CN107315318A

CN107315318A - Photosensitive composite

Info

Publication number: CN107315318A
Application number: CN201710281862.XA
Authority: CN
Inventors: 田所惠典; 盐田大
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2016-04-27
Filing date: 2017-04-26
Publication date: 2017-11-03
Anticipated expiration: 2037-04-26
Also published as: CN107315318B; KR20170122682A; KR102391780B1; JP2017198865A; JP6860978B2

Abstract

The present invention relates to photosensitive composite.The problem of the present invention is the forming method for providing the excellent photosensitive composite of susceptibility, the solidfied material of the photosensitive composite, the dielectric film formed by the solidfied material of the photosensitive composite, the colour filter of the solidfied material comprising the photosensitive composite, the display device with the colour filter and the cured film carried out using the photosensitive composite.The solution of the present invention is to coordinate following compounds as Photoepolymerizationinitiater initiater in photosensitive composite, and the compound is the oxime ester compound as main framing comprising carbazole ring or fluorenes ring, and is had on carbazole ring or fluorenes ring：The chain fatty race alkyl of with electron withdraw group, arlydene, inferior heteroaryl or more than a kind of the key comprising more than 1 in carbon-carbon double bond and triple carbon-carbon bonds.

Description

Photosensitive composite

Technical field

The present invention relates to photosensitive composite, the solidfied material of the photosensitive composite, the solidification by the photosensitive composite The dielectric film of thing formation, the colour filter of the solidfied material comprising the photosensitive composite, the display device with the colour filter and make The forming method of the cured film carried out with the photosensitive composite.

Background technology

The display devices such as liquid crystal display are formed as following structures：It is being formed with 2 of mutually opposing paired electrode The structure of liquid crystal layer is accompanied between substrate.Moreover, being formed with the inside of the substrate of a side including red (R), green (G), indigo plant The colour filter (color filter) of the pixel regions of a variety of colors such as color (B).In the colour filter, black square is conventionally formed with Battle array, to divide each pixel regions such as red, green, blueness.

Generally, colour filter can utilize photoetching process manufacture.I.e., first, the photosensitive composite of painting black is simultaneously on substrate It is dried, is then exposed, develops, black matrix" is formed.Next, for a variety of colors such as red, green, blueness Photosensitive composite, each repeats to be coated with, dry, expose and develop, the pixel of a variety of colors is formed in specific position Region, so as to manufacture colour filter.

In recent years, when manufacturing the display devices such as liquid crystal display, it is try to improve the shading brought by black matrix" Property, so as to further improve make the contrast of image that display device shows.Accordingly, it would be desirable to for forming black matrix" Substantial amounts of opacifier is included in photosensitive composite.If however, like this in photosensitive composite include a large amount of opacifiers, Formed by will be coated on substrate during the film exposure of photosensitive composite, the light for solidifying photosensitive composite is difficult to The bottom of film is reached, causing the susceptibility of photosensitive composite significantly reduces, so as to cause solidification bad.

As photosensitive composite, the composition containing oxime ester compound is widely used for.Oxime ester compound is as use It is widely used in the Photoepolymerizationinitiater initiater for making photopolymerizable compound polymerization.In addition, oxime ester compound has by exposure And the property of alkali is produced, using the property, promote the oxime ester compound as photosensitive solidification (reaction promotes) Agent is used, and the photosensitive solidification promotes (reaction promotes) agent to be used for the solidification for promoting epoxide etc., or promotes polyamides The ring-closure reactions such as the imidization reaction of imines precursor.In addition, oxime ester compound is also act as the photosensitive of LED exposure composition Agent.Therefore, the susceptibility of photosensitive composite can be included wherein Photoepolymerizationinitiater initiater, photosensitive curing accelerator The influence of species, this point is known.

In addition, in recent years, increase with the production number of units of the display devices such as liquid crystal display, the output of colour filter Correspondingly increase.Therefore, from the viewpoint of increasing productivity further, in the urgent need to pattern can be formed with low light exposure The photosensitive composite of high sensitive.

In this case, as that can cause the good Photoepolymerizationinitiater initiater of the susceptibility of photosensitive composite, patent is literary Offer and the oxime ester compound with cycloalkyl is proposed in 1.In embodiment described in patent document 1, followingization are specifically disclosed The compound that formula (a) and (b) is represented.

[chemical formula 1]

Prior art literature

Patent document

Patent document 1：Chinese publication publication the 101508744th

The content of the invention

Invent problem to be solved

However, when manufacturing various panels for display device using photosensitive composite, from the production for improving panel From the viewpoint of rate, light exposure when expecting to expose the coated film formed by photosensitive composite can be reduced all the more.But i.e. Make to be the photosensitive composite for including the compound described in patent document 1, also there is the situation that can not fully meet such requirement. It is therefore desirable to develop the susceptibility sense more excellent than the photosensitive composite comprising the compound described in patent document 1 Photosensitiveness composition.

The present invention makes in view of the above problems, it is therefore intended that the excellent photosensitive composite of offer susceptibility, The solidfied material of the photosensitive composite, the dielectric film formed by the solidfied material of the photosensitive composite, include the photosensitive composition The colour filter of the solidfied material of thing, the display device with the colour filter and the cured film that is carried out using the photosensitive composite Forming method.

Means for solving the problems

Inventors herein have recognized that, by coordinating following compounds as Photoepolymerizationinitiater initiater in photosensitive composite In, above-mentioned problem can be solved, so as to complete the present invention, the compound is to be used as main framing comprising carbazole ring or fluorenes ring Oxime ester compound, and have on carbazole ring or fluorenes ring：Respectively with electron withdraw group, aryl, heteroaryl, comprising 1 with On more than a kind of key in carbon-to-carbon double bond and carbon-to-carbon triple bond chain fatty race alkyl or base that they are combined Group.

The 1st mode of the present invention is a kind of photosensitive composite, and it contains the compound of following formula (1) expression.

[chemical formula 2]

(in formula (1), R¹Represent electron withdraw group, R⁶For arlydene, inferior heteroaryl (heteroarylene), comprising 1 with On more than a kind of key in carbon-to-carbon double bond and carbon-to-carbon triple bond chain fatty race alkyl or base that they are combined Group, R⁶Can have the substituent of more than 1 in electron withdraw group, mercapto and monovalent organic group, R⁴Represent that monovalence has Machine group or hydrogen atom, R⁵Represent monovalent organic group or hydrogen atom, n represent 0 or 1, T represent following formula (T_C) or formula (T_N) table The group shown,

[chemical formula 3]

Formula (T_C) and formula (T_N) in, R²And R³The alkyl or hydrogen atom that can be substituted, * expressions are represented independently of one another Learn key,

Formula (T_C) in, R²And R³It can combine and form ring.)

The 2nd mode of the present invention is a kind of solidfied material, and it is that the photosensitive composite that the 1st mode is related to includes (A) light The solidfied material of the photosensitive composite of polymerizable compound, wherein,

Photosensitive composite can include (C) colouring agent.

The 3rd mode of the present invention is a kind of dielectric film, and it is that the solidfied material being related to by the 2nd mode is formed.

The 4th mode of the present invention is a kind of colour filter, and it is the colour filter for the solidfied material being related to comprising the 2nd mode, wherein,

Photosensitive composite can include (C) colouring agent.

The 5th mode of the present invention is a kind of display device, and it has the colour filter that the 4th mode is related to.

The 6th mode of the present invention is the forming method of cured film, and methods described includes following process：

The photosensitive composite i.e. photosensitive composite comprising (A) photopolymerizable compound that 1st mode is related to is coated with In the process that coated film is formed on base material, and

The process being exposed to coated film；

In methods described, photosensitive composite can include (C) colouring agent.

The effect of invention

Pass through the present invention, it is possible to provide the excellent photosensitive composite of susceptibility, the solidfied material of the photosensitive composite, by this Photosensitive composite solidfied material formation dielectric film, the colour filter of the solidfied material comprising the photosensitive composite, with the filter The forming method of the display device of color chips and the cured film carried out using the photosensitive composite.

Brief description of the drawings

[Fig. 1] is schematic diagram of the expression using the cross sectional shape of the width of the pattern of photosensitive composite formation, (a) For the figure for the cross sectional shape for representing common pattern, (b) is the section for the pattern that expression generates undercut portions (undercut) 21 The figure of shape.

Description of reference numerals

1 is not present the section of the width of the pattern of undercut portions

2 have the section of the width of the pattern of undercut portions

Embodiment

《Photosensitive composite》

Photosensitive composite includes the compound that following formula (1) is represented.The compound that formula (1) is represented has following function： As the function of the Photoepolymerizationinitiater initiater of the photopolymerizable compound polymerization made for example with ethylenic unsaturated double-bond, by exposing Light and the function of producing alkali.Therefore, can for various purposes, the compound that formula (1) is represented is photosensitive as being assigned to composition The composition of property is used.The photonasty composition that the compound that formula (1) is represented can be used as the ultraviolets such as 365nm, 385nm is used, And can be used as the emulsion composition of the h lines comprising 405nm, the LED exposure of 435nm g lines.

As photosensitive composite, for example, it is preferably：The compound represented comprising formula (1) and (A) optical polymerism described later The composition of compound, the compound represented comprising formula (1) and consolidating with oxirane ring and/or oxetanes ring The composition of the compound for the property changed, compound and the composition of polyimide precursor for being represented comprising formula (1) etc..

For photosensitive composite, as needed, compound, (A) optical polymerism described later except formula (1) expression The compound of compound and curability with oxirane ring and/or oxetanes ring, polyimide precursor it Outside, various additives can also be included.

As the additive, specifically, can enumerate colouring agent, solvent, sensitizer, curing accelerator, photocrosslinking agent, Photosensitizer, dispersing aid, filler, closely sealed accelerator, antioxidant, ultra-violet absorber, deflocculant, thermal polymerization are prevented Agent, defoamer, surfactant etc..

On colouring agent and the preference of solvent, (A) optical polymerism will be included as preferred photosensitive composite The composition of the photosensitive composite of compound and describe in detail below.

The compound ＞ that ＜ formulas (1) are represented

Hereinafter, the compound that following formula (1) is represented is illustrated.

[chemical formula 4]

(in formula (1), R¹Represent electron withdraw group, R⁶Carbon-to-carbon double bond is selected from for arlydene, inferior heteroaryl, comprising more than 1 And the chain fatty race alkyl or group that they are combined of more than a kind of key in carbon-to-carbon triple bond, above-mentioned R⁶Can have The substituent of more than 1 in electron withdraw group, mercapto and monovalent organic group, R⁴Represent monovalent organic group or hydrogen Atom, R⁵Represent monovalent organic group or hydrogen atom, n represent 0 or 1, T represent following formula (T_C) or formula (T_N) represent group,

[chemical formula 5]

Formula (T_C) in, R²And R³It can combine and form ring.)

(on R¹And R⁶)

The compound represented by formula (1) has R by being combined in fluorenes ring or on carbazole ring¹-R⁶Electricity is inhaled in including for-expression The group of the group of subbase group and other regulation structures, so that susceptibility is excellent.

On R⁶The substituent that can have, as R¹Electron withdraw group, as long as usually as suction in chemical field Electron group and known functional group, are not particularly limited.

As the preference of electron withdraw group, the alkane sulphur of benzenesulfonyl, tosyl, carbon number 1~6 can be enumerated Acyl group, cyano group, nitro, halogen atom and haloalkyl etc..In these electron withdraw groups, chemically stability, formula (1) are represented Compound to the susceptibility of light, be readily synthesized in terms of the compound of formula (1) expression and consider, preferably nitro, cyano group and carbon are former The fluoroalkyl of subnumber 1~6.

R⁶For arlydene, inferior heteroaryl, comprising more than 1 more than a kind in carbon-to-carbon double bond and carbon-to-carbon triple bond The chain fatty race alkyl of key or the group that they are combined.In addition, R⁶Can have selected from electron withdraw group, mercapto and The substituent of more than 1 in monovalent organic group.

R⁶During for arlydene, as long as the arlydene 2 hydrogen atoms are removed from aromatic hydrocarbon obtained from group, just do not have There is special limitation.Arlydene is preferably the group formed by the phenyl ring of more than 1.It is many when arlydene includes the phenyl ring of more than 2 Individual phenyl ring can be mutually bonded by singly-bound, can be also fused to each other and be formed the condensed ring such as naphthalene nucleus.

Arlydene preferably comprises 1~3 phenyl ring, more preferably comprising 1 or 2 phenyl ring.

As the preference of arlydene, it can enumerate to phenylene, metaphenylene, adjacent phenylene, naphthalene -1,2- diyl, naphthalene -1, 3- diyls, naphthalene -1,4- diyls, naphthalene -1,5- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, naphthalene -2,6- two Base, naphthalene -2,7- diyls, biphenyl -4,4 '-diyl, biphenyl -3,3 '-diyl, biphenyl -2,2 '-diyl, biphenyl -3,4 '-diyl, connection Benzene -3,2 '-diyl and biphenyl -2,4 '-diyl.

R⁶During for inferior heteroaryl, as long as the inferior heteroaryl removes base obtained from 2 hydrogen atoms from heteroaromatic Group, is just not particularly limited.Preferably, inferior heteroaryl is the group formed by five yuan or hexa-atomic of aromatic rings and is comprising extremely The group of few 1 five yuan or hexa-atomic heteroaromatic.

Inferior heteroaryl is the group formed by five yuan or hexa-atomic of aromatic rings and is comprising five yuan or hexa-atomic of at least one During the group of heteroaromatic, multiple five yuan or hexa-atomic of aromatic rings can be mutually bonded by singly-bound, can be also fused to each other and shape Into condensed ring.

Inferior heteroaryl preferably comprises 1~3 five yuan or hexa-atomic of aromatic rings, more preferably comprising 1 or 2 five yuan or hexa-atomic Aromatic rings.

As the preference of inferior heteroaryl, can enumerate from furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, Isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indoles Piperazine, benzimidazole, BTA, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, scold Removed in the aromatic heterocyclic compounds such as quinoline and quinoxaline and be bonded to group obtained from 2 hydrogen atoms of carbon atom.

On the chain fatty race hydrocarbon comprising more than 1 more than a kind of the key in carbon-to-carbon double bond and carbon-to-carbon triple bond Base, the number of its carbon number, carbon-to-carbon double bond and carbon-to-carbon triple bond is no special in the range of the without prejudice to purpose of the present invention Limitation.

In addition, the chain fatty race hydrocarbon of more than a kind of the key comprising more than 1 in carbon-to-carbon double bond and carbon-to-carbon triple bond Base can be straight-chain or branched, preferably straight-chain.

The chain fatty race alkyl of more than a kind of the key comprising more than 1 in carbon-to-carbon double bond and carbon-to-carbon triple bond Carbon number is preferably 2~10, more preferably 2~6, particularly preferably 2~4.

Chain fatty race alkyl is preferably the alkylene group (alkenylene group) or bag for including 1 carbon-to-carbon double bond Alkynylene (alkynylene group) containing 1 carbon-to-carbon triple bond.

It is used as the chain fatty race hydrocarbon comprising more than 1 more than a kind of the key in carbon-to-carbon double bond and carbon-to-carbon triple bond The preference of base, can enumerate ethene -1,2- diyl, acetylene -1,2- diyl, propyl- 1- alkene -1,2- diyl, sub- propargyl (propargylene group), sub- pentynyl (pentynylene group).

For example, as by arlydene and comprising more than 1 more than a kind in carbon-to-carbon double bond and carbon-to-carbon triple bond The preference of group, can enumerate following divalent groups obtained from the chain fatty race alkyl combination of key.

It is used as more than a kind of the key by inferior heteroaryl and comprising more than 1 in carbon-to-carbon double bond and carbon-to-carbon triple bond The preference of group, can enumerate and replace the arlydene included in following divalent groups obtained from the alkyl combination of chain fatty race It is changed to group obtained from various inferior heteroaryls.

[chemical formula 6]

On R⁶, arlydene, inferior heteroaryl or comprising more than 1 a kind in carbon-to-carbon double bond and carbon-to-carbon triple bond with On the chain fatty race alkyl of key can have more than 1 in electron withdraw group, mercapto and monovalent organic group Substituent.

On electron withdraw group, as described above.R⁶During for arlydene, preferably taken in contraposition or ortho position by electron withdraw group Generation.On being used as R⁶The monovalent organic group for the substituent that can have, can enumerate alkyl (for example, methyl, ethyl) and alcoxyl Base (for example, methoxyl group, ethyoxyl) etc..R⁶It is preferably substituted in meta during for arlydene.

It is used as be described above, R¹-R⁶- the group for including electron withdraw group represented, is preferably the virtue replaced by nitro Base, the phenyl more preferably replaced by nitro.

The substitution number of nitro in aryl is not particularly limited, preferably 1~3, more preferably 1 or 2, particularly preferably 1.

As the concrete example of the aryl replaced by nitro (by R⁶The part of female skeleton of formula (1) is bonded to as 1), can Enumerate O-Nitrophenylfluorone, m-nitro base, p-nitrophenyl, 2,3- dinitrophenyls, dinitrophenyl group, 2,5- dinitros Phenyl, 2,6- dinitrophenyls, 3,4- dinitrophenyls, 3,5- dinitrophenyls, 2- nitronaphthalene -1- bases, 3- nitronaphthalenes -1- Base, 4- nitronaphthalene -1- bases, 5- nitronaphthalene -1- bases, 6- nitronaphthalene -1- bases, 7- nitronaphthalene -1- bases, 8- nitronaphthalene -1- bases, 3- nitre Base naphthalene -2- bases, 6- nitronaphthalene -2- bases, 8- nitronaphthalene -2- bases, 1- nitronaphthalene -2- bases and 7- nitronaphthalene -2- bases.

In these groups, more preferably O-Nitrophenylfluorone and p-nitrophenyl, 2,4- dinitrophenyls, 2,6- dinitros Phenyl, 2- nitronaphthalene -1- bases, 4- nitronaphthalene -1- bases, 5- nitronaphthalene -1- bases, 3- nitronaphthalene -2- bases, 6- nitronaphthalene -2- bases, 8- Nitronaphthalene -2- bases, 1- nitronaphthalene -2- bases.Particularly preferably p-nitrophenyl.

(on formula (T_C) and formula (T_N) in the R that includes²And R³)

T in formula (1) is above-mentioned formula (T_C) represent group or formula (T_N) represent group.Formula (T_C) and formula (T_N) in Comprising R²And R³The alkyl or hydrogen atom that can be respectively substituted.Formula (T_C) in, R²With R³It can be mutually bonded and form ring. In these groups, R is used as²And R³, it is preferably the alkyl that can be substituted.R²And R³For can be substituted alkyl when, alkyl can Think straight chained alkyl, or branched alkyl.

R²And R³During for alkyl without substituent, the carbon number of the alkyl is preferably 1~20, more preferably 1~ 10, particularly preferably 1~6.It is used as R²And R³Concrete example during for alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, just It is butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different Octyl group, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..

