阅读说明：本技术 聚合性组合物、黑色矩阵用感光性组合物及黑色柱状间隔物用感光性组合物 (Polymerizable composition, polymerizable composition, black matrix" photosensitive composite and black column spacer photosensitive composite ) 是由 中田祐也 松平桂典 六谷翔 于 2018-06-11 设计创作，主要内容包括：本发明的聚合性组合物为含有着色剂(A)、碱显影性化合物(B)及聚合引发剂(C)的聚合性组合物,上述着色剂(A)为含有有机着色剂(A1)及无机着色剂(A2)的着色剂。有机着色剂(A1)及无机着色剂(A2)分别优选为有机黑色颜料及无机黑色颜料。另外碱显影性化合物(B)也优选为下述通式(I)所表示的碱显影性化合物。(式中的符号的意思参照说明书。)<Image he="305" wi="700" file="DDA0002235370330000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(Polymerizable composition, polymerizable composition of the invention is the polymerizable composition, polymerizable composition containing colorant (A), alkali-developable compound (B) and polymerization initiator (C), and above-mentioned colorant (A) is the colorant containing toner (A1) and inorganic colourant (A2).Toner (A1) and inorganic colourant (A2) are respectively preferably organic black pigments and inorganic black pigments.In addition alkali-developable compound (B) is preferably also alkali-developable compound represented by the following general formula (I).(meaning of the symbol in formula is referring to specification.))

1. a kind of polymerizable composition, polymerizable composition is poly- containing colorant (A), alkali-developable compound (B) and polymerization initiator (C) Conjunction property composition, wherein the colorant (A) is the colorant containing toner (A1) and inorganic colourant (A2).

2. polymerizable composition, polymerizable composition according to claim 1, wherein toner (A1) and inorganic colourant (A2) are respectively For organic black pigments and inorganic black pigments.

3. polymerizable composition, polymerizable composition according to claim 1 or 2, wherein alkali-developable compound (B) is the following general formula (I) Represented alkali-developable compound,

In formula, R¹、R³And R⁵Separately indicate hydrogen atom or methyl,

R²、R⁴And R⁶The alkyl that separately expression carbon atom number is 1~20 or the carbon atom number containing heterocycle are 2~20 Group,

R³And R⁴There are it is multiple when, have identical situation, also there is different situations,

Y¹、Y²And Y³Indicate Direct Bonding, the alkyl that carbon atom number is 1~20 or the base that the carbon atom number containing heterocycle is 2~20 Group,

Y²There are it is multiple when, have identical situation, also there is different situations,

Z¹、Z²And Z³The alkyl that separately expression carbon atom number is 1~20 or the carbon atom number containing heterocycle are 2~20 Group,

Z²There are it is multiple when, have identical situation, also there is different situations,

R²、R⁴、R⁶、Y¹、Y²、Y³、Z¹、Z²And Z³Hydrogen atom in represented group is sometimes by halogen atom, nitro, cyano, hydroxyl Base, amino, carboxyl, methylacryloyl, acryloyl group, epoxy group, vinyl, sulfydryl, isocyanate group contain heterocycle The group that carbon atom number is 2~20 replaces,

R²、R⁴、R⁶、Y¹、Y²、Y³、Z¹、Z²And Z³Methylene in represented group sometimes also by-O- ,-CO- ,-COO- ,- OCO-、-S-、-SO₂,-SCO- or-COS- replace,

M indicates that 0 or 10 positive numbers below, a indicate that 0 or 4 positive numbers below, b indicate that 0 or 3 positive numbers below, c indicate 0 Or 4 positive numbers below,

When m is 2 or more, b has identical situation, also there is different situations.

4. polymerizable composition, polymerizable composition described in any one of claim 1 to 3, wherein polymerization initiator (C) is with following The polymerization initiator of group represented by logical formula (II),

In formula, R¹¹And R¹²Separately indicate hydrogen atom, halogen atom, nitro, cyano, the alkyl that carbon atom number is 1~20 Or the group that the carbon atom number containing heterocycle is 2~20, R¹¹And R¹²Hydrogen atom in represented group is sometimes by halogen original Son, nitro, cyano, hydroxyl, amino, carboxyl, methylacryloyl, acryloyl group, epoxy group, vinyl, vinyl ether group, mercapto The group that base, isocyanate group or the carbon atom number containing heterocycle are 2~20 replaces, R¹¹And R¹²Asia in represented group Methyl is sometimes also by-O- ,-CO- ,-COO- ,-OCO- ,-NR¹³-、-NR¹³CO-、-S-、-CS-、-SO₂-、-SCO-、-COS-、- OCS- or CSO- replaces,

R¹³The alkyl that expression hydrogen atom or carbon atom number are 1~20,

N indicates 0 or 1,

* in formula indicates bonding position.

5. a kind of black matrix" photosensitive composite is combined containing polymerism according to any one of claims 1 to 4 Object.

6. a kind of black column spacer photosensitive composite, contains polymerism according to any one of claims 1 to 4 Composition.

7. a kind of method, by described in polymerizable composition, polymerizable composition according to any one of claims 1 to 4, claim 5 Black matrix" photosensitive composite or black column spacer as claimed in claim 6 carry out light irradiation with photosensitive composite Or heating is to manufacture solidfied material.

It is polymerizable composition, polymerizable composition according to any one of claims 1 to 4, black described in claim 5 8. a kind of solidfied material The solidfied material of colour moment battle array photosensitive composite or black column spacer photosensitive composite as claimed in claim 6.

9. a kind of display device contains solidfied material according to any one of claims 8.

Technical field

The present invention relates to the colorant being characterized in that simultaneously containing inorganic colourant and toner, contain alkali-developable The polymerizable composition, polymerizable composition of compound and polymerizing initiator, black matrix" (being also recorded as BM below) photosensitive composite and black Color column spacer (being also recorded as BCS below) uses photosensitive composite and by the polymerizable composition, polymerizable composition or the photosensitive composition The solidfied material that object obtains.

Background technique

In the display devices such as liquid crystal display device, organic EL display device, for the top and lower part of holding unit Distance between substrate and used spacer.

Spacer by polymerizable composition, polymerizable composition is coated on substrate and via defined mask exposure after developed and It is formed.In recent years, the BCS that column spacer and black matrix" integration are made it have to light-proofness at 1 module has been used.

In patent document 1, the photonasty tree of the photomask containing the alkali soluble resin with fluorene skeleton is disclosed Oil/fat composition.In the publication, the composition spacer function excellent with light-proofness, insulating properties, elastic recovery rate is described Energy.In patent document 2, the photonasty containing black organic pigment (lactams is black) and black inorganic pigment (carbon black) is disclosed Resin combination.In the publication, the dielectric constant, light masking characteristic, resolution and elastic restoration ratio of the composition are described It is excellent.

Summary of the invention

Project to be solved by this invention is light-proofness, elasticity is restored, chemical resistance is excellent, dielectric constant is low, electric The good solidfied material of characteristic (especially BCS) is no so far.

Therefore, the purpose of the present invention is to provide can be obtained, light-proofness, elasticity is restored, chemical resistance is excellent, dielectric Constant is low, the polymerizable composition, polymerizable composition of the good BCS of electrical characteristics and BCS photosensitive composite, is used by the polymerizable composition, polymerizable composition, BM Solidfied material, the display device containing the solidfied material and the manufacture that photosensitive composite and BCS are obtained with photosensitive composite should The method of solidfied material.

The present invention has made intensive studies, and by providing following [1]~[9], has reached above-mentioned purpose.

[1] a kind of polymerizable composition, polymerizable composition is containing colorant (A), alkali-developable compound (B) and polymerization initiator (C) polymerizable composition, polymerizable composition, above-mentioned colorant (A) are the colorant containing toner (A1) and inorganic colourant (A2).

[2] polymerizable composition, polymerizable composition according to [1], wherein toner (A1) and inorganic colourant (A2) are respectively For organic black pigments and inorganic black pigments.

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

[chemical formula 1]

(in formula, R¹、R³And R⁵Separately indicate hydrogen atom or methyl,

R²、R⁴And R⁶Separately indicate alkyl that carbon atom number is 1~20 or carbon atom number containing heterocycle be 2~ 20 group,

R³And R⁴There are it is multiple when, have identical situation, also there is different situations,

Y¹、Y²And Y³Indicate that Direct Bonding, the alkyl that carbon atom number is 1~20 or the carbon atom number containing heterocycle are 2~20 Group,

Y²There are it is multiple when, have identical situation, also there is different situations,

Z¹、Z²And Z³Separately indicate alkyl that carbon atom number is 1~20 or carbon atom number containing heterocycle be 2~ 20 group,

Z²There are it is multiple when, have identical situation, also there is different situations,

R²、R⁴、R⁶、Y¹、Y²、Y³、Z¹、Z²And Z³Hydrogen atom in represented group is sometimes by halogen atom, nitro, cyanogen Base, hydroxyl, amino, carboxyl, methylacryloyl, acryloyl group, epoxy group, vinyl, sulfydryl, isocyanate group contain miscellaneous The group that the carbon atom number of ring is 2~20 replaces,

R²、R⁴、R⁶、Y¹、Y²、Y³、Z¹、Z²And Z³Methylene in represented group sometimes also by-O- ,-CO- ,- COO-、-OCO-、-S-、-SO₂,-SCO- or-COS- replace,

M indicates that 0 or 10 positive numbers below, a indicate that 0 or 4 positive numbers below, b indicate 0 or 3 positive numbers below, c Indicate 0 or 4 positive numbers below,

When m is 2 or more, b has identical situation, also there is different situations.)

[4] polymerizable composition, polymerizable composition according to any one of [1]~[3], wherein polymerization initiator (C) is under State the polymerization initiator of group represented by logical formula (II).

[chemical formula 2]

(in formula, R¹¹And R¹²Separately indicate that hydrogen atom, halogen atom, nitro, cyano, carbon atom number are 1~20 Alkyl or carbon atom number containing heterocycle be 2~20 group, R¹¹And R¹²Hydrogen atom in represented group is sometimes by halogen Plain atom, nitro, cyano, hydroxyl, amino, carboxyl, methylacryloyl, acryloyl group, epoxy group, vinyl, vinyl ethers The group that base, sulfydryl, isocyanate group or the carbon atom number containing heterocycle are 2~20 replaces, R¹¹And R¹²In represented group Methylene sometimes also by-O- ,-CO- ,-COO- ,-OCO- ,-NR¹³-、-NR¹³CO-、-S-、-CS-、-SO₂-、-SCO-、- COS- ,-OCS- or CSO- replace,

R¹³Indicate hydrogen atom, the alkyl that carbon atom number is 1~20,

N indicates 0 or 1,

* in formula indicates bonding position.)

[5] a kind of black matrix" photosensitive composite contains the combination of polymerism described in any one of [1]~[4] Object.

[6] a kind of black column spacer (black column spacer) use photosensitive composite, contain [1]~ Any one of [4] polymerizable composition, polymerizable composition described in.

[7] a kind of method uses polymerizable composition, polymerizable composition described in any one of [1]~[4], black square described in [5] Black column spacer photosensitive composite described in battle array photosensitive composite or [6] is simultaneously irradiated by light or is heated to make Make solidfied material.

[8] a kind of solidfied material is polymerizable composition, polymerizable composition described in any one of [1]~[4], black square described in [5] The solidfied material of black column spacer photosensitive composite described in battle array photosensitive composite or [6].

[9] a kind of display device contains solidfied material described in [8].

Specific embodiment

Hereinafter, polymerizable composition, polymerizable composition of the invention is described in detail based on preferred embodiment.

Polymerizable composition, polymerizable composition of the invention, which contains, is characterized in that the coloring containing inorganic colourant and toner simultaneously Agent, alkali-developable compound and polymerizing initiator.Hereinafter, being successively illustrated to each ingredient.

