CN107643654A - Photosensitive polymer combination, cured film, the manufacture method of colour filter and cured film - Google Patents

Abstract

The present invention provides herein below：Photosensitive polymer combination, the heating being not easy during because of rear baking and excess flow, and the staining and curing film of fine pattern can be formed with desired size；Use the manufacture method of the cured film of the photosensitive resin composition；Cured film, form photosensitive polymer combination solidification；Colour filter, possesses the cured film.In the photosensitive polymer combination comprising (A) alkali soluble resin, (B) photopolymerizable compound, (C) Photoepolymerizationinitiater initiater and (D) pigment, using novolac resin as (A) alkali soluble resin, and the dendritic that there is more than 2 ethene polymerizable groups in end is used to be used as (B) photopolymerizable compound.

Description

Photosensitive polymer combination, cured film, the manufacture method of colour filter and cured film

Technical field

The present invention relates to negative light-sensitive resin combination, make the photosensitive polymer combination solidification form cured film, Possess the cured film colour filter, using the negative light-sensitive resin combination cured film manufacture method.

Background technology

The display body structure of liquid crystal display etc. is that 2 pieces of substrates are formed with phase across liquid crystal layer between 2 pieces of substrates Mutually opposed paired electrode.Moreover, side substrate inner side formed with colour filter, the colour filter have red (R), The pixel that green (G), blue (B) etc. each color are formed.Moreover, in the colour filter, in order to prevent the difference in each pixel The colour mixture of color, or the pattern of buried electrode, are conventionally formed with black matrix", the black matrix" be configured to it is rectangular, to draw Divide R, G, B assorted pixel.

Colour filter is typically formed by photoetching process.Specifically, first on substrate painting black photoresist group Compound, exposure, development, so as to form black matrix".Afterwards, then by each in each red (R), green (G), blue (B) Repeat to be coated with the photosensitive polymer combination of color, expose, develop, the pattern of colors is formed in defined position, so as to be formed Colour filter.

As the forming method for the coloring film for forming colour filter, for example, the forming method on black matrix", it is proposed that having makes With the method for negative light-sensitive resin combination.

Specifically, it is proposed that have using following negative light-sensitive resin combination, it is included：Photopolymerizable compound, Photoepolymerizationinitiater initiater, the acrylic resin fine-particles dispersion liquid for being dispersed with acrylic resin fine-particles and solvent are (with reference to patent text Offer 1).

Following technology has also been opened up in recent years：Black anti-corrosion agent as the shading composition comprising black organic pigment etc. With photosensitive polymer combination, or, the dissipating resin composition comprising colouring agent, dendroid of the mixing with specific structure is gathered Compound.

According to above-mentioned technology, it can realize film coated surface smoothly without producing the rough surface caused by heat cure is shunk Spend the resin combination deteriorated, or adaptation or the excellent composition of pattern form during development (with reference to patent document 2,3).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-170075 publications

Patent document 2：Japanese Unexamined Patent Publication 2012-27448 publications

Patent document 3：Japanese Unexamined Patent Publication 2012-93591 publications

The content of the invention

Invention technical problems to be solved

In patent document 1, it is proposed that negative photosensitive resin group is mixed in using resin-coating carbon black as black pigment In compound.If using resin-coating carbon black as opacifier, the high black matrix" of impedance value is easily formed.

But in the case where using resin-coating carbon black as opacifier, it is difficult to form high black of optical density (OD) (OD) Colour moment battle array.

In order to eliminate the problem of above-mentioned optical density (OD) is low, and the high cured film of impedance value is formed, consideration uses aggregate particle size Small pigment.

But in the case of the pigment small using aggregate particle size, after the coloring for the colour filter for forming black matrix" etc. Cured film, situations below be present：Due to the heating of rear baking that is carried out after exposure and development and excess flow, so as to produce The change in shape of the unacceptable degree of cured film.

And then the general coloring film for requiring, the patterning for forming colour filter being accurately formed according to designed size.

Although in the case where using composition disclosed in patent document 2 or patent document 3, for described cured film Shape distortion shows certain inhibition, it can be difficult to forming pattern according to designed size.

The present invention be in view of above-mentioned technical problem and propose, and it is an object of the present invention to provide herein below：Photosensitive resin composition Thing, and heating excess flow during because of rear baking is not easy, and the coloring that fine pattern can be formed with desired size is consolidated Change film；Use the manufacture method of the cured film of the photosensitive polymer combination；Cured film, solidify the photosensitive polymer combination Form；Colour filter, possesses the cured film.

For solving the scheme of above-mentioned technical problem

The inventors discovered that by triggering comprising (A) alkali soluble resin, (B) photopolymerizable compound, (C) photopolymerization In the photosensitive polymer combination of agent and (D) pigment, using novolac resin as (A) alkali soluble resin, and use In end, the dendritic with the ethene polymerizable group of more than 2 is used as (B) photopolymerizable compound, can solve Certainly above-mentioned technical problem, so as to complete the present invention.Specifically, the present invention provides herein below.

The 1st scheme of the present invention is photosensitive polymer combination, comprising：

(A) alkali soluble resin；

(B) photopolymerizable compound；

(C) Photoepolymerizationinitiater initiater；With

(D) pigment,

(A) alkali soluble resin includes novolac resin,

(B) photopolymerizable compound is included in dendroid polymerization of the end with the ethene polymerizable group of more than 2 Thing.

The 2nd scheme of the present invention is cured film, is formed as the photosensitive polymer combination solidification described in the 1st scheme.

The 3rd scheme of the present invention is colour filter, possesses the cured film described in the 2nd scheme.

The 4th scheme of the present invention is the manufacture method of cured film, includes following process：

The process for forming film by being coated with the photosensitive polymer combination described in the 1st scheme；

The process that selection position is exposed to film；

Make the painting film development of exposure, the process for forming the cured film of patterning；

The process for toasting the cured film of patterning.

Invention effect

In accordance with the invention it is possible to provide herein below：Photosensitive polymer combination, the heating being not easy during because of rear baking and mistake Degree flowing, and the staining and curing film of fine pattern can be formed with desired size；Use the photosensitive resin composition The manufacture method of cured film；Cured film, form photosensitive polymer combination solidification；Colour filter, possesses the cured film.

Embodiment

Hereinafter, based on preferred embodiment, the present invention will be described.In addition, "~" in this specification, if do not had There is special instruction, then it represents that more than (lower limit) to following (higher limit).

《Photosensitive polymer combination》

Photosensitive polymer combination includes (A) alkali soluble resin, (B) photopolymerizable compound, (C) Photoepolymerizationinitiater initiater (D) pigment.

Photosensitive polymer combination includes the novolac resin as (A) alkali soluble resin.In addition, photoresist The dendritic that composition is included in end and has the ethene polymerizable group more than 2 is used as (B) optical polymerism Compound.

Photosensitive polymer combination is by comprising above-mentioned novolac resin and dendritic, being not easy to toast because after When heating and excess flow, and easily with desired size formed fine pattern staining and curing film.

Hereinafter, necessary or the arbitrary composition and photosensitive resin composition included to photosensitive polymer combination The preparation method of thing illustrates.

<(A) alkali soluble resin>

Photosensitive polymer combination includes (A) alkali soluble resin.

Herein, in this manual, (A) alkali soluble resin refers to possess the functional group with alkali-soluble in intramolecular The resin of (such as phenolic hydroxyl group, carboxyl, sulfonic group etc.).

(A) alkali soluble resin includes (A1) novolac resin.Photosensitive polymer combination is by including (A1) phenolic aldehyde Varnish gum is used as (A) alkali soluble resin, and easy formation is not easy the cured film of heating during because of rear baking and excess flow.

Hereinafter, (A1) novolac resin and the alkali soluble resin beyond (A1) novolac resin are illustrated.

﹝ (A1) Fen Novolac Shu Zhi ﹞

The various novolac resins for being mixed in photosensitive polymer combination in the past can be used to be used as (A1) novolaks Resin.Preferably through the aromatic compound (hreinafter referred to as " phenols ") and aldehydes for making there is phenolic hydroxyl group in acid catalyst Product obtained by lower addition polymerization is used as (A1) novolac resin.

(phenols)

As for making phenols during (A1) novolac resin, can enumerate, such as phenol；Orthoresol, metacresol, The cresols class of paracresol etc.；2,3 xylidine phenol, 2,4- xylenols, 2,5- xylenols, 2,6- xylenols, 3,4- diformazans The dimethylbenzene phenols of phenol, 3,5- xylenols etc.；The ethyl -phenol of o-ethyl phenol, m-ethylphenol, paraethyl phenol etc. Class；2- isopropyl-phenols, 3- isopropyl-phenols, 4- isopropyl-phenols, adjacent butylphenol, a butylphenol, p-butylphenol with And the alkylbenzene phenols of p-t-butyl phenol etc.；The trialkyl benzene of 2,3,5- pseudocuminols and 3,4,5- pseudocuminols etc. Phenols；Resorcinol, catechol, hydroquinones, hydroquinone monomethyl ether, 1,2,3,-thrihydroxy-benzene and phloroglucin etc. it is polynary Phenols；Alkyl polyatomic phenol (the carbon of all alkyl of alkyl-resorcin, alkyl catechol and alkyl hydroquinones etc. Atomicity is less than more than 1 4)；Alpha-Naphthol；Betanaphthol；Xenol and bisphenol-A etc..These phenols can individually make With two or more use can also be combined.

In these phenols, preferably metacresol and paracresol, more preferably and with metacresol and paracresol.This In the case of, by adjusting the mixed proportion of the two, can adjust using photosensitive polymer combination formed cured film it is heat-resisting Many characteristics such as property.

Although the mixed proportion of metacresol and paracresol is not particularly limited, the mol ratio of metacresol/paracresol Preferably less than more than 3/7 8/2.By using the metacresol and paracresol of above range ratio, being readily available to form The photosensitive polymer combination of the cured film of excellent heat resistance.

In addition, the it is also preferred that and novolac resin that is manufactured with metacresol and 2,3,5-TEP.Using institute In the case of stating novolac resin, the photosensitive polymer combination particularly easy to obtain with following performance：The photonasty Resin combination can be formed be not easy heating during because of rear baking and the cured film of excess flow.

Although the mixed proportion of cresols and 2,3,5-TEP is not particularly limited, metacresol/2,3,5- The mol ratio of pseudocuminol is preferably less than more than 70,/30 95/5.

(aldehydes)

As for making aldehydes during (A1) novolac resin, can enumerate, for example, formaldehyde, paraformaldehyde, furfural, Benzaldehyde, nitrobenzaldehyde and acetaldehyde etc..These aldehydes can be used alone, and can also combine two or more use.

(acid catalyst)

As for making acid catalyst during (A1) novolac resin, can enumerate, for example, hydrochloric acid, sulfuric acid, nitric acid, The inorganic acids of phosphoric acid and phosphorous acid etc.；The organic acid of formic acid, oxalic acid, acetic acid, diethyl sulfuric acid and p-methyl benzenesulfonic acid etc. Class；And metallic salt of zinc acetate etc. etc..These acid catalysts can be used alone, and can also combine two or more use.

(molecular weight)

From the cured film formed using photosensitive polymer combination to from the viewpoint of the patience that is flowed by heating, (A1) The polystyrene conversion weight average molecular weight (Mw of novolac resin；Hereinafter also referred to as " weight average molecular weight ") lower limit it is preferred It is 2000, more preferably 5000, particularly preferably 10000, and then preferably 15000, most preferably 20000, higher limit is preferred It is 50000, more preferably 45000, and then preferably 40000, most preferably 35000.

The novolac resin that can use at least two kinds of polystyrene conversion weight average molecular weight different in combination is used as (A1) Novolac resin.By size combinations using the resin that weight average molecular weight is different, photosensitive polymer combination can be balanced Developability with using photosensitive polymer combination formed cured film heat resistance.

﹝ (A2) has the Shu Zhi ﹞ for blocking more structures

From the viewpoint of the further resistance to mobility for improving cured film, it can also make to include in photosensitive polymer combination (A2) there is the resin (following, to be also denoted as (A2) and block more resins) for blocking more structures to be used as (A) alkali soluble resin.

Can use to have in its structure and block more skeletons, and the resin conduct (A2) with defined alkali-soluble with Block the resin of more skeletons.Block more skeletons to refer on 1 ring carbon atom for forming the 1st cyclic structure, be bonded the 2nd cyclic structure With the skeleton of the 3rd cyclic structure.In addition, the skeleton of the 2nd cyclic structure and the 3rd cyclic structure can be identical structure, also may be used To be different structures.

As the representative example of the more skeletons of card, it can enumerate on the carbon atom of 9 of fluorenes ring and be bonded 2 aromatic rings The skeleton of (such as phenyl ring).

Block more structural resins as (A2), be not particularly limited, known resin can be used.Wherein, preferably It is the resin that following formula (a-1) represents.

【Chemical formula 1】

In formula (a-1), X^aRepresent as the group shown in following formula (a-2).M1 represents 0~20 integer.

【Chemical formula 2】

In above-mentioned formula (a-2), R^a1Separately represent that hydrogen atom, the alkyl of carbon number 1~6 or halogen are former Son, R^a2Separately represent hydrogen atom or methyl, R^a3Separately represent the alkylidene of straight chain or side chain, m2 tables Show 0 or 1, W^aRepresent the group shown in following formula (a-3).

【Chemical formula 3】

In formula (a-2), the alkylidene that preferably carbon number is 1~20 is as R^a3, more preferably carbon number be 1~ 10 alkylidene, particularly preferably carbon number are 1~6 alkylidene, most preferably ethane -1,2- diyl, propane -1,2- bis- Base and propane -1,3- diyls.

Ring A in formula (a-3) represents aliphatic ring, can be condensed with aromatic ring, it is possible to have substituent.Aliphatic Ring can be aliphatic hydrocarbon ring or aliphatic heterocycle.

As aliphatic ring, monocyclic alkane, bicyclic alkane, three cycloalkane, Fourth Ring alkane etc. can be enumerated.

Specifically, monocyclic alkane or adamantane, the drop ice of pentamethylene, hexamethylene, cycloheptane, cyclooctane etc. can be enumerated Piece alkane, isoborneol alkane, tristane, tetracyclododecane.

Can be able to be aromatic series hydrocarbon ring or heteroaromatic with the aromatic ring of aliphatic cyclic condensation, preferably It is aromatic series hydrocarbon ring.Specifically, preferably phenyl ring and naphthalene nucleus.

Enumerate the preferable example of divalent group that following groups represents as formula (a-3).

【Chemical formula 4】

Divalent group X in formula (a-1)^a, by making offer residue Z^aTetracarboxylic dianhydride and following formula (a-2a) represent Diatomic alcohol compounds react, and are fed to (A1) and block in more resins.

【Chemical formula 5】

In formula (a-2a), R^a1、R^a2、R^a3And the explanation of the same formulas of m2 (a-2).The same formulas of ring A (a-3) in formula (a-2a) Explanation.

The diatomic alcohol compounds that formula (a-2a) represents, are to manufacture what is obtained for example, by following method.

First, as needed according to conventional method, the phenol hydroxyl that the diatomic alcohol compounds that following formula (a-2b) represents are had Hydrogen atom in base, is substituted by-R^a3After the group that-OH is represented, using glycidyls such as epichlorohydrins, following formula is obtained (a-2c) epoxide represented.

Then, reacted, obtained with acrylic or methacrylic acid by the epoxide for representing formula (a-2c) The diatomic alcohol compounds that formula (a-2a) represents.

In formula (a-2b) and formula (a-2c), R^a1、R^a2、R^a3And the explanation of the same formulas of m2 (a-2).Formula (a-2b) with And the explanation of the same formulas of ring A (a-3) in formula (a-2c).

In addition, the manufacture method for the diatomic alcohol compounds that formula (a-2a) represents, is not limited to the above method.

【Chemical formula 6】

The preferable example of diatomic alcohol compounds that following diatomic alcohol compounds represent as formula (a-2b) can be enumerated.