R²And R³During for alkyl with substituent, the carbon number of alkyl is preferably 1~20, and more preferably 1~10, it is special You Xuanwei 1~6.In this case, the carbon number of chain-like alkyl does not include the carbon number of substituent.With substituent Alkyl can be straight-chain, or branched, preferably straight-chain.

The substituent that alkyl can have is not particularly limited in the range of the without prejudice to purpose of the present invention.It is used as substitution The preference of base, can enumerate cyano group, halogen atom, cyclic organic group, alkoxy and alkoxy carbonyl.

As halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom can be enumerated.In these, preferably fluorine atom, chlorine Atom, bromine atoms.

As cyclic organic group, cycloalkyl, aromatic hydrocarbyl, heterocyclic radical can be enumerated.

The carbon number of cycloalkyl is preferably 3~10, and more preferably 3~6.As the concrete example of cycloalkyl, ring can be enumerated Propyl group, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl etc..

As aromatic hydrocarbyl, phenyl, naphthyl, xenyl, anthryl and phenanthryl etc. can be enumerated.

Heterocyclic radical is for five yuan comprising more than 1 N, S, O or hexa-atomic monocyclic, or for it is described it is monocyclic condense each other, Or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is condensed ring, the number of the ring of fusion is less than 3.Heterocyclic radical It can be aromatic group (heteroaryl), or non-aromatic group.As the heterocycle for constituting the heterocyclic radical, it 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, benzo thiophene Azoles, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperidines, tetrahydrochysene pyrrole Mutter and tetrahydrofuran etc..R²And R³During for heterocyclic radical, heterocyclic radical can further have substituent.

As the alkoxy of the alkoxy of alkoxy, preferably carbon number 1~10, more preferably carbon number 1~6, The particularly preferably alkoxy of carbon number 1~4.As concrete example, methoxyl group, ethyoxyl, n-propyl epoxide, isopropyl can be enumerated Base epoxide, normal-butyl epoxide, isobutyl group epoxide, sec-butyl epoxide, tert-butyl group epoxide, n-pentyl epoxide, isopentyl epoxide, secondary penta Base epoxide, tertiary pentyl epoxide and n-hexyl epoxide.

The alkoxy included in alkoxy carbonyl can be straight-chain, or branched, preferably straight-chain.Alcoxyl The carbon number of the alkoxy included in base carbonyl is preferably 1~10, and more preferably 1~6.As concrete example, methoxy can be enumerated Base carbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyloxycarbonyl group, normal-butyl Epoxide carbonyl, isobutyl group epoxide carbonyl Base, sec-butyl Epoxide carbonyl, t-butyloxycarbonyl, n-pentyl Epoxide carbonyl, isopentyl Epoxide carbonyl, sec-amyl epoxide carbonyl Base, t-amyloxycarbonyl group and n-hexyl Epoxide carbonyl.

When alkyl has substituent, the number of substituent is not particularly limited.It is preferred that substituent number according to chain The carbon number of alkyl and change.The number of substituent is typically 1~20, preferably 1~10, more preferably 1~6.

R²With R³It can be mutually bonded and form ring.Include R²With R³The group of the ring of formation is preferably cycloalkylidene (cycloalkylidene group)。R²With R³When being bonded and forming cycloalkylidene, the ring for constituting cycloalkylidene is preferably five yuan Ring~hexatomic ring, more preferably five-membered ring.

R²With R³When group formed by bonding is cycloalkylidene, cycloalkylidene can be condensed with other rings of more than 1. As the example for the ring that can be condensed with cycloalkylidene, phenyl ring, naphthalene nucleus, cyclobutane ring, pentamethylene ring, cyclohexane ring, ring can be enumerated Heptane ring, cyclooctane ring, furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine ring and pyrimidine ring etc..

The R being described above²And R³In, as the example of preferred group, formula-A can be enumerated¹-A²The group of expression.Formula In, A¹For straight-chain alkyl-sub, A²For alkoxy, cyano group, halogen atom, haloalkyl, cyclic organic group or alkoxy carbonyl.

A¹The carbon number of straight-chain alkyl-sub be preferably 1~10, more preferably 1~6.A²During for alkoxy, alkoxy can Think straight-chain, or branched, preferably straight-chain.The carbon number of alkoxy is preferably 1~10, and more preferably 1 ~6, particularly preferably 1~4.

A²During for halogen atom, preferably fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom, chlorine are former Son, bromine atoms.

A²During for haloalkyl, the halogen atom included in haloalkyl is preferably fluorine atom, chlorine atom, bromine atoms, iodine Atom, more preferably fluorine atom, chlorine atom, bromine atoms.Haloalkyl can be straight-chain, or branched, be preferably Straight-chain.

A²During for cyclic organic group, the example and R of cyclic organic group²And R³The ring-type having as substituent has Machine group is same.A²During for alkoxy carbonyl, the example and R of alkoxy carbonyl²And R³The alkoxy carbonyl having as substituent Base is same.

It is used as R²And R³Preferred concrete example, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, positive heptan can be enumerated The alkyl such as base and n-octyl；2- methoxy ethyls, 3- methoxyl groups n-propyl, 4- methoxyl groups normal-butyl, 5- methoxyl groups n-pentyl, 6- methoxyl groups n-hexyl, 7- methoxyl groups n-heptyl, 8- methoxyl groups n-octyl, 2- ethoxyethyl groups, 3- ethyoxyls n-propyl, 4- second The alkane such as epoxide normal-butyl, 5- ethyoxyls n-pentyl, 6- ethyoxyls n-hexyl, 7- ethyoxyls n-heptyl and 8- ethyoxyl n-octyls Epoxide 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- cyanogen The cyanoalkyl such as base n-heptyl and 8- cyano group n-octyls；2- phenylethyls, 3- phenyl n-propyl, 4- phenyl normal-butyl, 5- phenyl The phenylalkyls such as n-pentyl, 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.

It is used as R²And R³, preferred group is ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, 2- first in above-mentioned group Epoxide ethyl, 2- cyano ethyls, 2- phenylethyls, 2- cyclohexyl-ethyls, 2- dion es, 2- chloroethyls, 2- bromine second Base, 3,3,3- trifluoro propyls and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.

(on R⁴)

R⁴For monovalent organic group or hydrogen atom.Monovalent organic group does not have in the range of the without prejudice to purpose of the present invention Especially limitation.

It is used as R⁴Preferred organic group example, alkyl, alkoxy, cycloalkyl, cycloalkyloxy, saturated fat can be enumerated Fat race acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, the phenyl can with substituent, there can be substituent Phenoxy group, the benzoyl can with substituent, the phenyloxycarbonyl can with substituent, the benzene can with substituent Formoxyl epoxide, can have substituent phenylalkyl, can have substituent phenoxyalkyl, can have substituent Phenylsulfartyl alkyl, N- substituted-aminos alkyl, N, N- disubstituted amidos alkyl, can have substituent naphthyl, can have The naphthoxy of substituted base, can have substituent naphthoyl, can have substituent naphthoxycarbonyl, can have The naphthoyl epoxide of substituent, the naphthylalkyl can with substituent, the naphthoxy alkyl can with substituent, can be with Naphthylthio alkyl with substituent, the heterocyclic radical can with substituent, Heterocyclylcarbonyl, the quilt can with substituent Amino, morpholine -1- bases and piperazine -1- bases of 1 or 2 organic group substitution etc..

In addition, being used as R⁴, further preferably cycloalkyl-alkyl, on aromatic rings can have substituent phenoxyalkyl, There can be the phenylsulfartyl alkyl of substituent on aromatic rings.

R⁴During for alkyl, the carbon number of alkyl is preferably 1~20, and more preferably 1~6.In addition, R⁴, can be with during for alkyl For straight chain, or side chain.It is used as R⁴Concrete example during for alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, positive fourth It is base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different pungent Base, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, R⁴During for alkyl, alkyl can be in carbochain In include ehter bond (- O-).As in carbochain with ehter bond alkyl example, can enumerate methoxy ethyl, ethoxyethyl group, Methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..

R⁴During for alkoxy, the carbon number of alkoxy is preferably 1~20, and more preferably 1~6.In addition, R⁴For alkoxy When, can be straight chain, or side chain.It is used as R⁴Concrete example during for alkoxy, can enumerate methoxyl group, ethyoxyl, positive third Base epoxide, isopropyl epoxide, normal-butyl epoxide, isobutyl group epoxide, sec-butyl epoxide, tert-butyl group epoxide, n-pentyl epoxide, isoamyl Base epoxide, sec-amyl epoxide, tertiary pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide, iso-octyl epoxide, Zhong Xin Base epoxide, t-octyl epoxide, n-nonyl epoxide, isononyl epoxide, positive decyl epoxide and isodecyl epoxide etc..In addition, R⁴For alkane During epoxide, alkoxy can include ehter bond (- O-) in carbochain.As the example of the alkoxy with ehter bond in carbochain, it can lift Go out methoxy ethoxy, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propyl group epoxide second Epoxide ethyoxyl and methoxy-propyl epoxide etc..

R⁴During for cycloalkyl or cycloalkyloxy, the carbon number of cycloalkyl or cycloalkyloxy is preferably 3~10, more preferably 3~6.It is used as R⁴Concrete example during for cycloalkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring pungent Base etc..It is used as R⁴Concrete example during for cycloalkyloxy, can enumerate cyclopropyl epoxide, cyclobutyl epoxide, cyclopentyloxy, cyclohexyl Epoxide, suberyl epoxide and cyclooctyl epoxide etc..

R⁴During for representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyl The carbon number of base epoxide is preferably 2~21, and more preferably 2~7.It is used as R⁴Concrete example during for representative examples of saturated aliphatic acyl group, can Enumerate acetyl group, propiono, positive bytyry, 2- methylpropionyls, positive valeryl, 2,2- Dimethylpropanoyls, positive caproyl, just Heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, positive ten Four alkanoyls, n-pentadecane acyl group and hexadecane acyl group etc..It is used as R⁴Concrete example during for representative examples of saturated aliphatic acyloxy, Acetyl group epoxide, propiono epoxide, positive bytyry epoxide, 2- methylpropionyls epoxide, positive valeryl epoxide, 2,2- bis- can be enumerated Methylpropionyl epoxide, positive caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group epoxide, positive capryl oxygen Base, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, positive 15 Alkanoyl epoxide and hexadecane acyloxy etc..

R⁴During for alkoxy carbonyl, the carbon number of alkoxy carbonyl is preferably 2~20, and more preferably 2~7.It is used as R⁴For Concrete example during alkoxy carbonyl, can enumerate methoxycarbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyl epoxide carbonyl Base, normal-butyl Epoxide carbonyl, isobutyl group Epoxide carbonyl, sec-butyl Epoxide carbonyl, t-butyloxycarbonyl, n-pentyl epoxide carbonyl Base, isopentyl Epoxide carbonyl, sec-amyl Epoxide carbonyl, t-amyloxycarbonyl group, n-hexyl Epoxide carbonyl, n-heptyl epoxide carbonyl Base, n-octyl Epoxide carbonyl, iso-octyl Epoxide carbonyl, secondary octyl Epoxide carbonyl, t-octyl Epoxide carbonyl, n-nonyl epoxide carbonyl Base, isononyl Epoxide carbonyl, positive decyl Epoxide carbonyl and isodecyl Epoxide carbonyl etc..

R⁴During for phenylalkyl, the carbon number of phenylalkyl is preferably 7~20, and more preferably 7~10.In addition, R⁴For naphthalene During base alkyl, the carbon number of naphthylalkyl is preferably 11~20, and more preferably 11~14.

It is used as R⁴Concrete example during for phenylalkyl, can enumerate benzyl, 2- phenylethyls, 3- phenyl propyls and 4- phenyl Butyl.

It is used as R⁴Concrete example during for naphthylalkyl, can enumerate Alpha-Naphthyl methyl, betanaphthyl methyl, 2- (Alpha-Naphthyl) second Base and 2- (betanaphthyl) ethyl.

R⁴During for phenylalkyl or naphthylalkyl, R⁴Can further have substituent on phenyl or naphthyl.

R⁴During for phenoxyalkyl, phenylsulfartyl alkyl, naphthoxy alkyl and naphthylthio alkyl, wrapped in these groups The carbon number of the alkylidene contained is preferably 1~20, and more preferably 1~6.In addition, the alkylidene can be straight-chain, can also It is branched, preferably straight-chain.

As the concrete example of phenoxyalkyl, 2- Phenoxyethyls, 3- phenoxypropyls, the positive fourth of 4- phenoxy groups can be enumerated Base, 5- phenoxy groups n-pentyl and 6- phenoxy group n-hexyls.

As the concrete example of phenylsulfartyl alkyl, 2- phenylsulfartyls ethyl, 3- phenylsulfartyls n-propyl, 4- phenyl can be enumerated Sulfenyl normal-butyl, 5- phenylsulfartyls n-pentyl and 6- phenylsulfartyl n-hexyls.

As the concrete example of naphthoxy alkyl, 2- (alpha-naphthoxy base) ethyl, 3- (alpha-naphthoxy base) n-propyl, 4- can be enumerated (alpha-naphthoxy base) normal-butyl, 5- (alpha-naphthoxy base) n-pentyl, 6- (alpha-naphthoxy base) n-hexyl, 2- (β-naphthoxy) ethyl, 3- (β- Naphthoxy) n-propyl, 4- (β-naphthoxy) normal-butyl, 5- (β-naphthoxy) n-pentyls and 6- (β-naphthoxy) n-hexyl.

As the concrete example of naphthylthio alkyl, 2- (Alpha-Naphthyl sulfenyl) ethyl, 3- (Alpha-Naphthyl sulfenyl) positive third can be enumerated Base, 4- (Alpha-Naphthyl sulfenyl) normal-butyl, 5- (Alpha-Naphthyl sulfenyl) n-pentyl, 6- (Alpha-Naphthyl sulfenyl) n-hexyl, 2- (betanaphthyl sulphur Base) ethyl, 3- (betanaphthyl sulfenyl) n-propyl, 4- (betanaphthyl sulfenyl) normal-butyl, 5- (betanaphthyl sulfenyl) n-pentyls and 6- (betanaphthyl sulfenyl) n-hexyl.

R⁴During for phenoxyalkyl, phenylsulfartyl alkyl, naphthoxy alkyl or naphthylthio alkyl, R⁴Can be in phenyl or naphthalene Further there is substituent on base.

R⁴During for heterocyclic radical, heterocyclic radical is for five yuan comprising more than 1 N, S, O or hexa-atomic monocyclic, or is described Monocyclic fusion each other or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is condensed ring, the number of the ring of fusion is Less than 3.Heterocyclic radical can be aromatic group (heteroaryl), or non-aromatic group.It is used as the composition heterocyclic radical Heterocycle, furans, thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyrrole can be enumerated Pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, BTA, benzo Oxazole, benzothiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperazine Pyridine, oxinane and tetrahydrofuran etc..R⁴During for heterocyclic radical, heterocyclic radical can further have substituent.

R⁴During for Heterocyclylcarbonyl, the heterocyclic radical and R included in Heterocyclylcarbonyl⁴It is same during for heterocyclic radical.

R⁴It is excellent as the substituent for being bonded to nitrogen-atoms during for N- substituted-aminos alkyl or N, N- disubstituted amido alkyl Elect organic group as.

On the preference of organic group, can enumerate the alkyl of carbon number 1~20, the cycloalkyl of carbon number 3~10, The representative examples of saturated aliphatic acyl group of carbon number 2~21, the representative examples of saturated aliphatic acyloxy of carbon number 2~21, can have substitution The phenyl of base, can have substituent benzoyl, can have substituent carbon number 7~20 phenylalkyl, can With the naphthyl with substituent, there can be the naphthoyl of substituent, there can be the carbon number 11~20 of substituent Naphthylalkyl and heterocyclic radical etc..

The carbon number of the alkylidene included in N- substituted-aminos alkyl or N, N- disubstituted amido alkyl is preferably 1~ 20, more preferably 1~6.In addition, the alkylidene can be straight-chain, or branched.

As the concrete example of N- substituted-amino alkyl, 2- (methylamino) ethyl, 2- (ethylamino) ethyl, 2- can be enumerated (n-propyl amino) ethyl, 2- (n-butylamino) ethyl, 3- (methylamino) n-propyl, 3- (ethylamino) n-propyl, 3- (n-propyl amino) n-propyl, 3- (n-butylamino) n-propyl, 2- (methylamino) n-propyl, 2- (ethylamino) positive third Base, 2- (n-propyl amino) n-propyl, 2- (n-butylamino) n-propyl, 2- (acetyl-amino) ethyl, 2- (propiono ammonia Base) ethyl, 2- (acetoxyl group amino) ethyl, 2- (propiono epoxide amino) ethyl, 3- (acetyl-amino) n-propyl, 3- (propanoylamino) n-propyl, 3- (acetoxyl group amino) n-propyl, 3- (propiono epoxide amino) n-propyl, 2- (acetyl group Amino) n-propyl, 2- (propanoylamino) n-propyl, 2- (acetoxyl group amino) n-propyls and 2- (propiono epoxide amino) N-propyl.

As N, the concrete example of N- disubstituted amido alkyl can enumerate 2- (N, N- dimethylamino) ethyl, 2- (N, N- bis- Ethylamino) ethyl, 2- (N, N- diη-propyl amino) ethyl, 2- (N, N- di-n-butyl amino) ethyl, 3- (N, N- dimethyl Amino) n-propyl, 3- (N, N- diethylamino) n-propyl, 3- (N, N- diη-propyl amino) n-propyl, 3- (the positive fourths of N, N- bis- Base amino) n-propyl, 2- (N, N- dimethylamino) n-propyl, 2- (N, N- diethylamino) n-propyl, 2- (N, N- bis- positive third Base amino) n-propyl, 2- (N, N- di-n-butyl amino) n-propyl, 2- (N, N- diacetyl amino) ethyl, 2- (N, N- dipropyls Acyl amino) ethyl, 2- (N, N- diacetoxy amino) ethyl, 2- (N, N- dipropyl acyloxy amino) ethyl, 3- (N, N- Diacetyl amino) n-propyl, 3- (propanoylamino of N, N- bis-) n-propyl, 3- (N, N- diacetoxy amino) n-propyl, 3- (N, N- dipropyl acyloxy amino) n-propyl, 2- (N, N- diacetyl amino) n-propyl, 2- (the propiono ammonia of N, N- bis- Base) n-propyl, 2- (N, N- diacetoxy amino) n-propyl, 2- (N, N- dipropyl acyloxy amino) n-propyl, 2- (N- second Acyl group-N- acetoxyl groups amino) ethyl, 2- (N- propiono-N- propiono epoxides amino) ethyl, 3- (N- acetyl group-N- acetyl Epoxide amino) n-propyl, 3- (N- propiono-N- propiono epoxides amino) n-propyl, 2- (N- acetyl group-N- acetoxyl group ammonia Base) n-propyl and 2- (N- propiono-N- propiono epoxides amino) n-propyl.

