CN103502888A

CN103502888A - Negative photosensitive resin composition, cured film, partition wall, black matrix, method for producing partition wall, method for producing black matrix, color filter, and organic EL element

Info

Publication number: CN103502888A
Application number: CN201280020872.3A
Authority: CN
Inventors: 高桥秀幸
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2011-04-28
Filing date: 2012-04-19
Publication date: 2014-01-08
Anticipated expiration: 2032-04-19
Also published as: JP5910629B2; JPWO2012147626A1; CN103502888B; KR20140018319A; KR101842317B1; TW201248326A; WO2012147626A1; TWI522746B

Abstract

Provided are: a negative photosensitive resin composition which has good ink repellency and good reproducibility of a line width of a mask; and a partition wall which is obtained using the composition and has uniform quality. This negative photosensitive resin is characterized by containing: (A) an ink-repellent agent that has a side chain containing -CFXRf (wherein X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group, and Rf represents a fluorine atom or a fluoroalkyl group which may have an ether oxygen atom and has 20 or less carbon atoms, while having at least one hydrogen atom substituted by a fluorine atom) or -(SiR1R2-O)n-SiR3R4R5 (wherein, each of R1, R2, R3 and R4 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, R5 represents a hydrogen atom or an organic group having 1-10 carbon atoms, and n represents an integer of 1-200); (B) a photopolymerization initiator that is an oxime ester compound having a nitro group in each molecule; and (C) an alkali-soluble resin.

Description

Negative light-sensitive resin combination, cured film, partition wall and black matrix" and manufacture method thereof, color filter and organic EL

Technical field

The present invention relates to negative light-sensitive resin combination, cured film, partition wall and black matrix" and manufacture method thereof, color filter and organic EL.

Background technology

Anti-corrosion agent composition is as partition wall, organic EL(electroluminescence between the pixel that forms color filter, Electro-Luminescence) the interelement partition wall of the partition wall between the pixel of display element, organic EL illuminating, organic tft (Thin Film Transistor: the thin film transistor (TFT)) material of the permanent film such as partition wall of the partition wall of the ITO electrode of the partition wall that separates each TFT of array, liquid crystal display cells, wiring substrate and being attracted attention.

In the manufacture of wiring substrate, proposed to spray the ink-jet method of coating metal dispersion liquid when forming wiring.The wiring pattern is formed by anti-corrosion agent composition by photoetching process, and the coating film cured product thereof of anti-corrosion agent composition is used as partition wall.

In ink-jet method, need to prevent between neighbor that the partial coagulation beyond the material that produces black colour mixture, sprayed by ink jet printer is in the regulation zone is adhered to, propose to comprise the anti-corrosion agent composition (patent documentation 1～3) of refusing black agent.

The prior art document

Patent documentation

Patent documentation 1: No. 2008/146855th, International Publication

Patent documentation 2: No. 2010/001976th, International Publication

Patent documentation 3: No. 2010/013816th, International Publication

Summary of the invention

the problem that invention will solve

The exposure of anti-corrosion agent composition is used exposure machine to carry out.The wavelength that exposure machine irradiates is different because of the specification of device, in general, in the proximity printing mode for the color filter purposes, irradiates the following light of 330nm.On the other hand, in mirror surface projection (MPA) mode, block the following light of 330nm and irradiated.Therefore, sometimes also anti-corrosion agent composition is required to the composition that can tackle the MPA mode.In addition, the MPA mode of projection type also possesses and can form sharp partition wall shape etc., the advantage for the proximity printing mode.Sometimes require to form fine pattern in the MPA mode.

The object of the invention is to, block the following exposure light of 330nm even provide, refuse the also also good negative light-sensitive resin combination and use said composition and cured film, partition wall and black matrix" and the manufacture method thereof of the homogeneous that obtains of reproduction of the live width of good and mask of China ink.The present invention also aims to, color filter and organic EL with well behaved partition wall or black matrix" are provided.

for the scheme of dealing with problems

The present invention is following [1]～[15].

[1] a kind of negative light-sensitive resin combination, is characterized in that, it contains:

Refuse black agent (A), it has the side chain that comprises the group shown in the group shown in following formula (1) or following formula (2),

Photoepolymerizationinitiater initiater (B), it is for have an oxime ester compound of nitro in 1 molecule, and

Alkali soluble resin (C),

-CFXR ^f （1）

-（SiR ¹R ²-O） _n-SiR ³R ⁴R ⁵ （2）

In formula (1), X means hydrogen atom, fluorine atom or trifluoromethyl, R ^fexpression can have fluoroalkyl or the fluorine atom of at least 1 carbon number replaced by fluorine atom etheric oxygen atom, hydrogen atom below 20.