【Chemical formula 7】

In above-mentioned formula (a-1), R^a0For hydrogen atom or-CO-Y^aThe group that-COOH is represented.Herein, Y^aRepresent from dicarboxylic acids Acid anhydride removes the residue after anhydride group (- CO-O-CO-).As the example of dicarboxylic anhydride, can enumerate maleic anhydride, succinic anhydride, Itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrochysene neighbour's benzene Dicarboxylic acid anhydride (methyl endomethylene tetrahydrophthalic acid anhydride), chlorendic anhydride, first Base tetrabydrophthalic anhydride, glutaric anhydride etc..

In addition, in above-mentioned formula (a-1), Z^aRepresent from the residue after tetracarboxylic dianhydride's 2 anhydride groups of removing.As tetrabasic carboxylic acid The example of dianhydride, can enumerate following formula (a-4) expression tetracarboxylic dianhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic Dianhydride, bibenzene tetracarboxylic dianhydride, Biphenyl Ether tetracarboxylic dianhydride etc..

In addition, in above-mentioned formula (a-1), m represents 0~20 integer.

【Chemical formula 8】

(in formula (a-4), R^a4、R^a5And R^a6Separately represent from the alkyl by hydrogen atom, carbon number 1~10 with And a kind selected in the group of fluorine atom composition, m3 represents 0~12 integer.)

It is chosen as R in formula (a-4)^a4Alkyl be carbon number be 1~10 alkyl.Pass through the carbon atom for possessing alkyl Number is set in the scope, can further improve the obtained heat resistance of carboxylate.In R^a4In the case of for alkyl, from easily obtaining From the viewpoint of the more resins of card for obtaining excellent heat resistance, its carbon number is preferably 1~6, more preferably 1~5, and then preferably 1~4, particularly preferably 1~3.

In R^a4In the case of alkyl, the alkyl can be that straight-chain can also be branched.

From the viewpoint of the more resins of card for being readily available excellent heat resistance, as the R in formula (a-4)^a4, it is preferably only respectively It is on the spot the alkyl that hydrogen atom or carbon number are 1~10.Further preferably by hydrogen atom, methyl, ethyl, n-propyl or Isopropyl is as the R in formula (a-4)^a4, particularly preferably using hydrogen atom or methyl as the R in formula (a-4)^a4。

Because easily preparing the tetracarboxylic dianhydride of high-purity, multiple R in formula (a-4)^a4Preferably identical group.

M3 in formula (a-4) represents 0~12 integer.It is less than 12 by m3 value, tetracarboxylic dianhydride can be made Purifying become easy.

From the viewpoint of tetracarboxylic dianhydride easily purifies, the m3 upper limit is preferably 5, more preferably 3.

From the viewpoint of the chemical stability of tetracarboxylic dianhydride, m3 lower limit is preferably 1, more preferably 2.

M3 in formula (a-4) is particularly preferably 2 or 3.

It is chosen as R in formula (a-4)^a5And R^a6Carbon number be 1~10 alkyl, with being chosen as R^a4Carbon number It is identical for 1~10 alkyl.

From the viewpoint of tetracarboxylic dianhydride easily purifies, R^a5And R^a6Preferably hydrogen atom or carbon number be 1~ The alkyl of 10 (preferably 1~6, more preferably 1~5, and then preferably 1~4, particularly preferably 1~3), particularly preferably hydrogen Atom or methyl.

The tetracarboxylic dianhydride represented as formula (a-4), can enumerate for example：Norbornane -2- spiral shells-α-cyclopentanone-α ' - Spiral shell -2 "-norbornane -5,5 ", 6,6 "-tetracarboxylic dianhydride (alias " norbornane -2--cyclopentanone -5 '-of spiral shell -2 ' spiral shell -2 "-drop Bornylane -5,5 ", 6,6 "-tetracarboxylic dianhydride "), methyl norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-(methyl norborneol Alkane) -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclohexanone-α '-spiral shell -2 " and-norbornane -5,5 ", 6,6 " - Tetracarboxylic dianhydride " (alias " norbornane -2--cyclohexanone -6 '-of spiral shell -2 ' spiral shell -2 "-norbornane -5,5 ", 6,6 "-tetrabasic carboxylic acid two Acid anhydride "), methyl norbornane -2- spiral shells-α-cyclohexanone-α '-spiral shell -2 "-(methyl norbornane) -5,5 ", 6,6 "-tetracarboxylic dianhydride, Norbornane -2- spiral shells-α-cyclopropanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells - α-cyclobutanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclobutanone-α '-spiral shells - 2 "-norbornane -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclooctanone-α '-spiral shell -2 "-norbornane -5, 5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclononanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetrabasic carboxylic acid Dianhydride, norbornane -2- spiral shells-α-ring decanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane - 2- spiral shells-α-cycloundecanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-ring 12 Ketone-α '-spiral shell -2 "-norbornane -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclotridecanone-α '-spiral shell -2 " - Norbornane -5,5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclotetradecanone-α '-spiral shell -2 "-norbornane -5, 5 ", 6,6 "-tetracarboxylic dianhydride, norbornane -2- spiral shells-α-cyclopentadecanone-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic acid Acid dianhydride, norbornane -2- spiral shells-α-(methyl-cyclopentanone)-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride, drop Bornylane -2- spiral shells-α-(methyl cyclohexanone)-α '-spiral shell -2 "-norbornanes -5,5 ", 6,6 "-tetracarboxylic dianhydride etc..

(A2) weight average molecular weight for blocking more resins is preferably 1000~40000, more preferably 2000~30000.By making (A2) weight average molecular weight for blocking more resins is above range, can obtain good developability, and obtain sufficient heat resistance, Film-strength.

﹝ others alkali solubility Shu Zhi ﹞

In the range of without prejudice to the purpose of the present invention, (A) alkali soluble resin can also contain (A1) novolaks tree Fat and (A2) block other alkali soluble resins beyond more resins.Other alkali soluble resins, as long as with regulation Alkali-soluble resin, be just not particularly limited, can be from the various resins for being mixed in photosensitive polymer combination in the past In suitably selected.

From the viewpoint of many characteristics comprising alkali soluble resin etc. are easily adjusted, preferably by (A3) acrylic compounds Resin is as other alkali soluble resins.

It can use containing the construction unit from (methyl) acrylic acid, and/or from (methyl) acrylate etc. Other monomers construction unit acrylic resin be used as (A3) acrylic resin.(methyl) acrylic acid be acrylic acid or Person's methacrylic acid.(methyl) acrylate is the material that following formula (a-5) represents, as long as without prejudice to the purpose of the present invention, just It is not particularly limited.

【Chemical formula 9】

In above-mentioned formula (a-5), R^a7It is hydrogen atom or methyl, R^a8It is the organic group of 1 valency.The organic group also may be used To include key or substituent beyond the alkyl of hetero atom etc. in the organic group.In addition, the organic group can be straight chain Shape, branched, ring-type it is any.

As long as the effect of the present invention is not damaged, to as R^a8Organic group in alkyl beyond substituent just without spy Do not limit, halogen atom, hydroxyl, sulfydryl, thioether group, cyano group, isocyano group, cyanato, isocyanato, thio cyanogen can be enumerated Acyl group, different Thiocyanato, silicyl, silanol group, alkoxy, alkoxy carbonyl, carbamoyl, thiocarbamoyl Base, nitro, nitroso, carboxyl, carboxylic acid ester groups, acyl group, acyloxy, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphine Acyl group, phosphonate group, oximido, alkylether radicals, alkyl sulfide ether, aryl ether, aryl thioethers base, amino (- NH₂、-NHR、- NRR’：R and R ' separately represent alkyl) etc..Institute's hydrogen atoms can also be substituted by alkyl in above-mentioned substituent.This Outside, the alkyl or straight-chain that contains in above-mentioned substituent, branched and ring-type it is any.

Preferably using alkyl, aryl, aralkyl or heterocyclic radical as R^a8, can also use halogen atom, hydroxyl, alkyl or Person's heterocyclic radical substitutes these groups.In addition, in the case where these groups include alkylene moiety, alkylene moiety can also be by Ehter bond, thioether bond, ester bond interrupt.

In the case where alkyl is straight-chain or branched, its carbon number is preferably 1~20, more preferably 1~15, Particularly preferably 1~10.As the example of preferable alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, Secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl, isodecyl etc..

In the case where alkyl is ester ring type base or the group for including ester ring type base, as preferable contained by alkyl Ester ring type base, the monocyclic ester ring type base such as cyclopenta and cyclohexyl, or adamantyl, norborny, isoborneol can be enumerated Polycyclic ester ring type base of base, three cyclononyls, tricyclodecyl and tetracyclododecyl group etc. etc..

In addition, (A3) acrylic resin can also be the thing for making the monomer beyond (methyl) acrylate be polymerized Matter.As such monomer, (methyl) acrylic amide, unsaturated carboxylic acid class, allyl compound class, vinyl can be enumerated Ethers, vinyl ester, phenylethylene etc..These monomers can be used alone, or combine two or more use.

As (methyl) acrylic amide, (methyl) acrylamide, N- alkyl (methyl) acrylamide, N- virtues can be enumerated Base (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide, N, N- aryl (methyl) acrylamide, N- methyl-N- benzene Base (methyl) acrylamide, N- hydroxyethyl-N- methyl (methyl) acrylamide etc..

As unsaturated carboxylic acid class, the monocarboxylic acid of butenoic acid etc. can be enumerated；Maleic acid, fumaric acid, citraconic acid, middle health The dicarboxylic acids of acid, itaconic acid etc.；Acid anhydrides of these dicarboxylic acids etc..

As allyl compound, allyl acetate, allyl hexanoate, allyl octanoate, laurate allyl can be enumerated The pi-allyl of ester, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetoacetic acid allyl ester, allyl lactate etc. Esters；Allyloxyethanol etc..

As vinyl ethers, hexyl vinyl ethers, octyl vinyl ether, decave, ethyl hexyl can be enumerated Base vinyl ethers, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- methyl -2,2- two Methyl-propyl vinyl ethers, 2- ethylbutyl vinyl ethers, hydroxyethyl vinyl ether, diethylene glycol vinyl ethers, dimethyl Amino-ethyl vinyl ethers, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, four The alkyl vinyl ether of tetrahydrofurfuryl vinyl etc.；Vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, ethene Ethenyl aromatic yl ether of base -2,4 dichloro benzene base ether, vinyl naphthyl ether, vinyl anthryl ether etc. etc..

As vinyl ester, vinyl butyrate, vinyl isobutyrate ester, vinyl pivalate, diethyl can be enumerated Vinyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate ester, vinyl methoxyacetate Ester, butoxy acetic acid vinyl acetate, vinyl phenylacetate ester, acetoacetate vinyl acetate, lactate, beta-phenyl butyric acid ethene Ester, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate, naphthoic acid vinyl acetate etc..

As phenylethylene, styrene can be enumerated；Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl Styrene, diethyl, isopropyl styrene, butylstyrene, hexyl styrene, cyclohexylstyrenes, decyl benzene second Alkene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxymethylstyrene Deng ring-alkylated styrenes；The alkoxy benzene of methoxy styrene, 4- methoxyl group -3- methyl styrenes, dimethoxy styrene etc. Ethene；Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, dibromobenzene second The bromo- 4- trifluoromethyl styrenes of alkene, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-, the fluoro- 3- trifluoromethyl styrenes of 4- etc. Halogenated styrenes etc..

Within the scope without prejudice to the object of the present invention, to the knot of (methyl) acrylic acid in (A3) acrylic resin The amount of structure unit and the amount of the construction unit from other monomers do not limit especially.Relative to acrylic resin, come 5~50 mass % are preferably from the amount of the construction unit of (methyl) acrylic acid in (A3) acrylic resin, more preferably 10 ~30 mass %.

(A3) weight average molecular weight of acrylic resin is preferably 2000~50000, more preferably 5000~30000.It is logical Crossing makes the weight average molecular weight of (A3) acrylic resin be above-mentioned scope, the film for being readily available photosensitive polymer combination be present The tendency of the balance of developability after forming properties, exposure.

It is preferred relative to the quality that the solid state component of photosensitive polymer combination is overall, the content of (A) alkali soluble resin It is 10~65 mass %, more preferably 15~50 mass %.By making the content of (A) alkali soluble resin be above range, hold Easily obtain the excellent photosensitive polymer combination of developability.

In addition, relative to the overall quality of the solid state component of photosensitive polymer combination, (A1) novolac resin contains Amount is preferably 0.5~15 mass %, more preferably 1~10 mass %, and then preferably 1.2~5 mass %.By making (A1) phenol The content of Novolac resin is above range, can form the cured film for being not easy heating during because of rear baking and excess flow, is held It is easy to get to the excellent photosensitive polymer combination of developability.

In addition, in the case where using (A2) to block more resins, it is overall relative to the solid state component of photosensitive polymer combination Quality, its content is preferably 5~40 mass %, more preferably 10~35 mass %, and then preferably 15~30 mass %.It is logical The content that crossing makes (A2) to block more resins is above range, and can be formed and be less susceptible to consolidating for heating excess flow during because of rear baking Change film, be readily obtained the excellent photosensitive polymer combination of developability.

<(B) photopolymerizable compound>

Photosensitive polymer combination includes (B) photopolymerizable compound., can be preferred as (B) photopolymerizable compound Use the compound with ethene polymerizable group.

In addition, (B) photopolymerizable compound is included in dendroid of the end with the ethene polymerizable group of more than 2 Polymer.

Herein, although the photosensitive polymer combination of present embodiment can solve the problem that the technical task this point of the application Upper mechanism is not very clear and definite, but it is believed that being following mechanism.

I.e. photosensitive polymer combination is containing situation of the above-mentioned dendritic as (B) photopolymerizable compound Under, in exposure, the solidification progress of photosensitive polymer combination is good, even if being toasted after applying to cured film, it is solid to be not easy to generation Change the excessive heat flowing of film.

On the other hand, in the case where photosensitive polymer combination includes dendritic, solidify caused by exposure It can excessively carry out, exist after development, form the pattern with the width bigger than desired size or diameter.

But it polymerize in combination comprising described (A1) novolac resin with dendroid in photosensitive polymer combination In the case of thing, (A1) novolac resin using exposure carry out curing reaction progression in, moderately collected from By base, curing reaction is excessively carried out when can suppress exposure.

If it is therefore contemplated that use the photosensitive resin composition comprising (A1) novolac resin and dendritic simultaneously Thing, then the heating being not easy during because of rear baking and excess flow, easily form the fine pattern of desired size and shape.

﹝ Shu dendritic polymerization Wu ﹞

As it was previously stated, photosensitive polymer combination is included in end with the more of the ethene polymerizable group of more than 2 The dendritic of branching type is used as (B) photopolymerizable compound.

Dendritic in its structure have make the branch point that strand stretches on the direction more than 3.Branch The number of branch point in 1 molecule of shaped polymer is more than 3, preferably more than 4.

For example, the branch that (methyl) acrylate of dipentaerythritol six or dipentaerythritol five (methyl) acrylate have The quantity of point is 2.Therefore, (methyl) acrylate of dipentaerythritol six or dipentaerythritol five (methyl) acrylate are not belonging to Dendritic.

If in addition, consider using photosensitive polymer combination formed cured film heat flow or the patience to hydrolysis, Dendritic does not preferably include amino-formate bond.

Although the ethene polymerizable group that dendritic has, (methyl) acrylate chemical combination is preferably come from Thing, but it is not limited to this.

The dendritic of multiple branch has dendritic multiple-branching construction, as long as end has more than 2 The polymer of ethene polymerizable group, is just not particularly limited.

As such dendritic, preferably using being referred to as so-called dendritic or dissaving polymer Polymer.

As the dendritic in end with ethene polymerizable group of sale, Osaka can be enumerated and organised Learn the VISCOAT#1000 (trade name), VISCOAT#1020 (trade name) and (SIRIUS of STAR 501 of industrial society 501st, SUBARU 501) (trade name) etc..

