. As a group having one carbon atom, for example, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group can be mentioned.

The group containing a heterocyclic ring and having 2 to 20 carbon atoms represented by R ² , R ⁴ and R ⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ in the general formula (I) is not particularly limited, for example Examples include: pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, pyridyl, piperyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, tris', tris Methyl, pyrrolidinyl, quinolinyl, isoquinolinyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl , thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 𠰌line base, thiopyridine, 2-pyrrolidin-1-yl, 2-piperidin-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxyethyl When the oxazolidin-3-yl group and the like are specifically described including a substituent and the like, a group having the following structure and the like can be mentioned.

(上述式中，R分別獨立地表示氫原子或碳原子數為1～6之烷基，Z表示直接鍵或碳原子數為1～6之伸烷基。再者，作為式中之＊，該等式所表示之基以＊部分表示鍵結鍵)[hua 6]

(In the above formula, 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. Furthermore, as * in the formula, The base represented by this equation is represented by the * part to indicate the bond)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the alkyl group having 1 to 20 carbon atoms described above. Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include methylene group, ethylidene group, propylidene group, methyl ethylidene group, butylene group, and 1-methyl group. Propylidene, 2-methylbutylene, 1,2-dimethylbutylene, 1,3-dimethylbutylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, etc. straight or branched chain The extended alkyl.

Examples of halogen atoms that may substitute hydrogen atoms in groups represented by R ² , R ⁴ , R ⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ include fluorine, chlorine, bromine, and iodine.

Examples of unsaturated bonds that may substitute methylene groups in groups represented by R ² , R ⁴ , R ⁶ , Y ¹ to Y ³ and Z ¹ to Z ³ include -C=C-, - C≡C-etc.

The hydrocarbon group having 1 to 20 carbon atoms represented by M and R ²¹ to R ⁵⁸ in the general formula (III) may be the same as the hydrocarbon group having 1 to 20 carbon atoms described above.

The groups having 1 to 20 carbon atoms containing a heterocyclic ring represented by R ³⁰ to R ⁵⁸ in the general formula (III) may be the same as the above-mentioned groups containing 1 to 20 carbon atoms containing a heterocyclic ring.

As the halogen atom substituted for the hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M in the above general formula (III), and the halogen atom represented by R ²¹ to R ²⁸ and R ³⁰ to R ⁵⁸ , Fluorine, chlorine, bromine, and iodine can be mentioned.

R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ in the above general formula (III) , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ and R The ring formed by bonding between ⁵⁷ and R ⁵⁸ includes, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperidine, pyridine, thiopyridine, tetrahydropyridine, 5-7 membered rings such as ester ring and lactamide ring, condensed rings such as naphthalene and anthracene, etc.

The above-mentioned unsaturated monobasic acid refers to an acid having an unsaturated bond in the structure and one hydrogen atom that can be ionized to become a hydrogen ion in one molecule. Examples of the above-mentioned unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate-maleate, and hydroxypropyl methacrylate-maleate , hydroxypropyl acrylate-maleate and dicyclopentadiene-maleate, etc.

Moreover, as the above-mentioned polybasic acid anhydride which acts after the above-mentioned unsaturated monobasic acid acts, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, maleic anhydride can be mentioned. Acid anhydride, trimellitic anhydride, pyromellitic dianhydride, 2,2'-3,3'-benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, glycerol trianhydrotriphenylene Triesters, Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Natonic Anhydride, Methyl Natonic Anhydride, Trialkyl Tetrahydrophthalic Anhydride, Hexahydrophthalic Anhydride , 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride addition Compounds, dodecenyl succinic anhydride, methyl bicycloheptenedicarboxylic anhydride, etc.

It is preferable to set the reaction molar ratio of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride as follows. That is, the epoxy addition compound is preferably added at a ratio of 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid relative to one epoxy group of the epoxy compound, and the ethylene As for the sexually unsaturated compound, it is preferable that the acid anhydride structure of the said polybasic acid anhydride becomes a ratio of 0.1-1.0 pieces with respect to 1 hydroxyl group of the said epoxy adduct. The reaction of the epoxy compound represented by the above-mentioned general formula (III), the above-mentioned unsaturated monobasic acid, and the above-mentioned polybasic acid anhydride can be carried out conventionally.

In order to adjust the acid value and improve the developability of the polymerizable composition of the present invention, the photosensitive composition for BM, and the photosensitive composition for BCS, a monofunctional or polyfunctional compound may be further added together with the above-mentioned alkaline developable compound (B). functional epoxy reaction. The acid value of the solid content of the above-mentioned alkaline developable compound (B) is preferably in the range of 5 to 120 mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected to satisfy the above acid value. .

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isopropyl glycidyl ether, and Butyl glycidyl ether, tert-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethyl acetate Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether Ether, tolyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether Glyceryl ether, 2,3-glycidyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, ethylene monoxide, 1,2-epoxy-4-ethylene cyclohexane, ethylene oxide, pinene oxide, methyl ethylene oxide, cyclohexane oxide, propylene oxide, the following epoxy compounds No. E1, No. E2, and the like.

[hua 7]

[hua 8]

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers, since a polymerizable composition with further favorable properties can be obtained. As said bisphenol type epoxy compound, in addition to the epoxy compound represented by the said general formula (III), for example, bisphenol type epoxy compounds, such as a hydrogenated bisphenol type epoxy compound, can also be used. Further, as the above-mentioned glycidyl ethers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ,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(glycidyl ether) Glyceryloxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1,1 - Tetrakis(glycidoxymethyl)methane, etc. In addition, phenolic novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolak epoxy compounds, bisphenol A novolak epoxy compounds, dicyclopentadiene novolac epoxy compounds can also be used Novolak-type epoxy compounds such as epoxy compounds; 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3,4-epoxy-6-methylcyclohexylmethyl ester, 3,4-cyclohexyl Alicyclic epoxy compounds such as oxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate , glycidyl esters such as diglycidyl tetrahydrophthalate, glycidyl dimer acid; tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, N,N-diphenylmethane Glycidyl amines such as glycidyl aniline; 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate and other heterocyclic epoxy compounds; Dioxide Dioxide Dioxide compounds such as cyclopentadiene; naphthalene-type epoxy compounds; triphenylmethane-type epoxy compounds; dicyclopentadiene-type epoxy compounds, etc.

As an alkali developable compound (B), a commercial item can also be used suitably. Examples of such 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, SPRR-21X ( The above are manufactured by Showa Denko Co., Ltd.), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (the above are manufactured by Osaka Organic Chemical Co., Ltd.), CCR-1171H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

In the polymerizable composition of the present invention, the content of the alkali-developable compound (B) is not particularly limited, and is relative to the content of the colorant (A), the alkali-developable compound (B) and the polymerization initiator (C). 10-95 mass parts is preferable with a total of 100 mass parts, 30-90 mass parts is more preferable, 30-80 mass parts is still more preferable. When the content of the alkali-developable compound (B) is within the above-mentioned range, the alkali-developability of the polymerizable composition is good, and thus is preferred. For example, in the case of forming a cured film with a thickness of 2 to 5 μm, the content of the alkali developable compound (B) is not particularly limited, and is relative to the colorant (A), the alkali developable compound (B) and the polymerization initiator. The starting agent (C) is preferably 10 to 95 parts by mass, more preferably 30 to 90 parts by mass, and still more preferably 30 to 80 parts by mass, with respect to 100 parts by mass in total of the starting agent (C). In addition, when the alkaline developable compound (B) contains the compound represented by the general formula (I), the content of the compound represented by the general formula (I) is relative to the colorant (A), the alkaline developable compound The total of (B) and the polymerization initiator (C) is preferably 10 to 60 parts by mass, more preferably 20 to 50 parts by mass. In addition, the epoxy adduct compound (which has a structure in which an unsaturated monobasic acid is added to the compound represented by the general formula (III)), or by esterification of the epoxy adduct compound and a polybasic acid anhydride In the case of the reaction product obtained by the reaction (that is, the alkaline developable compound), 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 are relative It is preferable that it is 5-80 mass parts with respect to a total of 100 mass parts of a coloring agent (A), an alkali developable compound (B), and a polymerization initiator (C), More preferably, it is 5-40 mass parts. The content of the above-mentioned epoxy addition compound and the reaction product obtained by the esterification reaction of the epoxy addition compound and the polybasic acid anhydride is the case where only one of the epoxy addition compound and the reaction product is contained When it is the amount, when it contains both, it is the total amount.