In formula (2), R ¹, R ², R ³and R ⁴mean independently hydrogen atom, alkyl, naphthenic base or aryl, R ⁵mean the organic group of hydrogen atom or carbon number 1～10, n means 1～200 integer.

[2] according to the negative light-sensitive resin combination of [1], wherein, aforementioned Photoepolymerizationinitiater initiater (B) is the compound be comprised of following formula (3).

In formula (3), R ³¹mean the alkyl of carbon number 1～20, the aryl of carbon number 6～30, aralkyl or the cyano group of carbon number 7～30.R ³²mean R ⁴¹or OR ⁴², this R ⁴¹and R ⁴²mean respectively the alkyl of carbon number 1～20, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30.R ³³the alkyl, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30 that mean carbon number 1～20.R ³⁴and R ³⁵mean independently of one another R ⁴¹, OR ⁴², cyano group or halogen atom.A and b are 0～3 integer independently of one another, the integer that c is 1～3.

[3] according to the negative light-sensitive resin combination of [1] or [2], it also comprises black colorant (D).

[4] according to the described negative light-sensitive resin combination of any one in [1]～[3], it also comprises crosslinking chemical (G).

[5], according to the described negative light-sensitive resin combination of any one in [1]～[4], wherein, refuse black agent (A) for there is the compound that group (1) or group (2), main chain are hydrocarbon chain at side chain.

[6] according to the negative light-sensitive resin combination of [5], wherein, refuse black agent (A) and there is acidic-group.

[7], according to the described negative light-sensitive resin combination of any one in [1]～[4], wherein, refuse black agent (A) for there is the compound that group (1), main chain are the organopolysiloxane chain at side chain.

[8] according to the described negative light-sensitive resin combination of any one in [5]～[7], wherein, refuse black agent (A) and there is olefinic double bond.

[9] a kind of cured film, it is that the curing of coating of the described negative light-sensitive resin combination of any one in [1]～[8] that make to form on substrate forms.

[10] a kind of partition wall, its partition wall for forming for subregion is set on substrate, its cured film by [9] forms.

[11] a kind of black matrix", its black matrix" for forming for subregion is set on substrate, its cured film by [9] forms, and described cured film is formed by the negative light-sensitive resin combination of [3].

[12] a kind of manufacture method of partition wall, is characterized in that, the method possesses following operation successively: the described negative light-sensitive resin combination of any one in aforementioned [1]～[8] is coated on to the operation that on substrate, formation is filmed; By the aforementioned heating and after making film of filming, only the established part of this film is exposed and made the operation of its photocuring; Remove the operation except aforementioned film through the part of photocuring; And, the heating of the aforementioned part through photocuring is obtained to the operation of partition wall, before removing aforementioned films and the Thickness Variation of the aforementioned part through photocuring afterwards be below 60nm.

[13] a kind of manufacture method of black matrix", it uses the negative light-sensitive resin combination of [3] to obtain aforementioned partition wall as black matrix" in the manufacture method of aforementioned [12].

[14] a kind of color filter, is characterized in that, it possesses: a plurality of pixels on substrate, substrate and be positioned at the partition wall between neighbor, the cured film of this partition wall described negative light-sensitive resin combination of any one in [1]～[8] forms.

[15] a kind of organic EL, is characterized in that, it possesses: a plurality of pixels on substrate, substrate and be positioned at the partition wall between neighbor, the cured film of this partition wall described negative light-sensitive resin combination of any one in [1]～[8] forms.

the effect of invention

According to the present invention, even can provide in the situation that reduce exposure or block the exposure light below 330nm and exposed, also can manufacture the negative light-sensitive resin combination of the good partition wall of the reproduction of the live width of refusing the good and mask of China ink.According to the present invention, can provide the cured film of the homogeneous of the negative light-sensitive resin combination that has used the invention described above, well behaved partition wall and black matrix" and manufacture method thereof.And then, according to the present invention, can obtain the partition wall that possesses the invention described above and black matrix", well behaved color filter and organic EL.

The accompanying drawing explanation

Fig. 1 is for meaning to have used the diagrammatic cross-section of Production Example negative light-sensitive resin combination of the present invention, the used for optical elements partition wall.

Embodiment

Acid number in this instructions refer to for and the 1g sample in the milligram number of the required potassium hydroxide such as geocerellite, be the value of can the assay method based on JIS K0070 being measured.Unit is mgKOH/g.

Total solid composition in this instructions refers to the partition wall forming component in the contained composition of negative light-sensitive resin combination, means to wait the total composition volatile ingredient that volatilize because of heating except solvent (H) etc. in the partition wall forming process.