VISCOAT#1000 and VISCOAT#1020 is that (dendroid is gathered by having acrylate-based multiple-limb in end Compound type) polyester acrylate is as main component.In addition, VISCOAT#1000 molecular weight is 1000~2000 or so, VISCOAT#1020 molecular weight is 1000~3000 or so.

STAR 501 includes the core from dipentaerythritol, to have acrylate-based dipentaerythritol 6 third in end The multiple-limb polyacrylate of olefin(e) acid ester (DPHA) link type is main component.STAR 501 molecular weight is 16000~24000 Left and right.

In addition, the dendroid that dendritic, which can also be used in end, has hydroxyl, amino or carboxyl polymerize The polymer that thing or dissaving polymer are prepared.

According to known method, pass through the hydroxyl or amino for having dendritic or dissaving polymer in end Contained hydrogen atom, the end for being substituted by the acryloyl group, methylacryloyl or pi-allyl of desired amount etc. have double bond Alkenyl etc., the dendritic used as (B) photopolymerizable compound can be obtained.

In addition, according to known method, by using the alcohol or amine in end with ethene double bond, dendroid is polymerize The carboxyl esterification or amidatioon that thing or dissaving polymer have in end, can also be obtained as (B) photopolymerizable compound And the dendritic used.As the alcohol or amine in end with ethene double bond, such as (methyl) propylene can be enumerated Sour 2- hydroxy methacrylates, allyl alcohol, (methyl) acrylic acid 2- amino-ethyls ester and allylamine etc..

As the dendritic in end with hydroxyl, amino or carboxyl, can enumerate for example as PAMAM and Well known end has the polyamidoamine dendrimers of amino；Terminal amino group is substituted by the hydroxyl of 2- hydroxyethylaminos etc. The PAMAM type dendritics of alkyl amino；Terminal amino group is substituted by succinamide acidic group (- NH-CO-CH₂CH₂-COOH) Deng carboxyalkyl amide groups PAMAM type dendritics；The copolyesters of glycerine and succinic acid has hydroxyl in end Poly- (glycerine-succinic acid) dendritic of base；The copolyesters of glycerine and succinic acid is to have gathering for carboxyl in end (glycerine-succinic acid) dendritic；And the equal polyester of double (methylol) propionic acid (bis-MPA) of 2-2 has in end There is dendritic of hydroxyl etc..

As preferable dendritic, polymer described below can be enumerated.

First, known ethene polymerizable group is the group for having carbon-carbon double bond, and carbonyl linkage is on the carbon-carbon double bond The conjugated compound as α, beta-unsaturated carbonyl compound in, using mutual with nucleophilic reagent as sulfhydryl compound The most strong vinyl of effect causes Michael addition reaction.

Therefore, if making the chemical combination of multiple ethene polymerizable groups as there is α, beta-unsaturated carbonyl compound Thing, reacted with the compound with multiple nucleophilic reagents as more sulfhydryl compounds, then in the carbon of the β positions relative to carbonyl Upper generation addition reaction, if the group of addition reaction generation is multiple, multiple branches are produced so as to become dendritic. The dendritic is known because of No. 2008/47620 grade of International Publication No., can pass through the side described in the document Method obtains.

As dendritic, preferably following addition product：Multifunctional (methyl) propylene represented by following formula (1) More sulfhydryl compounds that ester compound represents with following formula (2), by Michael's addition (relative to carbonyl, to the carbon of α, β position The addition of carbon double bond) it is polymerized.

【Chemical formula 10】

(in formula (1), R¹It is the alkyl that hydrogen atom or carbon number are 1~4, R²It is by polyalcohol R₃(OH)_mM N hydroxyl among hydroxyl is provided to the n valency residues after the ester bond in formula (1), m and n separately for 2~20 it is whole Number, m >=n.)

(HS-CH₂-)_p-R⁴(2)

(in formula (2), R⁴It is the group that the carbon atom quantity of singly-bound or 2~6 valencys is 1~6 alkyl, in R⁴For singly-bound In the case of, p is 2, in R⁴In the case of the group containing alkyl for 2~6 valencys, p is 2~6 integer.)

Herein, multifunctional (methyl) acrylate compounds that more sulfhydryl compounds that formula (2) represents represent to formula (1) Michael's addition, preferably carry out in such a way：In order that it can also be based on carbon carbon after obtained dendritic Double bond carries out radiation polymerization, the carbon-carbon double bond that the compound for representing formula (1) has, and is rubbed relative to overall remaining for 0.1~50 Your % scope.

For example, multifunctional (methyl) acrylate that the sulfydryl of the more sulfhydryl compounds represented in formula (2) represents with formula (1) Compound carbon-carbon double bond (in formula (1), referred to as CH₂=C (R¹The double bond for)-represent, is referred to as in the case where calculating mol ratio Double bond.) addition ratio, preferably the mol ratio of sulfydryl/double bond be 1/100~1/3, more preferably 1/50~1/5, it is especially excellent Choosing is 1/20~1/8.

In addition, dendritic is preferably with for function polymerize more well by exposure, an adequate amount of Base.Therefore, the molecular weight as every mole of carbon-carbon double bond, the molecular weight of dendritic are preferably the model 100~10000 Enclose.The weight average molecular weight (Mw) of dendritic, preferably 8000~40000, more preferably 15000~25000.

In above-mentioned formula (1), preferably：R³(OH)_mIt is straight chain or branch based on the non-aromatic that carbon number is 2~8 The polyalcohol of the hydrocarbon skeleton of chain, or the polyalcohol multiple molecules linked by the dehydrating condensation of alcohol via ehter bond it is more First alcohol ether, the either ester of these polyalcohols or polyol ethers and carboxylic acid.

In above-mentioned formula (1), m and n independently represent 2~20 integer, m >=n.Preferably m and n is 2~10 Integer, m >=n.

The preferable concrete example of multifunctional (methyl) acrylate compounds represented as formula (1), can enumerate ethylene glycol Two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxy second Alkane be modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, Trimethylolethane trimethacrylate (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylic acid Ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, caprolactone modification pentaerythrite Three (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate, (first of caprolactone modification dipentaerythritol six Base) acrylate, epichlorohydrin be modified hexahydrophthalic acid two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified neopentyl glycol two (methyl) acrylate, Epoxy pronane modification neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylic acid Ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, trimethylolpropane benzoic ether (methyl) acrylic acid Ester, three ((methyl) acryloyl-oxyethyl) isocyanuric acid esters, alkoxy-modified trimethylolpropane tris (methyl) acrylate, Poly- (methyl) acrylate of dipentaerythritol, (methyl) acrylate of alkyl-modified dipentaerythritol three and two (trihydroxy methyls Propane) four (methyl) acrylate etc. (methyl) acrylate.These compounds can be used alone or and with two kinds More than.

In formula (2), R⁴Preferably singly-bound, or can have the alkyl that the carbon number of substituent is 1~6, or Person can also be the also alkyl containing oxygen atom in the skeleton of the alkyl, can be that straight chain can also be side chain.

In addition, these groups containing alkyl and then can also have the methyl mercapto (HS-CH with occurring in formula (2)₂-) one The carbonyloxy group of part bonding.In addition, in the case of including oxygen atom in hydrocarbyl backbone, its both ends can be alkyl.P represents 2 ~6 integer, corresponding to R⁴Valence mumber.

Therefore, if R⁴Then p is 2 during expression singly-bound, if R⁴Carbon number then p is 2~4 when being 1, if R⁴Carbon number For 2~6 when, then p be 2~6.

More sulfhydryl compounds that formula (2) represents, can enumerate 1,2- dimercaptoethanes, 1,3- dimercaptopropanes, Isosorbide-5-Nitrae-two Sulfydryl butane, double dimercapto ethyl mercaptans, trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (mercaptopropionic acid Ester), pentaerythrite four (mercaptoacetate), pentaerythrite three (mercaptoacetate), pentaerythrite four (mercaptopropionic acid ester), two seasons Penta tetrol six (mercaptoacetate) and dipentaerythritol six (mercaptopropionic acid ester) etc..

When synthesizing dendritic, polymerization inhibitor can be added as needed on.Also can be in the present invention using general Diphenol compounds, phenolic compound for the polymerization that prevents (methyl) acrylate compounds are as polymerization inhibitor.Although Hydroquinones, methoxyl group hydroquinones, catechol, p-tert-Butylcatechol, cresols, butylated hydroxy-a can be enumerated Benzene, 2, concrete example of 4, the 6- tri-butyl-phenols (BHT) as polymerization inhibitor, but it is not limited to these compounds.

Tree can be analyzed to identify by using liquid chromatography, gel filtration chromatography, other in general analytical instrument The synthesis of dendritic polymer is completed.

When synthesizing dendritic, produce what more sulfhydryl compounds that above-mentioned formula (2) represents represented to above-mentioned formula (1) The Michael addition reaction of the double bond addition of multifunctional (methyl) acrylate compounds.The reaction can be multifunctional by mixing (methyl) acrylate compounds and more sulfhydryl compounds, add base catalyst in room temperature or even 100 DEG C and carry out.Reaction Time is not particularly limited, but typically 30 minutes~20 hours, preferably 6~12 hours.

﹝ others optical polymerism He Wu ﹞

Within the scope without prejudice to the object of the present invention, in addition to the dendritic, for raising imaging clearly The purpose of spending, it can also make various containing being mixed in photosensitive polymer combination all the time in photosensitive polymer combination Photopolymerizable compound.

As other photopolymerizable compounds, the preferably monomer with ethene unsaturated group.In the monomer There are monofunctional monomer and polyfunctional monomer.

As monofunctional monomer, (methyl) acrylamide, methylol (methyl) acrylamide, methoxy can be enumerated (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy Methyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- hydroxymethyls (methyl) acrylamide, (methyl) propylene Acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acrylamides- 2- methyl propane sulfonic acids, tert-butyl acrylamide sulfonate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Acid butyl ester, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (first Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 2- phenoxy group -2- hydroxy propyl esters, 2- (methyl) acryloxy -2- hydroxy propyl esters phthalic acid ester, glycerine list (methyl) acrylate, (methyl) acrylic acid four Tetrahydrofurfuryl ester, dimethylamino (methyl) ethyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2- Trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3- tetrafluoros propyl ester, partly (methyl) acrylate etc. of phthalic acid derivatives.This A little monofunctional monomers may be used alone or in combination two or more use.

On the other hand, as polyfunctional monomer, ethylene glycol two (methyl) acrylate, (first of diethylene glycol two can be enumerated Base) acrylate, tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) Acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, the acrylic acid of pentaerythrite three Ester, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, the dipentaerythritol acrylate, (first of pentaerythrite two Base) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (the first of dipentaerythritol five Base) acrylate, dipentaerythritol six (methyl) acrylate, 2,2- double (4- (methyl) acryloxy diethoxy phenyl) Propane, 2,2- double (4- (methyl) acryloxypolyethoxyphenyl) propane, 2- hydroxyls -3- (methyl) acryloxypropyls (methyl) acrylate, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerol triacrylate, glycerine Poly- (methyl) acrylate of polyglycidyl ether, (methyl) propenoic methyl carbamate (that is, toluene di-isocyanate(TDI), trimethyl The reactant of hexamethylene diisocyanate or hexamethylene diisocyanate etc. and (methyl) acrylic acid 2- hydroxy methacrylates), Di-2-ethylhexylphosphine oxide (methyl) acrylamide, (methyl) acrylamide methylene ether, polyalcohol and N- methylols (methyl) acrylamide Polyfunctional monomer, the triacryl formal such as condensation product etc..These polyfunctional monomers may be used alone or in combination two or more And use.

Improved from existing after photosensitive polymer combination solidifies relative to the adaptation of substrate, photosensitive polymer combination From the aspect of the tendency of intensity, these have in the monomer of ethene unsaturated group, the multifunctional list preferably more than 3 functions Body, more preferably polyfunctional monomers more than 4 functions, and then the polyfunctional monomer preferably more than 5 functions.

Specifically, preferably and use polyfunctional monomer more than dendritic and 5 functions, be more preferably and with set Dendritic polymer and (methyl) acrylate of dipentaerythritol five and/or dipentaerythritol six (methyl) acrylate.

Relative to the quality of the solid state component of photosensitive polymer combination, (B) photopolymerizable compound is in photoresist Content in constituent, preferably 1~50 mass %, more preferably 5~40 mass %.By making (B) photopolymerizable compound Content in photosensitive resin composition is above-mentioned scope, exists and is readily available sensitiveness, developability, imaging definition The tendency of balance.

Relative to the quality of the solid state component of photosensitive polymer combination, dendritic is in photosensitive polymer combination In content, preferably 0.1~30 mass %, more preferably 0.5~25 mass %.By making dendritic in photonasty Content in resin combination is above-mentioned scope, can obtain following photosensitive polymer combination：When being not easy to toast because after Heat and excess flow, and easily form the fine pattern of desired size and shape.

In addition, the content Wn [g] of the novolac resin in photosensitive polymer combination and dendritic content Wd [g] ratio (Wn：Wd) preferably 20：1~1：In the range of 20, more preferably 18：1~1：In the range of 18, especially Preferably 15：1~1：In the range of 15, most preferably 5：1~1：In the range of 12.

<(C) Photoepolymerizationinitiater initiater>

Do not limited especially as (C) Photoepolymerizationinitiater initiater, known Photoepolymerizationinitiater initiater can be used.

Specifically, as (C) Photoepolymerizationinitiater initiater, 1- hydroxycyclohexylphenylketones, 2- hydroxyl -2- first can be enumerated Base -1- phenyl -1- acetone, 1- (4- (2- hydroxyl-oxethyls) phenyl) -2- hydroxy-2-methyl -1- acetone, 1- (4- cumenes Base) -2- hydroxy-2-methyl -1- acetone, 1- (4- dodecylphenyls) -2- hydroxy-2-methyl -1- acetone, 2,2- dimethoxies Base -1,2- diphenyl -1- ethyl ketones, double (4- dimethylaminophenyls) ketone, 2- methyl isophthalic acids-(4- (methylsulfany) phenyl) -2- Quinoline base -1- acetone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls) -1- butanone, O- acetyl group -1- [6- (2- methyl Benzoyl) -9- ethyl -9H- carbazole -3- bases] acetophenone oxime, (9- ethyl -6- nitro -9H- carbazole -3- bases) [4- (2- methoxies Base -1- methyl ethoxies) -2- aminomethyl phenyls] ketone O- acetyl group oxime, 2- (benzoyl epoxide imino group) -1- [4- (phenyl Sulfenyl) phenyl] -1- octanones, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 4- benzoyls -4 '-methyl dimethoxy base Sulphur, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- dimethyl Butyl aminobenzoate, 4- dimethylamino -2- ethylhexyl Benzoic acids, 4- dimethylamino -2- isoamyl benzenes formic acid, benzene are even Acyl-'beta '-methoxy ethyl acetals, benzil dimethyl ketal, 1- phenyl -1,2- pentanediones -2- (O- ethoxy carbonyls) oxime, The chloro- oxygen of 4- third of o-benzoyl yl benzoic acid methyl esters, 2,4- diethyl thioxanthones, CTX, 2,4- dimethyl thioxanthones, 1- Base thioxanthones, thioxanthene, 2- diurils ton, 2,4- diethyl thioxanthene, 2- methyl thioxanthene, 2- isopropylthioxanthones, 2- EAQs, eight first Base anthraquinone, 1,2 benzae thracene quinone, 2,3- diphenyl anthraquinone, azobis isobutyronitrile, benzoyl peroxide, cumyl hydroperoxide, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles, 2-mercaptobenzothiazole, (the meta-methoxy benzene of 2- (Chloro-O-Phenyl) -4,5- two Base)-imidazole radicals dimer, benzophenone, 2- chlorobenzophenones, p, p '-bis- dimethylamino benzophenones, 4,4 '-bis- diethyls Base aminobenzophenone, 4,4 '-dichloro benzophenone, 3,3- dimethyl -4- methoxy benzophenones, benzil, benzoin, benzene Acyloin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin fourth Base ether, acetophenone, 2,2- diethoxy acetophenones, to dimethyl acetophenone, to dimethylamino propiophenone, dichloroacetophenone, Trichloroacetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloro Acetophenone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2- methyl thioxanthones, ITX, dibenzo cycloheptyl Ketone, 4- dimethylaminobenzoic acids pentyl ester, 9- phenylacridines, 1,7- be double-and (9- acridinyls) heptane, 1,5- be double-(9- acridinyls) Pentane, 1,3- be double-(9- acridinyls) propane, to methoxyl group triazine, 2,4,6- tri- (trichloromethyl) s-triazine, 2- methyl -4,6- Double (trichloromethyl) s-triazine, 2- [2- (5- methylfuran -2- bases) vinyl] -4,6- double (trichloromethyl) s-triazine, 2- [2- (furans -2- bases) vinyl] -4,6- double (trichloromethyl) s-triazine, 2- [2- (4- diethylamino -2- aminomethyl phenyls) ethene Base] double (trichloromethyl) s-triazine of -4,6-, 2- [2- (3,4- Dimethoxyphenyls) vinyl] -4,6- double (trichloromethyls) be equal Double (trichloromethyl) s-triazine of triazine, 2- (4- methoxyphenyls) -4,6-, the double (trichlorines of 2- (4- ethoxystyrenes base) -4,6- Methyl) s-triazine, double (trichloromethyl) s-triazine of 2- (4- n-butoxyphenyls) -4,6-, 2,4- be double-trichloromethyl -6- (3- Bromo- 4- methoxyl groups) phenyl s-triazine, 2,4- be double-trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) phenyl s-triazine, 2,4- double-three Chloromethyl -6- (the bromo- 4- methoxyl groups of 3-) styryl phenyl s-triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) Styryl phenyl s-triazine etc..These Photoepolymerizationinitiater initiaters may be used alone or in combination two or more and use.