<colorant (A)>

Colorant used in polymerizable composition, polymerizable composition of the invention (A) contains toner (A1) and inorganic colourant (A2), known pigments or dyes can be used in mixed way.Here, so-called pigment refers to insoluble coloring in aftermentioned solvent Agent also comprising the colorant insoluble in solvent or obtains inorganic or organic dyestuff color lake in inorganic or toner Colorant.

As above-mentioned toner (A1), organic pigment and organic dyestuff can be enumerated.

As above-mentioned organic pigment, can enumerate black nigrosine, lactams, black (it is black to be referred to as perylene), No. 201 red, No. 202 red, No. 204 red, No. 205 red, No. 220 red, No. 226 red, No. 228 red, red 405 Number, it is No. 203 orange, No. 204 orange, yellow 205, yellow 401, blue 404, No. 3 red, No. 104 red, red No. 106, No. 227 red, No. 230 red, No. 401 red, red No. 505, No. 205 orange, yellow 4, Sunset Yellow FCF, yellow No. 202, yellow 203, green 3, blue No. 1 etc. with zirconium, barium or aluminum lake etc. be organic pigment of representative etc..

Among the above, with nigrosine, lactams is black and the side excellent from light-proofness for the organic black pigments of representative such as black It sets out preferably in face.

As above-mentioned organic dyestuff, the Anthraquinones such as astaxanthin, alizarin, anthocyanidin, beta carotene, Hu can be enumerated Radish element aldehyde, capsanthin, chalcone, carthamin, Quercetin, crocin, chlorophyll, curcumin, alkermes, alkannin etc. Naphthoquinones class, annatto (bixin), flavonoids, β anthocyanidin, henna, ferroheme, lycopene, riboflavin, rutin The autoxidations type dyes such as equal natural pigments/dyestuff, indoline；Dihydroxyacetone (DHA), nitroso compound, nitro compound, idol Nitrogen compound, diazonium compound, xanthene compound, quinoline compound, anthraquinone compounds, coumarin compound, cyanine compound, Phthalocyanine compound, isoindolinone compounds, isoindoline compounds, quinacridone compound, anthanthrone compound, purple ring Ketone compound, compound, pyrrolo-pyrrole-dione compound, thioindigo compound, dioxazines compound, triphenyl methane chemical combination Object, quinophthalone compound, naphthalene tetracarboxylic acid, azo dyes, metal complex compounds of cyanine dye etc..

As above-mentioned inorganic colourant (A2), inorganic pigment and inorganic dyestuff can be enumerated.

As above-mentioned inorganic pigment, the inorganic white pigments such as titanium dioxide, zinc oxide can be enumerated；mine,HCBlue 2, The nitro dyes such as Basic Blue 26；Disperse dyes；The inorganic white pigments such as titanium dioxide, zinc oxide；Iron oxide (colcother), Inorganic red system's pigment such as iron titanate；The inorganic brown pigments such as gamma-iron oxide；The inorganic yellows such as yellow ferric oxide, loess system face Material；The inorganic blacks such as Black Rouge, titanium suboxide system pigment；The inorganic violet face such as manganese violet (mango violet), cobalt violet Material；The inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate；The inorganic blue pigments such as ultramarine, Prussian blue；Oxidation Titanium coats mica, titanium-oxide-coated Bismuth Oxychloride, titanium-oxide-coated talcum, coloring titanium oxide coated mica, Bismuth Oxychloride foil etc. Pearl pigment；The metallic powdery pigments such as aluminium powder, copper powder, gold；It is surface-treated inorganic and metallic powdery pigment；To pass through oven process, slot The carbon blacks such as carbon black obtained from method or pyrolysis method or acetylene black, Ketjen black or lampblack, by above-mentioned carbon black with epoxy resin into Row adjustment or it is coating obtained from substance, above-mentioned carbon black is carried out in resin in a solvent in advance decentralized processing and with 20~ 200mg/g it is resin-coated obtained from substance, above-mentioned carbon black is carried out to substance obtained from the processing of acid or basic surface, is flat Equal partial size be 8nm or more and DBP oil absorption be 90ml/100g carbon black below, by the volatile ingredient at 950 DEG C CO and CO₂The every 100m of the total oxygen demand of calculating²Surface area is carbon black, Graphon, pigment black 7, graphite, the active carbon, carbon of 9mg or more Fiber, carbon nanotube, screw carbon fibre (Carbon microcoil), carbon nanohorn, carbon aerogels, fullerene, titanium are black etc. For the inorganic black pigments of representative.

In above-mentioned pigment, from the high aspect of light-proofness, it is preferable to use black pigment.

As above-mentioned inorganic dyestuff, can enumerate for example vanadium based dye (vfanadium compound, it is same as below.), chromium based dye, molybdenum Based dye, manganese systems dyestuff, iron series dyestuff (ferric oxalate etc.) etc. include the dyestuff etc. of metal (transition metal etc.).It needs to illustrate It is that the inorganic constituents coloured in resin particle is also contained in inorganic dyestuff [such as by the phase with the resin with fluorene skeleton Interaction (coordination or complexing formed etc.) and the ingredient coloured], such as metal ion (such as vanadium, chromium, manganese, cobalt, nickel, copper Cross the cation of metal) or the compound comprising metal ion etc..

As above-mentioned pigment, commercially available product also can be used, can enumerate for example paratonere 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 violet 1,19,23,27,29,30,32,37,40 and 50 etc..

In polymerizable composition, polymerizable composition of the invention, for the content of above-mentioned colorant (A), it is not particularly limited, relative to Following 100 mass parts of alkali-developable compound (B), preferably 5~10 mass parts, more preferably 10~80 mass parts, further Preferably 20~60 mass parts.The content of colorant (A) be above-mentioned range in the case where, due to polymerizable composition, polymerizable composition at To become without the light-proofness of the solidfied material of the composition and polymerizable composition, polymerizable composition of the excellent storage stability of the cohesion of colorant Height, it is advantageous to.

Such as it in the case where forming the solidfied material with a thickness of 1~3 μm, for the content of colorant (A), does not limit especially It is fixed, relative to 100 mass parts of alkali-developable compound (B), preferably 5~10 mass parts, more preferably 10~80 mass parts, into One step is preferably 20~60 mass parts.

In addition the aspect high from the transmissivity of 780nm, in polymeric compositions, relative to toner (A1) 100 Mass parts, inorganic colourant (A2) are preferably that 30 below the mass, more preferably 20 below the mass.On the other hand, from shading The high aspect of property is set out, and relative to 100 mass parts of toner (A1), inorganic colourant (A2) is preferably 2 mass parts or more, It is more than more preferably 5 mass parts.

<alkali-developable compound (B)>

Alkali-developable compound (B) according to the present invention is with hydrophilic radical and to show the change of alkali-developable Close object.In the present invention, as alkali-developable compound (B), as long as meet above-mentioned condition, it can be used and used in the past Compound.

As above-mentioned hydrophilic radical, hydroxyl, mercapto, carboxyl, sulfo group, amino, amide groups or its salt etc. can be enumerated, Hydroxyl and carboxyl since the alkali-developable of alkali-developable compound (B) is high, it is advantageous to.

The preferred functional equivalent of hydrophilic radical in alkali-developable compound (B) (includes 1 equivalents hydrophilic group High-molecular compound quality) be 50~10000.

In the case where the functional equivalent of hydrophilic radical is above-mentioned range, since alkali-developable is excellent, so excellent Choosing.

The preferred molecular weight of alkali-developable compound (B) is calculated as 2000~10000 with weight average molecular weight, particularly preferably 3000~6000.In addition 1000~8000 are calculated as with number-average molecular weight, specifically for 2000~5000.In alkali-developable compound (B) it is excellent since it is possible to obtain developability and chemical resistance is excellent consolidates in the case that molecular weight is above-mentioned range Compound, it is advantageous to.

The acid value of above-mentioned alkali-developable compound (B) is preferably 10~200mg/KOH, further preferably 30~150mg/ KOH.By acid value be 10mg/KOH or more, be easy fully obtain alkali-developable, by for 200mg/KOH hereinafter, being easy to make The manufacture of high-molecular compound becomes easy.Here, so-called acid value is the value measured according to JIS K 0050 and JIS K 0211.

As alkali-developable compound (B), specifically, compound, propylene represented by above-mentioned logical formula (I) can be used The copolymer of acid esters；Novolac and/or first rank phenolic resin varnish；Polyphenylene first with multi-functional epoxy's base Alkane type epoxy resin；Epocryl；With making epoxidation represented by unsaturated monoacid and the following general formula (III) Close the epoxy additive compound of structure obtained from the additions such as object；Make unsaturated monoacid and the following general formula with passing through to have (III) the epoxy additive compound of structure obtained from the epoxide addition represented by and the esterification of multi-anhydride and Resin (unsaturated compound) of obtained structure etc..

[chemical formula 3]

(in formula, M indicates the alkyl ,-O- ,-S- ,-SO of Direct Bonding, carbon atom number for 1~20₂-、-SS-、-SO-、- CO- ,-OCO- or selected from following formula (a), (b), (c) or (d) represented by group in substituent group,

The hydrogen atom in alkyl that carbon atom number represented by M is 1~20 is substituted with halogen atoms sometimes, R²¹、R²²、R²³、 R²⁴、R²⁵、R²⁶、R²⁷And R²⁸(hereinafter, being also recorded as R²¹~R²⁸) separately indicate that hydrogen atom, carbon atom number are 1~20 Alkyl or halogen atom, the number that k is 0~10, when k >=1, multiple R²¹~R²⁸And M has identical situation respectively, also has Different situations.)

[chemical formula 4]

(in formula, R²⁹Indicate that carbon atom number is 1~20 alkyl,

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、R⁵⁷And R⁵⁸(hereinafter, being also recorded as R³⁰~R⁵⁸) separately indicate that hydrogen atom, carbon are former The group or halogen atom that alkyl that subnumber is 1~20, the carbon atom number containing heterocycle are 2~20,

R³¹~R³⁸And R⁴⁰~R⁶⁸Methylene in represented group is replaced by unsaturated bond ,-O- or-S- sometimes,

R³⁰With R³¹、R3¹With R³²、R³²With R³³、R³³With R³⁴、R³⁵With R³⁶、R³⁶With R³⁷、R³⁷With R³⁸、R⁴³With R⁴⁴、R⁴⁴With R⁴⁵、 R⁴⁵With R⁴⁶、R⁵¹With R⁵²、R⁵²With R⁵³、R⁵³With R⁵⁴、R⁵⁵With R⁵⁶、R⁵⁶With R⁵⁷And R⁵⁷With R⁵⁸Sometimes it is bonded and forms ring,

(a), (b), (c) and (d) represented by group in * indicate bonding position.)

By using alkali-developable compound represented by above-mentioned logical formula (I), the solidfied material obtained by polymerizable composition, polymerizable composition Since chemical resistance is excellent, it is advantageous to.

If using having obtained from making epoxide addition represented by unsaturated monoacid and above-mentioned logical formula (III) The epoxy additive compound of structure；Or make epoxy represented by unsaturated monoacid and above-mentioned logical formula (III) using by having Reaction product obtained from the epoxy additive compound of structure obtained from compound addition and the esterification of multi-anhydride is Alkali-developable compound, then since the sensitivity of polymerizable composition, polymerizable composition is got higher, by the bullet for the solidfied material that the polymerizable composition, polymerizable composition obtains Property recovery rate is excellent, it is advantageous to.

Become good and the good aspect of heat resistance, above-mentioned alkali-developable chemical combination from the dispersibility of colorant (A) Object (B) is preferably epoxide represented by above-mentioned logical formula (III)；Make unsaturated monoacid and above-mentioned logical formula (III) institute table With the epoxide of following structures [(e)] obtained from the epoxide addition shown；Or unsaturationization in this way Close the unsaturated compound obtained from the esterification of object and multi-anhydride with following structures [(f)].