In this instructions " (methyl) acryloyl group ... " refer to " methacryl ... " " acryloyl group ... " general name.(methyl) acrylate, (methyl) acrylamide, (methyl) allyl ..., (methyl) acrylic resin is also identical therewith.

Alkyl in this instructions means the organic group only consisted of carbon and hydrogen.

In this instructions, by being coated with the film that negative light-sensitive resin combination forms, be called " filming ", will make its dried state be called " film ", and then will make it solidify and the film that obtains is called " cured film ".

In this instructions, " surface " of partition wall is as only meaning the term of the upper surface of partition wall.Therefore, " surface " of partition wall do not comprise the side of partition wall.

China ink in this instructions is to possess for example general name of the liquid of optics, electric function after dry solidification, the coloured material used since being not limited in the past.In addition, for injecting above-mentioned China ink, form " pixel ", similarly for meaning the division that possesses respectively optical function, electric function separated with partition wall.

The China ink of refusing in this instructions refers to the appropriate character that possesses water repellency and oil repellent in order to repel above-mentioned China ink, for example, can utilize method described later to estimate.

Below, embodiments of the present invention are described.Wherein, do not have in this manual in the situation of special instruction, % means quality %.

[refusing black agent (A)]

It is of the present invention that to refuse black agent (A) be to have that to comprise the group shown in following formula (1) (following also referred to as group (1).) or following formula (2) shown in group (following also referred to as group (2).) the compound of side chain.

-CFXR ^f （1）

-（SiR ¹R ²-O） _n-SiR ³R ⁴R ⁵ （2）

Therefore refuse black agent (A) and there is the side chain that comprises group (1) or group (2), there is surface migration, filming of will being formed by negative light-sensitive resin combination, heat also drying and while making film, move near film coated surface.Thus, show and refuse China ink on the surface of being solidified the curing film formed partition wall formed by film, the Mo Buhui that utilizes ink-jet method to inject overflows from peristome between the partition wall that is called as point (dot) (becoming the position of pixel), is difficult for occurring the colour mixture between neighbor.

The side chain that comprises group (1) or group (2) can directly form by polyreaction, also can form by the chemical conversion after polyreaction.

R in formula (1) ^ffor can have the fluoroalkyl of at least 1 carbon number replaced by fluorine atom etheric oxygen atom, hydrogen atom below 20 time, the hydrogen atom in this fluoroalkyl also can be replaced by other halogen atom beyond fluorine atom.As other halogen atom, be preferably the chlorine atom.In addition, etheric oxygen atom may reside between the carbon-carbon bond of this fluoroalkyl, also may reside in the end of this fluoroalkyl.In addition, the structure of this fluoroalkyl can list the structure of linear chain structure, branched structure, ring structure or part band, is preferably linear chain structure.

As group (1), be preferably the Polyfluoroalkyl that comprises 1 perfluoroalkyl or hydrogen atom, be particularly preferably perfluoroalkyl and (wherein, comprise the group with etheric oxygen atom.）。The China ink of refusing of the partition wall formed by negative light-sensitive resin combination thus, becomes good.

The carbon number of group (1) is, below 20, to be preferably 4～6.Now, partition wall is given and refused fully China ink, and it is good with the compatibility of other composition that forms negative light-sensitive resin combination to refuse black agent (A), be coated with negative light-sensitive resin combination and form while filming, refusing black agent (A) each other can aggegation, can form the good partition wall of outward appearance.

As group (1), the perfluoroalkyl that preferably carbon number is 4～6 or there is the perfluoroalkyl that the carbon number of etheric oxygen atom is 4～9.

Object lesson as group (1), be listed below.

-CF ₃,-CF ₂cF ₃,-CF ₂cHF ₂,-(CF ₂) ₂cF ₃,-(CF ₂) ₃cF ₃,-(CF ₂) ₄cF ₃,-(CF ₂) ₅cF ₃,-(CF ₂) ₆cF ₃,-(CF ₂) ₇cF ₃,-(CF ₂) ₈cF ₃,-(CF ₂) ₉cF ₃,-(CF ₂) ₁₁cF ₃,-(CF ₂) ₁₅cF ₃,-CF(CF ₃) O(CF ₂) ₅cF ₃,-CF ₂o(CF ₂cF ₂o) _pcF ₃(integer that p is 1～8) ,-CF(CF ₃) O(CF ₂cF(CF ₃) O) _qc ₆f ₁₃(integer that q is 1～4) ,-CF(CF ₃) O(CF ₂cF(CF ₃) O) _rc ₃f ₇(integer that r is 1～5).

As group (1), be particularly preferably-(CF ₂) ₃cF ₃or-(CF ₂) ₅cF ₃.