Wherein, from the aspect of sensitiveness, the Photoepolymerizationinitiater initiater of oxime system is particularly preferably used.The photopolymerization of oxime system triggers In agent, as the Photoepolymerizationinitiater initiater of particularly preferred oxime system, can enumerate O- acetyl group -1- [6- (2- methyl benzoyls) - 9- ethyl -9H- carbazole -3- bases] acetophenone oxime, ethyl ketone, 1- [9- ethyls -6- (pyrroles's -2- bases carbonyl) -9H- carbazole -3- bases], 1- (O- acetyl group oxime) and 2- (benzoyl epoxide imino group) -1- [4- (phenylsulfartyl) phenyl] -1- octanones.

Furthermore it is preferred that the oxime compound represented using following formula (c1) is used as Photoepolymerizationinitiater initiater.

【Chemical formula 11】

(R^C1It is that n1 is 0 selected from the group of group being made up of the organic group of 1 valency, amino, halogen, nitro and cyano group~ 4 integer, n2 are 0 or 1, R^C2It is the phenyl can with substituent, or can has the carbazyl of substituent, R^C3 It is the alkyl that hydrogen atom or carbon number are 1~6.)

In formula (c1), within the scope without prejudice to the object of the present invention, R^C1Do not limit especially, can have from various Properly selected in machine group.In R^C1In the case of for organic group, as preferable example, can enumerate alkyl, alkoxy, Cycloalkyl, cycloalkyloxy, representative examples of saturated aliphatic acyl group, representative examples of saturated aliphatic acyloxy, alkoxy carbonyl, there can be substituent Phenyl, can the phenoxy group with substituent, can the benzoyl with substituent, can the phenoxy group carbonyl with substituent Base, can the benzoyl epoxide with substituent, can the phenylalkyl with substituent, can the naphthalene with substituent Base, can the naphthoxy with substituent, can the naphthoyl with substituent, can the naphthoxy carbonyl with substituent Base, can the naphthoyl epoxide with substituent, can the naphthylalkyl with substituent, can the heterocycle with substituent Base, amino, the amino substituted by 1 or 2 organic groups, morpholine -1- bases and piperazine -1- bases, halogen, nitro and cyano group Deng.In the case that n1 is 2~4 integer, R^C1Can be with identical or different.In addition, the carbon number of substituent does not include substituent And then the carbon number for the substituent having.

In R^C1In the case of alkyl, carbon number is preferably 1~20, more preferably 1~6.In addition, in R^C1For alkyl In the case of, can be straight chain or side chain.As R^C1For the concrete example of the situation of alkyl, methyl, second can be enumerated Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, just oneself Base, n-heptyl, n-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, In R^C1In the case of alkyl, alkyl can include ehter bond (- O-) in carbochain.Example as the alkyl in carbochain with ehter bond Son, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyl group ethoxy can be enumerated Base ethyl and methoxy-propyl etc..

In R^C1In the case of alkoxy, carbon number is preferably 1~20, more preferably 1~6.In addition, in R^C1For alkane Can be straight chain or side chain in the case of epoxide.As in R^C1For alkoxy when concrete example, methoxy can be enumerated Base, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamyl Epoxide, secondary amoxy, tertiary amoxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, secondary octyloxy, tertiary octyloxy, Positive nonyl epoxide, different nonyl epoxide, n-decyloxy and isodecyl epoxide etc..In addition, in R^C1In the case of alkoxy, alkoxy can be Ehter bond (- O-) is included in carbochain.As in carbochain have ehter bond alkoxy example, can enumerate methoxy ethoxy, Ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propoxy ethoxyethoxy and methoxy Base propoxyl group etc..

In R^C1For cycloalkyl or cycloalkyloxy when, carbon number is preferably 3~10, more preferably 3~6.As R^C1For Concrete example during cycloalkyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl etc. can be enumerated.As R^C1For cycloalkyloxy when concrete example, can enumerate ring propoxyl group, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, cycloheptyl epoxide with And ring octyloxy etc..

In R^C1In the case of representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, carbon number is preferably 2~ 20, more preferably 2~7.As in R^C1For representative examples of saturated aliphatic acyl group when concrete example, acetyl group, propiono, positive fourth can be enumerated Acyl group, 2- methylpropionyls, positive valeryl, 2,2- Dimethylpropanoyls, positive caproyl, positive heptanoyl group, positive caprylyl, positive nonanoyl Base, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, n-tetradecane acyl group, n-pentadecane acyl group And hexadecane acyl group etc..As in R^C1For representative examples of saturated aliphatic acyloxy when concrete example, can enumerate acetyl group epoxide, Propiono epoxide, positive bytyry epoxide, 2- methylpropionyls epoxide, positive valeryl epoxide, 2,2- dimethylpropionyloxies, just Caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group epoxide, positive capryl epoxide, n-undecane acyl group oxygen Base, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, n-pentadecane acyloxy and just Hexadecane acyloxy etc..

In R^C1For alkoxy carbonyl when, carbon number is preferably 2~20, more preferably 2~7.As R^C1For alkoxy carbonyl Concrete example during base, methoxycarbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyloxycarbonyl group, positive fourth can be enumerated Base Epoxide carbonyl, isobutyl group Epoxide carbonyl, sec-butyl Epoxide carbonyl, t-butyloxycarbonyl, n-pentyloxycarbonyl, isoamoxy Carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, positive Epoxide carbonyl in heptan, n-octyloxy carbonyl, different pungent oxygen Base carbonyl, secondary carbonyl octyloxy, tertiary carbonyl octyloxy, positive nonyl epoxide carbonyl, different nonyl epoxide carbonyl, n-decyloxy carbonyl and different Decyloxy carbonyl etc..

In R^C1For phenylalkyl when, carbon number is preferably 7~20, more preferably 7~10.In addition, in R^C1For naphthylalkyl When, carbon number is preferably 11~20, more preferably 11~14.As R^C1For phenylalkyl when concrete example, benzyl can be enumerated Base, 2- phenylethyls, 3- phenyl propyls and 4- phenyl butyls.As R^C1For naphthylalkyl when concrete example, can enumerate α- Naphthyl methyl, betanaphthyl methyl, 2- (Alpha-Naphthyl) ethyls and 2- (betanaphthyl) ethyl.In R^C1For phenylalkyl or naphthyl alkane During base, R^C1Can further have substituent on phenyl or naphthyl.

In R^C1For heterocyclic radical when, heterocyclic radical is for five yuan comprising more than 1 N, S, O or hexa-atomic monocyclic, or the list The heterocyclic radical that ring condenses each other, or the monocyclic heterocyclic radical formed with phenyl ring fusion.When heterocyclic radical is condensed ring, number of rings For less than 3.As the heterocycle for forming the heterocyclic radical, furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiophene two can be enumerated Azoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, Yin Diindyl piperazine, benzimidazole, BTA, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, scold Quinoline and quinoxaline etc..In R^C1For heterocyclic radical when, heterocyclic radical can further have substituent.

In R^C1For substituted by 1 or 2 organic groups amino when, on the preference of organic group, carbon can be enumerated The alkyl of atomicity 1~20, the cycloalkyl of carbon number 3~10, carbon number 2~20 representative examples of saturated aliphatic acyl group, can have The phenyl of substituted base, can the benzoyl with substituent, can the octadecyloxy phenyl with the carbon number 7~20 of substituent Base, can the naphthyl with substituent, can the naphthoyl with substituent, can the carbon number 11 with substituent~ 20 naphthylalkyl and heterocyclic radical etc..The concrete example of these preferable organic groups, with R^C1It is identical.Have as by 1 or 2 The concrete example of the amino of machine group substitution, can enumerate methylamino, ethylamino, diethylamino, n-propyl amino, two just Propylcarbamic, isopropylamino, n-butylamino, di-n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, N-octyl amino, n-nonyl amino, positive decyl amino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive fourth Acyl amino, positive pentanoylamino, positive caproyl amino, positive heptanoyl group amino, positive octanoylamino, positive decanoylamino, benzene Formylamino, α-naphthoyl amino and β-naphthoyl amino etc..

As R^C1In the substituent of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, can enumerate The alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl group of carbon number 2~7, carbon number 2~7 alkoxy carbonyl, the representative examples of saturated aliphatic acyloxy of carbon number 2~7, have carbon number 1~6 alkyl list Alkyl amino, the dialkyl amido of alkyl with carbon number 1~6, morpholine -1- bases, piperazine -1- bases, halogen, nitro and Cyano group etc..In R^C1In in the case that the phenyl, naphthyl and the heterocyclic radical that include further have substituent, the number of the substituent It is unrestricted in the range of without prejudice to the purpose of the present invention, but preferably 1~4.R^C1In the phenyl, naphthyl and the heterocycle that include When base has multiple substituents, multiple substituents can be the same or different.

R^C1In, chemically property stabilization, steric hindrance are few, oxime ester compound synthesis is easy etc. considers, preferably selects In the alkoxy of alkyl, carbon number 1~6 and the representative examples of saturated aliphatic acyl group of carbon number 2~7 from carbon number 1~6 The alkyl of group, more preferably carbon number 1~6, particularly preferred methyl.

For R^C1The phenyl being bonded, using the position of phenyl and the chemical bond of the main framing of oxime ester compound as 1, During using the position of methyl as 2, R^C1The position being bonded on phenyl is preferably 4 or 5 of phenyl, more preferably 5.This Outside, n1 is preferably 0~3 integer, more preferably 0~2 integer, and particularly preferably 0 or 1.

R^C2It is the phenyl can with substituent, or there can be the carbazyl of substituent.In addition, in R^C2Being can In the case of with the carbazyl with substituent, the nitrogen-atoms on the alkyl substituted carbazole base of carbon number 1~6 can also be used.

In R^C2In, in the range of without prejudice to the object of the invention, the substituent that phenyl or carbazyl have does not have spy Do not limit.The example for the preferable substituent that can have as phenyl or carbazyl on carbon atom, carbon original can be enumerated The alkyl of subnumber 1~20, the alkoxy of carbon number 1~20, the cycloalkyl of carbon number 3~10, the ring of carbon number 3~10 Alkoxy, the representative examples of saturated aliphatic acyl group of carbon number 2~20, the alkoxy carbonyl of carbon number 2~20, carbon number 2~20 Representative examples of saturated aliphatic acyloxy, can the phenyl with substituent, can the phenoxy group with substituent, can with substitution The phenylsulfartyl of base, can the benzoyl with substituent, can the phenyloxycarbonyl with substituent, can with substitution The benzoyl epoxide of base, can the phenylalkyl with the carbon number 7~20 of substituent, can the naphthalene with substituent Base, can the naphthoxy with substituent, can the naphthoyl with substituent, can the naphthoxy carbonyl with substituent Base, can the naphthoyl epoxide with substituent, can the naphthylalkyl with the carbon number 11~20 of substituent, can be with Heterocyclic radical with substituent, can the Heterocyclylcarbonyl with substituent, amino, the ammonia substituted by 1 or 2 organic groups Base, morpholine -1- bases and piperazine -1- bases, halogen, nitro and cyano group etc..

In R^C2In the case of for carbazyl, the example for the preferable substituent that can have as carbazyl on nitrogen-atoms, The alkyl of carbon number 1~20, the cycloalkyl of carbon number 3~10, the representative examples of saturated aliphatic acyl of carbon number 2~20 can be enumerated Base, carbon number 2~20 alkoxy carbonyl, can the phenyl with substituent, can the benzoyl with substituent, can With the phenyloxycarbonyl with substituent, can the phenylalkyl with the carbon number 7~20 of substituent, can with substitution The naphthyl of base, can the naphthoyl with substituent, can the naphthoxycarbonyl with substituent, can be with substituent The naphthylalkyl of carbon number 11~20, can be with substituent heterocyclic radical and can the Heterocyclylcarbonyl with substituent Deng.In these substituents, the preferred alkyl of the alkyl of carbon number 1~20, more preferably carbon number 1~6, particularly preferred second Base.

For the concrete example for the substituent that phenyl or carbazyl can have, on alkyl, alkoxy, cycloalkanes Base, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, the phenyl can with substituent Alkyl, can the naphthylalkyl with substituent, can be with substituent heterocyclic radical and taken by 1 or 2 organic groups The amino in generation, with R^C1It is identical.

In R^C2In, enter as phenyl, naphthyl and the heterocyclic radical included in substituent possessed by phenyl or carbazyl The example of substituent when one step has a substituent, the alkyl of carbon number 1~6 can be enumerated；The alcoxyl of carbon number 1~6 Base；The representative examples of saturated aliphatic acyl group of carbon number 2~7；The alkoxy carbonyl of carbon number 2~7；The saturated fat of carbon number 2~7 Fat race acyloxy；Phenyl；Naphthyl；Benzoyl；Naphthoyl；By the alkyl selected from carbon number 1~6, morpholine -1- bases, The benzoyl of group substitution in piperazine -1- bases and phenyl；The alkyl monosubstituted amino of alkyl with carbon number 1~6；Tool There is the dialkyl amido of the alkyl of carbon number 1~6；Morpholine -1- bases；Piperazine -1- bases；Halogen；Nitro；Cyano group.Phenyl or When phenyl, naphthyl and the heterocyclic radical included in substituent possessed by carbazyl further has substituent, the substituent Number is unrestricted in the range of without prejudice to the purpose of the present invention, but preferably 1~4.Phenyl, naphthyl and heterocyclic radical have During multiple substituents, multiple substituents can be the same or different.

In R^C2In, from the viewpoint of the excellent Photoepolymerizationinitiater initiater of sensitiveness is readily obtained, preferably following formula (c2) Or the group that (c3) is represented, the base that the group that more preferably following formula (c2) represents, particularly preferably following formula (c2) represent The group that group and A are S.

【Chemical formula 12】

(R^c4For the group selected from the group being made up of the organic group of 1 valency, amino, halogen, nitro and cyano group, A be S or Person O, n3 are 0~4 integer.)

【Chemical formula 13】

(R^c5And R^c6The respectively organic group of 1 valency).