<Polymerization initiator (C)> As the polymerization initiator (C) used in the polymerizable composition of the present invention, a previously known radical polymerization initiator can be used.

The above-mentioned radical polymerization initiators are photo-radical polymerization initiators and thermal radical polymerization initiators. In view of high self-reactivity, it is more preferably a photo-radical polymerization initiator.

系化合物等作為較佳者。The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and previously known compounds can be used, for example, oxime ester-based compounds, acetophenone-based compounds, benzoyl Acetyl compounds, benzophenone compounds and 9-oxysulfur

Compounds and the like are preferred.

Examples of the oxime ester-based compound include compounds having a group represented by the general formula (II), and the like, and the above-mentioned photo-radical polymerization initiators have good sensitivity and can therefore be preferably used in the polymerizable combination of the present invention. thing.

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

In the case where R ¹¹ and R ¹² and the group represented by R ¹¹ or R ¹² in the above general formula (II) are modified, the group containing a heterocyclic ring having 2 to 20 carbon atoms and the above R ² , The groups having 2 to 20 carbon atoms containing a heterocyclic ring represented by R ⁴ , R ⁶ , and Z ¹ to Z ³ are the same.

Among the compounds having a group represented by the above general formula (II), the compound represented by the following general formula (IV) has particularly high sensitivity, and thus is preferably used in the polymerizable composition of the present invention.

(式中，R¹¹ 、R¹² 及n分別與通式(II)中之R¹¹ 、R¹² 及n相同， R⁶¹ 及R⁶² 分別獨立地表示氫原子、硝基、氰基、碳原子數為1～20之烷基、碳原子數為6～20之芳基、碳原子數為7～20之芳烷基或含有雜環之碳原子數為2～20之基， X¹ 表示氧原子、硫原子、硒原子、CR⁶³ R⁶⁴ 、CO、NR⁶⁵ 或PR⁶⁶ ， X² 表示無鍵結、直接鍵、碳原子數為1～20之烴基、CO，R⁶³ ～R⁶⁶ 分別獨立地表示氫原子、碳原子數為1～20之烴基或含有雜環之碳原子數為2～20之基，且亦存在R⁶¹ ～R⁶⁶ 所表示之基中之氫原子經鹵素原子、硝基、氰基、羥基、羧基或雜環基取代之情形， 亦存在R⁶¹ ～R⁶⁶ 所表示之基中之亞甲基於氧不相鄰之條件下取代為-O-之情形， 亦存在R⁶¹ ～R⁶⁶ 分別獨立地與鄰接之任意苯環成為一體而形成環之情形， g表示0～4之數， h表示0～3之數)[Chemical 9]

(in the formula, R ¹¹ , R ¹² and n are the same as R ¹¹ , R ¹² and n in the general formula (II), respectively, and R ⁶¹ and R ⁶² independently represent a hydrogen atom, a nitro group, a cyano group, and the number of carbon atoms It is an alkyl group with 1-20 carbon atoms, an aryl group with 6-20 carbon atoms, an aralkyl group with 7-20 carbon atoms or a group containing a heterocyclic ring with 2-20 carbon atoms, X ¹ represents an oxygen atom , sulfur atom, selenium atom, CR ⁶³ R ⁶⁴ , CO, NR ⁶⁵ or PR ⁶⁶ , X ² represents no bond, direct bond, hydrocarbon group with 1 to 20 carbon atoms, CO, and R ⁶³ to R ⁶⁶ are independently Represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group containing a heterocyclic ring having 2 to 20 carbon atoms, and there is also a hydrogen atom in the group represented by R ⁶¹ to R ⁶⁶ , through a halogen atom, a nitro group , cyano group, hydroxyl group, carboxyl group or heterocyclic group is substituted, there is also the case where the methylene group in the group represented by R ⁶¹ to R ⁶⁶ is substituted with -O- under the condition that oxygen is not adjacent, and there is also R ⁶¹ to R ⁶⁶ are independently integrated with any adjacent benzene ring to form a ring, g represents the number of 0 to 4, and h represents the number of 0 to 3)

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

In the above-mentioned general formula (IV), the groups containing 2 to 20 carbon atoms containing a heterocyclic ring represented by R ⁶¹ to R ⁶⁶ and the heterocyclic groups represented by the above R ² , R ⁴ , R ⁶ and Z ¹ to Z ³ The groups having 2 to 20 carbon atoms in the ring are the same.

As a polymerization initiator (C), the oxime ester type compound preferable, for example, the compound No.C1-1 to No.C1-14 shown below is mentioned. However, the polymerization initiator (C) used in the present invention is not limited by the following compounds.

[Chemical 10]

[Chemical 11]

In the general formula (IV), when X ¹ is a sulfur atom and X ² is not bonded, it becomes an oxime ester compound having a diphenyl sulfide skeleton exemplified by the above-mentioned compound Nos. C1-1 to C1-7 , is preferable in that a polymerizable composition with good sensitivity can be obtained by using it together as a polymerization initiator.

In the general formula (IV), when X ¹ is NR ⁶⁵ and X ² is a direct bond, it becomes an oxime ester compound having a carbazole skeleton exemplified by the above-mentioned compound No. C1-8 to C1-14, and This is particularly preferable in that a polymerizable composition with good sensitivity can be obtained.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2 -Methyl propiophenone, 2-hydroxymethyl-2-methyl propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminophenethyl Ketone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylidene acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 -[4-(Methylthio)phenyl]-2-𠰌olinylacetone-1,2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-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-propan-1-one, etc.

If the α-aminoacetophenone compound having a hydroxyl group among the above-mentioned acetophenone-based compounds is used as a polymerization initiator, the resulting cured product has less liquid crystal contamination, which is preferable. Preferred examples of the α-aminoacetophenone compound having a hydroxyl group include compounds represented by the following general formula (V).

(式中，X_r 表示下述通式(i)、(ii)或(iii)所表示之結構， X_s 表示硫原子或NR¹⁰⁰ ， R¹⁰⁰ 、R¹⁰¹ 、R¹⁰² 、R¹⁰³ 及R¹⁰⁴ 分別獨立地表示氫原子、碳原子數為1～12之烷基、苯基、碳原子數為7～20之芳烷基或碳原子數為2～12之烯基，存在該烷基經羥基、羧基、鹵素原子、氰基或硝基取代之情形，且存在該苯基及該芳烷基經碳原子數為1～4之烷基、羥基、羧基、鹵素原子、氰基或硝基取代之情形， 存在R¹⁰¹ 與R¹⁰² 連結而形成3～6員環之雜環之情形，且存在於該雜環中之氮原子上鍵結有R⁹⁹ 之情形， R¹⁰³ 與R¹⁰⁴ 可連結而形成3～6員環， R¹⁰⁵ 、R¹⁰⁶ 、R¹⁰⁷ 及R¹⁰⁸ 分別獨立地表示氫原子、鹵素原子、氰基、硝基、羥基、羧基或碳原子數為1～12之烷基，存在該烷基經鹵素原子、羧基、氰基、硝基或羥基取代之情形， R⁹⁹ 表示氫原子、碳原子數為1～12之烷基、苯基、碳原子數為7～20之芳烷基或碳原子數為2～12之烯基，存在該烷基經羥基、羧基、鹵素原子、氰基或硝基取代之情形，且存在該苯基及該芳烷基經碳原子數為1～4之烷基、羥基、羧基、鹵素原子、氰基或硝基取代之情形。 存在上述所列舉之各烷基及上述各芳烷基中之亞甲基被取代為-O-、-S-、-NR¹¹⁷ -、-CO-、-CO-O-、-O-CO-或-O-CO-O-之情形。 R¹¹⁷ 表示氫原子、碳原子數為1～12之烷基、苯基、碳原子數為7～20之芳烷基或碳原子數為2～12之烯基，存在該烷基經羥基、羧基、鹵素原子、氰基或硝基取代之情形，且存在該苯基及該芳烷基經碳原子數為1～4之烷基、羥基、羧基、鹵素原子、氰基或硝基取代之情形。 其中，式(V)所表示之化合物於分子中具有至少一個羥基)[Chemical 12]