[chemical formula 5]

(in formula, Y⁷Indicate the residue of unsaturated monoacid, Y⁸Indicate that the residue of multi-anhydride, * refer to bonding position.)

In the alkali-developable compound represented by above-mentioned logical formula (III), M be (b) or (c) represented by group feelings Under condition, since the solvent resistance of the solidfied material obtained by the polymerizable composition, polymerizable composition becomes well, so particularly preferably.

R in above-mentioned logical formula (I)²、R⁴、R⁶、Y¹~Y³And Z¹~Z³The alkyl that represented carbon atom number is 1~20 does not have It is particularly limited to, but preferably indicates the alkenyl that alkyl, carbon atom number that carbon atom number is 1~20 are 2~20, carbon atom number 3 The aryl and carbon atom number that cycloalkyl-alkyl that~20 naphthenic base, carbon atom number are 4~20, carbon atom number are 6~20 be 7~ 20 aralkyl etc..From as polymerization initiator (C) use when the good aspect of sensitivity, more preferable carbon atom number be 1 Naphthenic base that alkenyl that~10 alkyl, carbon atom number are 2~10, carbon atom number are 3~10, carbon atom number are 4~10 The aralkyl etc. that the aryl and carbon atom number that cycloalkyl-alkyl, carbon atom number are 6~10 are 7~10.

As above-mentioned carbon atom number be 1~20 alkyl, can enumerate for example methyl, ethyl, propyl, isopropyl, butyl, It is isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- ethylhexyl, tertiary pungent Base, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, myristyl, cetyl, octadecyl and 20 Alkyl etc..As above-mentioned carbon atom number be 1~10 alkyl, can enumerate for example methyl, ethyl, propyl, isopropyl, butyl, It is isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, tertiary pentyl, hexyl, heptyl, octyl, iso-octyl, 2- ethylhexyl, tertiary pungent Base, nonyl, isononyl, decyl and isodecyl etc..

As above-mentioned carbon atom number be 2~20 alkenyl, can enumerate for example vinyl, 2- acrylic, 3- cyclobutenyl, 2- cyclobutenyl, 4- pentenyl, 3- pentenyl, 2- hexenyl, 3- hexenyl, 5- hexenyl, 2- heptenyl, 3- heptenyl, 4- heptan Alkenyl, 3- octenyl, 3- nonenyl, 4- decene base, 3- undecenyl, 4- laurylene base, 3- cyclohexenyl group, 2,5- hexamethylene two 14 carbon trialkenyl allyl of alkenyl -1- methyl and 4,8,12- etc..The alkenyl for being 2~10 as above-mentioned carbon atom number, can arrange Enumerate such as vinyl, 2- acrylic, 3- cyclobutenyl, 2- cyclobutenyl, 4- pentenyl, 3- pentenyl, 2- hexenyl, 3- hexene Base, 5- hexenyl, 2- heptenyl, 3- heptenyl, 4- heptenyl, 3- octenyl, 3- nonenyl and 4- decene base etc..

The naphthenic base that so-called above-mentioned carbon atom number is 3~20 refers to the saturation monocyclic or full of the carbon atom with 3~20 With polycycle alkyl.Such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, ring can be enumerated Decyl, adamantyl, decahydro naphthalene, octahydro pentalene, two rings [1.1.1] amyl and ten tetrahydro anthryls etc..As above-mentioned The naphthenic base that carbon atom number is 3~10, it is pungent can to enumerate such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring Base, cyclononyl, cyclodecyl, adamantyl, decahydro naphthalene, octahydro pentalene and two rings [1.1.1] amyl etc..

The cycloalkyl-alkyl that so-called above-mentioned carbon atom number is 4~20 refers to that the hydrogen atom of alkyl is substituted by cycloalkyl and obtains With 4~20 carbon atom group.Such as Cvclopropvlmethvl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl can be enumerated Methyl, CycloheptylmethyI, cyclooctyl methyl, cyclononyl methyl, cyclodecyl methyl, 2- cyclobutylethyl, 2- cyclopentyl ethyl, 2- Cyclohexyl-ethyl, 2- cycloheptylethyl, 2- cyclooctyl ethyl, 2- cyclononyl ethyl, 2- cyclodecyl ethyl, 3- cyclobutylpropyl, 3- cyclopentylpropyi, 3- Cyclohexylpropyl, 3- cycloheptylpropyl, 3- cyclooctyl propyl, 3- cyclononyl propyl, 3- cyclodecyl third Base, 4- cyclobutyl butyl, 4- cyclopentylbutyl, 4- cyclohexylbutyl, 4- suberyl butyl, 4- cyclooctyl butyl, 4- cyclononyl Butyl, 4- cyclodecyl butyl, 3-3- adamantyl propyl and decahydro naphthylpropyl etc..It is 4~10 as above-mentioned carbon atom number Cycloalkyl-alkyl can enumerate such as Cvclopropvlmethvl, cyclobutylmethyl, cyclopentyl-methyl, cyclohexyl methyl, suberyl first Base, cyclooctyl methyl, cyclononyl methyl, 2- cyclobutylethyl, 2- cyclopentyl ethyl, 2- cyclohexyl-ethyl, 2- cycloheptylethyl, 2- cyclooctyl ethyl, 3- cyclobutylpropyl, 3- cyclopentylpropyi, 3- Cyclohexylpropyl, 3- cycloheptylpropyl, 4- cyclobutyl fourth Base, 4- cyclopentylbutyl and 4- cyclohexylbutyl etc..

The aryl for being 6~20 as above-mentioned carbon atom number, can enumerate such as phenyl, tolyl, xylyl, ethylo benzene Base, naphthalene, anthryl, phenanthryl etc., the phenyl for being replaced 1 or more by abovementioned alkyl, above-mentioned alkenyl or carboxyl, halogen atom etc., Xenyl, naphthalene, anthryl etc., such as 4- chlorphenyl, 4- carboxyl phenyl, 4- ethenylphenyl, 4- aminomethyl phenyl, 2,4,6- front three Base phenyl etc..The aryl for being 6~10 as above-mentioned carbon atom number, can enumerate such as phenyl, tolyl, xylyl, ethyl Phenyl and naphthalene etc., the phenyl for being replaced 1 or more by abovementioned alkyl, above-mentioned alkenyl or carboxyl, halogen atom etc., xenyl, Naphthalene, anthryl etc., such as 4- chlorphenyl, 4- carboxyl phenyl, 4- ethenylphenyl, 4- aminomethyl phenyl, 2,4,6- trimethylphenyl Deng.

The aralkyl that so-called above-mentioned carbon atom number is 7~20 refers to that the hydrogen atom of alkyl by above-mentioned carbon atom number is 6~20 Aryl in carbon atom number be 6~19 aryl replace obtained from 7~20 carbon atoms group.Example can be enumerated Such as benzyl, α-methylbenzyl, bis (alpha, alpha-dimethylbenzyl) base, phenylethyl and naphthylpropyl.It is 7~10 as above-mentioned carbon atom number Aralkyl, refer to the aryl that the carbon atom number in aryl that the hydrogen atom of alkyl is 6~10 by above-mentioned carbon atom number is 6~9 With the group of 7~10 carbon atoms obtained from substitution, such as benzyl, α-methylbenzyl, α, alpha-alpha-dimethyl benzyl can be enumerated Base and phenylethyl etc..

R in above-mentioned logical formula (I)²、R⁴And R⁶、Y¹~Y³And Z¹~Z³The represented carbon atom number containing heterocycle be 2~ 20 group is not particularly limited, but can enumerate such as pyrrole radicals, pyridyl group, pyridyl-ethyl group, pyrimidine radicals, pyridazinyl, piperazine Piperazine base, piperidyl, pyranose, pyranose ethyl, pyrazolyl, triazine radical, triazine ylmethyl, pyrrolidinyl, quinolyl, isoquinolin Base, imidazole radicals, benzimidazolyl, triazolyl, furyl (furyl), furyl (furanyl), benzofuranyl, thienyl, Thiophenyl, aisaa benzothiophenyl, thiadiazolyl group, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, different evil Oxazolyl, indyl, morpholinyl, thio-morpholinyl, 2-Pyrrolidone -1- base, 2- piperidones -1- base, bis- oxygroup imidazolidine of 2,4- - 3- base and 2, bis- oxygroup oxazolidine -3- base of 4- etc., if specifically being recorded inside comprising substituent group etc., can enumerate has The group etc. of following structures.

[chemical formula 6]

(in above-mentioned formula, R separately indicates that hydrogen atom or carbon atom number are 1~6 alkyl, Z indicate Direct Bonding or The alkylidene that carbon atom number is 1~6.It should be noted that the * in formula refers to group represented by these formulas with the part * for key Close position.)

The alkyl for being 1~6 as carbon atom number represented by the R in above-mentioned formula, can enumerate as above-mentioned carbon atom The group that number is 1~6 for the carbon atom number in 1~20 illustrated group out of alkyl.

As carbon atom number represented by the Z in above-mentioned formula be 1~6 alkylidene, can enumerate methylene, ethylidene, Propylidene, methyl ethylidene, butylidene, 1- methyl propylene, 2- methyl propylene, 1,2- dimethylpropylidene, 1,3- diformazan Base propylidene, 1- methylbutylene, 2- methylbutylene, 3- methylbutylene, 4- methylbutylene, 2,4- dimethyl Aden The alkylidene of the linear chain or branched chains such as base, 1,3- dimethylbutylene, pentylidene, hexylidene.

As sometimes by R²、R⁴、R⁶、Y¹~Y³And Z¹~Z³The halogen atom that hydrogen atom in represented group replaces, Fluorine, chlorine, bromine, iodine can be enumerated.

As replacing R sometimes²、R⁴、R⁶、Y¹~Y³And Z¹~Z³The unsaturated bond of methylene in represented group, can Enumerate-C=C- ,-C ≡ C- etc..

As the M and R in above-mentioned logical formula (III)²¹~R⁵⁸The alkyl that represented carbon atom number is 1~20, can enumerate Group same as the alkyl that above-mentioned carbon atom number is 1~20.

As the R in above-mentioned logical formula (III)³⁰~R⁵⁸The group that the represented carbon atom number containing heterocycle is 1~20, Group same as the group that the above-mentioned carbon atom number containing heterocycle is 1~20 can be enumerated.

Replace as the hydrogen atom in the alkyl for being 1~20 by carbon atom number represented by the M in above-mentioned logical formula (III) Halogen atom and R²¹~R²⁸And R³⁰~R⁵⁸Represented halogen atom can enumerate fluorine, chlorine, bromine, iodine.

As the R in above-mentioned logical formula (III)³⁰With R³¹、R³¹With R³²、R³²With R³³、R³³With^R34、R³⁵With R³⁶、R³⁶With R³⁷、R³⁷ With R³⁸、R⁴³With R⁴⁴、R⁴⁴With R⁴⁵、R⁴⁵With R⁴⁶、R⁵¹With R⁵²、R⁵²With R⁵³、R⁵³With R⁵⁴、R⁵⁵With R⁵⁶、R⁵⁶With R⁵⁷And R⁵⁷With R⁵⁸Key The ring for closing and being formed can enumerate such as pentamethylene, hexamethylene, cyclopentene, benzene, pyrrolidines, pyrroles, piperazine, morpholine, thio 5~7 member ring such as quinoline, tetrahydropyridine, lactonic ring and lactam nucleus and the condensed ring such as naphthalene and anthracene etc..

So-called above-mentioned unsaturated monoacid indicates to have unsaturated bond in structure and every 1 molecule can be ionized with 1 and Acid as hydrionic hydrogen atom.