R in formula (c2)^c4, can be from each in the range of without prejudice to the object of the invention in the case of for organic group Selected in the organic group of kind.In formula (c2), in R^c4For organic group when preference, carbon number 1 can be enumerated ~6 alkyl；The alkoxy of carbon number 1~6；The representative examples of saturated aliphatic acyl group of carbon number 2~7；The alkane of carbon number 2~7 Epoxide carbonyl；The representative examples of saturated aliphatic acyloxy of carbon number 2~7；Phenyl；Naphthyl；Benzoyl；Naphthoyl；By selected from Alkyl, morpholine -1- bases, piperazine -1- bases and the benzoyl of the group substitution in phenyl of carbon number 1~6；It is former with carbon The alkyl monosubstituted amino of the alkyl of subnumber 1~6；The dialkyl amido of alkyl with carbon number 1~6；Morpholine -1- bases；Piperazine- 1- bases；Halogen；Nitro；Cyano group.

In R^c4In, preferably benzoyl；Naphthoyl；By the alkyl selected from carbon number 1~6, morpholine -1- bases, piperazine Benzoyl, the more preferably nitro, benzoyl of group substitution in piperazine -1- bases and phenyl；Naphthoyl；2- methylbenzenes Base carbonyl；4- (piperazine -1- bases) phenylcarbonyl group；4- (phenyl) phenylcarbonyl group.

In addition, in formula (c2), n3 preferably 0~3 integer, more preferably 0~2 integer, particularly preferably 0 or 1. In the case where n3 is 1, R^c4The position of bonding, preferably with respect to R^c4The phenyl being bonded and oxygen atom or sulfur atom linkage Chemical bond for contraposition.

R in formula (c3)^c5, in the range of without prejudice to the object of the invention, can be selected from various organic groups Select.As R^c5Preference, the alkyl of carbon number 1~20, the cycloalkyl of carbon number 3~10, carbon number 2 can be enumerated ~20 representative examples of saturated aliphatic acyl group, the alkoxy carbonyl of carbon number 2~20, can the phenyl with substituent, can be with The benzoyl of substituent, can the phenyloxycarbonyl with substituent, can the benzene with the carbon number 7~20 of substituent Base alkyl, can the naphthyl with substituent, can the naphthoyl with substituent, can the naphthoxy carbonyl with substituent Base, can the naphthylalkyl with the carbon number 11~20 of substituent, can be with substituent heterocyclic radical and can have Heterocyclylcarbonyl of substituted base etc..

In R^c5In, the preferably alkyl of the alkyl of carbon number 1~20, more preferably carbon number 1~6, particularly preferably It is ethyl.

R in formula (c3)^c6, especially limited in the range of without prejudice to the object of the invention, can be from various Selected in organic group.As R^c6Preferable group concrete example, can enumerate carbon number 1~20 alkyl, can With the phenyl with substituent, can be with substituent naphthyl and can the heterocyclic radical with substituent.As R^c6, at this Among a little groups, can more preferably have the phenyl of substituent, particularly preferably 2- aminomethyl phenyls.

As R^c4、R^c5Or R^c6In the substitution of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent Base, the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl of carbon number 2~7 can be enumerated Base, the alkoxy carbonyl of carbon number 2~7, carbon number 2~7 representative examples of saturated aliphatic acyloxy, there is carbon number 1~6 Alkyl alkyl monosubstituted amino, have carbon number 1~6 alkyl dialkyl amido, morpholine -1- bases, piperazine -1- bases, halogen Element, nitro and cyano group etc..R^c4、R^c5Or R^c6In the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, The number of its substituent is unrestricted in the range of without prejudice to the purpose of the present invention, but preferably 1~4.R^c4、R^c5Or R^c6 In the phenyl, naphthyl and the heterocyclic radical that include when there is multiple substituents, multiple substituents can be the same or different.

R in formula (c1)^c3For hydrogen atom or the alkyl of carbon number 1~6.As R^c3, preferably methyl or second Base, particularly preferably methyl.

Most preferred compound in the oxime ester compound represented as formula (c1), can enumerate following PI-1~PI-42.

【Chemical formula 14】

【Chemical formula 15】

【Chemical formula 16】

【Chemical formula 17】

【Chemical formula 18】

【Chemical formula 19】

In addition, the oxime ester compound that following formula (c4) represents is it is also preferred that as Photoepolymerizationinitiater initiater.

【Chemical formula 20】

(R^c7For the organic group of hydrogen atom, nitro or 1 valency, R^c8And R^c9Can respectively have the chain of substituent Alkyl, the cyclic organic group or hydrogen atom can with substituent, R^c8With R^c9Landform cyclization, R can be mutually bonded^c10For The organic group of 1 valency, R^c11For hydrogen atom, can be with the carbon number 1~11 of substituent alkyl or can with substitution The aryl of base, n4 are 0~4 integer, and n5 is 0 or 1.)

Herein, what the oxime compound as the oxime ester compound for manufacturing formula (c4), preferably following formula (c5) represented Compound.

【Chemical formula 21】

(R^c7、R^c8、R^c9、R^c10, n4 and n5 it is identical with formula (c4).)

In formula (c4) and (c5), R^c7For the organic group of hydrogen atom, nitro or 1 valency.R^c7It is bonded in formula (c4) In fluorenes ring, and with-(CO)_n5On 6 yuan of different aromatic rings of -6 yuan of aromatic rings being bonded of group for representing.In formula (c4), R^c7 It is not particularly limited relative to the bonding position of fluorenes ring.There is the R of more than 1 in the compound that formula (c4) represents^c7Situation Under, from formula (c4) represent compound synthesis easily etc. consider, the R of preferably more than 1^c7Among, one is bonded to 2 in fluorenes ring.In R^c7In the case of multiple, multiple R^c7It can be the same or different.

In R^c7In the case of for organic group, it is not particularly limited in the range of without prejudice to the object of the invention, can R is properly selected from various organic groups^c7.As R^c7For organic group when preference, can enumerate alkyl, alkoxy, Cycloalkyl, cycloalkyloxy, representative examples of saturated aliphatic acyl group, representative examples of saturated aliphatic acyloxy, alkoxy carbonyl, there can be substituent Phenyl, can the phenoxy group with substituent, can the benzoyl with substituent, can the phenoxy group carbonyl with substituent Base, can the benzoyl epoxide with substituent, can the phenylalkyl with substituent, can the naphthalene with substituent Base, can the naphthoxy with substituent, can the naphthoyl with substituent, can the naphthoxy carbonyl with substituent Base, can the naphthoyl epoxide with substituent, can the naphthylalkyl with substituent, can the heterocycle with substituent Base, the Heterocyclylcarbonyl can with substituent, amino, morpholine -1- bases and the piperazine substituted by 1 or 2 organic groups - 1- bases etc..

In R^C7In the case of alkyl, the carbon number of alkyl is preferably 1~20, more preferably 1~6.In addition, in R^C7 Can be straight chain or side chain in the case of for alkyl.As R^C7For the concrete example of the situation of alkyl, first can be enumerated Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, uncle penta Base, n-hexyl, n-heptyl, n-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl Deng.In addition, in R^C7In the case of alkyl, alkyl can include ehter bond (- O-) in carbochain.As having ehter bond in carbochain The example of alkyl, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, third can be enumerated Epoxide ethoxyethyl group and methoxy-propyl etc..

In R^C7In the case of alkoxy, the carbon number of alkoxy is preferably 1~20, more preferably 1~6.In addition, R^C7Can be straight chain or side chain in the case of for alkoxy.As in R^C7For alkoxy when concrete example, Neng Goulie Lift methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, positive penta oxygen Base, isoamoxy, secondary amoxy, tertiary amoxy, positive hexyloxy, positive epoxide in heptan, n-octyloxy, different octyloxy, secondary octyloxy, uncle Octyloxy, positive nonyl epoxide, different nonyl epoxide, n-decyloxy and isodecyl epoxide etc..In addition, in R^C7In the case of alkoxy, alkane Epoxide can include ehter bond (- O-) in carbochain.As the example of the alkoxy in carbochain with ehter bond, methoxyl group can be enumerated Ethyoxyl, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propoxy ethoxyethoxy And methoxy propoxy etc..

In R^C7For cycloalkyl or cycloalkyloxy when, the carbon number of cycloalkyl or cycloalkyloxy is preferably 3~10, more Preferably 3~6.As R^C7For cycloalkyl when concrete example, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl can be enumerated Base and cyclooctyl etc..As R^C7For cycloalkyloxy when concrete example, can enumerate ring propoxyl group, cyclobutoxy group, cyclopentyloxy, Cyclohexyloxy, cycloheptyl epoxide and ring octyloxy etc..

In R^C7In the case of representative examples of saturated aliphatic acyl group or aliphatic acyl radical epoxide, representative examples of saturated aliphatic acyl group or fat The carbon number of race's acyloxy is preferably 2~21, more preferably 2~7.As in R^C7For representative examples of saturated aliphatic acyl group when it is specific Example, can enumerate acetyl group, propiono, positive bytyry, 2- methylpropionyls, positive valeryl, 2,2- Dimethylpropanoyls, just oneself Acyl group, positive heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl Base, n-tetradecane acyl group, n-pentadecane acyl group and hexadecane acyl group etc..As in R^C7For representative examples of saturated aliphatic acyloxy when Concrete example, acetyl group epoxide, propiono epoxide, positive bytyry epoxide, 2- methylpropionyls epoxide, positive valeryl can be enumerated Epoxide, 2,2- dimethylpropionyloxies, positive caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group oxygen Base, positive capryl epoxide, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyl Base epoxide, n-pentadecane acyloxy and hexadecane acyloxy etc..

In R^C7For alkoxy carbonyl when, the carbon number of alkoxy carbonyl is preferably 2~20, more preferably 2~7.As R^C7For alkoxy carbonyl when concrete example, methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy can be enumerated Carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isoamyl oxygen It is base carbonyl, secondary pentyloxy carbonyl, tert-pentyloxy carbonyl, positive hexyloxy carbonyl, positive Epoxide carbonyl in heptan, n-octyloxy carbonyl, different pungent Epoxide carbonyl, secondary carbonyl octyloxy, tertiary carbonyl octyloxy, positive nonyl epoxide carbonyl, different nonyl epoxide carbonyl, n-decyloxy carbonyl and Isodecyl Epoxide carbonyl etc..

In R^C7For phenylalkyl when, the carbon number of phenylalkyl is preferably 7~20, more preferably 7~10.In addition, in R^C7 For naphthylalkyl when, the carbon number of naphthylalkyl is preferably 11~20, more preferably 11~14.As R^C7For phenylalkyl when Concrete example, benzyl, 2- phenylethyls, 3- phenyl propyls and 4- phenyl butyls can be enumerated.As R^C7For naphthylalkyl when Concrete example, Alpha-Naphthyl methyl, betanaphthyl methyl, 2- (Alpha-Naphthyl) ethyls and 2- (betanaphthyl) ethyl can be enumerated.In R^C7 For phenylalkyl or naphthylalkyl when, R^C7Can further have substituent on phenyl or naphthyl.

In R^C7For heterocyclic radical when, heterocyclic radical is for five yuan comprising more than 1 N, S, O or hexa-atomic monocyclic, or the list The heterocyclic radical that ring condenses each other, or the monocyclic heterocyclic radical formed with phenyl ring fusion.When heterocyclic radical is condensed ring, number of rings For less than 3.Heterocyclic radical can be aromatic group (heteroaryl) or non-aromatic group.As the composition heterocycle The heterocycle of base, furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, three can be enumerated Azoles, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, benzo three Azoles, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines (cinnoline), quinoline Quinoline, piperidines, piperazine, morpholine, piperidines, oxinane and tetrahydrofuran etc..In R^C7For heterocyclic radical when, heterocyclic radical can further have Substituted base.

In R^C7For Heterocyclylcarbonyl when, heterocyclic radical and R contained by Heterocyclylcarbonyl^C7For heterocyclic radical when heterocyclic radical it is identical.

In R^C7For substituted by 1 or 2 organic groups amino when, on the preference of organic group, carbon can be enumerated The alkyl of atomicity 1~20, the cycloalkyl of carbon number 3~10, carbon number 2~21 representative examples of saturated aliphatic acyl group, can have The phenyl of substituted base, can the benzoyl with substituent, can the octadecyloxy phenyl with the carbon number 7~20 of substituent Base, can the naphthyl with substituent, can the naphthoyl with substituent, can the carbon number 11 with substituent~ 20 naphthylalkyl and heterocyclic radical etc..The concrete example of these preferable organic groups, with R^C7It is identical.Have as by 1 or 2 The concrete example of the amino of machine group substitution, can enumerate methylamino, ethylamino, diethylamino, n-propyl amino, two just Propylcarbamic, isopropylamino, n-butylamino, di-n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, N-octyl amino, n-nonyl amino, positive decyl amino, phenyl amino, naphthyl-amino, acetyl-amino, propanoylamino, positive fourth Acyl amino, positive pentanoylamino, positive caproyl amino, positive heptanoyl group amino, positive octanoylamino, positive decanoylamino, benzene Formylamino, α-naphthoyl amino and β-naphthoyl amino etc..

As R^C7In the substituent of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, can enumerate The alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl group of carbon number 2~7, carbon number 2~7 alkoxy carbonyl, the representative examples of saturated aliphatic acyloxy of carbon number 2~7, have carbon number 1~6 alkyl list Alkyl amino, the dialkyl amido of alkyl with carbon number 1~6, morpholine -1- bases, piperazine -1- bases, halogen, nitro and Cyano group etc..In R^C7In in the case that the phenyl, naphthyl and the heterocyclic radical that include further have substituent, the number of the substituent It is unrestricted in the range of without prejudice to the purpose of the present invention, but preferably 1~4.R^C7In the phenyl, naphthyl and the heterocycle that include When base has multiple substituents, multiple substituents can be the same or different.

Even if among group described above, if with nitro or R^c12The group that-CO- is represented is as R^C7, then exist and carry The tendency of hypersensitivity, so as to preferably.In the range of without prejudice to the object of the invention, R^c12It is not particularly limited, can be from various Selected in organic group.As R^c12The example of preferable group, the alkyl of carbon number 1~20 can be enumerated, can have and take Dai Ji phenyl, can be with substituent naphthyl and can the heterocyclic radical with substituent.Among these groups, R^c12 Particularly preferably 2- aminomethyl phenyls, thiophene -2- bases and Alpha-Naphthyl.

If in addition, R^C7For hydrogen atom, then the good tendency of the transparency be present, so as to preferably.If in addition, R^C7For hydrogen atom, And R^C10The group represented for formula described later (c4a) or (c4b), then the better tendency of the transparency be present.

In formula (c4), R^c8And R^c9Respectively can the chain-like alkyl with substituent, can the ring-type with substituent Organic group or hydrogen atom.R^c8With R^c9Landform cyclization can also be mutually bonded.Among these groups, can preferably have The chain-like alkyl of substituted base is as R^c8And R^c9.In R^c8And R^c9For it can have the chain-like alkyl of substituent in the case of, Chain-like alkyl can be that straight chained alkyl can also be branched alkyl.

In R^c8And R^c9In the case of the chain-like alkyl without substituent, the carbon number of chain-like alkyl is preferably 1 ~20, more preferably 1~10, particularly preferably 1~6.As R^c8And R^c9For chain-like alkyl when concrete example, can enumerate Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, uncle penta Base, n-hexyl, n-heptyl, n-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl Deng.In addition, in R^c8And R^c9In the case of alkyl, alkyl can include ehter bond (- O-) in carbochain.Have as in carbochain There is the example of the alkyl of ehter bond, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy ethoxy can be enumerated Base ethyl, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..

In R^c8And R^c9In the case of the chain-like alkyl with substituent, the carbon number of chain-like alkyl is preferably 1~ 20, more preferably 1~10, particularly preferably 1~6.In this case, the carbon number of chain-like alkyl does not include the carbon of substituent Atomicity.Chain-like alkyl with substituent, preferably straight-chain.