It is used as R⁴In the substituent of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, carbon can be enumerated former Alkyl, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl group of carbon number 2~7, the carbon number 2~7 of subnumber 1~6 Alkoxy carbonyl, the representative examples of saturated aliphatic acyloxy of carbon number 2~7, the monoalkyl of alkyl with carbon number 1~6 Dialkyl amido, morpholine -1- bases, piperazine -1- bases, halogen, nitro and the cyano group of amino, alkyl with carbon number 1~6 Deng.R⁴In the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, the number of its substituent is in the without prejudice to present invention Purpose in the range of do not limit, preferably 1~4.R⁴In the phenyl, naphthyl and the heterocyclic radical that include there are multiple substituents When, multiple substituents can be the same or different.

In organic group, R is used as⁴, preferably alkyl, cycloalkyl, can have substituent phenyl or cycloalkyl alkane Base, on aromatic rings can have substituent phenylsulfartyl alkyl.As the alkyl of alkyl, preferably carbon number 1~20, The more preferably alkyl of the alkyl of carbon number 1~8, particularly preferably carbon number 1~4, most preferably methyl.Can have In the phenyl of substituent, preferably aminomethyl phenyl, more preferably 2- aminomethyl phenyls.The carbon of the cycloalkyl included in cycloalkyl-alkyl Atomicity is preferably 5~10, and more preferably 5~8, particularly preferably 5 or 6.The carbon of the alkylidene included in cycloalkyl-alkyl is former Subnumber is preferably 1~8, more preferably 1~4, particularly preferably 2.In cycloalkyl-alkyl, preferably cyclopentyl ethyl.In fragrance The carbon number of the alkylidene included in the phenylsulfartyl alkyl can on ring with substituent is preferably 1~8, and more preferably 1 ~4, particularly preferably 2.Can have on aromatic rings in the phenylsulfartyl alkyl of substituent, preferably 2- (4- chlorphenyl sulphur Base) ethyl.

In addition, being used as R⁴, further preferably-A³-CO-O-A⁴The group of expression.A³For divalent organic group, preferably divalent hydrocarbon Base, more preferably alkylidene.A⁴For monovalent organic group, preferably monovalent hydrocarbon.

A³During for alkylidene, alkylidene can be straight-chain, or branched, preferably straight-chain.A³For alkylidene When, the carbon number of alkylidene is preferably 1~10, more preferably 1~6, particularly preferably 1~4.

It is used as A⁴Preference, the alkyl, the aralkyl of carbon number 7~20 and carbon that can enumerate carbon number 1~10 be former The aromatic hydrocarbyl of subnumber 6~20.It is used as A⁴Preferred concrete example, methyl, ethyl, n-propyl, isopropyl, positive fourth can be enumerated Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, Alpha-Naphthyl methyl and β-naphthalene Ylmethyl etc..

It is used as-A³-CO-O-A⁴The preferred concrete example of the group of expression, can enumerate 2- dion es, 2- ethoxies Base carbonylethyl, 2- n-propyl Epoxide carbonyls ethyl, 2- normal-butyl Epoxide carbonyls ethyl, 2- n-pentyl Epoxide carbonyls ethyl, 2- N-hexyl Epoxide carbonyl ethyl, 2- benzyloxycarbonyls ethyl, 2- phenyloxycarbonyls ethyl, 3- methoxycarbonyls n-propyl, 3- Ethoxy carbonyl n-propyl, 3- n-propyl Epoxide carbonyls n-propyl, 3- normal-butyl Epoxide carbonyls n-propyl, 3- n-pentyl epoxide carbonyls Base n-propyl, 3- n-hexyl Epoxide carbonyls n-propyl, 3- benzyloxycarbonyls n-propyl and 3- phenyloxycarbonyl n-propyls etc..

More than, to R⁴It is illustrated, is used as R⁴, the group that preferably following formula (R4-1) or (R4-2) are represented.

[chemical formula 7]

(in formula (R4-1) and (R4-2), R⁷And R⁸Respectively organic group, p is 0~4 integer, R⁷And R⁸It is present in benzene During adjacent position on ring, R⁷With R⁸It can be mutually bonded and form ring, q is 1~8 integer, r is 1~5 integer, and s is 0 ~(r+3) integer, R⁹For organic group.)

R in formula (R4-1)⁷And R⁸Organic group example and R¹Equally.It is used as R⁷, preferably alkyl or phenyl.R⁷For During alkyl, its carbon number is preferably 1~10, more preferably 1~5, particularly preferably 1~3, most preferably 1.That is, R⁷It is optimal Elect methyl as.R⁷With R⁸When being bonded and forming ring, the ring can be aromatic ring, or aliphatic ring.It is used as R⁷With R⁸Shape The preference of the group represented into the formula (R4-1) of ring, can enumerate naphthalene -1- bases, 1,2,3,4- naphthane -5- bases etc..Above-mentioned formula (R4-1) in, p is 0~4 integer, preferably 0 or 1, more preferably 0.

In above-mentioned formula (R4-2), R⁹For organic group.As organic group, it can enumerate with being directed to R¹And the organic group illustrated The same group of group.In organic group, preferably alkyl.Alkyl can be straight-chain, or branched.The carbon of alkyl is former Subnumber is preferably 1~10, more preferably 1~5, particularly preferably 1~3.It is used as R⁹, preferably enumerate methyl, ethyl, propyl group, Isopropyl, butyl etc., in these, more preferably methyl.

In above-mentioned formula (R4-2), r is 1~5 integer, preferably 1~3 integer, more preferably 1 or 2.Above-mentioned formula (R4- 2) in, s is 0~(r+3), preferably 0~3 integer, more preferably 0~2 integer, particularly preferably 0.Above-mentioned formula (R4-2) In, q is 1~8 integer, preferably 1~5 integer, more preferably 1~3 integer, particularly preferably 1 or 2.

(on R⁵)

In formula (1), R⁵For monovalent organic group or hydrogen atom.It is, for example, can have substitution as monovalent organic group The alkyl of the carbon number 1~11 of base or the aryl can with substituent.It is used as R⁵The substitution that can have during for alkyl Base, preferably enumerates phenyl, naphthyl etc..In addition, being used as R¹The substituent that can have during for aryl, preferably enumerates carbon atom Alkyl, alkoxy, halogen atom of number 1~5 etc..

In formula (1), R is used as⁵, preferably enumerate hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, phenyl, Benzyl, aminomethyl phenyl, naphthyl etc., in these, more preferably methyl or phenyl.

T is formula (T in formula (1)_C) represent group when, the compound for being used as formula (1) to represent, preferably following formula (1C) table The compound shown.

[chemical formula 8]

(in formula (1C), R¹、R²、R³、R⁴、R⁵、R⁶And n is as described above.)

In addition, in the compound that formula (1C) is represented, the compound that preferably following formula (1C-1) or (1C-2) are represented.

[chemical formula 9]

T is formula (T in formula (1)_N) represent group when, the compound for being used as formula (1) to represent, preferably following formula (1N) table The compound shown.

[chemical formula 10]

(in formula (1N), R¹、R²、R⁴、R⁵、R⁶And n is as described above.)

In addition, in the compound that formula (1N) is represented, the compound that preferably following formula (1N-1) or (1N-2) are represented.

[chemical formula 11]

The preferred concrete example of the compound represented as formula (1), can enumerate following 1~compound of compound 139.

[chemical formula 12]

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

[chemical formula 16]

[chemical formula 17]

[chemical formula 18]

[chemical formula 19]

[chemical formula 20]

The compound that the formula (1) being described above is represented is high sensitive, can provide susceptibility excellent photosensitive composition Thing.

The manufacture method ＞ for the compound that ＜ formulas (1) are represented

The manufacture method for the compound that above-mentioned formula (1) is represented is not particularly limited.For formula (1) represent compound and Speech, when n is 0, for example, being manufactured using following methods, methods described includes following process：

Importing-R in process (I), the ring skeleton represented by cross-coupling reaction to following formula (1a)⁶-R¹The base of expression Group,

[chemical formula 21]

(in formula (1a), T is as described above.)；With

In process (II), the ring skeleton represented to formula (1a), importing-CO-R⁴The acyl group of expression, then, by-CO-R⁴Represent Group be converted into-C (=N-OH)-R⁴The group of expression, and then, by-C (=N-OH)-R⁴The group esterification of expression, be converted into- C (=N-O-CO-R⁵)-R⁴The group of expression.

In addition, for the compound that formula (1) is represented, when n is 1, for example, being manufactured using following methods, the side Method includes following process：

[chemical formula 22]

(in formula (1a), T is as described above.)；With

In process (II), the ring skeleton represented to formula (1a), importing-CO-CH₂-R⁴The acyl group of expression, then, by-CO- CH₂-R⁴The group of expression is converted into-CO-C (=N-OH)-R⁴The group of expression, and then, by-CO-C (=N-OH)-R⁴Represent Group is esterified, and is converted into-CO-C (=N-O-CO-R⁵)-R⁴The group of expression.

In above-mentioned method, which process in process (I) and process (II) is first carried out can.In addition, process (II) Operation including multistep, process (I) can also be implemented on any opportunity of process (II).

In above-mentioned method, oximido (=N-OH) is converted into=N-O-COR in process (II)⁵The side of the oxime ester base of expression Method is not particularly limited.Typically, the hydroxyl and offer-COR made in oximido can be provided⁵The acylating agent of the acyl group of expression carries out anti- The method answered.As acylating agent, (R can be enumerated⁵CO)₂Acid anhydrides that O is represented, R⁵The carboxylic acid halides that COHal (Hal is halogen atom) is represented.

When n is 0, as one, the compound that formula (1) is represented can be synthesized according to following synthesis paths 1.

It should be noted that in following synthesis paths 1, having used the halogenation chemical combination of the ring skeleton represented with formula (1a) Thing and include-R⁶-R¹The boron compound of the group of expression carries out cross-coupling reaction, but can also be used and represent with formula (1a) Ring skeleton boron compound and include-R⁶-R¹The halogenated compound of the group of expression carries out cross-coupling reaction.

In addition, cross-coupling reaction can be in following opportunitys any opportunity implement：

Importing-CO-R in the ring skeleton represented to formula (1a)⁴After the acyl group of expression,

By-CO-R⁴The group of expression is converted into-C (=N-OH)-R⁴After the group of expression, and

By-C (=N-OH)-R⁴The group esterification of expression is so as to be converted into-C (=N-O-CO-R⁵)-R⁴The group of expression Afterwards.

First, using Friedel-Craft (Friedel-Crafts) acylation reaction, imported into compound 1A- CO-R⁴The acyl group of expression, obtains compound 1B.For importing-CO-R⁴The acylating agent of the acyl group of expression can be Hal-CO-R⁴Table The halo carbonyl compounds or (R shown⁴CO)₂The acid anhydrides that O is represented.It is used as acylating agent, preferably Hal-CO-R⁴Represent Halo carbonyl compounds.Hal is halogen atom.Importing the position of acyl group can be reacted by suitably changing Friedel-Craft Condition or implement to protect using the position beyond the position to acylation and the method for deprotection is selected.

T in compound 1A is formula (T_C) represent group when, for example, make the halo fluorenes such as bromine fluorenes (be preferably 2- bromines fluorenes) with The alkali such as potassium tert-butoxide and R²- Hal and R³- Hal is reacted, and can obtain compound 1A.R²- Hal and R³In-Hal, Hal is Halogen atom, preferably bromine atoms.

It should be noted that T is formula (T_C) represent group when, synthesize compound 1A when, sometimes as accessory substance Generate and be bonded with 2 R on 9 in fluorenes ring²Or 2 R³Compound.In this case, according to known to column chromatography etc. Method, only separation obtain target product.

Next, using so-called Suzuki palace Pu coupling reaction, making compound 1B and R¹-R⁶-B(OH)₂Deng comprising R¹- R⁶The boron compound condensation of-group represented, obtains compound 1C.

It should be noted that as cross-coupling reaction, being not limited to Suzuki palace Pu coupling reaction, it can intersect from known Suitably select and use in coupling reaction.

For the species of boron compound, as long as R can be imported into compound 1B¹-R⁶The boronation of-the group represented Compound, is just not particularly limited.

The catalyst that as long as workable catalyst is used in the reaction in the past in the coupling reaction of Suzuki palace Pu, just It is not particularly limited.[1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride for example, as preferred catalyst, can enumerate (II) chloride dichloromethane adduct (Pd (dppf) Cl₂·CH₂Cl₂), tetrakis triphenylphosphine palladium (0) (Pd (PPh₃)₄), [1,2- is double (diphenylphosphinoethane)] palladium chloride (II) (PdCl₂(dppe)), [1,3- is double (diphenylphosphino propane)] palladium chloride (II)(PdCl₂(dppp)), [1,1 '-bis- (diphenylphosphino) ferrocene] Nickel Chloride (II) chloride dichloromethane adduct (Ni (dppf)Cl₂·CH₂Cl₂), double (triphenylphosphine) Nickel Chloride (II) (NiCl₂(PPh₃)₂) etc..In addition, can also be incited somebody to action in system Acid chloride and/or palladium bichloride and appropriate part are mixed and used.

For the solvent used in the reaction, as long as the progress of without prejudice to reaction, is not particularly limited, example Such as, tetrahydrofuran (THF), methanol, ethanol, propyl alcohol, n-butanol, 2- butanol, toluene, ethyl acetate, N- methylpyrroles can be used Alkanone, cyclopentyl-methyl ether, dimethylformamide, dimethyl acetamide and water etc..From easily making Suzuki palace Pu coupling reaction From the aspect of carrying out well, further preferably using N, N, N ', N '-tetramethylurea, N, N, N ' and, the N, N, N such as N '-tetraethyl urea ', N '-tetraalkyl ureas is used as solvent.

Next, by the-CO-R in compound 1C⁴The group of expression is converted into-C (=N-OH)-R⁴The group of expression, is obtained To compound 1D.By-CO-R⁴The group of expression is converted into-C (=N-OH)-R⁴The method of the group of expression is not particularly limited, The oximate carried out preferably by hydroxylamine.By making compound 1D and acid anhydrides ((R⁵CO)₂) or carboxylic acid halides (R O⁵COHal, Hal are halogen Plain atom.) reacted, it can obtain the compound that the formula (1) that n is 0 is represented.

The ＞ of ＜ synthesis paths 1

[chemical formula 23]

In addition, when n is 1, as one, the compound that formula (1) is represented can according to following synthesis paths it is 2-in-1 into.

It should be noted that in following synthesis paths 2, having used the halogenation chemical combination of the ring skeleton represented with formula (1a) Thing and include-R⁶-R¹The boron compound of the group of expression carries out cross-coupling reaction, but can also be used and represent with formula (1a) Ring skeleton boron compound and include-R⁶-R¹The halogenated compound of the group of expression carries out cross-coupling reaction.

Importing-CO-CH in the ring skeleton represented to formula (1a)₂-R⁴After the acyl group of expression,

By-CO-CH₂-R⁴The group of expression is converted into-CO-C (=N-OH)-R⁴After the group of expression, and

By-CO-C (=N-OH)-R⁴The group esterification of expression is so as to be converted into-CO-C (=N-O-CO-R⁵)-R⁴Represent Group after.

In synthesis path 2, raw material is used as using above-mentioned compound 1A.In the same manner as synthesis path 1, using Fred- The reaction of gram Lay Ford, the importing-CO-CH into compound 1A₂-R⁴The acyl group of expression, can obtain compound 1E.It is excellent as acylating agent Elect Hal-CO-CH as₂-R⁴The acid halide of expression.

Next, using so-called Suzuki palace Pu coupling reaction, making compound 1E and R¹-R⁶-B(OH)₂The boron of expression Compound condensation, obtains compound 1F.Method of condensing and synthesis path 1 based on Suzuki palace Pu coupling reaction are same.

R will be present in obtained compound 1F⁴Methylene oximate between carbonyl, obtains compound 1G.By Asia The method of methyl oximate is not particularly limited, and nitrous acid ester is preferably made in the presence of hydrochloric acid, and (RONO, R are carbon number 1~6 Alkyl.) reaction method.Next, making compound 1G and acid anhydrides ((R⁵CO)₂) or carboxylic acid halides (R O⁵COHal, Hal are halogen Atom.) reacted, it can obtain the compound that the formula (1) that n is 1 is represented.

The ＞ of ＜ synthesis paths 2

[chemical formula 24]

It should be noted that in synthesis path 1, being included in compound 1B, compound 1C, compound 1D and final product R⁴It can be the same or different.That is, the R included in compound 1B, compound 1C, compound 1D and final product⁴Can be By chemical modification in the building-up process shown as synthesis path 1.As the example of chemical modification, esterification, ether can be enumerated Change, acylation, amidatioon, halogenation, substitution based on organic group of hydrogen atom in amino etc..R⁴Acceptable chemical modification It is not limited to these.

The R included in compound 1E, compound 1F, compound 1G and final product in synthesis path 2⁴Similarly It can be the same or different.The R included in compound 1E, compound 1F, compound 1G and final product⁴Conjunction can be used as By chemical modification in the building-up process shown into path 2, in the same manner as synthesis path 1.

For the compound represented using the formula (1) of the method being described above synthesis, according to utilizing solvent The conventional methods such as the washing of progress, recrystallization, post purifying and after appropriately generating, the sense such as Photoepolymerizationinitiater initiater can be suitably used for Photo etching purposes.

It should be noted that the purposes for the compound that formula (1) is represented is not limited to Photoepolymerizationinitiater initiater.The change that formula (1) is represented Compound can be used for the various emulsion purposes for having used oxime ester compound in the past.

《Include the photosensitive composite of (A) photopolymerizable compound》

As photosensitive composite, the compound represented preferably containing (A) photopolymerizable compound and comprising formula (1) (B) Photoepolymerizationinitiater initiater composition.

Hereinafter, the required composition or optional member included to the photosensitive composite is illustrated.

＜ (A) photopolymerizable compounds ＞

As (A) photopolymerizable compound contained in photosensitive composite, it is not particularly limited, can be used existing known Photopolymerizable compound.Wherein, it is however preferred to have the resin or monomer of ethylenic unsaturated group, more preferably by their groups Close.By the way that by the resin with ethylenic unsaturated group and the combination of monomers with ethylenic unsaturated group, sense can be improved The curability of photosensitiveness composition so that easily carry out pattern and formed.