As above-mentioned unsaturated monoacid, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorb can be enumerated Acid and hydroxyethyl methacrylate maleate, hydroxy propyl methacrylate maleate, dihydroxypropyl third Ester maleate and bicyclopentadiene maleate etc..

In addition, connection can be enumerated as the above-mentioned multi-anhydride to work after making above-mentioned unsaturated monoacid work Benzene tertacarbonic acid's dianhydride, tetrabydrophthalic anhydride, succinic anhydride, double phthalic anhydrides, maleic anhydride, trimellitic anhydride, Benzene tetracarboxylic acid acid anhydride, 2,2 ' -3,3 '-benzophenone tetracarboxylic anhydrides, ethylene glycol double trimellitic anhydrides, three trimellitic anhydride of glycerol, six Hydrogen phthalic anhydride, methyl tetrahydrophthalic anhydride, carbic anhydride, methylnadic anhydride, trialkyl tetrahydro neighbour's benzene Dicarboxylic acid anhydride, hexahydrophthalic anhydride, 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexene -1,2- dicarboxylic acids Acid anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methyl norbornene dioic anhydride Deng.

The reaction molar ratio of above-mentioned epoxide, above-mentioned unsaturated monoacid and above-mentioned multi-anhydride is preferably as follows Setting.

That is, above-mentioned epoxy additive compound is preferably according to 1 epoxy group relative to above-mentioned epoxide, above-mentioned insatiable hunger Reach the mode addition of 0.1~1.0 ratio with the carboxyl of monoacid, in addition the preferred phase of above-mentioned ethylenically unsaturated compounds For 1 hydroxyl of above-mentioned epoxy adduct, the acid anhydride structure of above-mentioned multi-anhydride reaches 0.1~1.0 ratio.

The reaction of epoxide represented by above-mentioned logical formula (III), above-mentioned unsaturated monoacid and above-mentioned multi-anhydride It can conventionally carry out.

Polymerizable composition, polymerizable composition of the invention, BM photosensitive composite and BCS sense are improved to carry out acid value adjustment The developability of photosensitiveness composition can further make simple function or multi-functional epoxy with above-mentioned alkali-developable compound (B) together Compound reaction.The range that the acid value of above-mentioned alkali-developable compound (B) preferably solid component is 5~120mgKOH/g, single official The usage amount of energy or multi-functional epoxy compound preferably select in the way of meeting above-mentioned acid value.

As above-mentioned monofunctional epoxy compound, can enumerate glycidyl methacrylate, methyl glycidyl ether, Ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl Ether, tertiary butyl glycidyl ether, amyl glycidol ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl Ether, nonyl glycidol ether, decyl glycidyl ether, undecyl glycidol ether, lauryl diglycidyl ether, tridecane Base glycidol ether, myristyl glycidol ether, pentadecyl glycidol ether, cetyl glycidyl ether, 2- ethyl Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidol ether, to methoxy ethyl glycidol ether, phenyl Glycidol ether, to methoxyl group glycidol ether, p-butylphenol glycidol ether, cresyl glycidyl ether, 2- methyl first Phenyl glycidyl ether, 4- nonyl phenyl glycidyl glycerin ether, benzyl glycidyl ether, to cumyl phenyl glycidol ether, triphen Methyl glycidyl ether, 2,3- glycidyl methacrylate, epoxidised soybean oil, epoxidised linseed oil, butyric acid shrink Glyceride, vinyl cyclohexane list oxide, 1,2- epoxy -4- vinyl cyclohexane, styrene oxide, epoxypinane, methyl Styrene oxide, 7-oxa-bicyclo[4.1.0, propylene oxide, following epoxide No.E1, No.E2 etc..

[chemical formula 7]

Epoxide No.E1

[chemical formula 8]

Epoxide No.E2

As above-mentioned multi-functional epoxy compound, if using selected from by biphenol type epoxy compound and glycidol ethers structure At one or more of group compound, then since characteristic further good polymerizable composition, polymerizable composition can be obtained, so excellent Choosing.

As above-mentioned biphenol type epoxy compound, in addition to epoxide represented by above-mentioned logical formula (III) can be used In addition, such as the biphenol type epoxies compound such as A Hydrogenated Bisphenol A type ring oxygen compound can also be used.

Additionally as above-mentioned glycidol ethers, ethylene glycol diglycidylether, propylene glycol 2-glycidyl can be used Ether, 1,4- butanediol diglycidyl ether, 1,6 hexanediol diglycidylether, 1,8- ethohexadiol diglycidyl ether, 1,10- Decanediol diglycidyl ether, 2,2- dimethyl -1,3- propylene glycol diglycidylether, diethylene glycol diglycidyl glycerin ether, three Ethylene glycol diglycidylether, tetraethylene glycol diglycidyl ether, six ethylene glycol diglycidylethers, 1,4 cyclohexane dimethanol Diglycidyl ether, 1,1,1- tri- (glycidyl oxy methyl) propane, 1,1,1- tri- (glycidyl oxy methyl) second Alkane, 1,1,1- tri- (glycidyl oxy methyl) methane, 1,1,1,1- tetra- (glycidyl oxy methyl) methane etc..

In addition to this, can also use phenol novolak-type epoxy compound, biphenyl novolak type epoxy compounds, Cresol novolak type epoxy compound, bisphenol A novolac type ring oxygen compound, the oxidation of dicyclopentadiene novolac type ring Close the novolak type epoxy compounds such as object；3,4- epoxy -6- methylcyclohexylmethyl -3,4- epoxy -6- hexahydrotoluene carboxylic The alicyclic rings such as acid esters, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate, 1- epoxy ethyl -3,4- 7-oxa-bicyclo[4.1.0 Formula epoxide；O-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, dimer acid shrink sweet The glycidols esters such as grease；Four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, N, N- bis- The glycidyls amine such as glycidyl aniline；1,3- diglycidyl -5,5- dimethyl hydantoin, three-glycidyl The hetero ring types epoxide such as base isocyanuric acid ester；The dioxide compounds such as titanium dioxide bicyclopentadiene；Naphthalene type epoxy compound Object；Triphenylmethane type epoxy compound；Dicyclopentadiene type epoxy compound etc..

It can also be suitable for using commercially available product as alkali-developable compound (B).

As the commercially available product, can enumerate such as 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 Showa electrician corporations), JET2000, AGOR1060, AGOR3060, ORGA1060, ORGA2060 (the above are Osaka organic chemistry corporation), CCR-1171H (Japanese chemical drug corporation) etc..

In polymerizable composition, polymerizable composition of the invention, for the content of alkali-developable compound (B), it is not particularly limited, phase For total 100 mass parts of colorant (A), alkali-developable compound (B) and polymerization initiator (C), preferably 10~95 matter Measure part, more preferably 30~90 mass parts, further preferably 30~80 mass parts.The content of alkali-developable compound (B) is When in above-mentioned range, since the alkali-developable of polymerizable composition, polymerizable composition is good, it is advantageous to.

In the case where for example forming the cured film with a thickness of 2~5 μm, for the content of alkali-developable compound (B), do not have It is particularly limited to, it is excellent relative to total 100 mass parts of colorant (A), alkali-developable compound (B) and polymerization initiator (C) It is selected as 10~95 mass parts, more preferably 30~90 mass parts, further preferably 30~80 mass parts.

In addition in the case where the compound represented by alkali-developable compound (B) contains logical formula (I), lead to formula (I) institute table Total 100 mass of the content of the compound shown relative to colorant (A), alkali-developable compound (B) and polymerization initiator (C) Part, preferably 10~60 mass parts, more preferably 20~50 mass parts.In addition, containing have make unsaturated monoacid with it is upper State the epoxy additive compound of structure obtained from compound addition represented by logical formula (III) or by the epoxy combine additively In the case where reaction product, that is, alkali-developable compound obtained from the esterification of object and multi-anhydride, the epoxy combine additively The content of object and the reaction product as obtained from the esterification of the epoxy additive compound and multi-anhydride is relative to coloring Agent (A), alkali-developable compound (B) and polymerization initiator (C) total 100 mass parts, preferably 5~80 mass parts are more excellent It is selected as 5~40 mass parts.So-called above-mentioned epoxy additive compound and the ester by the epoxy additive compound and multi-anhydride The content for changing reaction product obtained from reaction, is containing the feelings of only one in the epoxy additive compound and the reaction product It is its total amount in the case where containing the two for its amount under condition.

<polymerization initiator (C)>

As polymerization initiator used in polymerizable composition, polymerizable composition of the invention (C), previously known freedom can be used Base polymerization initiator.

Above-mentioned radical polymerization initiator is optical free radical polymerization initiator and hot radical polymerization initiator.From reactivity High aspect is set out, more preferable optical free radical polymerization initiator.

As optical free radical polymerization initiator, as long as not limited especially then by the substance that light irradiation generates free radicals System, can be used previously known compound, such as preferred substance, can exemplify oxime ester based compound, acetophenone system Compound, benzil based compound, benzophenone based compound and thioxanthones based compound etc..

As above-mentioned oxime ester based compound, the compound etc. with group represented by above-mentioned logical formula (II) can be enumerated, In above-mentioned optical free radical polymerization initiator, since sensitivity is good, so preferably being used in polymerizable composition, polymerizable composition of the invention.

R in above-mentioned logical formula (II)¹¹~R¹³The alkyl and above-mentioned R that represented carbon atom number is 1~20²、R⁴、R⁶、Y¹~ Y³And Z¹~Z³Represented alkyl is identical.

Sometimes to the R in above-mentioned logical formula (II)¹¹And R¹²And R¹¹Or R¹²What represented group was modified contains heterocycle Carbon atom number be 2~20 group and above-mentioned R²、R⁴、R⁶、Z¹~Z³The represented carbon atom number containing heterocycle is 2~20 Group is identical.

In compound with group represented by above-mentioned logical formula (II), compound represented by the following general formula (IV) due to Sensitivity is especially high, and it is advantageous in polymerizable composition, polymerizable composition of the invention.

[chemical formula 9]

(in formula, R¹¹、R¹²And n respectively with the R in logical formula (II)¹¹、R¹²And n is identical,

R⁶¹And R⁶²Separately indicate hydrogen atom, nitro, cyano, the alkyl that carbon atom number is 1~20, carbon atom number The group for being 2~20 for 6~20 aryl, the aralkyl that carbon atom number is 7~20 or carbon atom number containing heterocycle,

X¹Indicate oxygen atom, sulphur atom, selenium atom, CR⁶³R⁶⁴、CO、NR⁶⁵Or PR⁶⁶,

X²Indicate no bonding, Direct Bonding, the alkyl that carbon atom number is 1~20, CO, R⁶³~R⁶⁶Separately indicate hydrogen The alkyl that atom, carbon atom number are 1~20 or the group that the carbon atom number containing heterocycle is 2~20, R⁶¹~R⁶⁶Represented base Hydrogen atom in group is also replaced by halogen atom, nitro, cyano, hydroxyl, carboxyl or heterocycle sometimes,

R⁶¹~R⁶⁶Methylene in represented group is also replaced under the conditions of oxygen is non-conterminous by-O- sometimes,

R⁶¹~R⁶⁶Sometimes it separately also is formed together ring with any one adjacent phenyl ring,

G indicates 0~4 number,

H indicates 0~3 number.)

R in above-mentioned logical formula (IV)⁶¹~R⁶⁶Represented carbon atom number be 1~20 alkyl respectively with above-mentioned R²、R⁴、 R⁶、Y¹~Y³And Z¹~Z³The alkyl that represented carbon atom number is 1~20 is identical.

R in above-mentioned logical formula (IV)⁶¹~R⁶⁶The represented carbon atom number containing heterocycle be 2~20 group with it is above-mentioned R²、R⁴、R⁶And Z¹~Z³The group that the represented carbon atom number containing heterocycle is 2~20 is identical.