(wherein, X _r represents a structure represented by the following general formula (i), (ii) or (iii), X _s represents a sulfur atom or NR ¹⁰⁰ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ Each 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. , carboxyl group, halogen atom, cyano group or nitro group, and the phenyl group and the aralkyl group are substituted by an alkyl group with 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group In the case where R ¹⁰¹ and R ¹⁰² are linked to form a heterocycle of 3-6 membered rings, and there is a situation where R ⁹⁹ is bound to the nitrogen atom in the heterocycle, R ¹⁰³ and R ¹⁰⁴ can be linked to form a Form a 3-6 membered ring, R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group or an alkyl group with 1 to 12 carbon atoms, and there are When the alkyl group is substituted by a halogen atom, a carboxyl group, a cyano group, a nitro group or a hydroxyl group, R ⁹⁹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or an aralkane having 7 to 20 carbon atoms. group or an alkenyl group with 2 to 12 carbon atoms, the alkyl group is substituted by a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and there is a case where the phenyl group and the aralkyl group are substituted with a carbon number of 1 Substitution of alkyl, hydroxyl, carboxyl, halogen atom, cyano or nitro in ~4. Methylene groups in each of the above-listed alkyl groups and each of the above-mentioned aralkyl groups are substituted with -O-, -S -, -NR ¹¹⁷ -, -CO-, -CO-O-, -O-CO- or -O-CO-O-. R ¹¹⁷ 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, where the alkyl group is substituted by a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group, and there is a The case where the phenyl group and the aralkyl group are 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. Wherein, the compound represented by formula (V) has in the molecule at least a hydroxyl)

(式中，R¹⁰⁹ 及R¹¹⁰ 分別獨立地表示氫原子、羥基、羧基、鹵素原子或碳原子數為1～4之烷基，於p為2以上之情形時，可相同亦可不同， 式中之下述(i-1)[Chemical 13]

(In the formula, R ¹⁰⁹ and R ¹¹⁰ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and when p is 2 or more, they may be the same or different, formula of the following (i-1)

所表示之結構中之亞甲基亦可-O-、-S-、-NR¹¹⁷ 、-CO-、-CO-O-、-O-CO-或-O-CO-O-取代， R¹¹¹ 表示氫原子、鹵素原子、羥基、羧基、氰基、胺基或苯基，存在該苯基經碳原子數為1～4之烷基、羥基、羧基、鹵素原子、氰基或硝基取代之情形，p表示1～12之數)[Chemical 14]

The methylene group in the represented structure can also be substituted by -O-, -S-, -NR ¹¹⁷ , -CO-, -CO-O-, -O-CO- or -O-CO-O-, 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, and the phenyl group is substituted by an alkyl group with 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a halogen atom, a cyano group or a nitro group case, p represents a number from 1 to 12)

(式中，R¹¹² 、R¹¹³ 、R¹¹⁴ 、R¹¹⁵ 及R¹¹⁶ 分別獨立地表示氫原子、鹵素原子、氰基、硝基、羥基或碳原子數為1～12之烷基，存在該烷基經鹵素原子、氰基、硝基或羥基取代之情形，且存在該烷基中之亞甲基被取代為-O-、-S-、-NR¹¹⁷ 、-CO-、-CO-O-、-O-CO-或-O-CO-O-之情形， 存在R¹⁰⁶ 或R¹⁰⁷ 與R¹¹² 或R¹¹⁶ 鍵結而形成環之情形)[Chemical 15]

(in the formula, R ¹¹² , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ and R ¹¹⁶ each independently represent 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, and the alkane exists The case where the group is substituted by a halogen atom, a cyano group, a nitro group or a hydroxyl group, and the methylene group in the alkyl group is substituted with -O-, -S-, -NR ¹¹⁷ , -CO-, -CO-O- , -O-CO- or -O-CO-O-, there is a case where R ¹⁰⁶ or R ¹⁰⁷ is bonded to R ¹¹² or R ¹¹⁶ to form a ring)

(式中，R¹⁰¹ 、R¹⁰² 、R¹⁰³ 、R¹⁰⁴ 、R¹⁰⁵ 、R¹⁰⁶ 、R¹⁰⁷ 及R¹⁰⁸ 與上述通式(V)相同，R¹⁰⁹ 、R¹¹⁰ 及p與上述通式(i)相同)[Chemical 16]

(wherein, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are the same as the above general formula (V), and R ¹⁰⁹ , R ¹¹⁰ and p are the same as the above general formula (i) same)

Each of the alkyl groups having 1 to 12 carbon atoms described above in the description of the general formula (V) includes, for example, the hydrocarbon groups having 1 to 20 carbon atoms in the general formula (I) above. The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is 1 to 12.

Each of the alkyl groups having 1 to 4 carbon atoms described above as an explanation of the general formula (V) can be exemplified as an example of the hydrocarbon group having 1 to 20 carbon atoms in the above general formula (I). An alkyl group having 1 to 20 carbon atoms, and one of the above-mentioned ones having 1 to 4 carbon atoms.

Examples of the aralkyl groups having 7 to 20 carbon atoms described above for the description of the general formula (V) include benzyl, α-methylbenzyl, and α,α-dimethylbenzyl. , phenylethyl, etc.

Each of the alkenyl groups having 2 to 12 carbon atoms described above as an illustration of the general formula (V) includes vinyl, 1-propenyl, 2-propenyl, isopropenyl, and 1-butene. group, 2-butenyl, 3-butenyl, 1-octenyl, 1-decenyl and the like.

As the heterocyclic ring of 3-6 membered ring which can be formed by linking R ¹⁰¹ and R ¹⁰² in the general formula (V), for example, a piperidine ring, a piperidine ring, an oxaline ring, and a lactamide ring can be preferably mentioned. Wait.

As a 3- to 6-membered ring that can be formed by linking R ¹⁰³ and R ¹⁰⁴ in the general formula (V), for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a lactone ring, Lactamide ring, etc.

As the ring formed by R ¹⁰⁶ or R ¹⁰⁷ in the general formula (V) bonded with R ¹¹² or R ¹¹⁶ , the structure in which X _s and the adjacent benzene rings are combined together can include: carbazole ring, thien ring , dibenzothiophene ring.

As each halogen atom described above as an explanation in the general formula (V), fluorine, chlorine, bromine, and iodine are exemplified.

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

[Chemical 17]

As said benzil compound, benzil etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4 , 4'-Dichlorobenzophenone and 4-benzyl-4'-methyl diphenyl sulfide, etc.

系化合物，可列舉：9-氧硫𠮿

、2-甲基-9-氧硫𠮿

、2-乙基-9-氧硫𠮿

、2-氯-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、2,4-二乙基-9-氧硫𠮿

等。As the above-mentioned 9-oxosulfur 𠮿

series of compounds, such as: 9-oxosulfur 𠮿

, 2-methyl-9-oxothio

, 2-ethyl-9-oxothio

, 2-chloro-9-oxysulfur

, 2-isopropyl-9-oxothio

, 2,4-diethyl-9-oxothio

Wait.

Examples of other radical polymerization initiators include phosphine oxide-based compounds such as 2,4,6-trimethylbenzyldiphenylphosphine oxide, and bis(cyclopentadienyl)-bis[2,6 -Titanocene compounds such as difluoro-3-(pyrrol-1-yl)]titanium, etc.

Commercially available free radical initiators include: Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, NCI-930 (the above are manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (the above are manufactured by BASF Corporation); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (the above are manufactured by TRONLY Corporation), etc. .

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 can be exemplified. better.

As the azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl isobutyrate), 2,2'-azobis-2,4- Dimethylvaleronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), etc.

Examples of peroxides include benzyl peroxide, di-tert-butyl benzyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butyl peroxydicarbonate) hexyl ester) etc.

As persulfate, persulfate, such as ammonium persulfate, sodium persulfate, and potassium persulfate, etc. are mentioned.

Among the above-mentioned polymerization initiators (C), a polymerization initiator having a hydroxyl group is particularly preferable because a display device having low liquid crystal contamination properties and excellent electrical properties can be provided.

The above-mentioned polymerization initiator (C) can be used by 1 type or in mixture of 2 or more types exemplified so far.

In the polymerizable composition of the present invention, the content of the above-mentioned polymerization initiator (C) is not particularly limited, but is preferred in terms of good self-curing properties relative to 100 parts by mass of the alkaline developable compound (B). It is 0.1-20 mass parts, More preferably, it is 0.3-10 mass parts, More preferably, it is 0.3-5 mass parts. 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, which is preferable. For example, in the case of forming a cured film with a thickness of 2 to 5 μm, the content of the polymerization initiator (C) is not particularly limited. The total amount of the agent (C) 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.