[resin with ethylenic unsaturated group]

As the resin with ethylenic unsaturated group, (methyl) acrylic acid, fumaric acid, maleic acid, rich horse can be enumerated Sour mono-methyl, monomethyl ester, (methyl) acrylic acid 2- hydroxy methacrylates, ethylene glycol single methyl ether (methyl) acrylate, second Glycol list ethylether (methyl) acrylate, glycerine (methyl) acrylate, (methyl) acrylamide, acrylonitrile, metering system Nitrile, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid 2- ethyl hexyls Ester, (methyl) benzyl acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol Two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, (first of propane diols two Base) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol propane four (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, 1,6-HD two (methyl) acrylate, Cardo- epoxy diacrylates (cardo Epoxy diacrylate) etc. the oligomeric species that are polymerized；Making (methyl) acrylic acid, (it is will be more with polyester prepolyer Obtained from first alcohols and monoacid or polyacid condensation) reacted obtained from polyester (methyl) acrylate；Make it is many First alcohol with after the compound reaction with 2 NCOs, make (methyl) propylene acid reaction obtained from polyurethane (methyl) Acrylate；Make bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresols novolac Type epoxy resin, resol types epoxy resin, tris-phenol type epoxy resin, many ethylene oxidic esters of polycarboxylic acid, contracting polyalcohol more The epoxy resin such as water glyceride, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxy benzene-type epoxy resin and (first Base) epoxy (methyl) acrylate etc. obtained from propylene acid reaction.In addition, preferably making multi-anhydride and epoxy Resin obtained from the reaction of (methyl) acrylate.It should be noted that in this specification, " (methyl) propylene-" refers to " propylene-or metering system-".

In addition, as the resin with ethylenic unsaturated group, can suitably use：By making epoxide with containing Resin obtained from the reactant for having the carboxylic acid compound of unsaturated group is further reacted with multi-anhydride.

Wherein, the compound that preferably following formula (a1) is represented.The photo-curable of the compound that the formula (a1) is represented in itself Height, is preferred from this viewpoint.

[chemical formula 25]

In above-mentioned formula (a1), X represents the group that following formula (a2) is represented.

[chemical formula 26]

In above-mentioned formula (a2), R^1aHydrogen atom, the alkyl or halogen atom of carbon number 1~6, R are represented independently of one another^2a Hydrogen atom or methyl are represented independently of one another, and W represents the group that singly-bound or following structural formula (a3) are represented.It should be noted that In formula (a2) and structural formula (a3), " * " represents the end of the chemical bond of divalent group.

[chemical formula 27]

In above-mentioned formula (a1), Y represents to remove residue obtained from anhydride group (- CO-O-CO-) from dicarboxylic anhydride.As The example of dicarboxylic anhydride, can enumerate maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic acid Acid anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, chlorendic anhydride (Chlorendic Anhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride etc..

In addition, in above-mentioned formula (a1), Z represents to remove residue obtained from 2 anhydride groups from tetracarboxylic dianhydride.It is used as four The example of carboxylic acid dianhydride, can enumerate pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, diphenyl ether Tetracarboxylic acid dianhydride etc..In addition, in above-mentioned formula (a1), a represents 0~20 integer.

For the acid number of the resin with ethylenic unsaturated group, in terms of resin solid state component, preferably 10~ 150mgKOH/g, more preferably 70~110mgKOH/g.By making acid number be more than 10mgKOH/g, it can obtain relative to development The sufficient dissolubility of liquid, thus preferably.In addition, by making acid number be below 150mgKOH/g, sufficient curability is can obtain, It may be such that superficiality is good, thus preferably.

In addition, the weight average molecular weight of the resin with ethylenic unsaturated group is preferably 1000~40000, more preferably 2000~30000.By making weight average molecular weight be more than 1000, good heat resistance, film-strength are can obtain, thus preferably.Separately Outside, by making weight average molecular weight be less than 40000, good developability is can obtain, thus preferably.

[monomer with ethylenic unsaturated group]

Monomer with ethylenic unsaturated group includes monofunctional monomer and polyfunctional monomer.Hereinafter, to simple function list Body and polyfunctional monomer are illustrated successively.

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, neighbour Phthalic acid 2- (methyl) acryloyl group epoxide -2- hydroxy propyl esters, glycerine list (methyl) acrylate, (methyl) acrylic acid tetrahydrochysene Furfuryl group ester, (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2- tri- Fluorine ethyl ester, (methyl) acrylic acid 2,2,3,3- tetrafluoros propyl ester, (methyl) acrylate half ester of phthalic acid derivatives etc..It is above-mentioned Monofunctional monomer can be used alone, and two or more also can be combined and uses.

As polyfunctional monomer, can enumerate ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, Tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, fourth two Alcohol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, three hydroxyl first Base propane three (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythritol triacrylate, pentaerythrite tetrapropylene Acid esters, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, pentaerythrite two (methyl) acrylate, season penta Tetrol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons Double (4- (methyl) the acryloxy diethoxy phenyl) propane of penta tetrol six (methyl) acrylate, 2,2-, the double (4- of 2,2- (methyl) acryloyl-oxy Quito ethoxyl phenenyl) propane, (methyl) acrylic acid 2- hydroxyls -3- (methyl) acryloyl group epoxide propyl group Ester, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylic acid Ester, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerol tri-acrylate, glycerine poly epihydric alcohol base ether gather (methyl) acrylate, carbamate (methyl) acrylate (that is, oneself two isocyanides of toluene di-isocyanate(TDI), trimethyl -1,6- The reactant of acid esters or hexamethylene diisocyanate etc. and (methyl) acrylic acid 2- hydroxy methacrylates), di-2-ethylhexylphosphine oxide (methyl) propylene The multifunctional lists such as acid amides, (methyl) acrylamide methylene ether, the condensation product of polyalcohol and N- methylols (methyl) acrylamide Body, 1,3,5- triacryl hexahydro -1,3,5- triazines (triacrylformal) etc..Above-mentioned polyfunctional monomer can individually make With, also can be combined two or more and use.

For the content of (A) photopolymerizable compound, the solid state component relative to photosensitive composite adds up to 100 matter Measure part, preferably 10~99.9 mass parts.By making the content of (A) photopolymerizable compound relative to solid state component total 100 To be more than 10 mass parts for mass parts, thus, using photosensitive composite, easily formed heat resistance, chemical proofing and The film of mechanical strength.

＜ (B) Photoepolymerizationinitiater initiaters ＞

It is preferred that photosensitive composite contain comprising formula (1) represent compound (B) Photoepolymerizationinitiater initiater.On formula (1) compound represented, as described above.Photosensitive composite is because the compound represented comprising formula (1) is as (B) photopolymerization Initiator, thus susceptibility is excellent.

(B) Photoepolymerizationinitiater initiater can also include other Photoepolymerizationinitiater initiaters while the compound represented comprising formula (1). Other Photoepolymerizationinitiater initiaters can suitably be selected from the various Photoepolymerizationinitiater initiaters coordinated in various photosensitive composites in the past.

As other Photoepolymerizationinitiater initiaters, specifically, can enumerate 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyls- 1- phenyl-propane -1- ketone, 1- (4- (2- hydroxyl-oxethyls) phenyl) -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- isopropyls Base phenyl) it is -2- hydroxy-2-methyl propane -1- ketone, 1- (4- dodecylphenyls) -2- hydroxy-2-methyl propane -1- ketone, double (4- dimethylaminophenyls) ketone, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 4- -4 '-methyl dimethoxies of benzoyl Base thioether, 4- dimethylaminobenzoic acids, 4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- bis- Methylaminobenzoate butyl ester, 4- dimethylaminobenzoic acid -2- ethylhexyls, 4- dimethylaminobenzoic acid -2- isopentyl ester, Benzil-'beta '-methoxy ethyl acetals (benzyl- β-methoxyethyl acetal), benzil dimethyl ketal, 1- benzene Base -1,2- propanedione -2- (o- ethoxy carbonyls) oxime, o-benzoyl yl benzoic acid methyl esters, 2,4- diethyl thioxanthones, 2- diurils Ton ketone, 2,4- dimethyl thioxanthones, the chloro- 4- propoxythioxanthones of 1-, thioxanthene, 2- diurils ton, 2,4- diethyl thioxanthene, 2- methyl Thioxanthene, 2- isopropylthioxanthones, 2- EAQs, prestox anthraquinone, 1,2 benzae thracene quinone, 2,3- diphenyl anthraquinone, azo are double different Butyronitrile, benzoyl peroxide, cumyl hydroperoxide, 2-mercaptobenzimidazole, 2- mercaptobenzoxazoles, 2- sulfydryl benzo thiophenes Azoles, 2- (Chloro-O-Phenyl) -4,5- diphenyl-imidazoles dimer, (methoxyphenyl) the imidazoles dimerization of 2- (Chloro-O-Phenyl) -4,5- two Thing, 2- (o-fluorophenyl) -4,5- diphenyl-imidazoles dimer, 2- (o-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2- (p-methoxyphenyl) -4,5- diphenyl-imidazoles dimer, 2,4,5- triarylimidazoles dimer, benzophenone, 2- chlorodiphenyls Ketone, 4,4 '-bis- dimethylamino benzophenones (that is, Michler's keton (Michler ' s ketone)), 4,4 '-bis- diethylaminos Benzophenone (that is, ethyl Michler's keton), 4,4 '-dichloro benzophenone, 3,3- dimethyl -4- methoxy benzophenones, benzil, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl base Ether, benzoin butyl 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, right Tert-butyl group dichloroacetophenone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2- methyl thioxanthones, ITX, Dibenzosuberone (dibenzosuberone), 4- dimethylaminobenzoic acids pentyl ester, 9- phenylacridines, 1,7- pairs-(9- a word used for translations Piperidinyl) heptane, 1,5- be double-and (9- acridinyls) pentane, 1,3- be double-(9- acridinyls) propane, to methoxyl group triazine, 2,4,6- tri- Double (trichloromethyl) s-triazine of (trichloromethyl) s-triazine, 2- methyl -4,6-, 2- [2- (5- methylfuran -2- bases) vinyl] - Double (trichloromethyl) s-triazine of 4,6-, 2- [2- (furans -2- bases) vinyl] -4,6- double (trichloromethyl) s-triazine, 2- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] -4,6- double (trichloromethyl) s-triazine, 2- [2- (3,4- dimethoxy benzenes Base) vinyl] -4,6- couples of (trichloromethyl) s-triazine, 2- (4- methoxyphenyls) -4,6- double (trichloromethyl) s-triazine, 2- Double (trichloromethyl) s-triazine of (4- ethoxystyrenes base) -4,6-, 2- (4- n-butoxyphenyls) -4,6- are double (trichloromethyl) S-triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) phenyl s-triazine, 2,4- pairs-trichloromethyl -6- (the bromo- 4- of 2- Methoxyl group) phenyl s-triazine, 2,4- be double-and trichloromethyl -6- (the bromo- 4- methoxyl groups of 3-) styryl phenyl s-triazine, 2,4- be double - Trichloromethyl -6- (the bromo- 4- methoxyl groups of 2-) styryl phenyl s-triazine, " IRGACURE OXE02 ", " IRGACURE OXE01 ", " IRGACURE 369 ", " IRGACURE 651 ", the " (trade names of IRGACURE 907 "：BASF systems), " NCI-831 " (trade name：ADEKA systems) etc..These other Photoepolymerizationinitiater initiaters may be used alone or in combination two or more and use.

When the compound that formula (1) is represented is the compound with the nitro being bonded on aromatic rings, from photosensitive composite Susceptibility from the aspect of, using comprising represented by formula (1) and be bonded to nitro on aromatic rings compound, with (B) Photoepolymerizationinitiater initiater of the combination for the oxime ester compound that the formula (B1) of lower explanation is represented is also preferred.

Especially, when photosensitive composite is the transparent composition without (C) colouring agent described later, by making photonasty Composition includes above-mentioned (B) Photoepolymerizationinitiater initiater, so as to easily form the excellent solidfied material of the transparency.

It should be noted that relative to by formula (1) represent and with the compound of nitro being bonded on aromatic rings and under For the oxime ester compound that formula (B1) is represented, the Photoepolymerizationinitiater initiater being applied in combination beyond these compounds is also possible.

As the compound for representing and having the nitro being bonded on aromatic rings by formula (1), for example, it is preferable to be above-mentioned change Compound 1~17 and compound 69~85, more preferably compound 1~17.

The ratio of quality of the quality relative to (B) Photoepolymerizationinitiater initiater for the compound that formula (1) is represented is preferably 1~100 Quality %, more preferably 50~100 mass %, particularly preferably 70~100 mass %.With opacifier as described later (C) in the case that the situation of colouring agent or the photosensitive composite as LED exposure are used, the compound that formula (1) is represented The ratio of quality is more preferably 50~100 mass %, particularly preferably 70~100 mass %.

(B) Photoepolymerizationinitiater initiater include represented by formula (1) and be bonded to nitro on aromatic rings compound, with by When formula (1) represents and do not had the combination of the compound of nitro, represented by formula (1) and with the nitro being bonded on aromatic rings The quality of compound is suitably changed relative to the ratio of the quality of (B) Photoepolymerizationinitiater initiater according to the purposes of solidfied material, Preferably 0.5~99 mass %, more preferably 1~80 mass %, more preferably 2~50 mass %.

(B) Photoepolymerizationinitiater initiater, which is included, is represented by formula (1) and with the compound and formula of the nitro being bonded on aromatic rings (B1) during the combination of the oxime ester compound represented, the compound for the nitro being bonded on aromatic rings is represented and had by formula (1) Quality is suitably changed relative to the ratio of the quality of (B) Photoepolymerizationinitiater initiater according to the purposes of solidfied material, and preferably 0.5 ~99 mass %, more preferably 1~80 mass %, more preferably 2~50 mass %.As require the transparency it is photosensitive Situation that property composition is used or in the case of using the colouring agent beyond opacifier as (C) colouring agent described later, above-mentioned ratio Rate is particularly preferably 0.5~20 mass %.In addition, the quality for the oxime ester compound that formula (B1) is represented is drawn relative to (B) photopolymerization The ratio for sending out the quality of agent is preferably 1~99.5 mass %, more preferably 50~99 mass %, particularly preferably 70~98 matter Measure %.

(oxime ester compound that formula (B1) is represented)

Hereinafter, the oxime ester compound that the formula (B1) that pair compound that can be represented with formula (1) is suitably used simultaneously is represented enters Row explanation.

[chemical formula 28]

(R^b1For hydrogen atom or monovalent organic group, R^b2And R^b3Can respectively have substituent chain-like alkyl, can be with Cyclic organic group or hydrogen atom with substituent, R^b2With R^b3It can be mutually bonded and form ring, R^b4For any monovalent organic radical Group, R^b5For hydrogen atom, the alkyl of the carbon number 1~11 can with substituent or the aryl can with substituent, n1 is 0~4 integer, n2 is 0 or 1.Wherein, the compound that formula (B1) is represented does not have nitro.)

Therefore, as the oxime compound of the oxime ester compound for manufacturing formula (B1), the chemical combination that preferably following formula (B2) is represented Thing.

[chemical formula 29]

(R^b1、R^b2、R^b3、R^b4, n1 and n2 and formula (B1) it is same.)

In formula (B1) and (B2), R^b1For hydrogen atom or monovalent organic group.R^b1It is bonded in fluorenes ring in formula (B1) With-(CO)_n2The different hexa-atomic aromatic rings of-hexa-atomic aromatic rings that is bonded of group that represents.In formula (B1), R^b1Relative to fluorenes ring Bonding position be not particularly limited.The compound that formula (B1) is represented has the R of more than 1^b1When, from the formula that is readily synthesized (B1) table Consider in terms of the compound shown, it is preferable that the R of more than 1^b1In 1 R^b1It is bonded to 2 in fluorenes ring.R^b1To be multiple When, multiple R^b1It can be the same or different.

R^b1During for organic group, R^b1It is not particularly limited, can has from various in the range of the without prejudice to purpose of the present invention Suitably selected in machine group.But, R^b1It is not the organic group with nitro.It is used as R^b1Preference during for organic group, can Enumerate alkyl, alkoxy, cycloalkyl, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, representative examples of saturated aliphatic acyloxy, Can have substituent phenyl, can have substituent phenoxy group, can have substituent benzoyl, can have The phenyloxycarbonyl of substituent, the benzoyl epoxide can with substituent, the phenylalkyl can with substituent, can be with Naphthyl with substituent, can have substituent naphthoxy, can have substituent naphthoyl, can have substitution The naphthoxycarbonyl of base, can have substituent naphthoyl epoxide, can have substituent naphthylalkyl, can have The heterocyclic radical of substituent, can have the Heterocyclylcarbonyl of substituent, the amino replaced by 1 or 2 organic groups, morpholine- 1- bases and piperazine -1- bases etc..

R^b1During for alkyl, the carbon number of alkyl is preferably 1~20, and more preferably 1~6.In addition, R^b1, can during for alkyl Think straight chain, or side chain.It is used as R^b1Concrete example during for alkyl, can enumerate methyl, ethyl, n-propyl, isopropyl, just It is butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, different Octyl group, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, R^b1During for alkyl, alkyl can be in carbon Ehter bond (- O-) is included in chain.As the example of the alkyl with ehter bond in carbochain, methoxy ethyl, ethyoxyl second can be enumerated Base, methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and methoxy-propyl etc..

R^b1During for alkoxy, the carbon number of alkoxy is preferably 1~20, and more preferably 1~6.In addition, R^b1For alcoxyl Can be straight chain, or side chain during base.It is used as R^b1Concrete example during for alkoxy, can enumerate methoxyl group, ethyoxyl, just It is propyl group epoxide, isopropyl epoxide, normal-butyl epoxide, isobutyl group epoxide, sec-butyl epoxide, tert-butyl group epoxide, n-pentyl epoxide, different It is amyl group epoxide, sec-amyl epoxide, tertiary pentyl epoxide, n-hexyl epoxide, n-heptyl epoxide, n-octyl epoxide, iso-octyl epoxide, secondary Octyl group epoxide, t-octyl epoxide, n-nonyl epoxide, isononyl epoxide, positive decyl epoxide and isodecyl epoxide etc..In addition, R^b1For During alkoxy, alkoxy can include ehter bond (- O-) in carbochain., can as the example of the alkoxy with ehter bond in carbochain Enumerate methoxy ethoxy, ethoxy ethoxy, methoxyethoxyethoxy, ethoxy ethoxy ethoxy, propyl group epoxide Ethoxy ethoxy and methoxy-propyl epoxide etc..

R^b1During for cycloalkyl or cycloalkyloxy, the carbon number of cycloalkyl or cycloalkyloxy is preferably 3~10, more preferably 3~6.It is used as R^b1Concrete example during for cycloalkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and ring pungent Base etc..It is used as R^b1Concrete example during for cycloalkyloxy, can enumerate cyclopropyl epoxide, cyclobutyl epoxide, cyclopentyloxy, cyclohexyl Epoxide, suberyl epoxide and cyclooctyl epoxide etc..

R^b1During for representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyloxy, representative examples of saturated aliphatic acyl group or representative examples of saturated aliphatic acyl The carbon number of base epoxide is preferably 2~21, and more preferably 2~7.It is used as R^b1Concrete example during for representative examples of saturated aliphatic acyl group, can Enumerate acetyl group, propiono, positive bytyry, 2- methylpropionyls, positive valeryl, 2,2- Dimethylpropanoyls, positive caproyl, just Heptanoyl group, positive caprylyl, positive pelargonyl group, positive capryl, n-undecane acyl group, n-dodecane acyl group, n-tridecane acyl group, positive ten Four alkanoyls, n-pentadecane acyl group and hexadecane acyl group etc..It is used as R^b1Concrete example during for representative examples of saturated aliphatic acyloxy, Acetyl group epoxide, propiono epoxide, positive bytyry epoxide, 2- methylpropionyls epoxide, positive valeryl epoxide, 2,2- bis- can be enumerated Methylpropionyl epoxide, positive caproyl epoxide, positive heptanoyl group epoxide, positive caprylyl epoxide, positive pelargonyl group epoxide, positive capryl oxygen Base, n-undecane acyloxy, n-dodecane acyloxy, n-tridecane acyloxy, n-tetradecane acyloxy, positive 15 Alkanoyl epoxide and hexadecane acyloxy etc..