For for example following compounds represented can be enumerated as the preferred oxime ester based compound of polymerization initiator (C) No.C1-1~No.C1-14.But polymerization initiator (C) used in the present invention is not by any limit of compound below System.

[chemical formula 10]

[chemical formula 11]

In logical formula (IV), in X¹For sulphur atom and X²In the case where for no bonding, become above compound No.C1-1~ With the oxime ester based compound of diphenyl sulfide skeleton illustrated by C1-7, from by being used in combination as polymerization initiator, to obtain sensitivity good It sets out in terms of good polymerizable composition, polymerizable composition, is preferred.

In logical formula (IV), in X¹For NR⁶⁵And X²In the case where for Direct Bonding, become above compound No.C1-8~ Illustrated by C1-14 with carbazole skelton oxime ester based compound, from obtain the good polymerizable composition, polymerizable composition of sensitivity in terms of go out Hair, particularly preferably.

As acetophenone based compound, such as diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl third can be enumerated Alkane -1- ketone, 4 '-isopropyl -2- hydroxy-2-methyl propiophenones, 2- hydroxymethyl -2- methyl phenyl ketone, dimethoxy -1 2,2-, 2- diphenylethane -1- ketone, to dimethylamino benzoylformaldoxime, to tert-butyl dichloroacetophenone, to tert-butyl trichloroacetophenone, right Nitrine benzylidene acetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-[4- (methyl thio) phenyl]-2- morpholino third Ketone -1,2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1, benzoin, benzoin methyl ether, benzoin second Base ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1- [4- (2- hydroxyl-oxethyl)-benzene Base] -2- hydroxy-2-methyl -1- propane -1- ketone etc..

In above-mentioned acetophenone based compound, if the alpha-aminoacetophenone compound with hydroxyl is used to cause as polymerization Agent, then since the liquid crystal pollution of obtained solidfied material is few, it is advantageous to.As the alpha-aminoacetophenone chemical combination with hydroxyl Object can preferably enumerate compound represented by the following general formula (V).

[chemical formula 12]

(in formula, Xr indicates structure represented by the following general formula (i), (ii) or (iii),

Xs indicates sulphur atom or NR¹⁰⁰,

R¹⁰⁰、R¹⁰¹、R¹⁰²、R¹⁰³And R¹⁰⁴Separately indicate hydrogen atom, carbon atom number be 1~12 alkyl, phenyl, The alkenyl that the aralkyl or carbon atom number that carbon atom number is 7~20 are 2~12, the alkyl are sometimes former by hydroxyl, carboxyl, halogen Son, cyano or nitro replace, the phenyl and the aralkyl sometimes by carbon atom number be 1~4 alkyl, hydroxyl, carboxyl, halogen it is former Son, cyano or nitro replace,

R¹⁰¹With R¹⁰²Sometimes the heterocycle of 3~6 member rings is connected and formed, is bonded on the miscellaneous ring nitrogen sometimes R⁹⁹,

R¹⁰³With R¹⁰⁴Also it can connect and form 3~6 member rings,

R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸Separately indicate hydrogen atom, halogen atom, cyano, nitro, hydroxyl, carboxyl or carbon The alkyl that atomicity is 1~12, the alkyl are replaced by halogen atom, carboxyl, cyano, nitro or hydroxyl sometimes,

R⁹⁹Indicate the aralkyl or carbon original that alkyl, phenyl, carbon atom number that hydrogen atom, carbon atom number are 1~12 are 7~20 The alkenyl that subnumber is 2~12, which is replaced by hydroxyl, carboxyl, halogen atom, cyano or nitro sometimes, the phenyl and this Aralkyl is replaced by alkyl, hydroxyl, carboxyl, halogen atom, cyano or nitro that carbon atom number is 1~4 sometimes.

The methylene in each alkyl and above-mentioned each aralkyl enumerated among the above is sometimes by-O- ,-S- ,-NR¹¹⁷-、-CO-、- CO-O- ,-O-CO- or-O-CO-O- replace.

R¹¹⁷Indicate the aralkyl or carbon that alkyl, phenyl, carbon atom number that hydrogen atom, carbon atom number are 1~12 are 7~20 The alkenyl that atomicity is 2~12, which is replaced by hydroxyl, carboxyl, halogen atom, cyano or nitro sometimes, the phenyl and The aralkyl is replaced by alkyl, hydroxyl, carboxyl, halogen atom, cyano or nitro that carbon atom number is 1~4 sometimes.

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

[chemical formula 13]

(in formula, R¹⁰⁹And R¹¹⁰Separately indicate that hydrogen atom, hydroxyl, carboxyl, halogen atom or carbon atom number are 1~4 Alkyl, p be 2 or more when, they may be the same or different,

Methylene in structure represented by following (i-1) in formula can also be by-O- ,-S- ,-NR¹¹⁷、-CO-、-CO- O- ,-O-CO- or-O-CO-O- replace,

[chemical formula 14]

R¹¹¹Indicate hydrogen atom, halogen atom, hydroxyl, carboxyl, cyano, amino or phenyl, the phenyl is sometimes by carbon atom number For the substitution of 1~4 alkyl, hydroxyl, carboxyl, halogen atom, cyano or nitro, p indicates 1~12 number.)

[chemical formula 15]

(in formula, R¹¹²、R¹¹³、R¹¹⁴、R¹¹⁵And R¹¹⁶Separately indicate hydrogen atom, halogen atom, cyano, nitro, hydroxyl The alkyl that base or carbon atom number are 1~12, which is replaced by halogen atom, cyano, nitro or hydroxyl sometimes, in the alkyl Methylene is sometimes by-O- ,-S- ,-NR¹¹⁷,-CO- ,-CO-O- ,-O-CO- or-O-CO-O- replace,

R¹⁰⁶Or R¹⁰⁷Sometimes with R¹¹²Or R¹¹⁶It is bonded and forms ring.)

[chemical formula 16]

(in formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴、R¹⁰⁵、R¹⁰⁶、R¹⁰⁷And R¹⁰⁸It is identical as above-mentioned logical formula (V), R¹⁰⁹、R¹¹⁰And p with Above-mentioned general formula (i) is identical.)

As the alkyl for being 1~12 in each carbon atom number described among the above to lead to the explanation of formula (V), example can be enumerated The carbon atom in alkyl that the example i.e. carbon atom number for the alkyl that carbon atom number in such as above-mentioned general formula (I) is 1~20 is 1~20 The alkyl that number is 1~12.

As the alkyl for being 1~4 in each carbon atom number described among the above to lead to the explanation of formula (V), work can be enumerated For the carbon atom number in above-mentioned logical formula (I) be 1~20 alkyl example i.e. carbon atom number be 1~20 alkyl and describe above Alkyl in carbon atom number be 1~4 alkyl.

As the aralkyl for being 7~20 in each carbon atom number described among the above to lead to the explanation of formula (V), can enumerate Such as benzyl, α-methylbenzyl, bis (alpha, alpha-dimethylbenzyl) base, phenylethyl etc..

As the alkenyl for being 2~12 in each carbon atom number described among the above to lead to the explanation of formula (V), can enumerate Vinyl, 1- acrylic, 2- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- octenyl, 1- decene The groups such as base.

As the R in logical formula (V)¹⁰¹With R¹⁰²The heterocycle of 3~6 member rings that can be connected and be formed, preferably enumerates for example Piperidine ring, piperazine ring, morpholine ring, lactam nucleus etc..

As the R in logical formula (V)¹⁰³With R¹⁰⁴3~6 member rings that can be connected and be formed, preferably enumerate such as pentamethylene Ring, cyclohexane ring, cyclopentene ring, lactonic ring, lactam nucleus etc..

As the R in logical formula (V)¹⁰⁶Or R¹⁰⁷With R¹¹²Or R¹¹⁶Ring made of bonding, as the benzene adjacent with the left and right of Xs Structure after cyclization simultaneously, can enumerate carbazole ring, thianthrene ring, dibenzothiophenes ring.

As with the explanation led in formula (V) and in each halogen atom described among the above, fluorine, chlorine, bromine, iodine can be enumerated.

As the specific example of the alpha-aminoacetophenone based compound with hydroxyl, following compound N o.C2- can be enumerated 1~compound N o.C2-11 etc..

[chemical formula 17]

As above-mentioned benzil based compound, benzil etc. can be enumerated.

As above-mentioned benzophenone based compound, such as benzophenone, o-benzoyl yl benzoic acid methyl esters, rice can be enumerated Chi ketone, 4,4 '-bis- diethylamino benzophenone, 4,4 '-dichloro benzophenones and 4- benzoyl -4 '-methyldiphenyl thioether Deng.

As above-mentioned thioxanthones based compound, thioxanthones, 2- methyl thioxanthones, 2- ethyl thioxanthones, 2- chlorine can be enumerated Thioxanthones, 2-isopropylthioxanthone, 2,4- diethyl thioxanthone etc..

As other radical polymerization initiators, 2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. can be enumerated The titanocenes based compound such as phosphine oxide based compound and bis- (cyclopentadienyl groups)-bis- [the fluoro- 3- of 2,6- bis- (pyrroles -1- base)] titaniums Deng.

As commercially available radical initiator, can enumerate Adeka Optomer N-1414, N-1717, N-1919, ADEKAARKLS NCI-831, NCI-930 (the above are Asahi Denka Co., Ltd.'s systems)；IRGACURE184,IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (the above are BASF AG's system)；TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (the above are TRONLY corporations) Deng.

As hot radical polymerization initiator, as long as not limited especially then by heating the substance generated free radicals System, can be used previously known compound, can exemplify the conduct such as azo compound, peroxide and persulfate Preferred compound.

As azo compound, can enumerate 2,2 '-azobis isobutyronitriles, 2,2 '-azos bis- (methyl isobutyrates), Double -2,4- the methyl pentane nitriles of 2,2 '-azos, 1,1 '-azos bis- (1- acetoxyl group -1- diphenylphosphino ethanes) etc..

As peroxide, it is new that benzoyl peroxide, di-t-butyl peroxide benzoyl, tert-butyl hydroperoxide can be enumerated Valerate and two (4- tert-butylcyclohexyl) peroxy dicarbonates etc..

As persulfate, persulfates such as ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate etc. can be enumerated.

Liquid crystal pollution is low, electric spy due to that can provide for polymerization initiator in above-mentioned polymerization initiator (C) with hydroxyl The excellent display device of property, so particularly preferably.

For above-mentioned polymerization initiator (C), can will so far illustrated by one or more be used in mixed way.

In polymerizable composition, polymerizable composition of the invention, for the content of above-mentioned polymerization initiator (C), it is not particularly limited, phase It is more excellent from the good aspect of curability preferably 0.1~20 mass parts for 100 mass parts of alkali-developable compound (B) It is selected as 0.3~10 mass parts, more preferably 0.3~5 mass parts.When the content of polymerization initiator (C) is in above-mentioned range, by In the polymerizable composition, polymerizable composition that excellent storage stability of the curability well and without the precipitation of polymerization initiator can be obtained, so It is preferred that.

In the case where for example forming the cured film with a thickness of 2~5 μm, for the content of polymerization initiator (C), without spy It does not limit, relative to total 100 mass parts of colorant (A), alkali-developable compound (B) and polymerization initiator (C), preferably 0.1~20 mass parts, more preferably 0.3~10 mass parts, more preferably 0.3~5 mass parts.