An ethylenically unsaturated compound may be further added to the polymerizable composition of the present invention. By adding an ethylenically unsaturated compound, the sensitivity and chemical resistance are improved, which is preferable. The said ethylenically unsaturated compound is a compound which has an ethylenically unsaturated bond, and is not the said alkali developable compound (B). Examples of ethylenically unsaturated compounds include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, Zhongkang acid, mono[2-(meth)acryloyloxyethyl succinate], mono[2-(meth)acryloyloxyethyl phthalate], ω-carboxypolycaprolactone mono(methyl) Mono(meth)acrylates of polymers with carboxyl groups and hydroxyl groups at both ends, such as acrylates; (meth)acrylate hydroxyethyl-maleate, (meth)acrylate-hydroxypropyl-maleic acid Unsaturated polybasic acids such as esters, dicyclopentadiene-maleate or polyfunctional (meth)acrylates with one carboxyl group and two or more (meth)acryloyl groups; (meth)acrylic acid-2- Hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following acrylic compounds No.1 to No.4, methyl (meth)acrylate, (meth) Butyl 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, (methyl) ) poly(ethoxy) ethyl acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate Tetrahydrofuran acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylic acid ester, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate ester, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tris[(meth)isocyanurate Esters of unsaturated monobasic acids such as meth)acryloylethyl]esters, polyester (meth)acrylate oligomers, and polyols or polyphenols; zinc (meth)acrylates, magnesium (meth)acrylates, etc. Metal salts of unsaturated polybasic acids; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5 -(2,5-two Pendant tetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride , Anhydrides of unsaturated polybasic acids such as methylbicycloheptenedicarboxylic acid anhydride; (meth)acrylamide, methylenebis(meth)acrylamide, diethylenetriamine tri(meth)acrylamide Amines of unsaturated monobasic acids and polyamines such as amines, xylylene bis(meth)acrylamides, α-chloroacrylamides, N-2-hydroxyethyl(meth)acrylamides, and polyamines; acrolein and other unsaturated aldehydes; (meth)acrylonitrile, α-chloroacrylonitrile, dicyanide, allyl nitrile and other unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4- -Methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidol Vinyl ethers such as ethers; unsaturated imines such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; 1 ,3-butadiene, isoprene, chloroprene and other aliphatic conjugated dienes; polystyrene, poly(methyl)acrylate, poly(n-butyl)(meth)acrylate, polysilicon Oxane and other macromonomers with a mono(meth)acryloyl group at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triphosphate Allyl ester, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and Vinyl urethane compound of polyisocyanate compound, vinyl monomer containing hydroxyl group and vinyl epoxy compound of polyepoxy compound. The above-mentioned ethylenically unsaturated compounds may be used alone or in combination of two or more.

As the said ethylenically unsaturated compound, a commercial item can also be used. Examples of such commercial products include Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, and R-684 (the above are manufactured by Nippon Kayaku Co., Ltd.); ARONIX M-215, M -350 (above manufactured by Toagosei Co., Ltd.); NK-ESTER A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ); SPC-1000, SPC-3000 (the above are manufactured by Showa Denko Corporation); 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 (the above are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, AI-600, UA-101T, UA-101I, UA -306T, UA-306I (the above are 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 (the above are manufactured by Negami Industries ), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (made by Sartomer Company), EBECRYL8810 (made by Daicel), etc.

[Chemical 18]

[Chemical 19]

[hua 20]

[Chemical 21]

In the polymerizable composition of the present invention, the content of the ethylenically unsaturated compound is not particularly limited, and is relative to the colorant (A), the alkaline developable compound (B), the polymerization initiator (C) and the ethylenically unsaturated compound. 1-50 mass parts is preferable with respect to 100 mass parts of total saturated compounds, 1-30 mass parts is more preferable, 5-20 mass parts is still more preferable. When the content of the ethylenically unsaturated compound is within the above-mentioned range, the cured product obtained is excellent in curability and light-shielding property, which is preferable. For example, in the case of forming a cured film with a thickness of 1 to 3 μm, the content of the ethylenically unsaturated compound is not particularly limited. The amount of the ethylenically unsaturated compound 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, based on 100 parts by mass in total of B) and the ethylenically unsaturated compound.

A solvent may be further added to the polymerizable composition of the present invention. As the solvent, a solvent capable of dissolving or dispersing the above-mentioned components (colorant (A), alkaline developable compound (B), polymerization initiator (C), ethylenically unsaturated compound, etc.) is usually used as necessary. For example, ketone-based solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-acetic acid Propyl, isopropyl acetate, n-butyl acetate, 3-methoxybutyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and TEXANOL and other ester solvents; ethylene glycol monomethyl ether and Cellosolve solvents such as ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and Ether ester solvents such as ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine, D-limonene and pinene Terpene-based hydrocarbon oils such as alkene; paraffin-based solvents such as mineral spirits, Swasol #310 (the above are manufactured by Cosmo Pine Mountain Oil Co., Ltd.) and Solvesso #100 (the above are manufactured by Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloromethane Halogenated aliphatic hydrocarbon-based solvents such as vinyl chloride, dichloromethane, and 1,2-dichloroethane; halogenated aromatic hydrocarbon-based solvents such as chlorobenzene; carbitol-based solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile , carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and water, etc. These solvents can be used as one or as Two or more mixed solvents are used.

Among them, ketone-based solvents, ester-based solvents, ether-ester-based solvents, etc., especially cyclohexanone, 3-methoxybutyl acetate, dimethyl succinate, and PGMEA, etc., are resistant to corrosion in polymerizable compositions. The compatibility between the agent and the polymerization initiator is good and preferable.

If PGMEA, 3-methoxybutyl acetate, and dimethyl succinate are used in combination, a uniform coating surface is obtained, so it is preferable to further use the above-mentioned solvent mass ratio (PGMEA: 3-methoxybutyl acetate: Dimethyl succinate) is especially preferable when it is 15-25:2-5:1.

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, in 100% by mass of the total amount of the polymerizable composition. When the content of the solvent is in the above-mentioned range, the workability (viscosity or wettability of the polymerizable composition), the reduction of unevenness during drying, and the liquid stability (not accompanied by the components contained in the composition) A polymerizable composition with excellent precipitation or precipitation) is preferable because the thickness of the hardened product can be appropriately controlled when the hardened product is obtained.

In the polymerizable composition of the present invention, epoxy compounds, alkaline developability imparting agents, dispersants, latent additives, organic polymers, inorganic compounds, coupling agents, chain transfer agents, sensitizers, Surfactants and melamine compounds, p-anisole, hydroquinone, catechol, tertiary butylcatechol and phenothiazine and other thermal polymerization inhibitors; plasticizers; then accelerators; fillers; Foaming agent; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anti-agglomeration agent; catalyst; effect accelerator; cross-linking agent; tackifier, etc.

As said epoxy compound, methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, phenyl- 2-Methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2 -Methyl octyl glycidyl ether, phenyl glycidyl ether, 4-n-butyl phenyl glycidyl ether, 4-phenylphenol glycidyl ether, tolyl glycidyl ether, dibromotolyl glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether Glyceryl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol Glycidyl ethers such as alcohol diglycidyl ether, 1,1,2,2-tetrakis(glycidyloxyphenyl)ethane, and pentaerythritol tetraglycidyl ether; glycidyl acetate, glycidyl stearate, etc. Glycerides; 2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methyldiethane, methylenebis(3,4-epoxy) cyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylidene bis(3 ,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl adipate), 3,4-epoxycyclohexanecarboxylate 3,4-epoxycyclohexylmethyl Esters, 3,4-epoxy-1-methylhexanecarboxylic acid 3,4-epoxy-1-methylhexyl ester, 6-methyl-3,4-epoxycyclohexanecarboxylic acid 6-methyl 3,4-epoxycyclohexylmethyl ester, 3,4-epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethylester, 3,4-cyclohexylmethyl ester Oxy-5-methylcyclohexanecarboxylic acid 3,4-epoxy-5-methylcyclohexylmethyl ester, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxycyclohexane -2-Epoxyethylcyclohexane, Diepoxydicyclopentadiene, 3,4-Epoxy-6-Methylcyclohexylcarboxylate, α-Pinene Oxide, Ethylene Oxide, Cyclo Epoxycycloalkyl compounds such as oxycyclohexane and epoxycyclopentane, and N-glycidylphthalimide, etc.