R^b1During for alkoxy carbonyl, the carbon number of alkoxy carbonyl is preferably 2~20, and more preferably 2~7.It is used as R^b1 Concrete example during for alkoxy carbonyl, can enumerate methoxycarbonyl, ethoxy carbonyl, n-propyl Epoxide carbonyl, isopropyl epoxide Carbonyl, normal-butyl Epoxide carbonyl, isobutyl group Epoxide carbonyl, sec-butyl Epoxide carbonyl, t-butyloxycarbonyl, n-pentyl epoxide carbonyl Base, isopentyl Epoxide carbonyl, sec-amyl Epoxide carbonyl, t-amyloxycarbonyl group, n-hexyl Epoxide carbonyl, n-heptyl epoxide carbonyl Base, n-octyl Epoxide carbonyl, iso-octyl Epoxide carbonyl, secondary octyl Epoxide carbonyl, t-octyl Epoxide carbonyl, n-nonyl epoxide carbonyl Base, isononyl Epoxide carbonyl, positive decyl Epoxide carbonyl and isodecyl Epoxide carbonyl etc..

R^b1During for phenylalkyl, the carbon number of phenylalkyl is preferably 7~20, and more preferably 7~10.In addition, R^b1For During naphthylalkyl, the carbon number of naphthylalkyl is preferably 11~20, and more preferably 11~14.It is used as R^b1During for phenylalkyl Concrete example, can enumerate benzyl, 2- phenylethyls, 3- phenyl propyls and 4- phenyl butyls.It is used as R^b1It is specific during for naphthylalkyl Example, can enumerate Alpha-Naphthyl methyl, betanaphthyl methyl, 2- (Alpha-Naphthyl) ethyls and 2- (betanaphthyl) ethyl.R^b1For phenylalkyl or During naphthylalkyl, R^b1Can further have substituent on phenyl or naphthyl.

R^b1During for heterocyclic radical, heterocyclic radical is for five yuan comprising more than 1 N, S, O or hexa-atomic monocyclic, or is described Monocyclic fusion each other or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is condensed ring, number of rings is less than 3.Heterocycle Base can be aromatic group (heteroaryl), or non-aromatic group.As the heterocycle for constituting the heterocyclic radical, it can lift Go out furans, it is thiophene, pyrroles, oxazole, isoxazoles, thiazole, thiadiazoles, isothiazole, imidazoles, pyrazoles, triazole, pyridine, pyrazine, phonetic Pyridine, pyridazine, benzofuran, benzothiophene, indoles, iso-indoles, indolizine, benzimidazole, BTA, benzoxazole, benzo Thiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperidines, tetrahydrochysene pyrrole Mutter and tetrahydrofuran etc..R^b1During for heterocyclic radical, heterocyclic radical can further have substituent.

R^b1During for Heterocyclylcarbonyl, the heterocyclic radical and R included in Heterocyclylcarbonyl^b1It is same during for heterocyclic radical.

R^b1For replaced by 1 or 2 organic groups amino when, on the preference of organic group, carbon atom can be enumerated The alkyl of number 1~20, the cycloalkyl of carbon number 3~10, the representative examples of saturated aliphatic acyl group of carbon number 2~21, can have and take Dai Ji phenyl, can have substituent benzoyl, can have substituent carbon number 7~20 phenylalkyl, Can have substituent naphthyl, can have substituent naphthoyl, can have substituent carbon number 11~20 Naphthylalkyl and heterocyclic radical etc..The concrete example and R of these preferred organic groups^b1Equally.As by 1 or 2 organic groups The concrete example of the amino of group's substitution, can enumerate methylamino, ethylamino, diethylamino, n-propyl amino, diη-propyl ammonia Base, 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 bytyry ammonia Base, positive pentanoylamino, positive caproyl amino, positive heptanoyl group amino, positive octanoylamino, positive decanoylamino, benzoyl Amino, α-naphthoyl amino and β-naphthoyl amino etc..

It is used as R^b1In the substituent of the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, carbon can be enumerated former Alkyl, the alkoxy of carbon number 1~6, the representative examples of saturated aliphatic acyl group of carbon number 2~7, the carbon number 2~7 of subnumber 1~6 Alkoxy carbonyl, the representative examples of saturated aliphatic acyloxy of carbon number 2~7, the monoalkyl of alkyl with carbon number 1~6 Amino, dialkyl amido, morpholine -1- bases, piperazine -1- bases, halogen and the cyano group of alkyl with carbon number 1~6 etc..R^b1 In the phenyl, naphthyl and the heterocyclic radical that include when further there is substituent, the mesh of the number of its substituent in the without prejudice to present invention In the range of do not limit, preferably 1~4.R^b1In the phenyl, naphthyl and the heterocyclic radical that include when there is multiple substituents, it is many Individual substituent can be the same or different.

In the group being described above, R is used as^b1, it is R^b6During the group that-CO- is represented, there is the tendency of susceptibility raising, It is preferred.R^b6As long as the group without nitro, is not particularly limited in the range of the without prejudice to purpose of the present invention, It can be selected from various organic groups.On preferably as R^b6Group example, can enumerate carbon number 1~20 alkyl, Can have substituent phenyl, can have substituent naphthyl and can have substituent heterocyclic radical.These groups In, it is used as R^b6, particularly preferably 2- aminomethyl phenyls, thiophene -2- bases and Alpha-Naphthyl.

In addition, R^b1During for hydrogen atom, there is hyalinosis and obtain good tendency, be preferred.It should be noted that R^b1 For hydrogen atom and R^b4For formula described later (b1b) represent group when, there is hyalinosis and obtain better tendency.

In formula (B1), R^b2And R^b3The chain-like alkyl respectively can with substituent, the ring-type that can have substituent have Machine group or hydrogen atom.Wherein, R^b2And R^b3It is not the group with nitro.R^b2With R^b3It can be mutually bonded and form ring.This In a little groups, R is used as^b2And R^b3, it is preferably the chain-like alkyl can with substituent.R^b2And R^b3For that can have substituent During chain-like alkyl, chain-like alkyl can be straight chained alkyl, or branched alkyl.

R^b2And R^b3During for chain-like alkyl without substituent, the carbon number of chain-like alkyl is preferably 1~20, more excellent Elect 1~10, particularly preferably 1~6 as.It is used as R^b2And R^b3Concrete example during for chain-like alkyl, can enumerate methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, n-hexyl, positive heptan Base, n-octyl, iso-octyl, secondary octyl, t-octyl, n-nonyl, isononyl, positive decyl and isodecyl etc..In addition, R^b2And R^b3For During alkyl, alkyl can include ehter bond (- O-) in carbochain.As the example of the alkyl with ehter bond in carbochain, first can be enumerated Epoxide ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxyethoxyethyl, propyl group epoxide ethoxyethyl group and first Epoxide propyl group etc..

R^b2And R^b3During for chain-like alkyl with substituent, the carbon number of chain-like alkyl is preferably 1~20, more preferably For 1~10, particularly preferably 1~6.In this case, the carbon number of chain-like alkyl does not include the carbon number of substituent.Tool The chain-like alkyl of substituted base is preferably straight-chain.

The substituent that alkyl can have is not particularly limited in the range of the without prejudice to purpose of the present invention.It is used as substitution The preference of base, can enumerate cyano group, halogen atom, cyclic organic group and alkoxy carbonyl.As halogen atom, it can enumerate Fluorine atom, chlorine atom, bromine atoms, iodine atom.In these, preferably fluorine atom, chlorine atom, bromine atoms.It is used as ring-type organic group Group, can enumerate cycloalkyl, aromatic hydrocarbyl, heterocyclic radical.As the concrete example of cycloalkyl, with R^b1Preference during for cycloalkyl is same Sample.As the concrete example of aromatic hydrocarbyl, phenyl, naphthyl, xenyl, anthryl and phenanthryl etc. can be enumerated.It is used as the tool of heterocyclic radical Style, with R^b1Preference during for heterocyclic radical is same.R^b1During for alkoxy carbonyl, the alkoxy included in alkoxy carbonyl can Think straight-chain, or branched, preferably straight-chain.The carbon number of the alkoxy included in alkoxy carbonyl is preferred For 1~10, more preferably 1~6.

When chain-like alkyl has substituent, the number of substituent is not particularly limited.It is preferred that substituent number according to The carbon number of chain-like alkyl and change.The number of substituent is typically 1~20, preferably 1~10, more preferably 1~6.

R^b2And R^b3During for cyclic organic group, cyclic organic group can be ester ring type group, or aromatic series base Group.As cyclic organic group, aliphatic cyclic alkyl, aromatic hydrocarbyl, heterocyclic radical can be enumerated.R^b2And R^b3It is organic for ring-type During group, substituent and R that cyclic organic group can have^b2And R^b3It is same during for chain-like alkyl.

R^b2And R^b3During for aromatic hydrocarbyl, aromatic hydrocarbyl is preferably that phenyl or multiple phenyl ring are bonded via carbon-carbon bond Formed by group or multiple phenyl ring fusion formed by group.Aromatic hydrocarbyl is phenyl or the bonding of multiple phenyl ring or condensed Formed by group when, the number of rings of the phenyl ring included in aromatic hydrocarbyl is not particularly limited, preferably less than 3, more preferably 2 Hereinafter, particularly preferably 1.As the preferred concrete example of aromatic hydrocarbyl, can enumerate phenyl, naphthyl, xenyl, anthryl and Phenanthryl etc..

R^b2And R^b3During for aliphatic cyclic alkyl, aliphatic cyclic alkyl can be that monocyclic can also be polycycle.Fat The carbon number of fat race cyclic hydrocarbon group is not particularly limited, preferably 3~20, more preferably 3~10.It is used as the ring-type of monocyclic The example of alkyl, can enumerate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, norborny, isobornyl, Three cyclononyls, tricyclodecyl, tetracyclododecyl group and adamantyl etc..

R^b2And R^b3During for heterocyclic radical, heterocyclic radical is five yuan or hexa-atomic of monocyclic, the Huo Zhewei comprising more than 1 N, S, O The monocyclic fusion each other or the monocyclic heterocyclic radical condensed with phenyl ring.When heterocyclic radical is condensed ring, number of rings is less than 3. Heterocyclic radical can be aromatic group (heteroaryl), or non-aromatic group.As the heterocycle for constituting 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, benzene And thiazole, carbazole, purine, quinoline, isoquinolin, quinazoline, phthalazines, cinnolines, quinoxaline, piperidines, piperazine, morpholine, piperidines, tetrahydrochysene Pyrans and tetrahydrofuran etc..

R^b2With R^b3It can be mutually bonded and form ring.Include R^b2With R^b3The group of the ring of formation is preferably cycloalkylidene. R^b2With R^b3When being bonded and forming cycloalkylidene, the ring for constituting cycloalkylidene is preferably five-membered ring~hexatomic ring, more preferably five yuan Ring.

R^b2With R^b3When group formed by bonding is cycloalkylidene, cycloalkylidene can be thick with other rings of more than 1 Close.As can with cycloalkylidene condense ring example, can enumerate phenyl ring, naphthalene nucleus, cyclobutane ring, pentamethylene ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, furan nucleus, thiphene ring, pyrrole ring, pyridine ring, pyrazine ring and pyrimidine ring etc..

The R being described above^b2And R^b3In, as the example of preferred group, formula-A can be enumerated^b1-A^b2The group of expression. In formula, A^b1For straight-chain alkyl-sub, A^b2For alkoxy, cyano group, halogen atom, haloalkyl, cyclic organic group or alkoxy Carbonyl.

A^b1The carbon number of straight-chain alkyl-sub be preferably 1~10, more preferably 1~6.A^b2During for alkoxy, alkoxy Can be straight-chain, or branched, preferably straight-chain.The carbon number of alkoxy is preferably 1~10, more preferably 1~6.A^b2During for halogen atom, preferably fluorine atom, chlorine atom, bromine atoms, iodine atom, more preferably fluorine atom, chlorine atom, Bromine atoms.A^b2During for haloalkyl, the halogen atom included in haloalkyl is preferably fluorine atom, chlorine atom, bromine atoms, iodine original Son, more preferably fluorine atom, chlorine atom, bromine atoms.Haloalkyl can be straight-chain, or branched, be preferably straight Chain.A^b2During for cyclic organic group, the example and R of cyclic organic group^b2And R^b3The ring-type having as substituent is organic Group is same.A^b2During for alkoxy carbonyl, the example and R of alkoxy carbonyl^b2And R^b3The alkoxy carbonyl having as substituent Base is same.

It is used as R^b2And R^b3Preferred concrete example, ethyl, n-propyl, normal-butyl, n-hexyl, n-heptyl and just can be enumerated The alkyl such as octyl group；2- methoxy ethyls, 3- methoxyl groups n-propyl, 4- methoxyl groups normal-butyl, 5- methoxyl groups n-pentyl, 6- methoxyl groups N-hexyl, 7- methoxyl groups n-heptyl, 8- methoxyl groups n-octyl, 2- ethoxyethyl groups, 3- ethyoxyls n-propyl, the positive fourth of 4- ethyoxyls The alkoxyalkyls such as base, 5- ethyoxyls n-pentyl, 6- ethyoxyls n-hexyl, 7- ethyoxyls n-heptyl and 8- ethyoxyl n-octyls； 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 n-heptyl, And the cyanoalkyl such as 8- cyano group n-octyls；2- phenylethyls, 3- phenyl n-propyl, 4- phenyl normal-butyl, 5- phenyl n-pentyl, 6- The phenylalkyls such as phenyl n-hexyl, 7- phenyl n-heptyl and 8- phenyl n-octyls；2- cyclohexyl-ethyls, 3- cyclohexyl n-propyl, 4- cyclohexyl normal-butyl, 5- cyclohexyl n-pentyl, 6- cyclohexyl n-hexyl, 7- cyclohexyl n-heptyl, 8- cyclohexyl n-octyl, 2- Cyclopentyl ethyl, 3- cyclopenta n-propyl, 4- cyclopenta normal-butyl, 5- cyclopenta n-pentyl, 6- cyclopenta n-hexyl, 7- rings penta The cycloalkyl-alkyl such as base n-heptyl and 8- cyclopenta n-octyls；2- dion es, 3- methoxycarbonyls n-propyl, 4- Methoxycarbonyl normal-butyl, 5- methoxycarbonyls n-pentyl, 6- methoxycarbonyls n-hexyl, 7- methoxycarbonyls n-heptyl, 8- Methoxycarbonyl n-octyl, 2- ethoxycarbonylethyl groups, 3- ethoxy carbonyls n-propyl, 4- ethoxy carbonyls normal-butyl, 5- second The alkane such as Epoxide carbonyl n-pentyl, 6- ethoxy carbonyls n-hexyl, 7- ethoxy carbonyls n-heptyl and 8- ethoxy carbonyl n-octyls Epoxide carbonyl alkyl；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- bromines n-heptyl, 8- The haloalkyls such as bromine n-octyl, 3,3,3- trifluoro propyls and the fluorine n-pentyls of 3,3,4,4,5,5,5- seven.

It is used as R^b2And R^b3, preferred group is ethyl, n-propyl, normal-butyl, n-pentyl, 2- methoxyl groups in above-mentioned group Ethyl, 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.

R^b4For monovalent organic group, but the organic group does not have nitro.It is used as R^b4Preferred organic group example Son, with R^b1Equally, alkyl, alkoxy, cycloalkyl, cycloalkyloxy, representative examples of saturated aliphatic acyl group, alkoxy carbonyl, saturation can be enumerated Aliphatic acyl radical epoxide, the phenyl can with substituent, the phenoxy group can with substituent, the benzene can with substituent Formoxyl, can have substituent phenyloxycarbonyl, can have substituent benzoyl epoxide, can have substituent Phenylalkyl, can have substituent naphthyl, can have substituent naphthoxy, can have substituent naphthalene formyl Base, the naphthoxycarbonyl can with substituent, the naphthoyl epoxide can with substituent, the naphthalene can with substituent Base alkyl, the heterocyclic radical can with substituent, there can be the Heterocyclylcarbonyl of substituent, be taken by 1 or 2 organic groups Amino, morpholine -1- bases and the piperazine -1- bases in generation etc..The concrete example of these groups is with being directed to R^b1And the concrete example illustrated is same. In addition, being used as R^b4, further preferably cycloalkyl-alkyl, on aromatic rings can have substituent phenoxyalkyl, on aromatic rings There can be the phenylsulfartyl alkyl of substituent.Substituent and R that phenoxyalkyl and phenylsulfartyl alkyl can have^b1In Comprising the substituent that can have of phenyl it is same.

In organic group, R is used as^b4, preferably alkyl, cycloalkyl, can have substituent phenyl or cycloalkyl alkane Base, on aromatic rings can have substituent phenylsulfartyl alkyl.As the alkyl of alkyl, preferably carbon number 1~20, The more preferably alkyl of the alkyl of carbon number 1~8, particularly preferably carbon number 1~4, most preferably methyl.Can have In the phenyl of substituent, preferably aminomethyl phenyl, more preferably 2- aminomethyl phenyls.The carbon of the cycloalkyl included in cycloalkyl-alkyl Atomicity is preferably 5~10, and more preferably 5~8, particularly preferably 5 or 6.The carbon of the alkylidene included in cycloalkyl-alkyl is former Subnumber is preferably 1~8, more preferably 1~4, particularly preferably 2.In cycloalkyl-alkyl, preferably cyclopentyl ethyl.In fragrance The carbon number of the alkylidene included in the phenylsulfartyl alkyl can on ring with substituent is preferably 1~8, and more preferably 1 ~4, particularly preferably 2.Can have on aromatic rings in the phenylsulfartyl alkyl of substituent, preferably 2- (4- chlorphenyl sulphur Base) ethyl.

In addition, being used as R^b4, it is also preferably-A^b3-CO-O-A^b4The group of expression.A^b3For divalent organic group, preferably two Valency alkyl, preferably alkylidene.A^b4For monovalent organic group, preferably monovalent hydrocarbon.

A^b3During for alkylidene, alkylidene can be straight-chain, or branched, preferably straight-chain.A^b3For alkylene During base, the carbon number of alkylidene is preferably 1~10, more preferably 1~6, particularly preferably 1~4.

It is used as A^b4Preference, the alkyl, the aralkyl of carbon number 7~20 and carbon that can enumerate carbon number 1~10 be former The aromatic hydrocarbyl of subnumber 6~20.It is used as A^b4Preferred concrete example, methyl, ethyl, n-propyl, isopropyl, positive fourth can be enumerated Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, Alpha-Naphthyl methyl and β-naphthalene Ylmethyl etc..