Ethylenically unsaturated compounds can be further added in polymerizable composition, polymerizable composition of the invention.By adding ethylenic bond Unsaturated compound, since sensitivity and chemical resistance improve, it is advantageous to.Above-mentioned ethylenically unsaturated compounds be with The compound of ethylenic bond unsaturated bond and not above-mentioned alkali-developable compound (B).As ethylenically unsaturated compounds, The unsaturated lipid such as ethylene, propylene, butylene, isobutene, vinyl chloride, vinylidene chloride, vinylidene, tetrafluoroethene can be enumerated Fat race hydrocarbon；(methyl) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, carbic acid, crotons Acid, iso-crotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono succinate [2- (methyl) propylene Trimethylammonium] ester, phthalic acid list [2- (methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) Two end such as acrylate has list (methyl) acrylate of the polymer of carboxyl and hydroxyl；(methyl) dihydroxypropyl second Ester maleate, (methyl) hydroxypropyl acrylate maleate, bicyclopentadiene maleate have 1 carboxylic The unsaturated polyacid such as multifunctional (methyl) acrylate of (methyl) acryloyl group of base and 2 or more；(methyl) acrylic acid- 2- hydroxy methacrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following acrylic compounds No.1~No.4, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid The tert-butyl ester, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid Different nonyl ester, (methyl) stearyl acrylate, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (methyl) Acrylate methyl esters, (methyl) acrylate, (methyl) acrylic-amino propyl ester, (methyl) third Poly- (ethyoxyl) ethyl ester of olefin(e) acid dimethylamino propyl ester, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid, (methyl) third Olefin(e) acid Butoxyethoxy ethyl ester, (methyl) ethylhexyl acrylate, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid Tetrahydrofuran ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two seasons Penta tetrol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, season Penta tetrol three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) acryloyl group second Base] the unsaturated monoacid such as isocyanuric acid ester, polyester (methyl) acrylate oligomer and polyalcohol or polyphenol ester；(first Base) the unsaturated polyacid such as zinc acrylate resin, (methyl) Magnesium Acrylate Prepared metal salt；Maleic anhydride, itaconic anhydride, citraconic anhydride, Methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, 5- (2,5- dioxo four Hydrogen furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, The acid anhydrides of the unsaturation polyacid such as dodecenylsuccinic anhydride, methyl norbornene dioic anhydride；(methyl) acrylamide, methylene Double-(methyl) acrylamide, diethylenetriamines three (methyl) acrylamide, bis- (methyl) acrylamides of xyxylene, α-chlorine The amide of the unsaturation monoacid such as acrylamide, N-2- hydroxyethyl (methyl) acrylamide and polyamines；The unsaturations such as methacrylaldehyde Aldehyde；The unsaturated nitriles such as (methyl) acrylonitrile, α-chloro-acrylonitrile, vinylidene cyanide, allyl cyanide；Styrene, 4- methylbenzene second Alkene, 4- ethyl styrene, 4- methoxy styrene, 4-Vinyl phenol, 4- chlorostyrene, divinylbenzene, vinyltoluene, Vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4- vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinyl benzyl The unsaturation aromatic compound such as glycidol ether；The beta-unsaturated ketones such as methyl vinyl ketone；Vinyl amine, allyl amine, N- second The unsaturated amine compounds such as vinyl pyrrolidone, vinylpiperidine；The vinyl alcohols such as allyl alcohol, crotonyl alcohol；Vinyl methyl The vinyl ethers such as ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether；Malaysia The unsaturated acyls imines such as acid imide, N-phenylmaleimide, N- N-cyclohexylmaleimide；The indenes such as indenes, 1- methyl indenes； The aliphatic conjugated dienes class such as 1,3- butadiene, isoprene, chlorobutadiene；Polystyrene, gathers poly- (methyl) methyl acrylate The end of the polymer molecular chains such as (methyl) n-butyl acrylate, polysiloxanes has the macromolecular list of single (methyl) acryloyl group Body class；Vinyl chloride, vinylidene chloride, divinyl succinate ester, diallyl phthalate, triallyl phosphate, isocyanide urea Sour triallyl, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, ethylene The vinyl carbamate compounds of yl pyridines, the vinyl monomer of hydroxyl and polyisocyanate compounds, hydroxyl The vinyloxirane of vinyl monomer and polyepoxides.

Above-mentioned ethylenically unsaturated compounds can be used alone or be used in mixed way two or more.

As above-mentioned ethylenically unsaturated compounds, commercially available product also can be used.As the commercially available product, can enumerate for example (the above are Japanizations by KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 Medicine corporation)；ARONIX M-215, M-350 (the above are East Asia Synesis Company systems)；NK ESTER A-DPH,A-TMPT,A- DCP, A-HD-N, TMPT, DCP, NPG and HD-N (the above are chemical industrial company, the village Xin Zhong systems)；SPC-1000,SPC-3000 (the above are Showa electrician corporations)；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 chemical industrial company, the village Xin Zhong systems), UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I (the above are chemical company, common prosperity society systems), Art Resin 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 Gen Shang industrial group systems), Sartomer CN968, CN975, CN989, CN9001, CN9010, CN9025, CN9029, CN9165, CN2260 (the above are Sartomer Company system), EBECRYL8810 (Daicel corporation) etc..

[chemical formula 18]

Acyclic compound No.1

[chemical formula 19]

Acyclic compound No.2

[chemical formula 20]

Acyclic compound No.3

[chemical formula 21]

Acyclic compound No.4

In polymerizable composition, polymerizable composition of the invention, for the content of ethylenically unsaturated compounds, it is not particularly limited, phase For total 100 matter of colorant (A), alkali-developable compound (B), polymerization initiator (C) and ethylenically unsaturated compounds Measure part, preferably 1~50 mass parts, more preferably 1~30 mass parts, further preferably 5~20 mass parts.Ethylenic bond insatiable hunger When content with compound is in above-mentioned range, since the curability and light-proofness of obtained solidfied material are excellent, so excellent Choosing.

Such as in the case where being formed with a thickness of 1~3 μm of cured film, for the content of ethylenically unsaturated compounds, It is not particularly limited, relative to polymerization initiator (C), colorant (A), alkali-developable compound (B) and ethylenic bond unsaturation Total 100 mass parts of object are closed, ethylenically unsaturated compounds are preferably 1~50 mass parts, more preferably 1~30 mass parts, Further preferably 5~20 mass parts.

Solvent can be further added in polymerizable composition, polymerizable composition of the invention.As the solvent, usually can according to need Using can (colorant (A), alkali-developable compound (B), polymerization initiator (C) and ethylenic bond be unsaturated by above-mentioned each ingredient Compound etc.) dissolution or dispersion solvent.It is different that such as methyl ethyl ketone, methyl amyl ketone, metacetone, acetone, methyl can be enumerated The ketone series solvents such as propyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone and 2-HEPTANONE；Ethylether, dioxanes, tetrahydrofuran, 1,2- diformazan The ether series solvents such as oxygroup ethane, 1,2- diethoxyethane and dipropylene glycol dimethyl ether；Methyl acetate, ethyl acetate, acetic acid N-propyl, isopropyl acetate, n-butyl acetate, 3- methoxybutyl acetic acid esters, cyclohexyl acetate, ethyl lactate, succinic acid two The ester series solvents such as methyl esters and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate (Texanol)；Ethylene glycol single methyl ether and second The cellosolves series solvents such as glycol list ethylether；The alcohol such as methanol, ethyl alcohol, isopropanol or normal propyl alcohol, isobutanol or n-butanol and amylalcohol Series solvent；Ethylene glycol monomethyl acetic acid esters, ethylene glycol list ethylhexoate, propylene glycol -1- monomethyl ether (PGM), propylene glycol -1- are single Methyl ether -2- acetic acid esters (PGMEA), dipropylene glycol monomethyl ether acetic acid esters, 3- methoxybutyl acetic acid esters and ethoxyethyl group propionic acid The ether-ethers series solvent such as ester；The BTX series solvent such as benzene, toluene and dimethylbenzene；The aliphatic hydrocarbon system such as hexane, heptane, octane and hexamethylene Solvent；The terpenic series hydrocarbon ils such as turpentine oil, D- limonene and firpene；(the above are the Guia Hill COSMO stones by mineral spirits, SWAZOL#310 Oily Co. Ltd. system)；And the alkanes hydrocarbon system solvent such as SOLVESSO#100 (the above are Exxon Chemical Co., Ltd. systems)；Four chlorinations The halogenated aliphatics hydrocarbon system solvents such as carbon, chloroform, trichloro ethylene, methylene chloride and 1,2- dichloroethanes；The halogenated aromatics such as chlorobenzene Hydrocarbon system solvent；Carbitol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N, N- dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and water etc., these solvents can be used a kind or as 2 kinds with On mixed solvent use.

In them, ketone series solvent, ester series solvent and ether-ether series solvent etc., particularly cyclohexanone, 3- methoxybutyl acetic acid Ester, dimethyl succinate and PGMEA etc. are since the compatibility of resist and polymerization initiator in polymerizable compositions is good, institute With preferred.

If by PGMEA, 3- methoxybutyl acetic acid esters, dimethyl succinate and if since it is possible to obtain uniform coating Face, it is advantageous to, and then the quality ratio (PGMEA:3- methoxybutyl acetic acid esters: dimethyl succinate) of above-mentioned solvent is 15 It is particularly preferred when~25:2~5:1.

In polymerizable composition, polymerizable composition of the invention, the content of above-mentioned solvent is not particularly limited, but preferably in polymerism group It closes in 100 mass % of object total amount and reaches 30~95 mass %, more preferably 50~95 mass %.

When the content of solvent is above range, when becoming treatability (viscosity or wetability of polymerizable composition, polymerizable composition), drying The excellent polymerism group of uneven reduction and liquid stability (without the precipitation or sedimentation of the ingredient for including in composition) Close object, when obtaining solidfied material can with the thickness of suitable control solidfied material, therefore preferably.

It can according to need further addition epoxide, alkali-developable in polymerizable composition, polymerizable composition of the invention to assign Agent, dispersing agent, potentiality additive, organic polymer, inorganic compound, coupling agent, chain-transferring agent, sensitizer, surface-active Agent and melamine compound, to thermal polymerization inhibitors such as anisole, quinhydrones, pyrocatechol, tert-butyl catechol and phenthazine； Plasticizer；Adhesion promoters；Filler；Defoaming agent；Levelling agent；Surface conditioner；Antioxidant；Ultraviolet absorbing agent；Dispersion Auxiliary agent；Anti- flocculating agent；Catalyst；Effect promotor；Crosslinking agent；The usual additive such as thickener.

As above-mentioned epoxide, such as methyl glycidyl ether, 2- hexyl glycidyl ether, fourth can be enumerated The mixed alkyl of base glycidol ether, decyl glycidyl ether, C12~13 glycidol ether, phenyl -2- methyl glycidyl ether, Cetyl glycidyl ether, stearyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, alkene Propyl glycidyl ether, ethyl ether, 2- Methyl Octyl glycidol ether, phenyl glycidyl ether, 4- n-butylbenzene Base glycidol ether, 4- phenylphenol glycidol ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl Glycidol ether, methoxy poly (ethylene glycol) monoglycidyl ether, ethyoxyl polyethylene glycol monoglycidyl ether, the poly- second two of butoxy Alcohol monoglycidyl ether, phenoxy group polyethylene glycol monoglycidyl ether, dibromo phenyl glycidol ether, 1,4- butanediol two shrink Glycerin ether, 1,5- neopentyl glycol diglycidyl glycerin ether, 1,6 hexanediol diglycidylether, neopentylglycol diglycidyl ether, 1, The glycidol ethers compounds such as four glycidol ether of (glycidyloxyphenyl) ethane of 1,2,2- tetra- and pentaerythrite；Acetic acid contracting The glycidols esters such as water glyceride, stearic acid glycidyl ester；2- (3,4- epoxycyclohexyl -5,5- spiral shell -3,4- epoxy) ring Hexane -1,3- dioxanes, di-2-ethylhexylphosphine oxide (3,4- 7-oxa-bicyclo[4.1.0), propane -2,2- diyl-bis- (3,4- 7-oxa-bicyclo[4.1.0), 2, Bis- (3,4- epoxycyclohexyl) propane of 2-, ethylenebis (3,4- epoxycyclohexane carboxylate), bis- (3,4- epoxycyclohexyl first Base) adipate ester, 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexane carboxylate, 3,4- epoxy -1- methylcyclohexyl 3,4- Epoxy -1- methyl hexane carboxylate, 6- methyl -3,4- epoxycyclohexyl-methyl 6- methyl -3,4- epoxycyclohexane carboxylate, 3, 4- epoxy -3- methylcyclohexylmethyl 3,4- epoxy -3- methylcyclohexanecarboxylic acid ester, 3,4- epoxy -5- methylcyclohexylmethyl 3,4- epoxy -5- methylcyclohexanecarboxylic acid ester, 1- epoxy ethyl -3,4- 7-oxa-bicyclo[4.1.0,1,2- epoxy group -2- epoxy ethyl ring Hexane, bicyclopentadiene epoxides, 3,4- epoxy -6- methylcyclohexyl carboxylate, α-epoxypinane, styrene oxide, ring The epoxies such as oxygen hexamethylene and cyclopentane epoxide naphthenic base type compound and N- glycidyl phthalimide etc..