As said epoxy compound, an epoxidized polyolefin can also be used. The so-called epoxidized polyolefin refers to a polyolefin in which an epoxy group is introduced by modifying the polyolefin with a monomer containing an epoxy group. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and other monomers as needed by any method of a copolymerization method or a graft method. Ethylene or α-olefin having 3 to 20 carbon atoms, epoxy group-containing monomer and other monomers can be polymerized separately, or they can be polymerized with other monomers in plural. Moreover, it can also be obtained by epoxidizing the double bond of the non-conjugated polybutadiene which has a hydroxyl group at the terminal by a peracetic acid method, and what has a hydroxyl group in a molecule|numerator can also be used. Moreover, an epoxy group can also be introduce|transduced by urethane-forming a hydroxyl group with an isocyanate, and making the epoxy compound containing a primary hydroxyl group react here.

Examples of the ethylene or α-olefin having 3 to 20 carbon atoms include ethylene, propylene, butene, isobutylene, 1,3-butadiene, 1,4-butadiene, and 1,3-pentadiene. , 2,3-dimethyl-1,3-butadiene, pentadiene, 3-butyl-1,3-octadiene and isoprene, etc.

As said epoxy group containing monomer, the glycidyl ester of alpha, beta-unsaturated acid, vinylbenzyl glycidyl ether, allyl glycidyl ether, etc. are mentioned, for example. Specific examples of the glycidyl ester of the α,β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferred.

As the above-mentioned epoxy compound, a commercially available product can also be commonly used. Examples of suitable commercial products include: Epolight 40E, 1500NP, 1600, 80MF, 4000, and 3002 (the above are manufactured by Kyoeisha Chemical Co., Ltd.); Adeka Glycilol 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 (the above are manufactured by ADEKA) ;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 (the above are manufactured by Nagase Chemical Co., Ltd.); EHPE-3150, Celloxide 2021P, 2081, 2000 and 3000 (The above are manufactured by Daicel Corporation); EPIOL M, EH, L-41, SK, SB, TB, and OH (the above are manufactured by NOF Corporation); Epolight M-1230 and 100MF (the above are manufactured by Kyoeisha Chemical Corporation) ; ARONE OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (the above are manufactured by Toa Gosei Corporation); Etanacol OXBP and OXTP (the above are manufactured by Ube Industries Ltd.) ; 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether (the above are manufactured 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 (manufactured by Nagase Kasei Co., Ltd. above); OGSOL PG-100, EG-200, EG-210 and EG-250 (manufactured by Osaka Gas Chemicals Co., Ltd. above); HP4032, HP4032D and HP4700 (above by DIC ESN-475V (manufactured by Todo Chemical Co., Ltd.); Marproof G-0105SA and G-0130SP (manufactured by NOF Corporation above); EPICLON N-665 and HP-7200 (above by DI C company); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (the above are manufactured by Nippon Kayaku) company) etc.

The above-mentioned alkaline developability imparting agent is a compound imparting alkaline developability that does not have radical polymerizability, and as such a compound, if it is a compound that is soluble in an alkaline aqueous solution due to its acid value, it does not have any properties. In particular, as a representative compound, an alkali-soluble novolak resin (hereinafter abbreviated as "novolak resin") can be mentioned. Novolak resins can be obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

As the above-mentioned phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol are used. , 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethyl Phenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, alpha-naphthol, bisphenol A, dihydroxybenzoate and Stolic acid esters, etc. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-xylenol are preferred Trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A, etc. These phenols can be used individually or in mixture of 2 or more types.

As said aldehydes, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzene can be used. Formaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzene Formaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, etc. Among these compounds, formaldehyde, acetaldehyde, benzaldehyde, etc. are preferred. These aldehydes may be used alone or in combination of two or more. The aldehydes are used in a ratio of preferably 0.7 to 3 moles, more preferably 0.7 to 2 moles per 1 mole of the phenols.

As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid can be used. The usage amount of these acid catalysts is preferably 1×10 ^-4 to 5×10 ^-1 moles per 1 mole of phenols. In the condensation reaction, water is usually used as the reaction medium, but the phenols used in the condensation reaction are not dissolved in the aqueous solution of aldehydes, and the hydrophilicity can also be used when the system becomes a heterogeneous system from the initial stage of the reaction. The solvent serves as the reaction medium. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol, and butanol, and cyclic ethers such as tetrahydrofuran and diethylene. The usage-amount of these reaction media is usually 20-1000 mass parts per 100 mass parts of reaction raw materials. The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, and is usually 10 to 200°C, preferably 70 to 150°C. After the condensation reaction is over, in order to remove the unreacted raw materials, acid catalyst and reaction medium in the system, the internal temperature is generally raised to 130-230°C, and the volatiles are removed by distillation under reduced pressure. The resin is cast on a steel belt or the like and recovered. Moreover, it can also be recovered by the following method: after the condensation reaction is completed, the reaction mixture is dissolved in the aforementioned hydrophilic solvent, and added to a precipitating agent such as water, n-hexane and n-heptane, whereby the novolak resin is precipitated, The precipitate was separated and dried by heating.

As an example other than the said novolak resin, a polyhydroxystyrene or its derivative(s), a styrene-maleic anhydride copolymer, polyvinyl benzoate, etc. are mentioned.

As the above-mentioned dispersing agent, any one can be used as long as it can disperse and stabilize the colorant (A), and commercially available dispersing agents such as BYK series manufactured by BYK-Chemie, Inc. can be suitably used. Polyester, polyether and polyurethane polymer dispersants with basic functional groups, with nitrogen atom as basic functional group, the functional group with nitrogen atom is amine and/or its quaternary salt, amine value 1 to 100 mgKOH/g.

The above-mentioned latent additives are inert in normal temperature, light exposure step and pre-baking step, and are protected by heating at 100-250°C, or heating at 80-200°C in the presence of acid/alkali catalyst. Activated by detachment from the base. Antioxidation, ultraviolet absorption, antifouling property, recoatability, adhesiveness, etc. are mentioned as an effect acquired by activating. As the above-mentioned latent additive, those described in the specification of WO2014/021023 can be preferably used.

As said latent additive, a commercial item can be used, for example, ADEKA ARKLS GPA-5001 etc. are mentioned.

Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, polyurethane resin, poly Carbonate, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamide resin, epoxy resin, etc., Among these, polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferable. The characteristics of hardened|cured material can also be improved by using the said organic polymer together with the said alkali developable compound (B). When an organic polymer is used, it is preferable that the usage-amount is 10-500 mass parts with respect to 100 mass parts of said alkali developable compounds (B).

The above-mentioned inorganic compounds 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 oxide, and aluminum oxide; layered clay minerals, Milo Blue blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, selenide, aluminum silicate, calcium silicate, hydroxide Aluminum, platinum, gold, silver, copper, etc., among these, titanium oxide, silicon oxide, layered clay minerals, and silver are preferred.

Since the polymerizable composition of the present invention contains an inorganic compound, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form calcination patterns such as partition wall patterns, dielectric patterns, electrode patterns, and black matrix patterns between plasma display panels. Moreover, these inorganic compounds can also be used as a filler, an antireflection agent, a conductive agent, a stabilizer, a flame retardant, a mechanical strength improving agent, a special wavelength absorber, an ink repellent agent, etc., for example.

When adding an inorganic compound 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 100 parts by mass relative to 100 parts by mass of the alkaline developable compound (B). One or more of these inorganic compounds may be used in an amount of 20 parts by mass.

As the above-mentioned coupling agent, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and methyltrimethoxysilane can be used. alkyl-functional alkoxysilanes such as methylsilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltrimethoxysilane Ethoxysilane, allyltrimethoxysilane and other alkenyl functional alkoxysilanes, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane Silane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 2-methacryloyloxypropyltrimethy (Meth)acrylate functional alkoxysilanes such as oxysilanes, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3 ,4-Epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane and other epoxy functional alkoxysilanes, N-β(aminoethyl) Amino-functional alkoxysilanes such as)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. , mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane Urea-functional alkoxysilanes such as silane, isocyanurate-functional alkoxysilanes such as tris(trimethoxysilylpropyl)isocyanurate, titanium tetraisopropoxide, tetra-n-butanol Titanium alkoxides such as titanium, titanium chelates such as dioctyl titanium bis(octanediol), diisopropoxide titanium bis(ethyl acetate), zirconium tetraacetylpyruvate, tributoxide Zirconium chelates such as zirconium monoacetyl pyruvate, zirconium chelates such as zirconium tributoxy monostearate, isocyanate silanes such as methyl triisocyanate silane, etc. By adding a coupling agent, the adhesiveness between the cured product and the substrate (especially glass) can be improved, which is preferable.