In formula (2), R ¹and R ²in each siloxane unit, can be the same or different.Show the excellent aspect of refusing China ink, R from the partition wall formed by negative light-sensitive resin combination ¹, R ²be preferably alkyl, naphthenic base or the aryl of hydrogen atom, carbon number 1～10, more preferably hydrogen atom, methyl or phenyl, the particularly preferably R in all siloxane units ¹, R ²for methyl.

In formula (2), R ³, R ⁴and R ⁵the group with the silicon atom bonding of the end of siloxane bond, as R ³and R ⁴, can with R ¹, R ²identical, preferred form is also identical.In addition, R ⁵during for organic group, can comprise nitrogen-atoms, oxygen atom etc., R ⁵be preferably the alkyl of hydrogen atom or carbon number 1～5.N is preferably 1～200 integer, is particularly preferably 2～100 integer.

As group (2), preferred R ¹, R ², R ³, R ⁴and R ⁵it is all methyl.

Refuse black agent (A) and preferably also there is acidic-group.Refusing black agent (A) while having acidic-group, is preferred from improving the deliquescent viewpoint of negative light-sensitive resin combination developer solution.

As acidic-group, be preferably the acidic-group more than a kind in the group of selecting free carboxyl, phenol hydroxyl and sulfonic group to form.

Acidic-group preferably is present in side chain from synthetic easy viewpoint.Polyreaction with monomer that the side chain of acidic-group can be by having acidic-group forms, and also can form by the chemical conversion after polyreaction.

Refuse black agent (A) and preferably there is polyoxy alkylidene.Refuse black agent (A) while thering is polyoxy alkylidene, even in the situation that improve pressure in developing procedure and also can maintain and refuse China ink.And then, from the viewpoint that can prevent not to remove fully by developing the residual film that remains in a part, be preferred.It should be noted that, as the polyoxy alkylidene used in the present invention, particularly, can list the group shown in following formula (11) (following also referred to as group (11).) etc.

-（R ²¹O） _m（R ²²O） _jR ²³ …（11）

In formula (11), R ²¹and R ²²the alkylidene that means independently of one another carbon number 2～4, R ²³mean that hydrogen atom maybe can have the alkyl of substituent carbon number 1～10, m means 0～100 integer, and j means 0～100 integer, the integer that m+j is 4～100.

In group (11), R ²¹and R ²²the alkylidene that means independently of one another carbon number 2～4.The structure of alkylidene can be linear chain structure, can be also branched structure.R ²¹and R ²²can be the same or different.At such R ²¹and R ²²among, preferably both are-CH independently of one another ₂cH ₂-or-C ₃h ₆-or be-CH ₂cH ₂-with-C ₄h ₈-combination, particularly preferably both are-CH ₂cH ₂-or be-CH ₂cH ₂-with-CH ₂cH(CH ₃)-combination.

In group (11), m means 0～100 integer, and j means 0～100 integer, and m and j are preferably respectively 0～50, are particularly preferably 0～30.

In addition, the integer that m+j is 4～100, be preferably 6～50 integer, is particularly preferably 8～30 integer.When the lower limit that m+j is above-mentioned scope is above, while being used the jet douche operation of water under high pressure after developing procedure, refuses China ink and be difficult for reducing.And then, be difficult for producing residual film.When the higher limit that m+j is above-mentioned scope is following, after refuse black agent (A) while curing and can not migrate to peristome, between partition wall, the ink affinity of peristome becomes fully, while using ink-jet method coating China ink, China ink is in peristome moistening diffusion fully.

Group (11) has m (R for meaning ²¹o) unit and j (R ²²o) group of unit, to (R ²¹o) unit and (R ²²o) bonding of unit sequentially is not particularly limited.In other words, in group (11), m (R ²¹o) unit and j (R ²²o) unit can be for example alternately or randomly or with the block form bonding.

In group (11), R ²³for can have the alkyl of substituent carbon number 1～10 time, its structure can be the structure of linear chain structure, branched structure, ring structure, part band etc.In addition, as substituting group, particularly, can list the alkoxy of carboxyl, hydroxyl, carbon number 1～5 etc.In the present invention, as the R in group (11) ²³, be preferably the straight chain of carbon number 1～5, non-substituted alkyl, be particularly preferably methyl and ethyl.

As (the R in group (11) ²¹o) and (R ²²o) object lesson, can list-CH ₂c ₆h ₁₀cH ₂in the O-(formula, C ₆h ₁₀for cyclohexenyl group.) ,-CH ₂o-,-CH ₂cH ₂o-,-CH ₂cH(CH ₃) O-,-CH(CH ₃) O-,-CH ₂cH ₂cH ₂o-,-C(CH ₃) ₂o-,-CH(CH ₂cH ₃) O-,-CH ₂cH ₂cH ₂cH ₂o-,-CH(CH ₂cH ₂cH ₃) O-,-CH ₂(CH ₂) ₃cH ₂o-,-CH(CH ₂cH(CH ₃) ₂) O-etc.As the object lesson of group (11), can list (R ²¹o) and (R ²²o) all being selected from the above oxyalkylene exemplified, m+j is 4～100 and R ²³for CH ₃group.