As above-mentioned epoxide, epoxidized polyolefin also can be used.Epoxidized polyolefin refers to containing epoxy group Monomer polyolefin is modified and has been imported the polyolefin of epoxy group.It can be by utilizing appointing in copolymerization method or Graft Method One occurs that the alpha-olefin of ethylene or carbon number 3~20 altogether with other monomers used as needed with the monomer containing epoxy group Gather to manufacture.Alpha-olefin, the monomer containing epoxy group and the other monomers that ethylene or carbon number are 3~20 can individually polymerize, Can also with other monomers are multiple polymerize.Furthermore it is also possible to which end to be had to the unconjugated poly- fourth of hydroxyl using peracetic acid method The double bond of diene carries out epoxidation and obtains, and the epoxide that intramolecular has hydroxyl also can be used.Furthermore it is also possible to Hydroxyl is carried out urethane by isocyanates, is reacted with it the epoxide containing primary hydroxyl group and is imported epoxy group.

The alpha-olefin for being 3~20 as above-mentioned ethylene or carbon number, can enumerate ethylene, propylene, butylene, isobutene, 1,3- Butadiene, 1,4- butadiene, 1,3- pentadiene, 2,3- dimethyl -1,3- butadiene, piperylene, 3- butyl -1,3- octadiene And isoprene etc..

As the above-mentioned monomer containing epoxy group, such as α, ethylene oxidic ester, the vinyl benzyl of beta-unsaturated acid can be enumerated Base glycidol ether and allyl glycidyl ether etc..As α, the ethylene oxidic ester of beta-unsaturated acid can specifically be enumerated Glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate etc. out, particularly preferred methyl Glycidyl acrylate.

As above-mentioned epoxide, it can also disclose and use commercially available product.As suitable commercially available product, can enumerate for example Epolight 40E, 1500NP, 1600,80MF, 4000 and 3002 (the above are chemical company, common prosperity society systems)；Adeka Glycirol ED-503、ED-503D、ED-503G、ED-523T、ED-513、ED-501、ED-502、ED-509、ED-518、 ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085 (the above are Asahi Denka Co., Ltd.'s systems)； 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 Nagase ChemteX Co. Ltd. systems)；EHPE-3150, Celloxide 2021P, 2081,2000 and 3000 (the above are Daicel corporations)；EPIOL M, EH, L-41, SK, SB, TB and OH (the above are day oil corporations)；Epolight M-1230 and 100MF (the above are chemical company, common prosperity society systems)；ARON OXETANE OXT-121,OXT-221,EXOH,POX, OXA, OXT-101, OXT-211 and OXT-212 (the above are East Asia Synesis Company systems)；ETERNACOLL OXBP and OXTP (more than For the emerging production corporation in space portion)；2- hydroxyethyl vinyl ether, diethylene glycol monovinyl base ether and 4- hydroxybutyl vinyl ether (the above are balls to be apt to petrochemistry corporation)；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 (the above are Nagase ChemteX Co. Ltd. systems)；Ogsol PG-100,EG-200,EG- 210 and EG-250 (the above are Osaka Gas Chemicals corporations)；(the above are DIC by HP4032, HP4032D and HP4700 Corporation)；ESN-475V (Dongdu chemical conversion corporation)；(the above are You companies by Marproof G-0105SA and G-0130SP System)；EPICLON N-665 and HP-7200 (the above are DIC corporations)；EOCN-1020,EOCN-102S,EOCN-103S, (the above are Japan by EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L Chemical drug corporation) etc..

Above-mentioned so-called alkali-developable imparting agent refers to the compound for without free-radical polymerised and assigning alkali-developable, makees For such compound, as long as the compound dissolved in aqueous alkali and with acid value is not particularly limited, but As representative examples, alkali-soluble novolac resin (hereinafter referred to as " novolac resin ") can be enumerated.Novolaks tree Rouge is in the presence of acid catalyst to obtain phenols with aldehyde condensation polymer.

As above-mentioned phenols, such as phenol, o-cresol, metacresol, paracresol, o-ethyl phenol, ethylo benzene can be used Phenol, paraethyl phenol, adjacent butylphenol, butylphenol, p-butylphenol, 2,3 xylidine phenol, 2,4- dimethlbenzene, 2,5- Dimethlbenzene, 3,4- dimethlbenzene, 3,5- dimethlbenzene, 2,3,5- pseudocuminol, p-phenyl phenol, quinhydrones, catechol, Benzenediol, 2- methyl resorcinol, pyrogallol, alpha-Naphthol, bisphenol-A, dihydroxy-benzoic acid ester and gallate etc., these In phenols, preferably phenol, o-cresol, metacresol, paracresol, 2,5- dimethlbenzene, 3,5- dimethlbenzene, 2,3,5- trimethylbenzenes Phenol, resorcinol, 2- methyl resorcinol and bisphenol-A etc..These phenols can be used alone or be used in mixed way two or more.

As above-mentioned aldehydes, such as formaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde, ethylalbenzene, α-phenyl can be used Propionic aldehyde, beta-phenyl propionic aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, P-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, paranitrobenzaldehyde, o-tolualdehyde, tolyl aldehyde, P-tolyl aldehyde, p-ethylbenzaldehyde and to n-butylbenzene formaldehyde etc., preferably formaldehyde, acetaldehyde and benzaldehyde in these compounds Deng.These aldehydes can be used alone or two or more is used in mixed way.Aldehydes is with preferably 0.7~3 mole of every 1 mole of phenols, especially excellent 0.7~2 mole of ratio is selected to use.

As above-mentioned acid catalyst, the inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or formic acid, oxalic acid, acetic acid etc. can be used Organic acid.The preferably every 1 mole of phenols of the usage amount of these acid catalysts is 1 × 10^-4~5 × 10^-1Mole.In the condensation reaction, Usually using water as reaction medium, but the phenols used in the condensation reaction is not dissolved in the aqueous solution of aldehydes, from reaction From initial stage as heterogeneous system in the case where, hydrophilic solvent also can be used as reaction medium.As these hydrophilies Solvent can enumerate the ring-type ethers such as the alcohols such as methanol, ethyl alcohol, propyl alcohol and butanol or tetrahydrofuran and dioxanes.These The usage amount of reaction medium usually every 100 mass parts reaction raw materials are 20~1000 mass parts.The reaction temperature of condensation reaction can The appropriate adjustment with the reactivity according to reaction raw materials, but usually 10~200 DEG C, preferably 70~150 DEG C.Condensation reaction knot Shu Hou generally makes interior temperature rise to 130 to remove unreacting material existing in system, acid catalyst and reaction medium ~230 DEG C, it will volatilize ingredient under reduced pressure and be distilled off, then the novolac resin after melting is cast on steel band etc. And it recycles.

In addition after condensation reaction, can also be led to by the way that reaction mixture to be dissolved in above-mentioned hydrophilic solvent It crosses and is added in the precipitating reagents such as water, n-hexane and normal heptane and novolac resin is precipitated, precipitate is separated, and is added Heated drying and recycle.

As the example in addition to above-mentioned novolac resin, polycarboxylated styrene or derivatives thereof, benzene second can be enumerated Alkene-copolymer-maleic anhydride and polyvinyl hydroxybenzoate etc..

As above-mentioned dispersing agent, as long as colorant (B) can be dispersed, stabilize and then can be arbitrary substance, it can be with It is suitable for using comprising with basic functionality using the BYK series etc. of commercially available dispersing agent such as BYK Chemie corporation Polyester polyethers, the macromolecule dispersing agent of polyurethane, with nitrogen-atoms as basic functionality and with the functional group of nitrogen-atoms is Amine and/or its quaternary ammonium salt, the dispersing agent that amine value is 1~100mgKOH/g.

It is torpescence that so-called above-mentioned potentiality additive, which refers in room temperature, light exposure process and prebake conditions process, is passed through It carries out heating or being heated at 80~200 DEG C in the presence of acid/base catalyst and protecting group is de- at 100~250 DEG C From and activate substance.As the effect as obtained from activation, anti-oxidant, ultraviolet radiation absorption can be enumerated, soil resistance, applied again Property and adaptation etc..

As above-mentioned potentiality additive, it is preferable to use the substances recorded in WO2014/021023 pamphlet.

As above-mentioned potentiality additive, commercially available product can be used, such as ADEKA ARKLS GPA-5001 can be enumerated Deng.

As above-mentioned organic polymer, such as polystyrene, polymethyl methacrylate, methyl methacrylate can be enumerated Ester-ethyl acrylate copolymer, poly- (methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid-first Base methyl acrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl ester copolymer, Corvic, ABS resin, Nylon 6, nylon 12, polyurethane resin, polycarbonate, polyvinyl butyral, cellulose esters, polyacrylamide, is satisfied at nylon66 fiber It is excellent in them with polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin etc. Select polystyrene, (methyl) acryl acid-methyl methacrylate copolymer, epoxy resin.

By being used together above-mentioned organic polymer with above-mentioned alkali-developable compound (B), solidfied material can also be improved Characteristic.

When using organic polymer, usage amount is relative to above-mentioned 100 mass parts of alkali-developable compound (B), preferably 10~500 mass parts.

Above-mentioned inorganic compound can be contained.As the inorganic compound, such as nickel oxide, iron oxide, oxygen can be enumerated Change the metal oxides such as iridium, titanium oxide, zinc oxide, magnesia, calcium oxide, potassium oxide, silica and aluminium oxide；Lamellar clay It is mineral, milori blue, calcium carbonate, magnesium carbonate, cobalt system, manganese systems, glass powder, mica, talcum, kaolin, ferrocyanide, each Kind of metal sulfate, sulfide, selenides, alumina silicate, calcium silicates, aluminium hydroxide, platinum, gold, silver and copper etc., in them, preferably Titanium oxide, silica, layered clay mineral and silver etc..

By containing inorganic compound in polymerizable composition, polymerizable composition of the invention, photonasty cream paste composite, which can be made, to be made With.The photonasty cream paste composite is spaced walls pattern, the dielectric pattern, electrode in order to form plasm display panel The roast patterns such as pattern and black matrix pattern and use.

In addition, these inorganic compounds are for example also used as filler, antireflection agent, conductive agent, stabilizer, fire retardant, machine Tool intensity enhancer, special wavelength absorbent and anti-ink agent etc. are suitable for using.

In polymerizable composition, polymerizable composition of the invention, when adding inorganic compound, the content of inorganic compound is relative to above-mentioned 100 mass parts of alkali-developable compound (B), preferably 0.1~50 mass parts, more preferably 0.5~20 mass parts, these are inorganic Compound can be used one kind or two or more.