In the range of without prejudice to the object of the invention, substituent that alkyl can have does not limit especially.As The preferable example of substituent, can enumerate cyano group, halogen atom, cyclic organic group and alkoxy carbonyl.As halogen Atom, fluorine atom, chlorine atom, bromine atoms, iodine atom can be enumerated.Among these atoms, preferably fluorine atom, chlorine atom, Bromine atoms.As cyclic organic group, cycloalkyl, aromatic hydrocarbyl, heterocyclic radical can be enumerated.As the concrete example of cycloalkyl, With R^c7For cycloalkyl when preferable example it is identical.As the concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, xenyl, Anthryl and phenanthryl etc..As the concrete example of heterocyclic radical, with R^c7For heterocyclic radical when preferable example it is identical.In R^c7For alkoxy During carbonyl, the alkoxy contained by alkoxy carbonyl can be straight-chain or branched, preferably straight-chain.Alkoxy The carbon number of alkoxy contained by carbonyl is preferably 1~10, more preferably 1~6.

In the case where chain-like alkyl has substituent, the quantity of substituent is not particularly limited.Preferable substituent Quantity changed according to the carbon number of chain-like alkyl.Typically, the quantity of substituent is 1~20, preferably 1~10, more Preferably 1~6.

In R^c8And R^c9In the case of cyclic organic group, cyclic organic group can be ester ring type group, can also It is aromatic group.As cyclic organic group, aliphatic cyclic alkyl, aromatic hydrocarbyl, heterocyclic radical can be enumerated.In R^c8With And R^c9In the case of cyclic organic group, substituent that cyclic organic group can have, with R^c8And R^c9For chain-like alkyl Shi Xiangtong.

In R^c8And R^c9In the case of aromatic hydrocarbyl, aromatic hydrocarbyl is preferably phenyl, or multiple phenyl ring via The group that carbon-carbon double bond bonding forms, or the group that multiple phenyl ring are condensed and formed.It is phenyl in aromatic hydrocarbyl, Huo Zheduo In the case of the group that individual phenyl ring bonding or fusion are formed, the number of rings of the phenyl ring contained by aromatic hydrocarbyl does not limit especially It is fixed, but preferably less than 3, more preferably less than 2, particularly preferably 1.As the preferable concrete example of aromatic hydrocarbyl, Neng Goulie Lift phenyl, naphthyl, xenyl, anthryl and phenanthryl etc..

In R^c8And R^c9In the case of aliphatic cyclic alkyl, aliphatic cyclic alkyl can be monocyclic, can also It is polycycle.The carbon number of aliphatic cyclic alkyl is not particularly limited, but preferably 3~20, more preferably 3~10. As the example of the cyclic hydrocarbon group of monocyclic, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, Norborny, isobornyl, three cyclononyls, tricyclodecyl, tetracyclododecyl group and adamantyl etc..

In R^c8And R^c9In the case of heterocyclic radical, heterocyclic radical is five yuan or hexa-atomic of the list comprising more than 1 N, S, O Ring, the heterocyclic radical that either the monocyclic heterocyclic radical condensed each other or the fusion of described monocyclic and phenyl ring form.Heterocyclic radical For condensed ring when, number of rings be less than 3.Heterocyclic radical can be aromatic series base (heteroaryl) or non-aromatic base.As composition The heterocycle of the heterocyclic radical, can enumerate furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, Pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, BTA, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperazine Pyridine, piperazine, morpholine, piperidines, oxinane and tetrahydrofuran etc..

R^c8And R^c9Ring can also reciprocally be bonded together to form.By R^c8With R^c9The group that the ring of formation is formed, preferably sub- ring Alkyl.In R^c8With R^c9In the case of bonding together to form cycloalkylidene, the ring of cycloalkylidene is formed, preferably five-membered ring~hexatomic ring, More preferably five-membered ring.

In R^c8With R^c9In the case that the group that bonding ground is formed is cycloalkylidene, cycloalkylidene can also be and more than 1 Other rings fusion form.As the example for the ring that can be condensed with cycloalkylidene, phenyl ring, naphthalene nucleus, cyclobutane can be enumerated Ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine ring and Pyrimidine ring etc..

As R described above^c8And R^c9Among preferable group example, formula-A can be enumerated¹-A²The group of expression. In formula, A¹For straight-chain alkyl-sub, A²Alkoxy, cyano group, halogen atom, haloalkyl, cyclic organic group and alkane can be enumerated Epoxide carbonyl.

A¹The carbon number of straight-chain alkyl-sub be preferably 1~10, more preferably 1~6.In A²In the case of for alkoxy, Alkoxy can be that straight-chain can also be branched, preferably straight-chain.The carbon number choosing of alkoxy is 1~10, more excellent Choosing is 1~6.In A²In the case of for halogen atom, preferably fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine Atom, chlorine atom, bromine atoms.In A²In the case of haloalkyl, the halogen atom contained by haloalkyl, preferably fluorine are former Son, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom, chlorine atom, bromine atoms.Haloalkyl can be that straight-chain also may be used To be branched, preferably straight-chain.In A²In the case of cyclic organic group, the example of cyclic organic group is with being used as R^c8 And R^c9The cyclic organic group that substituent has is identical.In A²In the case of alkoxy carbonyl, the example of alkoxy carbonyl With as R^c8And R^c9The alkoxy carbonyl that substituent has is identical.

As R^c8And R^c9Preferable concrete example, can enumerate ethyl, n-propyl, normal-butyl, n-hexyl, n-heptyl with And the alkyl such as n-octyl；2- methoxy ethyls, 3- methoxyl groups n-propyl, 4- methoxyl groups normal-butyl, 5- methoxyl groups n-pentyl, 6- first Epoxide n-hexyl, 7- methoxyl groups n-heptyl, 8- methoxyl groups n-octyl, 2- ethoxyethyl groups, 3- ethyoxyls n-propyl, 4- ethyoxyls The alkoxies such as normal-butyl, 5- ethyoxyls n-pentyl, 6- ethyoxyls n-hexyl, 7- ethyoxyls n-heptyl and 8- ethyoxyl n-octyls Alkyl；2- cyano ethyls, 3- cyano group n-propyl, 4- cyano group normal-butyl, 5- cyano group n-pentyl, 6- cyano group n-hexyl, 7- cyano group are just The cyanoalkyl such as heptyl and 8- cyano group n-octyls；2- phenylethyls, 3- phenyl n-propyl, 4- phenyl normal-butyl, 5- phenyl are just The phenylalkyls such as amyl group, 6- phenyl n-hexyl, 7- phenyl n-heptyl and 8- phenyl n-octyls；2- cyclohexyl-ethyls, 3- hexamethylenes Base n-propyl, 4- cyclohexyl normal-butyl, 5- cyclohexyl n-pentyl, 6- cyclohexyl n-hexyl, 7- cyclohexyl n-heptyl, 8- cyclohexyl N-octyl, 2- cyclopentyl ethyls, 3- cyclopenta n-propyl, 4- cyclopenta normal-butyl, 5- cyclopenta n-pentyl, 6- cyclopenta just oneself The cycloalkyl-alkyls such as base, 7- cyclopenta n-heptyl and 8- cyclopenta n-octyls；2- dion es, 3- methoxycarbonyls N-propyl, 4- methoxycarbonyls normal-butyl, 5- methoxycarbonyls n-pentyl, 6- methoxycarbonyls n-hexyl, 7- methoxycarbonyls N-heptyl, 8- methoxycarbonyls n-octyl, 2- ethoxycarbonylethyl groups, 3- ethoxy carbonyls n-propyl, 4- ethoxy carbonyls are just Butyl, 5- ethoxy carbonyls n-pentyl, 6- ethoxy carbonyls n-hexyl, 7- ethoxy carbonyls n-heptyl and 8- ethoxy carbonyls The alkoxy carbonyl alkyls such as n-octyl；2- chloroethyls, 3- chlorine n-propyl, 4- chloro-n-butyls, 5- chlorine n-pentyl, 6- chlorine n-hexyl, 7- chlorine n-heptyl, 8- chlorine n-octyl, 2- bromoethyls, 3- bromines n-propyl, 4- bromines normal-butyl, 5- bromines n-pentyl, 6- bromines n-hexyl, 7- The haloalkyls such as bromine n-heptyl, 8- bromines n-octyl, 3,3,3- trifluoro propyls and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.

As R^c8And R^c9, preferable group is ethyl, n-propyl, normal-butyl, n-pentyl, 2- methoxyl group second in above-mentioned Base, 2- cyano ethyls, 2- phenylethyls, 2- cyclohexyl-ethyls, 2- dion es, 2- chloroethyls, 2- bromoethyls, 3,3, 3- trifluoro propyls and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.

As R^c10The example of preferable organic group, such as R^c7Similarly, alkyl, alkoxy, cycloalkyl, ring can be enumerated Alkoxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, the phenyl can with substituent, can be with Phenoxy group with substituent, can the benzoyl with substituent, can the phenyloxycarbonyl with substituent, can have The benzoyl epoxide of substituted base, can the phenylalkyl with substituent, can the naphthyl with substituent, can be with The naphthoxy of substituent, can the naphthoyl with substituent, can the naphthoxycarbonyl with substituent, can be with taking Dai Ji naphthoyl epoxide, can the naphthylalkyl with substituent, can the heterocyclic radical with substituent, can be with taking Dai Ji Heterocyclylcarbonyl, the amino substituted by 1 or 2 organic groups, morpholine -1- bases and piperazine -1- bases etc..These bases The concrete example and R of group^c7Explanation it is identical.In addition, it is also preferred that cycloalkyl-alkyl, can on aromatic rings have substituent benzene oxygen Base alkyl, there can be the phenylsulfartyl alkyl of substituent on aromatic rings as R^c10.Phenoxyalkyl and phenylsulfartyl alkane The substituent that base can have, with R^c7The substituent that contained phenyl can have is identical.

Even if in organic group, it is also preferred that alkyl, cycloalkyl, the phenyl can with substituent or cycloalkyl-alkyl, There can be the phenylsulfartyl alkyl of substituent on aromatic rings as R^c10.Alkane as alkyl, preferably carbon number 1~20 The alkyl of base, more preferably carbon number 1~8, the alkyl of particularly preferred carbon number 1~4, most preferable.Can have and take In Dai Ji phenyl, preferably aminomethyl phenyl, more preferably 2- aminomethyl phenyls.The carbon number of the cycloalkyl included in cycloalkyl-alkyl Preferably 5~10, more preferably 5~8, particularly preferably 5 or 6.The carbon number of the alkylidene included in cycloalkyl-alkyl is excellent Elect 1~8, more preferably 1~4, particularly preferably 2 as.In cycloalkyl-alkyl, preferred cyclopentyl ethyl.Can be on aromatic rings The carbon number of the alkylidene included in phenylsulfartyl alkyl with substituent is preferably 1~8, and more preferably 1~4, especially Preferably 2.Can be on aromatic rings in the phenylsulfartyl alkyl with substituent, preferably 2- (4- chlorophenyl sulfanyls) ethyl.

Furthermore it is preferred that-A³-CO-O-A⁴- the group represented is as R^c10。A³For the hydrocarbon of the organic group of divalent, preferably divalent Base, preferably alkylidene.A⁴For the alkyl of the organic group of 1 valency, preferably 1 valency.

In A³In the case of alkylidene, alkylidene can be that straight-chain can also be branched, preferably straight-chain. A³In the case of alkylidene, the carbon number of alkylidene is preferably 1~10, more preferably 1~6, particularly preferably 1~4.

As A⁴Preference, can enumerate the alkyl of carbon number 1~10, the aralkyl of carbon number 7~20 and The aromatic hydrocarbyl of carbon number 6~20.As A⁴Preferable concrete example, methyl, ethyl, n-propyl, isopropyl can be enumerated Base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, Alpha-Naphthyl methyl And betanaphthyl methyl etc..

It is used as-A³-CO-O-A⁴The preferable concrete example of-group represented, can enumerate 2- dion es, 2- second Epoxide carbonyl ethyl, 2- positive propoxy carbonyls ethyl, 2- n-butoxycarbonyls ethyl, 2- n-pentyloxycarbonyls ethyl, 2- just oneself Epoxide carbonyl ethyl, 2- benzyloxycarbonyls ethyl, 2- phenyloxycarbonyls ethyl, 3- methoxycarbonyls n-propyl, 3- ethyoxyl carbonyls Base n-propyl, 3- positive propoxy carbonyls n-propyl, 3- n-butoxycarbonyls n-propyl, 3- n-pentyloxycarbonyls n-propyl, 3- are just Hexyloxy carbonyl n-propyl, 3- benzyloxycarbonyls n-propyl and 3- phenyloxycarbonyl n-propyls etc..

Although above to R^c10It is illustrated, but is used as R^c10, preferably following formula (c4a) or (c4b) represent Group.

【Chemical formula 22】

(in formula (c4a) and (c4b), R^c13And R^c14Respectively organic group, n6 is 0~4 integer, in R^c13And R^c8When being present in the adjacent position on phenyl ring, R^c1With R^c14Ring can reciprocally be bonded together to form, n7 is 1~8 integer, n8 1 ~5 integer, n9 be 0~(n8+3) integer, R^c15For organic group.)

On the R in formula (c4a)^c13And R^c14Organic group example, with R^c7It is identical.As R^c13, preferably alkyl Or phenyl.In R^c13In the case of alkyl, its carbon number is preferably 1~10, more preferably 1~5, particularly preferably 1~ 3, most preferably 1.That is, R^c13Most preferably methyl.In R^c13With R^c14In the case of being bonded landform cyclization, the ring can be fragrance Race's ring or aliphatic ring.The group that formula (c4a) represents, as R^c13With R^c14The preferable example of the group of ring is formed, Naphthalene -1- bases, 1,2,3,4- naphthane -5- bases etc. can be enumerated.In above-mentioned formula (c4a), n6 be 0~4 integer, preferably 0 or 1, more preferably 0.

In above-mentioned formula (c4b), R^c15For organic group.As organic group, it can enumerate and be directed to R^c7And illustrate organic The same group of group.In organic group, preferred alkyl.Alkyl can be that straight-chain can also be branched.The carbon of alkyl Atomicity is preferably 1~10, more preferably 1~5, particularly preferably 1~3.As R^c15, can preferably list methyl, ethyl, Propyl group, isopropyl, butyl etc., in these more preferably methyl.

In above-mentioned formula (c4b), n8 be 1~5 integer, preferably 1~3 integer, more preferably 1 or 2.Above-mentioned formula (c4b) in, n9 is 0~(n8+3), preferably 0~3 integer, more preferably 0~2 integer, particularly preferably 0.Above-mentioned formula (c4b) in, n7 be 1~8 integer, preferably 1~5 integer, more preferably 1~3 integer, particularly preferably 1 or 2.

In formula (c4), R^c11For hydrogen atom, can be with the carbon number 1~11 of substituent alkyl or can be with The aryl of substituent.As R^c11For the substituent that can have during alkyl, phenyl, naphthyl etc. are preferably enumerated.In addition, conduct R^c7For the substituent that can have during aryl, alkyl, alkoxy, halogen atom of carbon number 1~5 etc. are preferably enumerated.

In formula (c4), as R^c11, preferably enumerate hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, benzene Base, benzyl, aminomethyl phenyl, naphthyl etc., in these more preferably methyl or phenyl.

The compound that formula (c4) represents, is manufactured by following method, and methods described is included the formula (c5) table Contained by the compound shown oximido (>C=N-OH) it is converted into>C=N-O-COR^c11The process of the oxime ester base of expression.R^c11With formula (c4) R in^c11It is identical.

Oximido (>C=N-OH) it is converted into>C=N-O-COR^c11The oxime ester base of expression is by representing the formula (c5) Compound and acylation reaction and carry out.

As offer-COR^c11The acylating agent of the oxime ester base of expression, (R can be enumerated^c11C0)₂The acid anhydrides of O expressions, R^c11The carboxylic acid halides that COHal (Hal is halogen atom) is represented.

The preferable concrete example of compound represented as formula (c4), can enumerate following PI-43~PI-83.