Group (11) can be used singly or in combination of two or more.In addition, about to refusing in black agent (A) to import the side chain with group (11), as described later, while utilizing the polymerization manufacture of starting monomer to refuse black agent (A), the monomer that will have a group (11) suitably is adjusted into and does not damage effect of the present invention and can carry out refusing black agent (A) to give the compounding amount of the effect that above-mentioned developability improves with respect to the compounding amount of starting monomer integral body.

Refuse black agent (A) and preferably there is olefinic double bond.Refuse black agent (A) while thering is olefinic double bond, what move to the film surface when dry refuses black agent (A) by this is refused black agent (A) maybe this refuses that black agent (A) reacts with alkali soluble resin (C) and the surface that easily is fixed on partition wall is preferred from this viewpoint each other when the exposure.

As olefinic double bond, can list the unsaturated group of the addition polymerizations such as (methyl) acryloyl group, allyl, vinyl, vinyl ether etc.The hydrogen atom of these groups can partly or entirely be replaced by alkyl.As alkyl, be preferably methyl.

Import the side chain with olefinic double bond and undertaken by following operation to refusing black agent (A): as described later, in starting monomer while to manufacture, refusing black agent (A), the monomer that the interpolation of compounding amount limit has reactive group is suitably adjusted on limit, carry out copolymerization, then make the gained multipolymer with having and can reacting with the functional group of previous reaction group bonding and the compound of olefinic double bond.

As refusing black agent (A), preferably at side chain, there is the compound that group (1) or group (2), main chain are hydrocarbon chain.Below, black agent (A) that to be also hydrocarbon chain by main chain refuse is called " refuses black agent (A ¹) ".

Refuse black agent (A ¹) for example by the starting monomer copolymerization by following, manufacture, described starting monomer comprise there is group (1) monomer (a1) or have group (2) monomer (a2), have as required acidic-group monomer (a3), there is as required the monomer (a4) of polyoxy alkylidene.

In addition, refuse black agent (A ¹) while thering is olefinic double bond, can manufacture by the following method: make in the above-mentioned raw materials monomer further to have added the starting monomer that monomer (a5) with reactive group forms and carry out copolymerization, then make the gained multipolymer with having and can reacting with the functional group of previous reaction group bonding and the compound of olefinic double bond (z1).

(monomer (a1))

As the monomer with group (1) (a1), be preferably following monomer (a11).

CH ₂=CR ⁶COO-Y-CFXR ^f （a11）

In formula, R ⁶mean hydrogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, methyl or trifluoromethyl.Y means the divalent organic group that does not comprise fluorine atom of singly-bound or carbon number 1～6, from obtaining easness, is preferably the alkylidene of carbon number 2～4.X and R ^fmean the implication identical with group (1), preferred form is also identical.

As the example of monomer (a11), can be listed below.

CH ₂=CR ⁶COOR ⁷CFXR ^f

CH ₂=CR ⁶COOR ⁸NR ⁹SO ₂CFXR ^f

CH ₂=CR ⁶COOR ¹⁰NR ¹¹COCFXR ^f

CH ₂=CR ⁶COOCH ₂CH（OH）R ¹²CFXR ^f

Herein, R ⁶mean implication same as described above, R ⁷, R ⁸and R ¹⁰the alkylidene that means carbon number 1～6, R ⁹and R ¹¹mean hydrogen atom or methyl, R ¹²the alkylidene that means singly-bound or carbon number 1～4.

As R ⁷, R ⁸and R ¹⁰object lesson, can list respectively-CH ₂-,-CH ₂cH ₂-,-CH(CH ₃)-,-CH ₂cH ₂cH ₂-,-C(CH ₃) ₂-,-CH(CH ₂cH ₃)-,-CH ₂cH ₂cH ₂cH ₂-,-CH(CH ₂cH ₂cH ₃)-,-CH ₂(CH ₂) ₃cH ₂-,-CH(CH ₂cH(CH ₃) ₂)-etc.

As R ¹²object lesson, can list-CH ₂-,-CH ₂cH ₂-,-CH(CH ₃)-,-CH ₂cH ₂cH ₂-,-C(CH ₃) ₂-,-CH(CH ₂cH ₃)-,-CH ₂cH ₂cH ₂cH ₂-,-CH(CH ₂cH ₂cH ₃)-etc.