It is used as-A^b3-CO-O-A^b4The preferred concrete example of the group of expression, can enumerate 2- dion es, 2- second Epoxide carbonyl ethyl, 2- n-propyl Epoxide carbonyls ethyl, 2- normal-butyl Epoxide carbonyls ethyl, 2- n-pentyl Epoxide carbonyls ethyl, 2- n-hexyl Epoxide carbonyls ethyl, 2- benzyloxycarbonyls ethyl, 2- phenyloxycarbonyls ethyl, 3- methoxycarbonyls n-propyl, 3- ethoxy carbonyls n-propyl, 3- n-propyl Epoxide carbonyls n-propyl, 3- normal-butyl Epoxide carbonyls n-propyl, 3- n-pentyl epoxides Carbonyl n-propyl, 3- n-hexyl Epoxide carbonyls n-propyl, 3- benzyloxycarbonyls n-propyl and 3- phenyloxycarbonyl n-propyls Deng.

More than, to R^b4It is illustrated, but is used as R^b4, the group that preferably following formula (b1a) or (b1b) are represented.

[chemical formula 30]

(in formula (b1a) and (b1b), R^b7And R^b8Respectively organic group, n3 is 0~4 integer, R^b7With R^b8It is present in benzene During adjacent position on ring, R^b7With R^b8It can be mutually bonded and form ring, n4 is 1~8 integer, n5 is 1~5 integer, N6 is 0~(n5+3) integer, R^b9For organic group.)

R in formula (b1a)^b7And R^b8Organic group example and R^b1Equally.It is used as R^b7, preferably alkyl or phenyl. R^b7During for alkyl, its carbon number is preferably 1~10, more preferably 1~5, particularly preferably 1~3, most preferably 1.That is, R^b7 Most preferably methyl.R^b7With R^b8When being bonded and forming ring, the ring can be aromatic ring, or aliphatic ring.It is used as R^b7 With R^b8The preference of the group of formula (b1a) expression of ring is formd, naphthalene -1- bases, 1,2,3,4- naphthane -5- bases etc. can be enumerated. In above-mentioned formula (b1a), n3 is 0~4 integer, preferably 0 or 1, more preferably 0.

In above-mentioned formula (b1b), R^b9For organic group.As organic group, it can enumerate with being directed to R^b1And the organic group illustrated The same group of group.In organic group, preferably alkyl.Alkyl can be straight-chain, or branched.The carbon of alkyl is former Subnumber is preferably 1~10, more preferably 1~5, particularly preferably 1~3.It is used as R^b9, preferably enumerate methyl, ethyl, propyl group, Isopropyl, butyl etc., in these, more preferably methyl.

In above-mentioned formula (b1b), n5 is 1~5 integer, preferably 1~3 integer, more preferably 1 or 2.Above-mentioned formula (b1b) in, n6 is 0~(n5+3), preferably 0~3 integer, more preferably 0~2 integer, particularly preferably 0.Above-mentioned formula (b1b) in, n4 is 1~8 integer, preferably 1~5 integer, more preferably 1~3 integer, particularly preferably 1 or 2.

In formula (B1), R^b5For hydrogen atom, can have substituent carbon number 1~11 alkyl or can have take Dai Ji aryl.It is used as R^b5The substituent that can have during for alkyl, preferably enumerates phenyl, naphthyl etc..In addition, being used as R^b1 The substituent that can have during for aryl, preferably enumerates alkyl, alkoxy, halogen atom of carbon number 1~5 etc..

In formula (B1), R is used as^b5, preferably enumerate hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, phenyl, Benzyl, aminomethyl phenyl, naphthyl etc., in these, more preferably methyl or phenyl.

The compound that formula (B1) is represented can pass through the oximido (＞ including will be included in the compound of above-mentioned formula (B2) expression C=N-OH ＞ C=N-O-COR) are converted into^b5The method of the process of the oxime ester base of expression and manufacture.R^b5With the R in formula (B1)^b5Together Sample.

Oximido (＞ C=N-OH) is to ＞ C=N-O-COR^b5The conversion of the oxime ester base of expression can be by making above-mentioned formula (B2) The compound of expression is carried out with acylation reaction.

Offer-COR is provided^b5The acylating agent of the acyl group of expression, can enumerate (R^b5CO)₂Acid anhydrides that O is represented, R^b5COHal(Hal For halogen atom) represent carboxylic acid halides.

For the compound that formula (B1) is represented, when n2 is 0, for example, can be synthesized according to following synthesis paths 3.Close Into in path 3, the fluorene derivative represented using following formula (b1-1) is used as raw material.R^b1During for monovalent organic group, formula (b1-1) The fluorene derivative of expression can by using known method to 9 by R^b2And R^b3Substituent R is imported in substituted fluorene derivative^b1 And obtain.For 9 by R^b2And R^b3For substituted fluorene derivative, for example, R^b2And R^b3, can be in the following manner during for alkyl Obtain：As described in Japanese Unexamined Patent Publication 06-234668 publications, in the presence of an alkali metal hydroxide, non-proton In property polar organic solvent, make fluorenes and alkylation reactions.In addition, by the organic solvent solution to fluorenes, adding alkyl halide Etc alkylating agent, the phase transfer catalysis (PTC) of the aqueous solution of alkali metal hydroxide and tetrabutylammonium iodide, potassium tert-butoxide etc Agent, and alkylated reaction is carried out, it can obtain 9,9- alkyl substituted fluorenes.

Using Friedel-Craft acylation reaction, importing-CO-R in the fluorene derivative represented to formula (b1-1)^b4Table The acyl group shown, obtains the fluorene derivative of formula (b1-3) expression.For importing-CO-R^b4The acylating agent of the acyl group of expression can be halogen For carbonyls or acid anhydrides.As acylating agent, the halo carbonyl compounds that preferably formula (b1-2) is represented.Formula (b1-2) in, Hal is halogen atom.The position that acyl group is imported in fluorenes ring can be anti-by suitably changing Friedel-Craft The condition answered using the position beyond the position to acylation is implemented to protect and the method for deprotection is selected.

Next,-the CO-R in the fluorene derivative that obtained formula (b1-3) is represented^b4The group of expression be converted into-C (= N-OH)-R^b4The group of expression, obtains the oxime compound of formula (b1-4) expression.By-CO-R^b4The group of expression be converted into-C (= N-OH)-R^b4The method of the group of expression is not particularly limited, the oximate carried out preferably by hydroxylamine.Make formula (b1-4) oxime Compound, the acid anhydrides ((R represented with following formula (b1-5)^b5CO)₂O) or following formula (b1-6) represent carboxylic acid halides (R^b5COHal, Hal are Halogen atom.) reacted, it can obtain the compound of following formula (b1-7) expression.

It should be noted that in formula (b1-1), (b1-2), (b1-3), (b1-4), (b1-5), (b1-6) and (b1-7), R^b1、R^b2、R^b3、R^b4And R^b5It is same with formula (B1).

In addition, in synthesis path 3, formula (b1-2), formula (b1-3) and formula (b1-4) it is various in the R that includes^b4Can be with identical Can be different.That is, the R in formula (b1-2), formula (b1-3) and formula (b1-4)^b4Can be in the synthesis shown as synthesis path 3 By chemical modification in journey.As the example of chemical modification, it can enumerate in esterification, etherificate, acylation, amidatioon, halogenation, amino The substitution based on organic group of hydrogen atom etc..R^b4Acceptable chemical modification is not limited to these.

The ＞ of ＜ synthesis paths 3

[chemical formula 31]

For the compound that formula (B1) is represented, when n2 is 1, for example, can be synthesized according to following synthesis paths 4.Synthesis In path 4, the fluorene derivative represented using following formula (b2-1) is used as raw material.The fluorene derivative that formula (b2-1) is represented can pass through profit With the method same with synthesis path 3, reacted using Friedel-Craft, imported in the compound represented to formula (b1-1)- CO-CH₂-R^b4The acyl group of expression and obtain.It is used as acylating agent, preferably formula (b1-8)：Hal-CO-CH₂-R^b4The carboxylic acyl of expression Halogen.Next, being present in R in the compound that formula (b2-1) is represented^b4Methylene oximate between carbonyl, obtains following formula (b2-3) ketoxime compounds represented.The method of methylene oximate is not particularly limited, under preferably making in the presence of hydrochloric acid (RONO, R are the alkyl of carbon number 1~6 to the nitrous acid ester that formula (b2-2) is represented.) reaction method.Next, making following formula (b2-3) ketoxime compounds represented, the acid anhydrides ((R represented with following formula (b2-4)^b5CO)₂O) or following formula (b2-5) represent Carboxylic acid halides (R^b5COHal, Hal are halogen atom.) reacted, it can obtain the compound of following formula (b2-6) expression.Need explanation , in following formula (b2-1), (b2-3), (b2-4), (b2-5) and (b2-6), R^b1、R^b2、R^b3、R^b4And R^b5It is same with formula (B1) Sample.

When n2 is 1, there is following tendency：Can further it reduce in the photonasty using the compound represented containing formula (B1) The foreign matter produced in the pattern of composition formation.

In addition, in synthesis path 4, formula (b1-8), formula (b2-1) and formula (b2-3) it is various in the R that includes^b4Can be with identical Can be different.That is, the R in formula (b1-8), formula (b2-1) and formula (b2-3)^b4Can be in the synthesis shown as synthesis path 4 By chemical modification in journey.As the example of chemical modification, it can enumerate in esterification, etherificate, acylation, amidatioon, halogenation, amino The substitution based on organic group of hydrogen atom etc..R^b4Acceptable chemical modification is not limited to these.

The ＞ of ＜ synthesis paths 4

[chemical formula 32]

The preferred concrete example of the compound represented as formula (B1), can enumerate following PI-1~PI-37.

[chemical formula 33]

[chemical formula 34]

For the content of (B) Photoepolymerizationinitiater initiater in photosensitive composite, (do not wrapped relative to photosensitive composite Include solvent) total 100 mass parts, preferably 0.001~30 mass parts, more preferably 0.1~20 mass parts, further preferably For 0.5~10 mass parts.

In addition, for the content of (B) Photoepolymerizationinitiater initiater, relative to the quality and (B) of (A) photopolymerizable compound The summation of the quality of Photoepolymerizationinitiater initiater, preferably 0.1~50 mass %, more preferably 0.5~30 mass %, further preferably For 1~20 mass %.

＜ colouring agents ＞

Photosensitive composite can also include (C) colouring agent.By making photosensitive composite include (C) colouring agent, so as to It is preferably used to form the purposes of the colour filter of the display device such as liquid crystal display.In addition, by making photosensitive composite bag Containing opacifier as (C) colouring agent, so as to the use for the black matrix" being preferably used to form in the colour filter of such as display device On the way.

As (C) colouring agent coordinated in photosensitive composite, it is not particularly limited, for example, it is preferable to use Colour Index (C.I.；The Society of Dyers and Colourists companies issue) in be classified as pigment (Pigment) change Compound, specifically, preferably uses the compound numbered with Colour Index (C.I.) as described below.

As the example for the yellow uitramarine that can suitably use, (following, the also " C.I. of C.I. pigment yellows 1 can be enumerated Pigment yellow ", 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、167、 168th, 175,180 and 185.

As the example for the orange pigment that can suitably use, (following, the also " C.I. of C.I. pigment oranges 1 can be enumerated Pigment orange ", only records numbering.)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、 71 and 73.

As the example for the violet pigment that can suitably use, C.I. pigment violet 1s (following, also " C.I. can be enumerated Pigment violet ", only records numbering.), 19,23,29,30,32,36,37,38,39,40 and 50.

As the example for the red pigment that can suitably use, (following, the also " C.I. of C.I. paratoneres 1 can be enumerated Paratonere ", 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 for the blue pigment that can suitably use, C.I. pigment blue 1s (following, also " C.I. can be enumerated Alizarol saphirol ", only records numbering.)、2、15、15：3、15：4、15：6th, 16,22,60,64 and 66.

As the example of the pigment of the tone outside can suitably using, above-mentioned, C.I. pigment Green 7s, C.I. can be enumerated The viridine greens such as pigment green 36, C.I. naphthol greens 37, C.I. pigment browns 23, C.I. pigment brown 25s, C.I. pigment browns 26, C.I. face Expect the black pigments such as brown 28 grade brown, C.I. pigment blacks 1, C.I. pigment blacks 7.

In addition, when making (C) colouring agent for opacifier, preferably using black pigment as opacifier., can as black pigment Enumerate carbon black, perylene pigments, lactams series pigments, black titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc. metal oxide, The various pigment such as composite oxides, metal sulfide, metal sulfate or metal carbonate (whether organic matter or inorganic matter ).In these, the carbon black with high light-proofness is preferably used.

As carbon black, channel black (channel black), furnace black (furnace black), hot tearing charcoal can be used Carbon black known to black (thermal black), lampblack (lamp black) etc., preferably uses the excellent channel black of light-proofness. In addition, it is possible to use through resin-coated carbon black.

Compared with without resin-coated carbon black, the electric conductivity through resin-coated carbon black is low.Therefore, using comprising through resin During the photosensitive composite formation black matrix" of coated carbon black, the leakage of the electric current in display element as liquid crystal display It is few, the display of the high low power consumption of reliability can be manufactured.

In addition, the tone in order to adjust carbon black, can also be properly added above-mentioned organic pigment as auxiliary pigment.

In order that above-mentioned (C) colouring agent is dispersed in photosensitive composite, dispersant can be further used.As Such dispersant, preferably uses polyethyleneimine amine system, polyurethane resin system, the macromolecule dispersing agent of acrylic resin.Especially It is during using carbon black as (C) colouring agent, to preferably use the dispersant of acrylic resin as dispersant.

In addition, inorganic pigment and organic pigment can individually using or and use two or more.And use in the case of, phase For the mass parts of total amount 100 of inorganic pigment and organic pigment, organic pigment is preferably used with the scope of 10~80 mass parts, more It is preferred that using organic pigment with the scope of 20~40 mass parts.

The usage amount of (C) colouring agent in photosensitive composite is suitably determined i.e. according to the purposes of photosensitive composite Can.As one, the solid state component relative to photosensitive composite adds up to 100 mass parts, and preferably 5~70 mass parts are more excellent Elect 25~60 mass parts as.By that can be preferred with target pattern formation black matrix", each dyed layer for above-mentioned scope.

Especially, in the case of using photosensitive composite formation black matrix", preferably with every 1 μm of envelope of black matrix" OD values turn into more than 4 mode, adjustment photosensitive composite in opacifier amount.If every 1 μm of envelope of black matrix" OD values are more than 4, then in the case of the black matrix" in for display devices such as liquid crystal displays, can obtain sufficient display Contrast.

Preferably, (C) colouring agent is disperseed and after dispersion liquid is made, is added to sense with appropriate concentration using dispersant In photosensitiveness composition.

＜ (D) alkali soluble resins ＞

Photosensitive composite can be comprising (D) alkali soluble resins as in addition to the resin for being used as photopolymerizable compound Other resins.By coordinating (D) alkali soluble resins in photosensitive composite, alkali-developable can be assigned to photosensitive composite.

In this specification, (D) alkali soluble resins refers to：Utilize the resin solution (solvent that resin concentration is 20 mass %：Third Glycol monomethyl ether acetic acid esters) on substrate formed thickness be 1 μm of resin film, by it in the KOH that concentration is 0.05 mass % When being impregnated 1 minute in the aqueous solution, thickness has been dissolved more than 0.01 μm of resin.

(D) in alkali soluble resins, the characteristic of resin is adjusted in terms of Film making properties are excellent, easily by the selection of monomer In terms of consider, the polymer of the monomer with ethylenic unsaturated double-bond is preferred.As unsaturated double with ethylenic The monomer of key, can enumerate (methyl) acrylic acid；(methyl) acrylate；(methyl) acrylamide；Crotonic acid；Maleic acid, rich horse Acid, citraconic acid, mesaconic acid, itaconic acid, the acid anhydride of these dicarboxylic acids；Allyl acetate, allyl hexanoate, allyl octanoate, bay Allyl propionate, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetoacetic acid allyl ester, allyl lactate and The allyl compound of pi-allyl ethoxy-ethanol etc；Hexyl vinyl ethers, octyl vinyl ether, decave, ethyl Hexyl vinyl ethers, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- methyl -2,2- Dimethylpropyl vinyl ether, 2- ethylbutyl vinyl ethers, hydroxyethyl vinyl ether, diethylene glycol vinyl ethers, diformazan Base amino-ethyl vinyl ethers, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ethers, vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl -2,4 dichloro benzene The vinyl ethers of base ether, vinyl naphthyl ether and vinyl anthryl ether etc；Vinyl butyrate, vinyl isobutyrate ester, trimethyl Vinyl acetate, diethacetic acid vinyl acetate, vinyl valerate (vinyl valerate), vinyl caproate, vinyl chloroacetate Ester, vinyl dichloroacetate ester, vinyl methoxyacetate ester, butoxy acetic acid vinyl acetate, vinyl phenylacetate ester, acetoacetate second Alkene ester, lactate, beta-phenyl vinyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, four The vinyl esters of chlorobenzoic acid vinyl acetate and naphthoic acid vinyl acetate etc；Styrene, methyl styrene, dimethyl styrene, three Methyl styrene, ethyl styrene, diethyl, isopropyl styrene, butylstyrene, hexyl styrene, cyclohexyl Styrene, decyl styrene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, second Pivaloyloxymethyl styrene, methoxy styrene, 4- methoxyl group -3- methyl styrenes, dimethoxy styrene, chlorostyrene, Dichlorostyrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene The styrene or benzene of the bromo- 4- trifluoromethyl styrenes of ethene, trifluorostyrene, 2- and the fluoro- 3- trifluoromethyl styrenes of 4- etc Ethene derivatives；Ethene, propylene, 1- butylene, 1- amylenes, 1- hexenes, 3-methyl-1-butene, 3- Methyl-1-pentenes, 3- ethyls- 1- amylenes, 4-methyl-1-pentene, 4- methyl isophthalic acids-hexene, 4,4- dimethyl -1- hexenes, 4,4- dimethyl -1- amylenes, 4- second Base -1- hexenes, 3- ethyl -1- hexenes, 1- octenes, 1- decene, 1- dodecylenes, tetradecene, cetene, 1- 18 The alkene of carbene and 1- eicosylenes etc.

Generally comprised as (D) alkali soluble resins of the polymer of the monomer with ethylenic unsaturated double-bond from insatiable hunger With the unit of carboxylic acid.As the example of unsaturated carboxylic acid, (methyl) acrylic acid can be enumerated；(methyl) acrylamide；Crotonic acid；Horse Come sour, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, the acid anhydride of these dicarboxylic acids.For being used as having for (D) alkali soluble resins For the amount of the unit from unsaturated carboxylic acid included in the polymer of the monomer of ethylenic unsaturated double-bond, as long as resin has There is desired alkali solubility, be not particularly limited.For being used as coming from unsaturation in the resin of (D) alkali soluble resins For the amount of the unit of carboxylic acid, relative to the quality of resin, more preferably preferably 5~25 mass %, 8~16 mass %.