As above-mentioned coupling agent, such as dimethyldimethoxysil,ne, dimethyl diethoxysilane, methyl can be used Ethyldimethoxysilane, Methylethyl diethoxy silane, methyltrimethoxysilane, methyltriethoxysilane, ethyl The alkyl functionals such as trimethoxy silane, ethyl trimethoxy silane alkoxy silane, vinyl trichlorosilane, vinyl front three The alkenyls functionality such as oxysilane, vinyltriethoxysilane, allyltrimethoxysilanis alkoxy silane, 3- methyl Acryloxypropyl triethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxy Hydroxypropyl methyl diethoxy silane, 3- methacryloxypropylmethyl dimethoxysilane, 2- methacryloxy third The acrylate-functional alkoxy silane of base trimethoxy silane etc. (methyl), γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl diethoxy silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-(3,4- Epoxycyclohexyl) the epoxy functionals alkoxy silane, N- β (amino-ethyl)-gamma-amino propyl three such as propyl trimethoxy silicane The amino functionals such as methoxy silane, γ aminopropyltriethoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane The Mercaptofunctionals such as alkoxy silane, γ mercaptopropyitrimethoxy silane alkoxy silane, three ethoxy of 3- isocyanates propyl The urea/ureido functionals alkoxyl silicones such as the isocyanate-functionals such as base silane alkoxy silane, 3- ureidopropyltrialkoxysilane The isocyanuric acid esters functionality alkoxy silanes such as alkane, three (trimethoxy-silylpropyl) isocyanuric acid esters, titanium tetraisopropylate, The titaniums chelas such as bis- (ethohexadiol) titaniums of the Titanium alkoxides such as four n-butyl titaniums class, two octyloxies, bis- (ethyl acetoacetate) titaniums of diisopropoxy It is acylated to close zirconium chelates class, the three butoxy monostearate zirconiums such as species, four acetylacetone,2,4-pentanedione zirconiums, three butoxy single acetyl acetone zirconiums etc. Isocynate silanes classes such as zirconium class, methyl triisocyanate silane etc..

By adding coupling agent, the adaptation of (especially glass) between solidfied material and substrate is improved, therefore preferably.

As above-mentioned coupling agent, commercially available product can be used, can enumerate such as 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、 (the above are Shin- by KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504 and KF-99 Etsu Silicone corporation) etc..

As above-mentioned chain-transferring agent and sensitizer, the compound of sulfur atom-containing is generally used.Such as sulfydryl second can be enumerated Acid, thiomalic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3- mercaptopropionic acid, 3- mercaptobutyric acid, N- (2- mercapto radical propionyl group) are sweet Propylhomoserin, 2- mercaptonicotinic acid, 3- [N- (2- mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2- mercaptoethyl) amino] propionic acid, N- (3- mercapto radical propionyl group) alanine, mistabrom, 3- thiohydracrylic acid, 4- sulfydryl fourth sulfonic acid, dodecyl (4- methyl It is thio) phenyl ether, 2 mercapto ethanol, 3- sulfydryl -1,2- propylene glycol, 1- sulfydryl -2- propyl alcohol, 3- sulfydryl -2- butanol, sulfydryl benzene Phenol, 2- mercaptoethyl amine, 2- mercaptoimidazole, 2-mercaptobenzimidazole, 2- sulfydryl -3- pyridine alcohol, 2-mercaptobenzothiazole, sulfydryl The sulfhydryl compounds such as acetic acid, trimethylolpropane tris (3-thiopropionate) and pentaerythrite four (3-thiopropionate)；It should Disulfide compound, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2- iodine ethanesulfonic acid and 3- iodine third obtained from sulfhydryl compound oxidation The iodate alkyl compound such as sulfonic acid；Trimethylolpropane tris (3- mercaptoisobutanoic acid esters), butanediol bis- (3- mercaptoisobutanoic acid esters), The double thiopropionates of ethanthiol, two mercaptan of the last of the ten Heavenly stems, 1,4- dimethyl sulfydryl benzene, butanediol, butanediol double thiacetates, second two The double thiacetates of alcohol, trimethylolpropane tris thiacetate, the double thiopropionates of butanediol, trimethylolpropane tris are thio Propionic ester, trimethylolpropane tris thiacetate, pentaerythrite tetrathio propionic ester, pentaerythrite tetrathio acetic acid esters, three Three thiopropionate of hydroxyethyl, following compound N o.C1, Showa electrician corporation Karenz PE1 and NR1 etc..

[chemical formula 22]

Compound N o.C1

By adding above-mentioned chain-transferring agent and sensitizer, since the pattern of obtained solidfied material becomes fine, so It is preferred that.

As above-mentioned surfactant, the fluorine surface-active such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used The anionic surfactants such as agent, higher aliphatic acid alkali metal salt, alkylsulfonate, alkyl sulfate, higher amines halogen acids The cationic systems such as salt, quaternary ammonium salt surfactant, polyethylene glycol alkyl ether, cithrol, sorbitan esters of fatty The tables such as the nonionic surfactants such as acid esters, glycerine monofatty ester, amphoteric surfactant and silicone based surfactants Face activating agent, they can also be applied in combination.

As above-mentioned melamine compound, (poly-) melamine methylol, (poly-) methylol glycoluril, (poly-) can be enumerated Active methylol (CH in the nitrogen compounds such as methylolbenzoguanamine and (poly-) methylolurea₂OH yl) in all or part of (at least two) compound obtained from alkyl etherified.Here, as the alkyl for constituting alkyl ether, methyl, ethyl can be enumerated And butyl, it can be mutually the same, it can also be different.In addition, can not self condensed in an intramolecular by alkyl etherified methylol, It can also be in two intermolecular condensations, as a result, forming oligomer ingredient.Specifically, hexamethoxy methyl trimerization can be used Cyanamide, six butoxymethyl melamines, tetramethoxymethylglycoluril and four butoxymethyl glycolurils etc..In them, preferably six Methoxy melamine and six butoxymethyl melamines etc. are by alkyl etherified melamine.

In polymerizable composition, polymerizable composition of the invention, for removing colorant (A), alkali-developable compound (B), polymerization initiator (C), the content of any ingredient other than ethylenically unsaturated compounds, solvent and inorganic compound can use purpose according to it And suitably select, as long as not damaging effect of the invention, it is not particularly limited, preferably with respect to polymerization initiator (C), coloring Agent (A), alkali-developable compound (B) and ethylenically unsaturated compounds total 100 mass parts, add up to 20 mass parts with Under.

BM of the invention is containing colorant (A), alkali-developable compound (B) and polymerization initiator with photosensitive composite (C) as essential component and with photonasty and alkali-developable, the composition for being particularly suitable to form BM.

BCS of the invention with photosensitive composite is caused containing colorant (A), alkali-developable compound (B) and polymerization Agent (C) is as essential component and has photonasty and alkali-developable, the composition for being particularly suitable to form BCS.

Polymerizable composition, polymerizable composition, BM photosensitive composite or BCS photosensitive composite of the invention and solidfied material can With (colour television set, PC monitor, portable for curable coating, varnish, curability bonding agent, printed base plate, display device The colour filter of colour filter, various display purposes in the liquid crystal display panel of the colored display such as information terminal and digital camera, Colour filter, touch panel, the electrical luminous display unit (the interval wall material of miniature LED), plasma of ccd image sensor The black interval wall of display panel, organic EL), powder coating, printing ink, galley, bonding agent, gel coat, electronics work Photoresist, platedresist, etching resist, solder resist, insulating film, black matrix" and the manufacture in LCD of Cheng Xueyong Be used to form in process the resist of structure, the composition for enclosed electrical and electronic component, solder resist, magnetic recording material, Milli machine component, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coatings, Silk-screen printing template, the material for manufacturing three-dimension object by stereolithography, holographic recording material, image Recording materials, fine electronic circuit, decoloring material, the decoloring material for image recording material, the note of the image using microcapsules Record the light of the decoloring material of material, printed wiring board-use photo anti-corrosion agent material, UV and visible laser through image system Cause photo anti-corrosion agent material and guarantor used in the dielectric layer formation in the gradually stacking of anticorrosive additive material, printed circuit board Its purposes is not particularly limited in the various uses such as cuticula, in such use, can be particularly suitable for display device.

Display device of the invention other than having solidfied material of the invention (especially BCS), be with it is known The identical composition of display device, but BCS is arranged between unit and unit preferably.

As organic EL black interval wall and when using polymerizable composition, polymerizable composition of the invention, from the vertical of pattern form The aspect that change, the raising of development adaptation, heat resistance improve is set out, it is preferable to use the alkali development that weight average molecular weight is 5000 or more Property compound, further preferably using weight average molecular weight be 7000~15000 alkali-developable compound.In turn, particularly preferably Alkali-developable compound is the unsaturation with structure obtained from the esterification as epoxy additive compound and multi-anhydride The case where compound, wherein the epoxy additive compound, which has, to be made represented by unsaturated monoacid and above-mentioned logical formula (III) Structure obtained from epoxide addition.

Below to use polymerizable composition, polymerizable composition of the invention, BM photosensitive composite and BCS with photosensitive composite come The method of manufacture solidfied material is described in detail.

Polymerizable composition, polymerizable composition, BM photosensitive composite and BCS photosensitive composite of the invention can pass through spin coating Machine, roll coater, bar coater, die coating machine, curtain coater, various printings, means well known to impregnating are applied to soda-lime glass, quartz In the support substrates such as glass, semiconductor substrate, metal, paper, plastics.Alternatively, it is also possible to be implemented in the support substrates such as film for the time being Afterwards, it is transferred in other support substrates, being applied to method, there is no limit.

In addition, as keeping polymerizable composition, polymerizable composition of the invention, BM photosensitive composite and BCS solid with photosensitive composite The light source of the energy-ray used when change can use and be steamed by ultrahigh pressure mercury lamp, high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, mercury Vapour arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excited quasi-molecular lampbulb, bactericidal lamp, light emitting diode, Electromagnetic wave energy or electron ray, X-ray, radioactive ray of the wavelength with 2000 angstroms~7000 angstroms that CRT light source etc. obtains etc. High-energy rays can preferably enumerate ultrahigh pressure mercury lamp, the mercuryvapour arc lamp, carbon arc for issuing the light that wavelength is 300~450nm Lamp, xenon arc lamp etc..

In turn, by using laser in exposure light source, from just direct by computer digital information without the use of mask Raising of the direct picture of laser of image due to can not only seek productivity is formed, clarity or position precision etc. can be also sought Raising so being useful be suitable for that also can be used using the light of the wavelength of 340~430nm and be excited standard as the laser Molecular laser, argon ion laser, helium cadmium laser, He-Ne laser, krypton ion laser, various is partly led at nitrogen laser Body laser and YAG laser etc. issue the laser of the light of visible infrared region.Using these lasers, The sensitizing coloring matter absorbed from the visible infrared region can be added.

When being solidified by heating, 100 seconds prebake conditions are carried out at 70~100 DEG C, after solvent is removed, 150 DEG C~250 DEG C at carry out 30 minutes~1 hour heating and solidify.If solidification temperature is lower than 150 DEG C, do not cause sometimes sufficiently Solidification, be 250 DEG C or more when, it is possible to cause the coloring or decomposition of cured film.

Solidfied material of the invention is particularly useful as BCS.BCS is preferably formed by following process: (1) being formed on substrate The process of the film of BCS photosensitive composite of the invention；(2 across the mask with defined pattern form to the film Irradiate the process of radioactive ray；(3) roasting procedure after exposing；(4) process developed to the envelope after exposure；(5) will The process that the envelope after development is heated.

As aforementioned mask, more gray scale masks such as half-tone mask or gray-tone mask also can be used.