As the object lesson of monomer (a11), can list (methyl) acrylic acid-2-(perfluoro hexyl) ethyl ester, (methyl) acrylic acid-2-(perfluoro butyl) ethyl ester etc.

Monomer (a11) can be used singly, or in combination of two or more kinds.

(monomer (a2))

As the monomer with group (2) (a2), be preferably following monomer (a21).

CH ₂=CR ¹³COO-Z-（SiR ¹R ²-O） _n-SiR ³R ⁴R ⁵ （a21）

In formula, R ¹³mean hydrogen atom or methyl, Z means the divalent organic group of singly-bound or carbon number 1～6.R ¹, R ², R ³, R ⁴and R ⁵and n means the implication identical with group (2), preferred form is also identical.

Z is preferably the divalent alkyl of carbon number 1～6.As object lesson, can list-CH ₂-,-CH ₂cH ₂-,-CH(CH ₃)-,-CH ₂cH ₂cH ₂-,-C(CH ₃) ₂-,-CH(CH ₂cH ₃)-,-CH ₂cH ₂cH ₂cH ₂-,-CH(CH ₂cH ₂cH ₃)-,-CH ₂(CH ₂) ₃cH ₂-,-CH(CH ₂cH(CH ₃) ₂)-etc.

As the object lesson of monomer (a21), can list CH ₂=CHCOO-CH ₂cH ₂-(Si(CH ₃) ₂-O) _n-Si(CH ₃) ₃, CH ₂=CCH ₃cOO-CH ₂cH ₂-(Si(CH ₃) ₂-O) _n-Si(CH ₃) ₃, CH ₂=CHCOO-CH ₂cH ₂cH ₂-(Si(CH ₃) ₂-O) _n-Si(CH ₃) ₃, CH ₂=CCH ₃cOO-CH ₂cH ₂cH ₂-(Si(CH ₃) ₂-O) _n-Si(CH ₃) ₃deng.It should be noted that, n is about 4,60,160.

As monomer (a21), can use commercially available product.As commercially available product, can list the following material of arbitrary trade name.KCC of X-22-174DX(SHIN-ETSU HANTOTAI system), KCC of X-22-2426(SHIN-ETSU HANTOTAI system), KCC of X-22-2475(SHIN-ETSU HANTOTAI system).

Monomer (a21) can be used singly, or in combination of two or more kinds.

(monomer (a3))

Refuse black agent (A ¹) while thering is acidic-group, preferably make monomer (a1)～(a2) carry out copolymerization together with the monomer with acidic-group (a3).

As the monomer with acidic-group (a3), can list monomer, the monomer with phenol hydroxyl with carboxyl, there is sulfonic monomer etc.

As the monomer with carboxyl, can list acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt etc.

As the monomer with phenol hydroxyl, can list o-hydroxy ethene, a hydroxy styrenes, 4-Vinyl phenol etc.Perhaps 1 of their phenyl ring above hydrogen atom is by alkyl such as methyl, ethyl, normal-butyls; The alkoxys such as methoxyl, ethoxy, n-butoxy; The compound that the haloalkyl that 1 above hydrogen atom of halogen atom, alkyl is replaced by halogen atom, nitro, cyano group, amide group replace etc.

As thering is sulfonic monomer, can list vinyl sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propane sulfonic acid, (methyl) acrylic acid-2-sulphur ethyl ester, (methyl) acrylic acid-2-sulphur propyl ester, 2-hydroxyl-3-(methyl) acryloxy propane sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic.

As monomer (a3), from the viewpoint of easily obtaining, be preferably acrylic or methacrylic acid.

Monomer (a3) can be used singly, or in combination of two or more kinds.

(monomer (a4))

As refusing black agent (A ¹) manufacture in the monomer with group (11) that uses, be preferably the compound shown in following formula (12) (following also referred to as compound (12).) or (13) shown in compound (following also referred to as compound (13).）。They can be used singly or in combination of two or more.

CH ₂=CR ²⁴-COO-W-（R ²¹O） _m（R ²²O） _jR ²³ （12）

CH ₂=CR ²⁵-O-W-（R ²¹O） _m（R ²²O） _jR ²³ （13）

In formula (12) and (13), R ²⁴and R ²⁵be respectively the alkyl of hydrogen atom, chlorine atom, bromine atoms, iodine atom, cyano group, carbon number 1～20, alkyl, the aryl of carbon number 6～20 or the naphthenic base of carbon number 3～20 replaced by the aryl of carbon number 7～20.W is the divalent organic group that does not have fluorine atom that singly-bound or carbon number are 1～10.-(R ²¹o) _m(R ²²o) _jr ²³group (11), R ²¹, R ²², R ²³, m and j mean the meaning identical with group (11), preferred scope is also identical.