It is being used as the polymer, unsaturated with ethylenic of more than a kind of the monomer in monomer exemplified as above In the polymer of the monomer of double bond, the polymerization of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate Thing is preferred.Hereinafter, the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate is entered Row explanation.

For in the preparation of the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate , can be from as long as in the range of the without prejudice to purpose of the present invention, being just not particularly limited for (methyl) acrylate used Suitably selected in known (methyl) acrylate.

As the preferred example of (methyl) acrylate, (methyl) methyl acrylate, (methyl) acrylic acid second can be enumerated (the first of the straight-chains such as ester, (methyl) propyl acrylate, (methyl) amyl acrylate, the tertiary monooctyl ester of (methyl) acrylic acid or branched Base) alkyl acrylate；(methyl) acrylic acid chloroethene ester, (methyl) acrylic acid 2,2- dimethyl hydroxyls propyl ester, (methyl) propylene Sour 2- hydroxy methacrylates, trimethylolpropane list (methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid furfuryl group Ester；(methyl) acrylate comprising the group with epoxy radicals；(methyl) propylene comprising the group with alicyclic skeleton Acid esters.(methyl) acrylate comprising the group with epoxy radicals and (methyl) comprising the group with alicyclic skeleton The detailed content of acrylate is as described later.

In the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate, from using From the aspect of the transparent insulating film of photosensitive composite formation is for the adaptation of base material, mechanical strength, preferably wrap Resin containing following units, the unit carrys out (methyl) acrylate of the self-contained group with epoxy radicals.

(methyl) acrylate comprising the group with epoxy radicals, can be comprising with chain fatty race epoxy radicals (methyl) acrylate of group, or aftermentioned such (methyl) propylene for including the group with ester ring type epoxy radicals Acid esters.

(methyl) acrylate comprising the group with epoxy radicals can also include aromatic group.It is used as composition aromatic series The example of the aromatic rings of group, can enumerate phenyl ring, naphthalene nucleus.As with aromatic group and including the base with epoxy radicals The example of (methyl) acrylate of group, can enumerate (methyl) acrylic acid 4- glycidyloxyphenyls ester, (methyl) propylene Sour 3- glycidyloxyphenyls ester, (methyl) acrylic acid 2- glycidyloxyphenyls ester, (methyl) acrylic acid 4- contractings Water glyceryl phenyl methyl ester, (methyl) acrylic acid 3- glycidyloxyphenyls methyl ester and (methyl) acrylic acid 2- glycidyloxyphenyl methyl esters etc..

When requiring the transparency to the film using photosensitive composite formation, (methyl) third comprising the group with epoxy radicals Olefin(e) acid is preferably free of aromatic group.

As the example of (methyl) acrylate comprising the group with chain fatty race epoxy radicals, it can enumerate (methyl) As acrylic acid epoxy base Arrcostab and (methyl) acrylic acid epoxy base alkyloxyalkyl ester etc., at ester group (- O-CO-) In epoxide (- O-) on bonding chain fatty race epoxy radicals (methyl) acrylate.Such (methyl) acrylate is had Some chain fatty races epoxy radicals can include one or more epoxides (- O-) in chain.The carbon number of chain fatty race epoxy radicals It is not particularly limited, preferably 3~20, more preferably 3~15, particularly preferably 3~10.

As the concrete example of (methyl) acrylate comprising the group with chain fatty race epoxy radicals, (first can be enumerated Base) glycidyl acrylate, (methyl) acrylic acid 2- methylglycidyl esters, (methyl) acrylic acid 3,4- epoxy radicals butyl ester, (methyl) acrylic acid epoxy base Arrcostab such as (methyl) acrylic acid 6,7- epoxy radicals heptyl esters；(methyl) acrylic acid 2- glycidyls Epoxide ethyl ester, (methyl) acrylic acid 3- glycidyl epoxides n-propyl, the positive fourth of (methyl) acrylic acid 4- glycidyl epoxides (the first such as ester, the just own ester of (methyl) acrylic acid 5- glycidyls epoxide, the just own ester of (methyl) acrylic acid 6- glycidyls epoxide Base) acrylic acid epoxy base alkyloxyalkyl ester.

Containing come the self-contained group with epoxy radicals (methyl) acrylate it is unit, selected from (methyl) propylene In the polymer of acid and more than a kind of monomer in (methyl) acrylate, carry out (the first of the self-contained group with epoxy radicals Base) acrylate unit content preferably with respect to for the weight of resin be 1~95 mass %, more preferably 40~80 matter Measure %.

In addition, in the polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate, from Easily formed using photosensitive composite from the aspect of the excellent transparent insulating film of the transparency, also preferably comprising following units Resin, the unit carrys out (methyl) acrylate of the self-contained group with alicyclic skeleton.

In (methyl) acrylate comprising the group with alicyclic skeleton, the group with alicyclic skeleton can be Group with alicyclic type hydrocarbon, or the group with ester ring type epoxy radicals.Constitute the ester ring type base of alicyclic skeleton Group can be monocyclic, or polycyclic.As monocyclic ester ring type group, cyclopenta, cyclohexyl etc. can be enumerated.In addition, making For polycyclic ester ring type group, norborny, isobornyl, three cyclononyls, tricyclodecyl, tetracyclododecyl group etc. can be enumerated.

In (methyl) acrylate comprising the group with alicyclic skeleton, as including the base with alicyclic type hydrocarbon (methyl) acrylate of group, can enumerate the compound of such as following formula (d1-1)~(d1-8) expressions.It is preferably following in these The compound that the compound that formula (d1-3)~(d1-8) is represented, more preferably following formula (d1-3) or (d1-4) are represented.

[chemical formula 35]

In above-mentioned formula, R^d1Represent hydrogen atom or methyl, R^d2Represent the bivalent aliphatic saturation of singly-bound or carbon number 1~6 Alkyl, R^d3Represent the alkyl of hydrogen atom or carbon number 1~5.It is used as R^d2, the preferably alkylene of singly-bound, straight-chain or branched Base, for example, it is preferable to for methylene, ethylidene, propylidene, Isosorbide-5-Nitrae-butylidene, ethylethylene residue, 1,5- pentylidene, 1,6- it is sub- oneself Base.It is used as R^d3, preferably methyl, ethyl.

In (methyl) acrylate comprising the group with alicyclic skeleton, as comprising with ester ring type epoxy radicals The concrete example of (methyl) acrylate of group, can enumerate the compound of such as following formula (d2-1)~(d2-16) expressions.These In, in order that level of the developability of photosensitive composite for appropriateness, the chemical combination that preferably following formula (d2-1)~(d2-6) is represented The compound that thing, more preferably following formula (d2-1)~(d2-4) are represented.

[chemical formula 36]

In above-mentioned formula, R^d4Represent hydrogen atom or methyl, R^d5The bivalent aliphatic saturated hydrocarbyl of carbon number 1~6 is represented, R^d6The bivalent hydrocarbon radical of carbon number 1~10 is represented, n represents 0~10 integer.It is used as R^d5, preferably straight-chain or branched Alkylidene, for example preferably methylene, ethylidene, propylidene, Isosorbide-5-Nitrae-butylidene, ethylethylene residue, 1,5- pentylidene, 1,6- are sub- Hexyl.It is used as R^d6, for example preferably methylene, ethylidene, propylidene, Isosorbide-5-Nitrae-butylidene, ethylethylene residue, 1,5- pentylidene, 1,6- hexylidenes, phenylene, cyclohexylidene ,-CH₂-Ph-CH₂- (Ph represents phenylene).

The polymer of more than a kind of the monomer in (methyl) acrylic acid and (methyl) acrylate is containing from bag It is next self-contained with alicyclic ring in resin during the resin of the unit of (methyl) acrylate containing the group with alicyclic skeleton The amount of the unit of (methyl) acrylate of the group of formula skeleton is preferably 5~95 mass %, more preferably 10~90 mass %, More preferably 30~70 mass %.

In addition, containing come the self-contained group with alicyclic skeleton (methyl) acrylate it is unit, selected from (first Base) acrylic acid and more than a kind of monomer in (methyl) acrylate polymer in, contain the list from (methyl) acrylic acid The resin of the unit of (methyl) acrylate of member and the next self-contained group with ester ring type epoxy radicals is preferred.Use Excellent adhesion of the film of photosensitive composite formation comprising such (D) alkali soluble resins for base material.Used in addition, working as During such resin, it may occur however that the carboxyl and the autoreactivity of ester ring type epoxy radicals included in resin.Therefore, using comprising During the photosensitive composite of such resin, using method for heating film etc. so that occur carboxyl and ester ring type epoxy radicals Autoreactivity, thus improve the mechanical properties of the hardness of film of formation etc.

At (methyl) containing the unit from (methyl) acrylic acid and the next self-contained group with ester ring type epoxy radicals In the resin of the unit of acrylate, the amount of the unit from (methyl) acrylic acid in resin is preferably 1~95 mass %, more Preferably 10~50 mass %.Containing the unit from (methyl) acrylic acid and coming self-contained with ester ring type epoxy radicals In the resin of the unit of (methyl) acrylate of group, the next self-contained group with ester ring type epoxy radicals in resin The amount of the unit of (methyl) acrylate is preferably 1~95 mass %, more preferably 30~70 mass %.

At (methyl) containing the unit from (methyl) acrylic acid and the next self-contained group with ester ring type epoxy radicals In the polymer of more than a kind of monomer unit, in (methyl) acrylic acid and (methyl) acrylate of acrylate, Unit containing the unit from (methyl) acrylic acid, from (methyl) acrylate with alicyclic type hydrocarbon and from bag The resin of the unit of (methyl) acrylate containing the group with ester ring type epoxy radicals is preferred.

In the list containing the unit from (methyl) acrylic acid, from (methyl) acrylate with alicyclic type hydrocarbon In the resin of the unit of (methyl) acrylate of member and the next self-contained group with ester ring type epoxy radicals, coming in resin Amount from the unit of (methyl) acrylic acid is preferably 1~95 mass %, more preferably 10~50 mass %.Containing from (first Base) unit of acrylic acid, the unit from (methyl) acrylate with alicyclic type hydrocarbon and self-contained there is ester ring type In the resin of the unit of (methyl) acrylate of the group of epoxy radicals, in resin from (methyl) with alicyclic type hydrocarbon The amount of the unit of acrylate is preferably 1~95 mass %, more preferably 10~70 mass %.Containing from (methyl) propylene Acid unit, the unit from (methyl) acrylate with alicyclic type hydrocarbon and come it is self-contained have ester ring type epoxy radicals Group (methyl) acrylate unit resin in, the next self-contained group with ester ring type epoxy radicals in resin The amount of the unit of (methyl) acrylate is preferably 1~95 mass %, more preferably 30~80 mass %.

(D) weight average molecular weight (Mw of alkali soluble resins：Change using gel permeation chromatography (GPC) and according to polystyrene Measured value obtained from calculation.It is identical in this specification.) it is preferably 2000~200000, more preferably 2000~18000.Pass through For above-mentioned scope, so that there is the balance of the developability after the film Forming ability for easily obtaining photosensitive composite, exposure Tendency.

When photosensitive composite includes (D) alkali soluble resins, for containing for (D) alkali soluble resins in photosensitive composite For amount, in the solid state component of photosensitive composite, preferably 15~95 mass %, more preferably 35~85 mass % are special You Xuanwei not 50~70 mass %.

＜ other compositions ＞

In photosensitive composite, as needed, various additives can be included.Specifically, solvent, sensitization can be enumerated Agent, curing accelerator, photocrosslinking agent, photosensitizer, dispersing aid, filler, closely sealed accelerator, antioxidant, ultraviolet are inhaled Receive agent, deflocculant, thermal polymerization inhibitor, defoamer, surfactant etc..

As the solvent used in photosensitive composite, can enumerate for example ethylene glycol single methyl ether, ethylene glycol monomethyl ether, Ethylene glycol 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, Propylene glycol monoethyl, propane diols list n-propyl ether, propane diols list n-butyl ether, DPGME, DPG list Ethylether, DPG list n-propyl ether, DPG list n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethyl Ether etc. (poly-) alkylene glycol monoalkyl ethers class；Ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethyl two Alcohol monomethyl ether acetate, TC acetic acid esters, propylene glycol monomethyl ether, 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- methyl -3- methoxybutyls, propionic acid 3- methyl -3- methoxybutyls, acetic acid Ethyl ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, propionic acid are just Butyl ester, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, methyl pyruvate, ethyl pyruvate, pyruvic acid are just Other esters such as propyl ester, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester；The aromatic hydrocarbons such as toluene, dimethylbenzene Class；Amide-types such as 1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..These solvents can be independent Use, also can be combined and use two or more.

In above-mentioned solvent, propylene glycol monomethyl ether, ethylene glycol single methyl ether acetic acid esters, propylene glycol monomethyl ether, Propylene glycol monoethyl acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, acetic acid 3- methoxyl groups Butyl ester shows excellent dissolubility to above-mentioned (A) composition and (B) composition, and can cause the scattered of above-mentioned (C) composition Property it is good, therefore be preferred；Particularly preferably using propylene glycol monomethyl ether, acetic acid 3- methoxybutyls.To solvent For, it can suitably be determined according to the purposes of photosensitive composite, as one, consolidating relative to photosensitive composite can be enumerated State is into being 50~900 mass parts or so for the mass parts of subtotaling 100.

As workable thermal polymerization inhibitor in photosensitive composite of the present invention, such as quinhydrones, hydrogen can be enumerated Quinone list ethylether etc..In addition, respectively, as defoamer, the compound of polysiloxane series, fluorine system etc. can be enumerated；It is used as surface Activating agent, can enumerate the compound of anion system, cation system, nonionic system etc..

Photosensitive composite can be prepared by the way that above-mentioned each composition is all mixed with mixer.It should be noted that When the photosensitive composite of preparation does not include the insoluble compositions such as pigment, filter can be used to be filtered, it is photosensitive to cause Property composition becomes uniform.

《Solidfied material》

(B) photopolymerization for the compound represented containing (A) photopolymerizable compound, comprising formula (1) being described above is drawn The photosensitive composite of hair agent and optional (C) colouring agent is cured by exposure.The solidfied material of the photosensitive composite Available for multiple use.

For example, as the purposes of solidfied material, dielectric film can be enumerated.When photosensitive composite is free of (C) colouring agent, form saturating Bright dielectric film.When photosensitive composite includes (C) colouring agent, the dielectric film of coloring is formed.Especially, (C) colouring agent is black Opacifier when, formed light-proofness black insulating film.

As the preference of the black insulating film of light-proofness, can enumerate the panel of various device used for image display is had , the spaced walls of black in black matrix", black column spacer (black column spacer).

In addition, when photosensitive composite is comprising colored (C) colouring agent such as RGB, can be in the area divided by black matrix" Domain forms the cured film of coloring to manufacture colour filter.

For example, above-mentioned can fill comprising black matrix", colored cured film as the colour filter of solidfied material in various displays Suitably used in putting.

《The forming method of cured film》

Hereinafter, to using the photosensitive composite formation dielectric film being described above or the cured film that can be used as colour filter Method is illustrated.For the cured film using photosensitive composite formation, it can be patterned as needed.

In order that with the photosensitive composite formation cured film of the present invention, first, using roll coater, reversing coating machine The contact transfer printing type such as (reverse coater), bar coater apparatus for coating, spinner (rotary apparatus for coating), curtain flow are applied The non-contact type apparatus for coating such as glassware (curtain flow coater), are coated with photosensitive composite on substrate.

Next, making the photosensitive composite of coating dry and form coated film.Drying means is not particularly limited, and can lift Go out such as following methods：(1) heating plate is utilized, in 80~120 DEG C, preferably 90~100 DEG C of temperature, is dried 60~120 seconds Method；(2) method for placing a few hours~a couple of days at room temperature；(3) it is put into tens of in storage heater, infrared heater Minute~a few hours and the method for removing solvent；Etc..

Next, being exposed to the coated film irradiation ultraviolet radiation, PRK isoreactivity energy-ray.For example may be used Method being exposed using the mask across minus etc., is exposed regioselectivity.The energy-ray amount of irradiation according to Different and different, such as preferably 40~200mJ/cm of the composition of photosensitive composite²Left and right.Such as be described above that Sample, the susceptibility of photosensitive composite of the present invention is excellent, therefore, can by using the photosensitive composite of the present invention Improve the productivity ratio of the display device of panel of LCD etc.

In the case that optionally coated film is exposed in position, make the film development after exposure by using developer solution, from And form the pattern of desired shape.Developing method is not particularly limited, for example, using infusion process, spray-on process etc..Development Liquid can suitably be selected according to the composition of photosensitive composite.Alkali solubility of the photosensitive composite comprising alkali soluble resins etc into Timesharing, as developer solution, can be used the developer solution of the organic systems such as MEA, diethanol amine, triethanolamine；Sodium hydroxide, hydrogen The aqueous solution of potassium oxide, sodium carbonate, ammonia, quaternary ammonium salt etc..

Next, for the pattern after development, baking is preferred after being carried out in 200~250 DEG C or so.

The patterned cured film being formed as described above can be suitably used for for example in liquid crystal display or the like The purposes such as the dielectric film, the pixel of composition colour filter and the black matrix" that are used in display device.Such dielectric film, colour filter, The display device for having used the colour filter is also one of the solution of the present invention.

Embodiment

Embodiment described below further specifically describes the present invention, but the scope of the present invention is not limited to these implementations Example.

Hereinafter, by reference to example 1~5, the summary of the synthetic method for the compound that formula (1) is represented is shown.

[reference example 1]

The synthesis of compound 2

According to following synthetic method, above-mentioned compound 2 is synthesized.It should be noted that the contracting in following synthesis paths The implication write is as described below.

^tBu：The tert-butyl group

Pr：N-propyl

Ac：Acetyl group

[chemical formula 37]

Load 500 mass parts tetrahydrofurans (THF) and 68.7 mass parts potassium tert-butoxides in reaction vessel, then add 50.0 mass parts 2- bromine fluorenes.

Next, 56.1 mass parts 1- N-Propyl Bromides are added dropwise into reaction vessel, stirred 3 hours in 40 DEG C.By the reaction solution It is cooled to after room temperature, injection ethyl acetate, water carry out a point liquid, washing.Oil reservoir is concentrated, 67.2 mass parts 2- bromo- 9,9- are obtained (yield is 100%, HPLC purity for 92%) to dipropyl fluorenes.

The bromo- 9,9- dipropyl fluorenes of 2-, 500 parts by mass Methylene chloride and 30.4 mass parts that 50.0 mass parts are obtained without Water aluminium chloride is encased in reaction vessel, is cooled to 0 DEG C.

16.9 mass parts propionyl chlorides are added dropwise, are then stirred 3 hours in 10 DEG C.Reaction solution is injected into frozen water, a point liquid is carried out, With 5% sodium bicarbonate aqueous solution and water washing oil reservoir.Oil reservoir is concentrated, isolated and purified using silica gel column chromatography, is obtained (yield is 80%, HPLC purity for 95%) to 46.8 mass parts compound 2a.