As said coupling agent, a commercial item can be used, for example, 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 (the above are manufactured by Shin-Etsu Silicone Co., Ltd.), etc.

As said chain transfer agent and a sensitizer, the compound containing a sulfur atom is generally used. For example, 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)aminocarbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercapto Propionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic 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 -Sulfhydryl compounds such as 3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate); Disulfide compounds obtained by oxidation, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid and other iodoalkyl compounds; trimethylolpropane tris(3-mercapto) isobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-mercaptopropionate, butyl Glycol Dimercaptoacetate, Ethylene Glycol Dimercaptoacetate, Trimethylolpropane Trimercaptoacetate, Butylene Glycol Dimercaptopropionate, Trimethylolpropane Trimercaptopropionate, Trihydroxy Methylpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, the following compound No. C1, Karenz PE1 and NR1 manufactured by Showa Denko Corporation, etc.

[Chemical 22]

Since the pattern of the hardened|cured material obtained by adding the said chain transfer agent and a sensitizer becomes high-definition, it is preferable.

As the above-mentioned surfactant, fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carbonates, and anionic surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates can be used , cationic surfactants such as higher amine hydrohalide and quaternary ammonium salt, non-ionic interface such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, etc. Surfactants such as active agents, amphoteric surfactants, and silicone-based surfactants can also be used in combination.

Examples of the melamine compound include active hydroxyl groups in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. A compound obtained by etherifying all or a part of (at least two) alkyl groups of methyl groups (CH ₂ OH groups). Here, a methyl group, an ethyl group, and a butyl group are mentioned as an alkyl group which comprises an alkyl ether, and may be mutually the same or different. In addition, the methylol group which is not alkyl-etherified can be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component is formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, alkyl-etherified melamine such as hexamethoxymethyl melamine and hexabutoxymethyl melamine is preferable.

In the polymerizable composition of the present invention, the content of any components other than the colorant (A), the alkaline developable compound (B), the polymerization initiator (C), the ethylenically unsaturated compound, the solvent and the inorganic compound may be It is appropriately selected according to the purpose of use, and is not particularly limited as long as the effect of the present invention is not impaired, but it is preferably a polymerization initiator (C), a colorant (A), and an alkaline developable compound (B) and the total of 100 parts by mass of the ethylenically unsaturated compound, the total is 20 parts by mass or less.

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

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

The polymerizable composition, the photosensitive composition for BM, the photosensitive composition for BCS, and the cured product of the present invention can be used for curable paints, varnishes, curable adhesives, printed substrates, display devices (color TVs, PC monitors, portable Color filters in liquid crystal display panels for color displays such as digital information terminals and digital cameras, color filters for various display applications, color filters for CCD image sensors, touch panels, electroluminescent display devices (micro LED spacer material), plasma display panel, black spacer for organic EL, powder coating, printing ink, printing plate, adhesive, gel coat, photoresist for electronic engineering, electroplating resist, Etching resists, solder resists, insulating films, black matrices, and resists for structure formation in LCD manufacturing steps, compositions for encapsulating electrical and electronic parts, solder resists, magnetic recording materials, micro Mechanical parts, waveguides, optical switches, masks for plating, etching masks, color test systems, coating of fiberglass cables, stencils for screen printing, materials for the manufacture of three-dimensional objects by stereolithography, holograms Recording materials, image recording materials, fine electronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible light Various applications such as photoresist materials for laser direct imaging systems, photoresist materials used in the formation of dielectric layers in the sequential lamination of printed circuit boards, and protective films, etc. Suitable for use in display devices in the above-mentioned applications.

The display device of the present invention has the same structure as the previously known display device except that it has the cured product (especially the BCS) of the present invention, and the BCS is preferably provided between the units.

In the case of using the polymerizable composition of the present invention as a black partition wall of organic EL, it is preferable to use a material having a weight average molecular weight of 5,000 or more in view of verticalization of the pattern shape, improvement of development adhesion, and improvement of heat resistance. As an alkali developable compound, it is more preferable to use the alkali developable compound with a weight average molecular weight of 7000-15000. Furthermore, it is especially preferable when the alkali-developable compound is an unsaturated compound having a structure obtained by an esterification reaction having on the epoxy compound represented by the following general formula (III) Esterification reaction of epoxy addition compound with unsaturated monobasic acid structure and polybasic acid anhydride.

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

The polymerizable composition of the present invention, the photosensitive composition for BM, and the photosensitive composition for BCS can be applied by a spin coater, a roll coater, a bar coater, a die coater, or a curtain coater. Known means such as a coater, various printing, and dipping are used for supporting substrates such as soda glass, quartz glass, semiconductor substrates, metals, paper, and plastics. In addition, after being temporarily applied to a support substrate such as a film, it may be transferred onto another support substrate, and the method of application thereof is not limited.

Moreover, as the light source of the energy ray used when the polymerizable composition of the present invention, the photosensitive composition for BM, and the photosensitive composition for BCS are cured, there can be used an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, 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. Electromagnetic wave energy of angstrom wavelength or high-energy rays such as electron beam, X-ray, radiation, etc., preferably ultra-high pressure mercury lamp, mercury vapor arc lamp, carbon arc lamp, xenon arc lamp, etc. .

Furthermore, by using laser light as the exposure light source, the direct laser writing method in which a direct image is formed from digital information such as a computer without using a mask can not only improve productivity, but also achieve resolution and positional accuracy. Therefore, it is useful. The laser light can be suitably used with light with a wavelength of 340 to 430 nm, excimer lasers, nitrogen lasers, argon ion lasers, helium-cadmium lasers, helium-neon lasers, Krypton ion lasers, various semiconductor lasers, and YAG lasers emit light from the visible to infrared regions. In the case of using these lasers, sensitizing dyes that absorb in this region from visible to infrared can be added.

In the case of curing by heating, prebake at 70 to 100° C. for 100 seconds, remove the solvent, and then heat at 150° C. to 250° C. for 30 minutes to 1 hour for curing. If the curing temperature is lower than 150°C, sufficient curing may not occur, and if it is 250°C or higher, coloring or decomposition of the cured film may occur.

The cured product of the present invention is particularly useful as BCS. BCS can be 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) irradiating the coating film through a mask having a specific pattern shape The radiation step, (3) the post-exposure baking step, (4) the step of developing the film after exposure, and (5) the step of heating the film after the development. As the above-mentioned mask, a multi-step mask such as a halftone mask or a grayscale mask can also be used. [Example]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[Production Example 1] Preparation of lactamide black dispersion liquid A-1 An organic black pigment (Black 582 as lactamide black; manufactured by BASF), a dispersant (BYK-167), and a pigment for dispersion The polymer (the alkaline developable compound PGMEA solution B-2 described later) was mixed at 16 parts by mass, 3.2 parts by mass, and 3.6 parts by mass, respectively, and then propylene glycol monomethyl ether was weighed so that the solid content concentration would be 25% by mass. Acetate (PGMEA) was added to this mixture to make a mixture. After premixing the above mixture with a stirrer, zirconia beads with a diameter of 0.3 mm were added in the same weight as the dispersion (with the solvent PGMEA removed from the mixture), which was carried out at a temperature of 25 to 60 ° C for 6 hours. The dispersion was treated with a paint shaker, and then the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion liquid, it adjusted so that the dispersion concentration might be 20 mass %, and after making it uniform by a stirrer, lactamide black dispersion liquid A-1 was obtained.

[Production Example 2] Preparation of perylene black dispersion liquid A-2 An organic black pigment [C.I. Pigment Black 31 as perylene black (Paliogen Black S 0084; manufactured by BASF)], a dispersant (BYK-167) and The polymer of the dispersion (the alkaline developable compound PGMEA solution B-2 described later) was mixed at 12 parts by mass, 3.6 parts by mass, and 8 parts by mass, respectively, and then weighed so that the solid content concentration would be 25% by mass. Propylene glycol monomethyl ether acetate (PGMEA) was added to this mixture to prepare a mixture. After premixing the above mixture with a stirrer, zirconia beads with a diameter of 0.3 mm were added in the same weight as the dispersion (with the solvent PGMEA removed from the mixture), which was carried out at a temperature of 25 to 60 ° C for 6 hours. The dispersion was treated with a paint shaker, and then the zirconia beads were removed using a filter to obtain a dispersion. PGMEA was added to the obtained dispersion liquid, it adjusted so that the dispersion concentration might be 20 mass %, and after making it uniform by a stirrer, perylene black dispersion liquid A-2 was obtained.