In compound (12) and compound (13), W be carbon number be 1～10 do not there is the divalent organic group of fluorine atom the time, can list except R ²¹o, R ²²there are oxyalkylene that linear chain structure, branched structure, ring structure, part are 1～10 with the carbon number of ring structure, singly-bound etc. beyond O.As oxyalkylene, particularly, can list CH ₂c ₆h ₁₀cH ₂in the O(formula, C ₆h ₁₀for cyclohexenyl group.), CH ₂o, CH ₂cH ₂o, CH ₂cH(CH ₃) O, CH(CH ₃) O, CH ₂cH ₂cH ₂o, C(CH ₃) ₂o, CH(CH ₂cH ₃) O, CH ₂cH ₂cH ₂cH ₂o, CH(CH ₂cH ₂cH ₃) O, CH ₂(CH ₂) ₃cH ₂o, CH(CH ₂cH(CH ₃) ₂) O etc.Wherein, as the W in compound (12) and (13), from the viewpoint of easily obtaining, be preferably the oxyalkylene that carbon number is 2～4.

In compound (12) and (13), R ²⁴and R ²⁵be preferably respectively hydrogen atom, chlorine atom, methyl, phenyl, benzyl etc., be particularly preferably hydrogen atom, chlorine atom or methyl.

Compound as shown in compound (12), can be listed below.

CH ₂=CHOCH ₂C ₆H ₁₀CH ₂O（CH ₂CH ₂O） _mR ²³、

CH ₂=CHO（CH ₂） ₄O（CH ₂CH ₂O） _mR ²³。

Compound as shown in compound (13), can be listed below.

CH ₂=CHCOO（CH ₂CH ₂O） _mR ²³、

CH ₂=C（CH ₃）COO（CH ₂CH ₂O） _mR ²³、

CH ₂=CHCOO（CH ₂CH ₂O） _m（C ₃H ₆O） _jR ²³、

CH ₂=C（CH ₃）COO（CH ₂CH ₂O） _m（C ₃H ₆O） _jR ²³、

CH ₂=CHCOO（C ₂H ₄O） _m（C ₄H ₈O） _jR ²³。

In formula, m and j mean the implication identical with group (11), and preferred scope is also identical.C ₆h ₁₀for cyclohexenyl group.C ₂h ₄, C ₃h ₆, C ₄h ₈for any in linear chain structure or branched structure.R ²³mean the implication identical with group (11), about preferred scope, be preferably the straight chain of carbon number 1～10, non-substituted alkyl, be particularly preferably methyl.

As compound (12) and (13), can use commercially available product.As commercially available product, can be listed below.

BLEMMER PME-400(trade name, NOF Corp's system, CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kcH ₃.K in formula means intermolecular mean value, and the value of k is about 9.Below, the k in the molecular formula of each commercially available product, m, j all mean intermolecular mean value.), BLEMMER PME-1000(trade name, NOF Corp's system, CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kcH ₃.K in formula means intermolecular mean value, and the value of k is 23.), NK ESTER M-230G:(trade name ,Xin Zhong village KCC system, CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kcH ₃.In formula, k is about 9.), New Frontier NF Bisomer PEM6E(trade name, Di-ichi Kogyo Seiyaku Co., Ltd.'s system, CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kh: in formula, k is about 6.), LIGHT ESTER130A(trade name, Kyoeisha Chemical Co., Ltd.'s system, CH ₂=CHCOO(CH ₂cH ₂o) _kcH ₃.In formula, k is about 9.), BLEMMER AE-400(trade name, NOF Corp's system, CH ₂=CHCOO(CH ₂cH ₂o) _kh: in formula, k is about 10.), BLEMMER PP-800(trade name, NOF Corp's system, CH ₂=C(CH ₃) COO(C ₃h ₆o) _kh.In formula, k is about 13.), BLEMMER AP-800(trade name, NOF Corp's system, CH ₂=CHCOO(C ₃h ₆o) _kh.In formula, k is about 13.), BLEMMER70PEP-350B(trade name, NOF Corp's system, CH ₂=C(CH ₃) COO(C ₂h ₄o) _m(C ₃h ₆o) _jh.In formula, m is about 5, j is about 2.), BLEMMER55PET-800(trade name, NOF Corp's system, CH ₂=C(CH ₃) COO(C ₂h ₄o) _m(C ₄h ₈o) _jh.In formula, m is about 10, j is about 5.）。

(monomer (a5))

As the monomer with reactive group (a5), can list monomer, the anhydride monomers with olefinic double bond, the monomer with carboxyl with hydroxyl, there is the monomer of epoxy radicals etc.It should be noted that, monomer (a5) does not preferably comprise in fact group (1) and group (2).