【Chemical formula 23】

【Chemical formula 24】

It is preferred relative to the quality that the solid state component of photosensitive polymer combination is overall, the content of (C) Photoepolymerizationinitiater initiater It is 0.5~30 mass %, more preferably 1~20 mass %.By making the content of (C) Photoepolymerizationinitiater initiater be above range, energy Access and be difficult to produce the bad photosensitive polymer combination of pattern form.

In addition, light-initiated auxiliary agent can be combined in (C) Photoepolymerizationinitiater initiater.As light-initiated auxiliary agent, can enumerate Triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminobenzoic acids methyl esters, 4- dimethylaminobenzoic acid second Ester, 4- dimethylaminobenzoic acids isopentyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, benzoic acid 2- dimethylaminoethyls Ester, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) benzophenone, 9,10- dimethoxys anthracene, 2- ethyl -9, 10- dimethoxys anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 2-mercaptobenzothiazole, 2- sulfydryl benzene Bing oxazoles, 2-mercaptobenzimidazole, 2- sulfydryl -5- methoxybenzothiazoles, 3- mercaptopropionic acids, 3- mercapto-propionates, season penta Mercaptan compounds such as the mercaptoacetate of tetrol four, 3-thiopropionate etc..These light-initiated auxiliary agents can be used alone or combine 2 Used more than kind.

<(D) pigment>

Photosensitive polymer combination includes (D) pigment.As (D) pigment, although being not particularly limited, can make With for example, preferred coloring agent indexes (C.I.；Britain dyeing worker association (The Society of Dyers and Colourists) issue) in be classified as pigment (Pigment) compound, be preferably as described below with dye specifically The compound of material index (C.I.) numbering.

As the example of the yellow uitramarine preferably used, C.I. pigment yellows 1 (following, " C.I. pigment yellows " can be enumerated It is identical, only records numbering.)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73, 74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、 120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、 167th, 168,175,180 and 185.

As the example of the orange pigment preferably used, C.I. pigment oranges 1 (following, " C.I. pigment oranges " can be enumerated It is identical, only records numbering.)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、 64th, 71 and 73.

As the example of the violet pigment preferably used, C.I. pigment violet 1s (following, " C.I. pigment violets " can be enumerated It is identical, only records numbering.), 19,23,29,30,32,36,37,38,39,40 and 50.

As the example of the red pigment preferably used, C.I. paratoneres 1 (following, " C.I. paratoneres " can be enumerated It is identical, only records numbering.)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、 31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57： 2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、 112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、 177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、 220th, 223,224,226,227,228,240,242,243,245,254,255,264 and 265.

As the example of the blue pigment preferably used, C.I. pigment blue 1s (following, " C.I. alizarol saphirols " can be enumerated It is identical, only records numbering.)、2、15、15：3、15：4、15：6th, 16,22,60,64 and 66.

As the example of the pigment of other the above-mentioned tones preferably used, C.I. pigment Green 7s, C.I. face can be enumerated Expect the viridine greens of green 36, C.I. naphthol greens 37 etc., C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. face Expect the black pigment of the brown, C.I. pigment blacks 1, C.I. pigment blacks 7 of brown 28 grades etc..

In addition, photosensitive polymer combination is preferably used as (D) pigment comprising black pigment.By using including black face The photosensitive polymer combination of material, light-proofness can be assigned in the cured film of formation.Therefore, the photonasty comprising black pigment Resin combination, the formation of the black matrix" being preferred in liquid crystal display panel or black column spacer, or organic EL The formation of the separation levee of the division of luminescent layer in element.

As the example of black pigment, can enumerate black carbon black, series pigments, lactams series pigments, titanium, copper, iron, manganese, Metal oxide, composite oxides, metal sulfide, metal sulfate or the metal carbonate of cobalt, chromium, nickel, zinc, calcium, silver etc. Deng whether organic matter or the various pigment of inorganic matter.Among these black pigments, from being readily available or light-proofness is excellent And easily formed from the viewpoint of the high cured film of resistance, preferably carbon black.

In addition, the tone of black pigment, the netrual colour i.e. black being not limited on chromatics or atropurpureus, Black-and-blue, reddish black.

As carbon black, carbon black known to channel black, furnace black, thermal black, lampblack etc. can be used, in addition, Resin-coating carbon black can be used.

As carbon black, it is also preferred that implementing the carbon black for the processing for importing acidic-group.The acidic-group of carbon black is directed into, is Represent the acid functional group of bronsted definition.As the concrete example of acidic-group, carboxyl, sulfonic group, phosphoric acid can be enumerated Base etc..The acidic-group of carbon black is directed into, can also forming salt.With the cation of acidic-group forming salt, without prejudice to this hair In the range of improving eyesight, it is not particularly limited.As the example of cation, various metal ions, nitrogen can be enumerated The cation of compound, ammonium ion etc., the preferably alkali metal ion of sodium ion, potassium ion or lithium ion etc., or ammonium ion.

In the carbon black of processing of importing acidic-group described above is implemented, photosensitive resin composition is used from realizing From the viewpoint of the high impedance of the cured film for the light-proofness that thing is formed, preferably tool preferably is selected from carboxylic acid group, carboxylate group, sulfonic group And the carbon black of more than a kind of functional group of sulphonate-base.

Acidic-group is directed into the method for carbon black, is not particularly limited., can as the method for importing acidic-group Enumerate for example following method.

1) by using the direct method of substitution of the concentrated sulfuric acid, oleum, chlorosulfonic acid etc., or sulphite, sulfurous acid are used The indirect method of substitution of hydrogen salt etc., sulfonic method is imported to carbon black.

2) method for making there is the organic compound of amino and acidic-group and carbon black diazonium coupling.

3) by Williamson's etherification method, make organic compound with halogen atom and acidic-group with hydroxyl The method that carbon black reacts.

4) organic compound with halo carbonyl and the acidic-group by protection group protection is made, with the carbon black with hydroxyl The method to react.

5) using with halo carbonyl and the organic compound for the acidic-group protected by protection group, carried out relative to carbon black After friedel-craft reaction, the method that is then deprotected.

Among those methods, from the importing of acidic-group processing easily and it is safe from the viewpoint of, preferably method 2).As method 2) in the organic compound with amino and acidic-group that uses, be preferably bonded on aromatic group The compound of amino and acidic-group.As the example of the compound, benzene sulfonic acid as p-aminobenzene sulfonic acid can be enumerated, Or aminobenzoic acid as PABA.

In the range of without prejudice to the object of the invention, the molal quantity for being directed into the acidic-group of carbon black does not limit especially It is fixed.Relative to 100g carbon black, the molal quantity for being directed into the acidic-group of carbon black is preferably 1~200mmol, more preferably 5~ 100mmol。

Having imported the carbon black of acidic-group can also implement to handle using the cladding of resin.Using photosensitive resin composition In the case of thing, easy formation light-proofness and the light-proofness cured film that insulating properties is excellent, surface reflectivity is low, the photonasty Resin combination includes the carbon black by resin-coating.In addition, handled by the cladding of resin, especially will not be to using photonasty tree The light-proofness cured film conductance that oil/fat composition is formed produces harmful effect.Example as the resin for the cladding that can be used in carbon black Son, can enumerate phenolic resin, melmac, xylene resin, diallyl phthalate resin, glyptal resin, It is the thermosetting resins such as epoxy resin, alkylbenzene resin, polystyrene, makrolon, polyethylene terephthalate, poly- to benzene Dioctyl phthalate butanediol ester, Noryl, polysulfones, polyparaphenylene terephthalamide, polyamidoimide, polyimides, The thermoplastic resins such as PABM, polyethers sulfo group PPSU, polyarylate, polyether-ether-ketone.Resin relative to The covering amount of carbon black, relative to carbon black quality and resin quality total, preferably 1~30 mass %.

Furthermore it is possible to it is preferred that series pigments are used as black pigment.As the concrete example of series pigments, can enumerate down State the series pigments of formula (d-1) expression, the series pigments that following formula (d-2) represents and following formula (d-3) expression is face Material.In commercially available product, can preferably use BASF AG name of product KOO84 and K0086, or pigment black 21,30, 31st, 32,33 and 34 etc. series pigments are used as.

【Chemical formula 25】

In formula (d-1), R^d1And R^d2Separately represent the alkylidene of carbon number 1~3, R^d3And R^d4It is only respectively On the spot represent hydrogen atom, alkyl, methoxyl group or acetyl group.

【Chemical formula 26】

In formula (d-2), R^d5And R^d6Separately represent the alkylidene of carbon number 1~7.

【Chemical formula 27】

In formula (d-3), R^d7And R^d8Hydrogen atom, the alkyl of carbon number 1~22 are separately represented, can also be wrapped Containing these hetero atoms of N, O, S or P.In R^d7And R^d8In the case of alkyl, the alkyl can be straight-chain or Branched.

The side that such as Japanese Unexamined Patent Application 62-1753 publications, Japanese Patent Publication 63-26784 publications can be used to record Method, synthesize the compound of above-mentioned formula (d-1) expression, the compound that the compound that formula (d-2) represents and formula (d-3) represent.That is, With -3,5,9,10- tetracarboxylic acids or -3,5,9,10- tetracarboxylic acid dianhydrides and amine are raw material, in water or organic solvent Middle carry out heating response.And, so as to get rough thing in sulfuric acid reprecipitation, either in water, organic solvent or water with having The in the mixed solvent recrystallization of solvent, so as to obtain target substance.

In order that series pigments disperse in photosensitive polymer combination well, the mean particle diameter of series pigments is excellent Choosing is 10~1000nm.

In addition, as opacifier, lactams series pigments can be also included.As lactams series pigments, can enumerate for example The compound that following formula (d-4) represents.

【Chemical formula 28】

In formula (d-4), X^dDouble bond is represented, is separately E bodies or Z bodies as geometric isomer.R^d9Independently Ground represents hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R^d10Independently Ground represents hydrogen atom, methyl or phenyl, R^d11Hydrogen atom, methyl or chlorine atom are represented independently of one another.

The compound that formula (d-4) represents can be used alone or combine two or more and use.

From the viewpoint of the compound of formula (d-4) expression is easy to manufacture, R^d9Preferably it is bonded in dihydroindolone ring On six, R^d11Preferably it is bonded on four of dihydroindolone ring.From the viewpoint of same, R^d9、R^d10And R^d11It is preferred that It is hydrogen atom.

Formula (d-4) is although the compound represented has EE bodies, ZZ bodies, EZ bodies but it is also possible to be this as geometric isomer Any one a little single compounds or the mixture of these geometric isomers.

The compound that formula (d-4) represents can be for example, by International Publication No. 2000/24736 and International Publication No. The method manufacture of No. 2010/081624 record.

In order that lactams series pigments disperse in photosensitive polymer combination well, the average grain of lactams series pigments Sub- diameter is preferably 10~1000nm.

And then preferably use that (hereinafter referred to as " AgSn alloys are micro- using silver-colored tin (AgSn) alloy as the particulate of main component Grain ") it is used as black pigment.The AgSn alloy particles can using AgSn alloys as main component, can also contain such as Ni, Pd, Au etc. is used as other metal ingredients.

The mean particle diameter of the AgSn alloy particles, preferably 1~300nm.

In the case where representing AgSn alloys with AgxSn, the x of the stable AgSn alloys of chemical property scope can be obtained For 1≤x≤10, while the scope for obtaining the stable x with degree of blackness of chemical property is 3≤x≤4.

Herein, if in the range of above-mentioned x, the mass ratio of the Ag in AgSn alloys is obtained, then

During X=1, Ag/AgSn=0.4762

During X=3,3Ag/Ag3Sn=0.7317

During X=4,4Ag/Ag4Sn=0.7843

During X=10,10Ag/Ag10Sn=0.9008.

Therefore, the AgSn alloys are in the case of the Ag containing 47.6~90 mass %, and chemical property is stable, containing In the case of 73.17~78.43 weight % Ag, it can obtain relative to the effective chemical stability of Ag amounts and degree of blackness.

The AgSn alloy particles can be made using common particulate synthetic method.As particulate synthetic method, gas can be enumerated Phase reaction method, spray heating decomposition, spray-on process, liquid phase reactor method, freeze-dried method, hydrothermal synthesis method etc..

Although AgSn alloy particle insulating properties is higher, according to the purposes of photosensitive polymer combination, in order to improve absolutely Edge, dielectric film can also be covered on the surface of AgSn alloy particles.As the material of the dielectric film, preferably metal oxide Or organic high molecular compound.

As metal oxide, preferably using the metal oxide with insulating properties, such as silica (silica), oxygen Change aluminium (alundum (Al2O3)), zirconium oxide (zirconium dioxide), yittrium oxide (yttria), titanium oxide (titanium dioxide) etc..

In addition, as organic high molecular compound, preferably using the resin with insulating properties, such as polyimides, polyethers, Polyacrylate, polyamino compound etc..

In order to fully improve the insulating properties on the surface of AgSn alloy particles, the thickness of dielectric film is preferably 1~100nm thickness Degree, more preferably 5~50nm.

Dielectric film can be readily formed by the coating technology of surfaction technology or surface.Particularly, if made With the alkoxide of tetraethoxysilane, three aluminium ethylates etc., then the dielectric film of uniform film thickness can be formed at a lower temperature, so as to It is preferred that.

As black pigment, above-mentioned series pigments, lactams series pigments, AgSn alloy particles can be used alone, These materials can be used in combination.

In addition, for purpose for adjusting tone etc., black pigment can also contain the pigment of the form and aspect such as red, blue, green, yellow. The pigment of other form and aspect beyond black pigment, it can be properly selected from known pigment.For example, it can use above-mentioned various Pigment of the pigment as other form and aspect beyond black pigment.The usage amount of form and aspect beyond black pigment, relative to black The overall quality of pigment, preferably below 15 mass %, more preferably below 10 mass %.

In order that (D) pigment described above is evenly dispersed in photosensitive polymer combination, can also and then use Dispersant.As such dispersant, preferably using polyethyleneimine amine, polyurethane type resin, crylic acid resin high score Sub- dispersant.When especially, using carbon black as (D) pigment, preferably dispersant is used as using the dispersant of crylic acid resin.

It additionally, there are because of dispersant and the situation of corrosive gas produced in cured film.Therefore, (D) pigment is preferred Decentralized processing is carried out without using dispersant.

In addition, inorganic pigment and organic pigment can be used individually, or also can and with two or more, and feelings Under condition, relative to the mass parts of total amount 100 of inorganic pigment and organic pigment, preferably used with the scope of 10~80 mass parts organic Pigment, organic pigment is more preferably used with the scope of 20~40 mass parts.

In addition, in photosensitive polymer combination, dyestuff can also with (D) pigment combination be used.As long as from known The dyestuff is properly selected in material.

As the dyestuff that can be used in photosensitive polymer combination, such as azo dyes can be enumerated, metallic complex salt is even Nitrogen dyestuff, anthraquinone dye, kiton colors, xanthene dye, cyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dye Material, phthalocyanine dyestuff etc..

In addition, on these dyestuffs, it is set to be dispersed in organic solvent etc. (into salinization) by color lake, can be as (D) pigment uses.

In addition to these dyestuffs, preferably it can use for example, Japanese Unexamined Patent Publication 2013-225132 publications, Japanese Unexamined Patent Publication 2014-178477 publications, Japanese Unexamined Patent Publication 2013-137543 publications, Japanese Unexamined Patent Publication 2011-38085 publications, Japanese Unexamined Patent Publication Dyestuff of the records such as 2014-197206 publications etc..

In the range of without prejudice to the object of the invention, (D) pigment in photosensitive polymer combination can be properly selected Usage amount, typically, relative to the quality that the solid state component of photosensitive polymer combination is overall, preferably 2~75 mass %, More preferably 3~70 mass %.

Preferably in the case of presence or in the absence of dispersant, by pigment (D) so that debita spissitudo disperses and is formed and divided After dispersion liquid, it is added in photosensitive polymer combination.

In addition, in this manual, the usage amount of above-mentioned (D) pigment, it can be defined as comprising its existing dispersant Value.