[Production Example 3] Preparation of Carbon Black Dispersion Liquid A-3 20 parts by mass of MA100 (manufactured by Mitsubishi Chemical Corporation) as carbon black, and 12.5 parts by mass of BYK161 (manufactured by BYK-Chemie (BYK) Co., Ltd.) as a dispersant (solid 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 liquid A-3.

[Production Example 4] Preparation of alkaline developable compound PGMEA solution B-2 was charged with 184 g of 1,1-bis[4-(2,3-glycidoxy)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 stirred at 120° C. for 16 hours. The reaction liquid was cooled to room temperature, 160 g of PGMEA, 59 g of biphenyltetracarboxylic dianhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120° C. for 4 hours. Furthermore, 20 g of tetrahydrophthalic anhydride was added, followed by stirring at 120°C for 4 hours, at 100°C for 3 hours, at 80°C for 4 hours, at 60°C for 6 hours, and at 40°C After 11 hours, 128 g of PGMEA was added to obtain an alkaline developable compound B-2 (Mw=5000, Mn=2100, acid value (solid content): 92.7 mgKOH/g) as a PGMEA solution. The content rate of the alkaline developable compound in the alkaline developable compound PGMEA solution B-2 was 45 mass %.

[Production Example 5] Production of alkaline developable compound PGMEA solution B-3 75.0 g of 9,9-bis(4-glycidyloxyphenyl)pyrene, 23.8 g of acrylic acid, 2,6-bis-tertiary Butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g, and PGMEA 65.9 g, stirred at 90°C for 1 hour, at 100°C for 1 hour, at 110°C for 1 hour, and at 120°C under stirring 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 the mixture was stirred at 100° C. for 5 hours. Furthermore, 30.0 g of 9,9-bis(4-glycidyloxyphenyl)pyrene, 0.269 g of 2,6-di-tert-butyl-p-cresol, and 1.50 g of PGMEA were added, and the mixture was stirred at 90° C. for 90 minutes. , after stirring for 4 hours at 120°C, 122.2 g of PGMEA was added to obtain the target alkaline developable compound B-3 in the form of a PGMEA solution (Mw=4190, Mn=2170, acid value (solid content): 52 mg・KOH/g). The content rate of the alkaline developable compound in the alkaline developable compound PGMEA solution B-3 was 45 mass %.

[Examples 1 to 15 and Comparative Examples 1 to 4] Preparation of polymerizable compositions The components were mixed according to the compositions of [Table 1] to [Table 4] to obtain polymerizable compositions (Examples 1 to 15 and Comparative Examples Examples 1 to 4). In addition, the numerical value of the composition in the table|surface represents a mass part. In addition, the symbol of each component in the table|surface represents the following component. A1-1 Lactamide black dispersion A-1 A1-2 Perylene black dispersion A-2 A2-1 Carbon black dispersion A-3 B-1 CCR-1171H [Alkaline development represented by general formula (I) The solid content of PGMEA solution is 69.5%; manufactured by Nippon Kayaku Co., Ltd.] B-2 Alkaline developable compound PGMEA solution B-2 B-3 Alkaline developable compound PGMEA solution B-3 C-1 Compound No.C1 -1 C-2 Compound No. C1-8 C-3 Compound No. C2-1 D-1 Kayarad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku Co., Ltd.) D-2 UA-306H (Acrylic urethane Esters, manufactured by Kyeisha Chemical Co., Ltd.) D-3 M-450 (ethylenically unsaturated compound; manufactured by Toagosei Co., Ltd.) E-1 γ-glycidoxypropyltrimethoxysilane (coupling agent) E-2 Karenz PE-1 (thiol compound; manufactured by Showa Denko Corporation) F-1 PGMEA F-2 3-methoxybutyl acetate F-3 dimethyl succinate

[Evaluation of Cured Products Obtained from Polymerizable Compositions] 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 property (OD) in the following order. value), relative permittivity, low liquid crystal contamination (VHR), chemical resistance and transmittance at 780 nm. The results are collectively described in [Table 1] to [Table 4].

(Elastic Recovery Rate) The polymerizable compositions of Examples 1 to 15 and the comparative polymerizable compositions of Comparative Examples 1 to 3 were coated on a glass substrate by spin coating (3 μm thickness, 300 rpm×7 seconds), After drying, prebaking was performed at 90° C. for 100 seconds to remove the solvent. Next, after exposure to 100 mJ/cm ² by a high-pressure mercury lamp using a photomask, development was performed using a 0.04 wt % KOH aqueous solution. Then, it heated at 230 degreeC for 30 minutes, and formed a pattern. On the 20 μm portion of the obtained pattern, a load-unload test was performed with a load of 40 mN using a dynamic microhardness tester DUH-211 from Shimadzu Corporation. The elastic response rate (%) was calculated by the following formula. Elastic recovery rate (%) = [(recovery distance/compression displacement) × 100] Hardened material with elastic recovery rate (%) of 60% or more can be used as BCS, and elastic recovery rate (%) of hardened material of 70% or more It can be preferably used as a BCS, and a cured product with an elastic recovery rate (%) of 80% or more can be preferably used as a BCS.

(OD value) 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, dried, and then dried at 90°C. Pre-bake for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, it baked at 230 degreeC for 30 minutes, and set it as a hardened|cured material. The OD value of the obtained film was measured using a Macbeth transmission densitometer, the OD value was divided by the film thickness after post-baking, and the OD value per unit film thickness was calculated. Cured products with an OD value of 1.0 or more per unit thickness can be used as general-purpose BCS, and cured products with an OD value of 1.5 or more per unit thickness have high light-shielding properties, so they can be used as high-light-shielding BCS. A cured product with an OD value of 1.75 or more can be preferably used as a high light-shielding BCS, and a cured product with an OD value of 2.0 or more per film thickness can be preferably used as a BCS. Cured products whose OD value per unit thickness is less than 1.0 cannot be used as BCS.

(Relative dielectric constant) 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 thickness, 300 rpm×7 seconds) and dried After that, pre-baking was performed at 90°C for 100 seconds, and after exposure at 100 mJ/cm ² by a high-pressure mercury lamp without using a mask, heating at 230°C for 180 minutes was performed to prepare the above-mentioned evaluation sample. (Evaluation method) The above-mentioned evaluation samples were measured by applying AC1V and 1 kHz using an LCR meter, Agilent's 4284A. Hardened materials with a relative permittivity of less than 5.0 can be used as BCS. Hardened materials with a relative permittivity of less than 4.5 can be used as BCS. Hardened materials with a relative permittivity of less than 4.0 can be used as BCS. Use it well. A cured product with a relative permittivity of 5.0 or more cannot be used as BCS.

(VHR) The polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were coated on a glass substrate (100 mm×100 mm) using a spin coater, and then Pre-baking was performed at 90°C for 100 seconds to form a coating film with a thickness of 3.0 μm. Next, using a mirror projection alignment exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet rays at an irradiation dose of 200 mJ/cm ² without a mask. Then, post-baking was performed at 230 degreeC for 30 minutes. 1 part by mass of the coating film after post-baking was mixed with 40 parts by mass of liquid crystal "RS-182" manufactured by ADEKA, and it was stored at 120° C. for 1 hour. After taking it out and standing at room temperature, the supernatant was collected. The VHR (Voltage Holding Ratio) of the taken liquid crystal composition was measured. The detailed evaluation method is as follows. The liquid crystal composition was injected into a TN cell for liquid crystal evaluation (cell thickness: 5 μm, electrode area: 8 mm×8 mm, alignment film: JALS2096), and VHR was measured using VHR-1A (manufactured by Toyo Technology Co., Ltd.). (Measurement conditions: pulse voltage width of 60 μs, frame period of 16.7 ms, wave height of ±5 V, and measurement temperature of 60°C) Cured products with a VHR of 90% or more have 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 a BCS, and a cured product with a VHR of 98% or more can be preferably used as a BCS. Hardened materials with a VHR of less than 90% cannot be used as BCS.