150 mass parts THF are added into 30.0 mass parts compound 2a, next 15.6 mass parts 4- nitrobenzophenones of addition Boric acid and 21.5 mass parts potassium carbonate.Next, addition 0.6 mass parts [1,1 '-bis- (diphenylphosphino) ferrocene] dichloride Palladium (II) chloride dichloromethane adduct and 3 mass parts water, are then stirred 5 hours at a reflux temperature.

The reaction solution is cooled to after room temperature, insoluble composition is filtered, filtrate progress concentration is solid, then utilize silicon Glue chromatography is isolated and purified, and obtaining 24.7 mass parts compound 2b, (yield is 75%, HPLC purity for 95%).

Into 15.0 mass parts compound 2b, 75.0 mass parts Methanols of addition, 7.4 mass parts hydroxylamine hydrochlorides and 6.9 mass Part sodium acetate, is stirred 5 hours in 60 DEG C.The reaction solution is cooled to room temperature, 25 mass parts water is added, is filtered, use methanol Washing, is then washed with water.Be dried by forced air drying, obtain 15.5 mass parts compound 2c (yield is 100%, 90%) HPLC purity is.

Into 10.0 mass parts compound 2c, 50.0 mass parts ethyl acetate of addition and 9.3 mass parts acetic anhydrides, in 40 DEG C Stirring 5 hours.Reaction solution is cooled to after room temperature, 10.0 mass parts Methanols are added, after stirring 30 minutes, what filtering was separated out consolidates Body.Obtained solid is isolated and purified using silica gel column chromatography, obtain 5.5 mass parts compounds 2 (yield is 50%, 98%) HPLC purity is.Utilize¹H-NMR wave spectrums (CDCl₃) confirm the obtained structure of compound 2.¹The following institute of H-NMR wave spectrums Show.

δ[ppm]：8.30-8.35(m：2H)、7.71-7.85(m：6H)、7.58-7.65(m：2H)、2.93(q：2H)、 2.30(s：3H)、1.98-2.10(m：4H)、1.24(t：3H)、0.64-0.76(m：10H)

[reference example 2]

The synthesis of compound 37

Propionyl chloride is changed to butyl chloride, and 4- nitrophenyl boronic acids are changed to 4- cyanophenyl boronic acids, except this it Outside, operated in the same manner as reference example 1, obtain following compounds 37.

According to following synthetic method, above-mentioned compound 37 is synthesized.It should be noted that the contracting in following synthesis paths The implication write and reference example 1 are same.

[chemical formula 38]

[chemical formula 39]

Propionyl chloride is changed to butyl chloride, in addition, is operated in the same manner as reference example 1, obtains compound 37a.

Into 20 mass parts compound 37a, addition 80 mass parts THF, 80 mass parts Methanols, 6.2 mass parts sodium acetates, 5.2 mass parts hydroxylamine hydrochlorides, are stirred 5 hours in 60 DEG C.The reaction solution is cooled to room temperature, 60 mass parts water is added, carried out Filter, is washed with methanol.It is dried by forced air drying, obtaining 19.8 mass parts compound 37b, (yield is 95%, HPLC 90%) purity be.

75 mass parts THF are added into 15.0 mass parts compound 37b, next 6.4 mass parts 4- cyano-phenyls of addition Boric acid and 7.6 mass parts potassium carbonate.Next, addition 0.3 mass parts [1,1 '-bis- (diphenylphosphino) ferrocene] dichloride Palladium (II) chloride dichloromethane adduct and 3 mass parts water, are then stirred 5 hours at a reflux temperature.

The reaction solution is cooled to after room temperature, insoluble composition is filtered, filtrate progress concentration is solid, then utilize silicon Glue chromatography is isolated and purified, and obtaining 8.1 mass parts compound 37c, (yield is 52%, HPLC purity for 95%).

25.0 mass parts ethyl acetate and 2.4 mass parts acetic anhydrides are added into 5.0 mass parts compound 37c, in 40 DEG C Stirring 5 hours.Reaction solution is cooled to after room temperature, 10.0 mass parts Methanols are added, after stirring 30 minutes, what filtering was separated out consolidates Body.Obtained solid is isolated and purified using silica gel column chromatography, obtain 2.7 mass parts compounds 37 (yield is 50%, 98%) HPLC purity is.

Utilize¹H-NMR wave spectrums (CDCl₃) confirm the obtained structure of compound 37.¹H-NMR wave spectrums are as follows.

δ[ppm]：7.67-7.82(m：8H)、7.55-7.60(m：2H)、2.90(t：2H)、2.30(s：3H)、1.93- 2.07(m：4H)、1.65(sep：2H)、1.12(t：3H)、0.65-0.70(m：10H)

[reference example 3]

The synthesis of compound 20

Propionyl chloride is changed to butyl chloride, and 4- nitrophenyl boronic acids are changed to 3- nitrophenyl boronic acids, except this it Outside, operated in the same manner as reference example 1, obtain following compounds 20.

[chemical formula 40]

Utilize¹H-NMR wave spectrums (CDCl₃) confirm the obtained structure of compound 20.¹H-NMR wave spectrums are as follows.

δ[ppm]：8.52(t：1H)、8.19-8.25(m：1H)、7.96-8.02(m：1H)、7.58-7.86(m：7H)、 2.91(q：2H)、2.29(s：3H)、1.96-2.12(m：4H)、1.58-1.70(m：2H)、1.02(t：3H)、0.58-0.75(m： 10H)

[reference example 4]

The synthesis of compound 28

According to following synthetic method, above-mentioned compound 28 is synthesized.It should be noted that the contracting in following synthesis paths The implication write and reference example 1 are same.

[chemical formula 41]

Propionyl chloride is changed to butyl chloride, and 4- nitrophenyl boronic acids are changed to 3- nitrophenyl boronic acids, except this it Outside, operated in the same manner as reference example 1, obtain compound 28b.

Into 20 mass parts compound 28b, 150 mass parts THF of addition, the hydrochloric acid of 12.0 mass parts 35%.Delay at room temperature 8.1 mass parts isoamyl nitrites of slow addition, are persistently stirred 7 hours.The progress concentration of obtained reaction solution is solid, utilize silica gel Column chromatography is isolated and purified, and obtaining 11.9 mass parts compound 28c, (yield is 55%, HPLC purity for 95%).

100 mass parts ethyl acetate, 2.6 mass parts acetic anhydrides are added in the compound 28c obtained to 10.0 mass parts, in 40 DEG C are stirred 5 hours.Reaction solution is cooled to after room temperature, progress concentration is solid, is isolated and purified using silica gel column chromatography, Obtaining 8.2 mass parts compounds 28, (yield is 75%, HPLC purity for 97%).

Utilize¹H-NMR wave spectrums (CDCl₃) confirm the obtained structure of compound 28.¹H-NMR wave spectrums are as follows.

δ[ppm]：8.53(t：1H)、8.20-8.26(m：1H)、8.07-8.16(m：2H)、7.96-8.02(m：1H)、 7.83(q：2H)、7.58-7.68(m：3H)、2.85(q：2H)、2.30(s：3H)、1.96-2.15(m：4H)、1.22(t：3H)、 0.58-0.80(m：10H)

[reference example 5]

The synthesis of compound 137

Bromo- 9, the 9- dipropyl fluorenes of 2- is changed to N- ethyl -3- bromine carbazoles, 4- nitrophenyl boronic acids are changed to 3- nitros Phenylboric acid, and propionyl chloride is changed to 4- ((1- methoxy propane -2- bases) epoxide) -2- methyl benzoyl chlorides, except this it Outside, operated in the same manner as reference example 1, obtain following compounds 137.

[chemical formula 42]

Utilize¹H-NMR wave spectrums (CDCl₃) confirm the obtained structure of compound 137.¹H-NMR wave spectrums are as follows.

δ[ppm]：8.54(brs：1H)、8.30(brs：2H)、8.00-8.20(m：2H)、7.86(dd：1H)、7.75(dd： 1H)、7.63(t：1H)、7.42(d：1H)、7.40(d：1H)、7.08(d：1H)、6.85-6.95(m：2H)、4.60-4.70(m： 1H)、4.42(q：2H)、3.50-3.70(m：2H)、3.46(s：3H)、2.18(s：3H)、2.12(s：3H)、1.50(t：3H)、 1.60(d：3H)

[embodiment 1~12, comparative example 1 and comparative example 2]

In embodiment and comparative example, Resin A and dipentaerythritol acrylate (Nippon Kayaku K. K's system) are used It is used as photopolymerizable compound.Resin A uses the product being synthesized into according to following formula.

First, in 500ml four-necked bottles, 235g bisphenol fluorene types epoxy resin (epoxide equivalent is 235), 110mg tetra- are loaded Ammonio methacrylate, 100mg 2,6- di-tert-butyl-4-methy phenols and 72.0g acrylic acid, while with the speed of 25ml/ minutes Air is blown into thereto, while being dissolved by heating in 90~100 DEG C.Next, slowly being risen in the state of solution is gonorrhoea Temperature, is heated to 120 DEG C, is completely dissolved it.Now, solution gradually becomes clear viscous, keeps the state persistently to stir.Herein Period determines acid number, and continuous heating stirring is until acid number gets lower than 1.0mgKOH/g.Needed untill acid number reaches desired value 12 hours.Then, room temperature is cooled to, the bisphenol fluorene type ring that water white transparency and the following structural formula (a4) for solid-like are represented is obtained Oxypropylene acid esters.

[chemical formula 43]

Next, adding 600g acetic acid in the above-mentioned bisphenol fluorene type epoxy acrylate that 307.0g is obtained as described above 3- methoxybutyls and after being dissolved, mixing 80.5g benzophenone tetracarboxylics dianhydride and 1g tetraethylammonium bromides slowly rise Temperature, carries out reacting for 4 hours in 110~115 DEG C.After the disappearance for confirming anhydride group, the 38.0g adjacent benzene of 1,2,3,6- tetrahydrochysenes is mixed Dicarboxylic acid anhydride, reacts 6 hours in 90 DEG C, obtains Resin A.The disappearance of anhydride group is confirmed by IR spectrum.The Resin A belongs to The compound that above-mentioned formula (a1) is represented.

In embodiment, as Photoepolymerizationinitiater initiater, following compounds 1, compound 4~10 and compound 13 have been used ~17.Following compound 1, compound 4~10 and compounds 13~17 are synthesized using the method same with reference example 1~5.

[chemical formula 44]

In comparative example, as Photoepolymerizationinitiater initiater, following comparative compounds 1 and comparative compound 2 have been used.

[chemical formula 45]

Using the mixed solvent for including acetic acid 3- methoxybutyls, cyclohexanone and propylene glycol monomethyl ether, to 25 Mass parts Resin A, 10 mass parts dipentaerythritol acrylates (Nippon Kayaku K. K's system), described in 5 mass parts tables 1 Species Photoepolymerizationinitiater initiater and 60 mass parts carbon dispersion liquids (CF is black, Mikoku Pigment Co., Ltd.'s system) be diluted so that Solid component concentration turns into 15 mass %, and then, these compositions are uniformly mixed, and obtains embodiment 1~12, comparative example 1 and ratio Compared with the photosensitive composite of example 2.The mass ratio of each solvent of in the mixed solvent is with acetic acid 3- methoxybutyls/cyclohexanone/the third two Alcohol monomethyl ether acetate is calculated as 60/20/20.

[sensitivity assessment]

The evaluation of susceptibility is implemented according to following step.First, using spin coater by the sense of each embodiment and comparative example Photosensitiveness composition is coated on glass substrate (10cm × 10cm), 120 seconds prebake conditions is carried out in 90 DEG C, on the surface of glass substrate The upper coated film for forming 1.0 μm of thickness.Then, exposer (mirror projection are directed at using mirror surface projection Aligner) (product name：TME-150RTO, TOPCON CORPORATION systems), exposing clearance is set as 50 μm, across shape Into there is minus mask of the width for 10 μm of pattern, to coated film irradiation ultraviolet radiation.Light exposure is set as 30,60,1200mJ/ cm²This 3 grades.With 26 DEG C of the 0.04 mass %KOH aqueous solution by the coating film development 30 seconds after exposure, then in 230 DEG C Toasted after carrying out 30 minutes, thus, obtain the pattern of each light exposure.With the line of the pattern under each light exposure of light microscope determining Width, by the line width and light exposure under each light exposure, by the approximate calculation based on least square method, calculates available 10 μm of line Wide light exposure.By the developing time calculated be 30 seconds when susceptibility (mJ/cm²) data be shown in table 1.It is quick shown in table 1 The data of sensitivity be expressed as being formed as defined in line width pattern (10 μm) and required light exposure, the numerical value is smaller, represents sense The susceptibility of photosensitiveness composition is higher.

[evaluation of OD values]

On 6 inches of glass substrates (Dow Corning systems, 1737 glass), the sense of each embodiment and comparative example is coated with Photosensitiveness composition, is then dried 60 seconds in 90 DEG C, forms coated film.Next, with 60mJ/cm²Light exposure to the coated film Irradiate ghi lines.Then, on hot plate, toasted after being carried out 20 minutes in 230 DEG C, form photomask.The film of the photomask of formation Thickness is 0.8 μm, 1.0 μm, 1.2 μm of this 3 ranks.For the photomask, using D200-II (Macbeth systems), each thickness is determined Under OD values, every 1 μm of OD values are calculated using matched curve.Formed using the photosensitive composite of each embodiment and comparative example The OD values calculated of photomask are 4.8/ μm.

[line pattern evaluation]

Using spin coater by the photosensitive composite of each embodiment and comparative example be coated on glass substrate (100mm × On 100mm), 120 seconds prebake conditions are carried out in 70 DEG C, coated film is formed.Next, being directed at exposer (product using mirror surface projection Name：TME-150RTO, TOPCON CORPORATION systems), exposing clearance is set as 50 μm, is 10 μm across being formed with width Line pattern minus mask, to coated film irradiation ultraviolet radiation.Light exposure is set as 20,40,60,120mJ/cm²This 4 etc. Level.With 26 DEG C of the 0.04 mass %KOH aqueous solution by the coating film development 50 seconds after exposure, then carried out 30 minutes in 230 DEG C After toast, thus, it is 3.5 μm of line pattern to form thickness.

(pattern, which is peeled off, to be evaluated)

The line pattern formed using observation by light microscope, confirmation has pattern-free peeling.The confirmation that will there is pattern-free to peel off As a result it is recorded in table 1.

(cone angle)

For with 40mJ/cm²Light exposure formation line pattern, cone angle (taper angle) is evaluated.Based on survey Fixed cone angle, the cross sectional shape of line pattern is judged according to following benchmark.

◎：Cone angle is less than more than 70 ° 85 °.

○：Cone angle is more than 85 ° and for less than 90 °.

△：Cone angle is more than 90 ° and for less than 100 °.

×：Cone angle is more than 100 °.

For cone angle, using SEM, it is measured as the engagement angles between pattern and substrate.Should The angle θ that cone angle corresponds in Fig. 1 (a) and (b).The cone angle of measure is shown in table 1.Cone angle represents patterned section closer to 90 DEG C Shape closer to desired rectangular shape.Cone angle is acute angle and when being the angle more much smaller than 90 DEG C, although do not produced in pattern Raw undercut portions, but the not desired rectangular shape of shape of patterned section.When cone angle is obtuse angle, undercutting is generated in pattern Portion.

[table 1]

It can be seen from table 1, for the knot of formula (1) expression comprising photopolymerizable compound and as Photoepolymerizationinitiater initiater For the photosensitive composite of the embodiment of the compound of structure, susceptibility is excellent.

It can be seen from embodiment 8~13, during using the compound that the n in formula (1) is 1, susceptibility is readily obtained especially excellent Different photosensitive composite.

In addition, as shown in Table 1, by using the photosensitive composite of embodiment, can be formed and be difficult to peel off from substrate, cut Face is shaped as the line pattern of desired rectangular shape.

On the other hand, it is known that for the photonasty of the comparative example of the Photoepolymerizationinitiater initiater comprising the structure outside formula (1) scope For composition, susceptibility is poor.In addition, when forming line pattern using the photosensitive composite of comparative example, according to light exposure not With pattern peeling can be produced, in addition, cone angle is obtuse angle, undercut portions are generated in line pattern.

Claims

1. photosensitive composite, it contains the compound of following formula (1) expression,

[chemical formula 1]

In formula (1), R¹Represent electron withdraw group, R⁶For arlydene, inferior heteroaryl or comprising more than 1 selected from carbon-to-carbon double bond and The chain fatty race alkyl of more than a kind of key in carbon-to-carbon triple bond, the R⁶Can have organic selected from electron withdraw group and monovalence The substituent of more than 1 in group, R⁴Represent monovalent organic group or hydrogen atom, R⁵Monovalent organic group or hydrogen atom are represented, N represent 0 or 1, T represent following formula (T_C) or formula (T_N) represent group,

[chemical formula 2]

Formula (T_C) and formula (T_N) in, R²And R³The alkyl or hydrogen atom that can be substituted are represented independently of one another, and * represents chemical bond,

Formula (T_C) in, R²And R³It can combine and form ring.

2. photosensitive composite as claimed in claim 1, wherein, the compound that the formula (1) represents is following formula (1C) table The compound shown,

[chemical formula 3]

In formula (1C), R¹、R²、R³、R⁴、R⁵、R⁶And n is as described above.

3. photosensitive composite as claimed in claim 1, wherein, the fluorene compound that the formula (1) represents is by following formula (1N) Represent,

[chemical formula 4]

In formula (1N), R¹、R²、R⁴、R⁵、R⁶And n is as described above.

4. such as photosensitive composite according to any one of claims 1 to 3, wherein, R¹-R⁶- the group represented is by electrophilic The aryl of substituent group.

5. photosensitive composite as claimed in claim 4, wherein, replaced in contraposition or ortho position by the electron withdraw group Aryl.

6. such as photosensitive composite according to any one of claims 1 to 3, the photosensitive composite includes (A) photopolymerization Property compound.

7. such as photosensitive composite according to any one of claims 1 to 3, the photosensitive composite includes (C) colouring agent.

8. solidfied material, it is the solidfied material of the photosensitive composite described in claim 6, wherein,

The photosensitive composite can include (C) colouring agent.

9. dielectric film, it is formed as the solidfied material described in claim 8.

10. colour filter, it includes the solidfied material described in claim 8, wherein,

The photosensitive composite can include (C) colouring agent.

11. display device, it has the colour filter described in claim 10.

12. the forming method of cured film, methods described includes following process：

Photosensitive composite described in claim 6 is coated on to the process for forming coated film on base material, and

The process being exposed to the coated film；

In methods described, the photosensitive composite can include (C) colouring agent.

13. the forming method of cured film as claimed in claim 12, wherein,

It is described exposure be regioselectivity carry out, and

Methods described also includes the process that the exposed coated film is developed.