<(S) organic solvent>

(S) organic solvent is preferably comprised in order to improve coating or regulation viscosity, photosensitive polymer combination.

As organic solvent (S), specifically, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list can be enumerated N-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl Ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propane diols Single ethylether, propane diols list n-propyl ether, propane diols list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, (poly-) such as DPG list n-propyl ether, DPG list n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylethers Alkylene glycol monoalkyl ethers class；Ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl Ether acetic acid ester, TC acetic acid esters, propylene glycol monomethyl ether (PGMEA), propylene glycol monoethyl second Acid esters etc. (poly-) alkylene glycol monoalkyl ethers acetate esters；Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl Other ethers such as glycol diethyl ether, tetrahydrofuran；The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；2- hydroxyls The lactic acid alkyl ester classes such as methyl propionate, 2 hydroxy propanoic acid ethyl ester；2- hydroxy-2-methyls ethyl propionate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, ethoxy ethyl acetate, hydroxyacetic acid second Ester, 2- hydroxy-3-methyls methyl butyrate, acetic acid 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, propionic acid 3- methyl - 3- methoxybutyls, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, Isoamyl acetate, phenylmethyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, third Ketone acid methyl esters, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester etc. its His esters；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；METHYLPYRROLIDONE, N,N-dimethylformamide, N, N- dimethyl Acetamide, N, N- dimethyl-isobutyramide, N, N- diethyl acetamides, N, N- diethylformamides, N- methyl caprolactams, Nitrogenous polar organic solvents such as DMI, pyridine and N, N, N', N'- tetramethylurea etc..

Wherein, preferably alkylene glycol monoalkyl ethers class, alkylene glycol monoalkyl ethers acetate esters, other above-mentioned ethers Class, lactic acid alkyl ester class, other above-mentioned esters, more preferably alkylene glycol monoalkyl ethers acetate esters, other above-mentioned ethers Other above-mentioned esters of class, benzyl acetate etc..

In addition, from the viewpoint of the dissolubility of each composition or the dispersiveness of (D) pigment etc., (S) organic solvent is preferably Include nitrogenous polar organic solvent.N, N, N', N'- tetramethylureas etc. can be used to be used as nitrogenous polar organic solvent.

These solvents may be used alone or in combination two or more and use.

(S) content of Elements in Organic Solvents is not particularly limited, and can pass through the concentration that can be coated on substrate etc., root Suitably set according to coating film thickness.The viscosity of photosensitive polymer combination is preferably 5~500cp, more preferably 10~50cp, enters one Step is preferably 20~30cp.In addition, solid component concentration is preferably 5~100 mass %, more preferably 15~50 mass %.

＜ other compositions ＞

In photosensitive polymer combination, as needed, surfactant, adaptation enhancer, thermal polymerization can be contained The additives such as inhibitor, defoamer, silane coupler.All additives can use known material.

From it is easy formed shape it is good, to from the viewpoint of the excellent cured film of substrate adaptation, photosensitive resin composition Thing preferably comprises silane coupler.As silane coupler, it is not particularly limited, known material can be used.

As surfactant, the compound of anion system, cation system, nonionic system etc. can be enumerated.As thermal polymerization Inhibitor, quinhydrones, Hydroquinone monoethylether etc. can be enumerated.As defoamer, polysiloxane series, fluorine system compound etc. can be enumerated.

The preparation method ＞ of ＜ photosensitive polymer combinations

After amount mixes according to the rules respectively by above-mentioned each composition, equably mixed, can obtained using mixer Photosensitive polymer combination described above.In addition, in order that obtained photosensitive polymer combination evenly, can also use Filter is filtered.

《The manufacture method of cured film》

As the manufacture method of cured film, do not limit especially, (B) optical polymerism chemical combination can be included using use The manufacture method of photosensitive polymer combination, the known cured film of thing.

As the preferable manufacture method of cured film, the method for including following process can be enumerated：

The process for forming film by being coated with described photosensitive polymer combination；

The process that selection position is exposed to film；

Make the painting film development after exposure, and the process for forming the cured film of patterning；

The process for toasting the cured film of patterning.

In order that cured film is formed with photosensitive polymer combination, first, in the substrate selected according to the purposes of cured film Upper photosensitive resin coating composition, form film.The forming method of film is not particularly limited, for example, roller can be used Painting machine, reverse coating machine, bar coater etc. contact transfer printing type apparatus for coating, or spin coater (rotary apparatus for coating), curtain The non-contact type apparatus for coating such as coating machine are flowed to carry out.

The photosensitive polymer combination of coating is dried as needed, forms film.Drying means does not limit especially System, for example, following methods can be enumerated：(1) heating plate is utilized, in 80~120 DEG C, preferably 90~100 DEG C of temperature, dries 60 The method of~120 seconds；(2) method for placing a few hours~a couple of days at room temperature；(3) it is put into storage heater or infrared ray adds Dozens of minutes~a few hours in hot device and method for removing solvent etc..

Then, film is exposed.Expose the active energy beam by irradiating ultraviolet, excimer laser etc. Carry out.Such as method by being exposed via negative mask etc., select position to be exposed.The energy-ray amount of irradiation because The composition of photosensitive polymer combination and different, such as preferably 40~200mJ/cm²Left and right.

In addition, when being comprehensively exposed to film, it can be formed with shape corresponding with the shape of film, do not schemed The cured film of case.

In the case of being exposed in selection position to film, the film after exposure is developed by developer solution, not exposed Light is partially dissolved in developer solution so as to be removed, and forms the cured film of patterning.Developing method is not particularly limited, and can be made With such as infusion process, gunite.Developer solution can be properly selected according to the composition of photosensitive polymer combination.As development Liquid, the alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt can be used.

Then, the cured film after patterning is toasted (rear baking).The temperature of baking is not particularly limited, but excellent Choosing is 180~250 DEG C, more preferably 220~230 DEG C.Baking time, typically 10~90 minutes, preferably 20~60 points Clock.

By being toasted as above, the cured film of photosensitive polymer combination can be obtained.

Cured film after coloring being formed like this, comprising (D) pigment, can be preferably according to the form and aspect of (D) pigment For the coloring film such as black matrix" or RGB in colour filter.

【Embodiment】

Embodiment described below further specifically illustrates to the present invention, but the scope of the present invention, not by this A little embodiments limit.

The ﹞ of ﹝ preparation examples 1

First, in 500ml four-hole boiling flask, bisphenol fluorene type epoxy resin 235g (epoxide equivalent 235), tetramethyl are added Ammonium chloride 110mg, 2,6- di-tert-butyl-4-methy phenols 100mg and acrylic acid 72.0g, wherein, while with 25ml/ points Speed is blown into air, while being dissolved by heating at 90~100 DEG C.Then, slowly heat up, be heated in the case where solution is in milkiness state 120 DEG C are completely dissolved it.Wherein, solution becomes clear viscous shape successively, now continues to stir.During this, continue to add Thermal agitation, and its acid number is determined, untill its is less than 1.0mgKOH/g.Acid number reaches desired value needs 12 hours.Then it is cold But to room temperature, so as to obtain the bisphenol fluorene type epoxy acrylate being expressed from the next of water white transparency solid-like.

Then, acetic acid -3- methoxyl group fourths are added in so obtained above-mentioned bisphenol fluorene type epoxy acrylate 307.0g Base ester 600g and after dissolving, 80.5g benzophenone tetracarboxylic dianhydrides and 1g tetraethylammonium bromides are mixed, slowly heats and makes Reacted 4 hours at 110~115 DEG C.It is determined that after anhydride group disappearance, 38.0g 1,2,3,6- tetrahydrochysene benzene two are mixed into Formic anhydride, it is reacted 6 hours at 90 DEG C, obtain Resin A -1.The disappearance of anhydride group is confirmed by infrared spectrum IR.

﹝ embodiments 1, embodiment 2 and the ﹞ of comparative example 1~3

In embodiment and comparative example, (A) alkali is used as using novolac resin, the more resins of card, acrylic resin Soluble resin.

TO-547 (trade name) using Sumitomo Bakelite company system is used as novolac resin.TO-547, it is in isophthalic Good fortune of the oxalic acid with concentration for 37 mass % is added in 90 moles of % of cresols and 10 moles of % of 2,3,5- pseudocuminols mixture You are Malin, and carrying out condensation reaction by conventional method obtains Mw30000 cresol novolac resin.

The more resins of card are used as using the Resin A -1 that above-mentioned preparation example 1 obtains.

Use the construction unit and the 80 moles of % knot from styrene comprising 20 moles of % from methacrylic acid The resin (chemical company of Xin Zhong villages system, NCF-3 (trade name), Mw=10000) of structure unit is used as acrylic resin.

In embodiment and comparative example, made using the polyfunctional monomer beyond dendritic, dendritic For (B) photopolymerizable compound.

SIRIUS 501 (trade name) using Osaka Organic Chemical Industry society is used as dendritic.

The polyfunctional monomer beyond dendritic is used as using DHPA (dipentaerythritol acrylate).

In embodiment and comparative example, OXE-02 (trade name, BASF societies system, O- acetyl group -1- [6- (2- first are used Base benzoyl) -9- ethyl -9H- carbazole -3- bases] acetophenone oxime) it is used as (C) Photoepolymerizationinitiater initiater.

In embodiment and comparative example, (D) pigment is used as using carbon black.

Carbon black (pigment A (dispersion liquid)) using the chemical conversion industry society of Datong District as D-A and imperial state's pigment as D-B The carbon black (pigment B (dispersion liquid)) of society is used as carbon black.

In addition, in the table 1 of the present embodiment, the number of the aggregate value of the solid state component of the pigment and dispersant is described Value.

The amount recorded respectively according to table 1, (A) alkali soluble resin, (B) photopolymerizable compound, (C) photopolymerization are triggered Agent and (D) pigment dissolved, be dispersed in (S) organic solvent, solid component concentration is changed into 15 mass %, obtain each embodiment, The photosensitive polymer combination of comparative example.

Use acetic acid 3- methoxybutyls:Propylene glycol monomethyl ether:Cyclohexanone=40：35：25 (mass ratioes) Mixed solvent is used as (S) organic solvent.

Use obtained photosensitive polymer combination, according to following method, the difficulty flowed to cured film by heating CD (the critical dimensions of cured film after (resistance to mobility), patterning；Critical Dimension) it is close with the fine rule of cured film Conjunction property is evaluated.

<Resistance to fluidity evaluating>

First, 100mm square glass substrate is cleaned with pure water, and is dried in 160 DEG C of baking box.Will embodiment with And the photosensitive polymer combination obtained in comparative example is coated on dried glass substrate, the heating plate using 100 DEG C adds Heat makes solvent volatilize in 2 minutes.Then, after being exposed using the mask of 5 μm of rays, show in 0.04%KOH developer solution Shadow 70 seconds.

The substrate that will be patterned into is split into two halves, and half is kept for 20 minutes in 230 DEG C of baking box is heated to.To in this wise Substrate after heating, after cooling is taken out from baking box, patterned features are cut, its section is observed using SEM.

In this content, compared with the substrate not heated using baking box, it is able to confirm that because of thermally-induced deformation (stream It is dynamic).

In this content, evaluated based on following benchmark.

○：If the cone angle of chamfering state, pattern to pattern top, the state of oozing out from the lower end of pattern are seen Examine, in terms of whether pattern keeps rectangular shape, bigger difference is not present with unheated substrate in the substrate after heating.

△：Although can be said to be problem of not improving quality in degree, if the cone of the chamfering state, pattern to pattern top Angle, from being carried out from the state of oozing out of the lower end of pattern, if the substrate and the unheated substrate that are able to observe that after heating are present Dry difference (shape crumbles).

×：If the cone angle of chamfering state, pattern to pattern top, the state of oozing out from the lower end of pattern are seen Examine, it can be found that the substrate after heating has significant difference with unheated substrate (shape crumbles).

<CD is evaluated>

With with it is above-mentioned<Resistance to fluidity evaluating>Identical method carries out operation until development operation, afterwards, will be patterned into Substrate dimidiation, half is kept for 20 minutes in 230 DEG C of baking box is heated to.

Afterwards, confirm pattern part using microscope, evaluated based on following benchmark.

○：Relative to the size of mask width, pattern is formed with the size within ± 10%.

×：Relative to the size of mask width, with more than+10% or the size of deficiency -10% forms pattern.Or Film reduction is significantly produced because developing.

<Fine rule adaptation is evaluated>

On mask, in addition to using the mask for the width for having 3~20 μm concurrently in one side, other with it is above-mentioned< Resistance to fluidity evaluating>Identical method carries out operation until exposing operation.Afterwards, 80 are developed in 0.04%KOH developer solution Second, confirm pattern part whether there is stripping under the microscope, be averaged according to following benchmark.

○：Even if 3 μm of pattern part, also do not observe and peel off.

×：In the partially observable stripping of 3 μm of patterns.

【Table 1】

It can be seen from embodiment, by following photosensitive polymer combination, it can be formed and be not easy because of heating and excess flow, And with defined size patterned cured film.The photosensitive polymer combination includes (A) alkali soluble resin, (B) light Polymerizable compound, (C) Photoepolymerizationinitiater initiater and (D) pigment, (A) alkali soluble resin is used as comprising novolac resin, and And it is used as (B) photopolymerizable compound included in the dendritic that end has more than 2 ethene polymerizable groups.

On the other hand, it can be seen from comparative example 1 and comparative example 3, photosensitive polymer combination is not comprising novolaks In the case of resin, it is difficult to the cured film of patterning is formed with defined size.

In addition, it can be seen from comparative example 2, photosensitive polymer combination has more than 2 ethene being not included in end In the case of the dendritic of polymerizable group, the cured film of formation easily flows because of heating.

Claims (10)

1. a kind of photosensitive polymer combination, draw comprising (A) alkali soluble resin, (B) photopolymerizable compound, (C) photopolymerization Agent and (D) pigment are sent out,

(A) alkali soluble resin includes novolac resin,

(B) photopolymerizable compound, which is included in end, has the dendritic of more than 2 ethene polymerizable groups.

2. photosensitive polymer combination as claimed in claim 1, the dendritic is more officials that following formula (1) represents The addition product for more sulfhydryl compounds that energy (methyl) acrylate compounds represent with following formula (2),

【Chemical formula 1】

In formula (1), R¹It is the alkyl that hydrogen atom or carbon number are 1~4, R²It is by polyalcohol R³(OH)_mM hydroxyl among N hydroxyl provide to the n valency residues after the ester bond in formula (1), m and n are separately 2~20 integer, m >=n；

(HS-CH₂-)p-R⁴ (2)

In formula (2), R⁴It is the group containing the alkyl that carbon number is 1~6 of singly-bound or 2~6 valencys, in R⁴For the feelings of singly-bound Under condition, p is 2, in R⁴In the case of the group containing alkyl for 2~6 valencys, p is 2~6 integer.

3. the photosensitive polymer combination as described in claim 1 or claim 2, (A) alkali soluble resin also wraps Containing the resin with the more structures of card.

4. the photosensitive polymer combination as described in any one of claims 1 to 3, the Weight-average molecular of the novolac resin Measure as less than more than 2,000 50000.

5. the photosensitive polymer combination as described in any one of Claims 1 to 4, (D) pigment is black pigment.

6. photosensitive polymer combination as claimed in claim 5, the black pigment is carbon black.

7. the photosensitive polymer combination as described in any one of claim 1~6, the content Wn of the novolac resin The ratio between the content Wd [g] of [g] and the dendritic (Wn：Wd) 20：1~1：In the range of 20.

8. a kind of cured film, formed as the photosensitive polymer combination solidification described in any one of claim 1~7.

9. a kind of colour filter, possesses the cured film described in claim 8.

10. a kind of manufacture method of cured film, includes following process：

The process for forming film by being coated with the photosensitive polymer combination described in any one of claim 1~7；

The process that selection position is exposed to the film；

Make the painting film development after exposure, and the process for forming the cured film of patterning；

The process for toasting the cured film of the patterning.