(NMP chemical resistance) The N-methylpyrrolidone (NMP) dissolution test was carried out in the following procedure. First, the prepared polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were coated with a spin coater so that the final film thickness would be 3 μm. It was clothed on a glass substrate, dried under reduced pressure for 1 minute, and then dried at 90° C. for 120 seconds on a hot plate. After exposure at 50 mJ/cm ² by a high-pressure mercury lamp, after a development step, heating in an oven at 230° C. for 40 minutes was performed to obtain a resist-coated substrate. Two measurement substrates (25 mm×35 mm square) were cut out from the prepared resist-coated substrate, and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP) middle. Next, the NMP dissolution test was carried out in a state where the vial containing the substrate for measurement was left to stand in a clean oven at 90° C. for 60 minutes. After standing for 40 minutes, the vial was taken out from the heating bath, and the concentration of the NMP eluted solution was measured at intervals of 1 nm in the wavelength range of 300 to 800 nm with a spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation). absorbance. A halogen lamp and a deuterium lamp (with a switching wavelength of 360 nm) were used as light sources, a photomultiplier was used as a detector, and a slit width of 2 nm was used as the measurement condition. Put the sample solution into a 1 cm square quartz cell for measurement. Absorbance is a dimensionless quantity that indicates how much light intensity is attenuated by passing light through a certain object in spectrometry, and is defined by the following formula.

A (absorbance)=-log ₁₀ (I/I ₀ ) (I: transmitted light intensity, I ₀ : incident light intensity)

In addition, the incident light intensity and transmitted light intensity in the above formula can be regarded as the light intensity I ₀ passing through the single NMP and the light intensity I passing through the sample solution when light is respectively incident on the sample solution and the single NMP from the same light source. Therefore, (I/I ₀ ) in the above formula represents the transmittance, and the absorbance A refers to the value of the reciprocal of the transmittance by logarithm. Absorbance A is a notation used to calculate the concentration of substances contained in a sample solution, etc. In the case of absorbance A=0, it represents a state of not absorbing light at all (transmittance 100%), and in the case of absorbance A=∞, it represents a state of not transmitting light at all (transmittance 0%). That is, the stronger the absorbance, the more the resist coating film components are eluted into NMP, and the NMP resistance is poor. The spectral area of the absorbance used as the evaluation criterion can be expressed as the sum of the absorbances of the respective wavelengths, and the total of the eluted resist components can be expressed. The spectral area (nm) of the measured absorbance was calculated, and the NMP chemical resistance was evaluated according to the following criteria.

NMP chemical resistance evaluation criteria: Judgment based on the area value of the absorption spectrum of the NMP elution solution (wavelength is 300 to 800 nm) ○: less than 20 (nm) △: 20 (nm) or more, less than 60 (nm) ×: 60 (nm) or more NMP chemical resistance evaluation of 0 can be used as BCS especially, NMP chemical resistance evaluation of △ can be used as BCS, NMP chemical resistance evaluation of × cannot be used Used as BCS.

(Transmittance at 780 nm) The polymerizable compositions obtained in Examples 1 to 15 and the comparative polymerizable compositions obtained in Comparative Examples 1 to 3 were coated on a glass substrate (100 mm×100 mm) using a spin coater ), prebake at 90°C for 100 seconds to form a coating film with a thickness of 3.0 μm. Next, using a mirror projection alignment exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the coating film was irradiated with ultraviolet rays at an irradiation dose of 200 mJ/cm ² without a mask. Then, post-baking was performed at 230 degreeC for 30 minutes, and the sample was produced. The 780 nm transmittance of the obtained sample was measured by an absorptiometry. A 780 nm transmittance of 80% or more was set as "○", more than 60% and less than 80% was set as "△", and 60% or less was set as "x". Those with 0 or Δ in the above evaluation can be used as BCS, and those with 0 in the above evaluation can be used particularly preferably. Those with the above evaluation of × cannot be used as BCS.

[Table 1]

[Table 2]

[table 3]

[Table 4]

According to [Table 1] to [Table 4], the cured product obtained from the polymerizable composition of the present invention satisfies light-shielding properties (OD value), relative permittivity, low liquid crystal contamination (VHR), and resistance to high levels at a high level. Chemical properties, 780 nm transmittance, and excellent elastic recovery make it useful as a BCS. [Industrial Availability]

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

Claims (9)

A polymerizable composition containing a colorant (A), an alkaline developable compound (B) and a polymerization initiator (C), wherein the colorant (A) contains an organic colorant (A1) and an inorganic colorant The coloring agent of agent (A2), the above-mentioned alkali-developable compound (B) is an alkali-developable compound represented by the following general formula (I);

(wherein, R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ² , R ⁴ and R ⁶ each independently represent a hydrocarbon group with 1 to 20 carbon atoms or a carbon atom containing a heterocyclic ring The base with the number of 2~20, when there are multiple R ³ and R ⁴ , there are the same situation and different situations, Y ¹ , Y ² and Y ³ represent direct bonds, and the number of carbon atoms is 1~20 In the case of a hydrocarbon group or a group containing a heterocyclic ring with a carbon number of 2 to 20, when there are multiple Y ² , there are the same situation and different situations, and Z ¹ , Z ² and Z ³ independently represent carbon atoms. In the case of a hydrocarbon group with 1 to 20 atoms or a group with a heterocyclic ring with 2 to 20 carbon atoms, when there are multiple Z ² , there are the same situation and different situations, there are R ² , R ⁴ , The hydrogen atoms in the groups represented by R ⁶ , Y ¹ , Y ² , Y ³ , Z ¹ , Z ² and Z ³ are replaced by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups , acryl group, epoxy group, vinyl group, mercapto group, isocyanato group or group containing a heterocyclic ring with 2 to 20 carbon atoms is substituted, there are also R ² , R ⁴ , R ⁶ , Y ¹ , Methylene groups in the groups represented by Y ² , Y ³ , Z ¹ , Z ² and Z ³ are substituted with -O-, -CO-, -COO-, -OCO-, -S-, -SO ₂ - , -SCO- or -COS-, m represents a positive number below 0 or 10, a represents a positive number below 0 or 4, b represents a positive number below 0 or 3, and c represents a positive number below 0 or 4, where m is 2 or more, b has the same situation and different situations). The polymerizable composition of claim 1, wherein the organic colorant (A1) and the inorganic colorant (A2) are an organic black pigment and an inorganic black pigment, respectively. The polymerizable composition according to claim 1 or 2, wherein the alkaline developable compound (B) contains a ring having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (III). Oxygen addition compound, or resin having a structure obtained by esterification reaction having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (III) Esterification of epoxy addition compounds and polybasic acid anhydrides;

(wherein, M represents a direct bond, a hydrocarbon group with 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO- or Substituents of the group represented by the following formula (a), (b), (c) or (d), there is a case where the hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms represented by M is replaced by a halogen atom , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ (hereinafter also referred to as "R ²¹ to R ²⁸ ") each independently represent a hydrogen atom and the number of carbon atoms is 1 to 1 20 of the hydrocarbon group or halogen atom, k is a number from 0 to 10, in the case of k≧1, the plurality of R ²¹ ~R ²⁸ and M exist in the same situation, and there are also different situations)

(wherein, 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 to R ⁵⁸ ”) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group containing a heterocyclic ring having 2 to 20 carbon atoms, or a halogen atom , there is a situation in which the methylene group in the groups represented by R ³¹ ~R ³⁸ and R ⁴⁰ ~R ⁶⁸ is substituted with an unsaturated bond, -O- or -S-, there are R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , and R ⁵⁷ and R ⁵⁸ are bonded to form a ring, (a), (b) , (c) and (d) in the group represented by * represents a bonding bond). The polymerizable composition of 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 independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a group containing a heterocyclic ring with 2 to 20 carbon atoms, and there are The hydrogen atoms in the groups represented by R ¹¹ and R ¹² are via halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryl groups, epoxy groups, vinyl groups, vinyl ether groups , mercapto group, isocyanato group or group containing a heterocyclic ring with 2 to 20 carbon atoms is substituted, and there are also cases where the methylene group in the group represented by R ¹¹ and R ¹² is substituted with -O-, - CO-, -COO-, -OCO-, -NR ¹³ -, -NR ¹³ CO-, -S-, -CS-, -SO ₂ -, -SCO-, -COS-, -OCS- or CSO- In this case, R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 0 or 1, and * in the formula represents a bond). A kind of photosensitive composition for black matrix, it contains as any one of claim 1 to 4 polymer Synthetic composition. A photosensitive composition for black column spacers, comprising the polymerizable composition according to any one of claims 1 to 4. A method for producing a hardened product, by which the polymerizability of any one of claims 1 to 4 is The composition is irradiated with light or heated to produce a cured product. A hardened product, which is the hardened product of the polymerizable composition according to any one of claims 1 to 4. A display device containing the cured product as claimed in claim 8.