As the monomer with acidic-group (a3), use has the monomer of carboxyl, as the above-mentioned monomer (a5) with reactive group, also use while thering is the monomer of carboxyl, using final importing of olefinic double bond and residual monomer is considered as monomer (a3) as carboxyl.

The reactive group that monomer after copolymerization (a5) has is with having and can react with the functional group of this reactive group bonding and the compound of olefinic double bond (z1), forms thus the black agent (A that refuses that possesses side chain with olefinic double bond ¹).

Object lesson as the monomer with hydroxyl, can list (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-3-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid-5-hydroxy pentane ester, (methyl) acrylic acid-own ester of 6-hydroxyl, (methyl) acrylic acid-4-hydroxyl cyclohexyl, neopentyl glycol single (methyl) acrylate, the chloro-2-hydroxypropyl acrylate of (methyl) acrylic acid-3-, glycerine list (methyl) acrylate, 2-hydroxyethyl vinethene, 4-hydroxyl butyl vinyl ether, cyclohexanediol list vinethene, 2-hydroxyethyl allyl ether, N-methylol (methyl) acrylamide, N, two (methylol) (methyl) acrylamides of N-etc.

And then, as the monomer with hydroxyl, can be the monomer with polyoxy alkylidene that end is hydroxyl.For example can list CH ₂=CHOCH ₂c ₆h ₁₀cH ₂o(C ₂h ₄o) _hh(herein, the integer that h is 1～100, below identical.), CH ₂=CHOC ₄h ₈o(C ₂h ₄o) _hh, CH ₂=CHCOOC ₂h ₄o(C ₂h ₄o) _hh, CH ₂=C(CH ₃) COOC ₂h ₄o(C ₂h ₄o) _hh, CH ₂=CHCOOC ₂h ₄o(C ₂h ₄o) _i(C ₃h ₆o) _gh(herein, the integer that i is 0～100, the integer that g is 1～100, i+g is 1～100.Below identical.), CH ₂=C(CH ₃) COOC ₂h ₄o(C ₂h ₄o) _i(C ₃h ₆o) _gh etc.

Object lesson as the anhydride monomers with olefinic double bond, can list maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norborene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, cis-1,2,3,6-tetrabydrophthalic anhydride, 2-butene-1-Ji succinic anhydride etc.

As the object lesson of the monomer with carboxyl, can list acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or their salt.

As the object lesson of the monomer with epoxy radicals, can list (methyl) glycidyl acrylate, acrylic acid-3,4-epoxy radicals cyclohexyl methyl esters.

(monomer (a6))

In the monomer used in polymerization of the present invention, comprise there is group (1) monomer (a1) or have group (2) monomer (a2), have as required acidic-group monomer (a3), there is as required the monomer (a4) of polyoxy alkylidene and then refuse black agent (A ¹) while thering is olefinic double bond, comprise the monomer (a5) with reactive group, also can comprise other monomer (a6) except these monomers.

As monomer (a6), can list hydrocarbon system olefines, ethene ethers, isopropyl alkene ethers, allyl ethers, vinyl ester, allyl ester class, (methyl) esters of acrylic acid, (methyl) acrylic amide, aromatic ethenyl compound, chloro-alkenes class, conjugated diene.Can comprise functional group in these compounds, as functional group, such as listing carbonyl, alkoxy etc.From the excellent heat resistance of partition wall, particularly preferably (methyl) esters of acrylic acid or (methyl) acrylic amide.

It should be noted that, for example, as the above-mentioned monomer with epoxy radicals that has the monomer (a5) of reactive group and list, (methyl) glycidyl acrylate, methacrylic acid 3,4-epoxy radicals cyclohexyl etc. also can be used as monomer (a6).In other words, while using these to have the monomer of epoxy radicals in polymerization of the present invention, in the situation that do not import olefinic double bond after copolymerization, the monomer that these are had to epoxy radicals is categorized as other monomer (a6).In addition, even in the situation that imported olefinic double bond, will finally not import olefinic double bond and residual monomer is considered as other monomer (a6) with the form of epoxy radicals yet.

(refuse black agent (A ¹) manufacture)

Refuse black agent (A ¹) for example can utilize following methods to synthesize.At first, by monomer, be dissolved in solvent and heating, add polymerization initiator and carry out copolymerization.In copolyreaction, preferably there is as required chain-transferring agent.Monomer, polymerization initiator, solvent and chain-transferring agent also can continuous addings.

As aforementioned solvents, can list the alcohols such as ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, ethylene glycol, the ketones such as acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, the cellosolve classes such as 2-methyl cellosolve, cellosolvo, butoxy ethanol, the 2-(2-methoxy ethoxy) ethanol, Transcutol, 2-(2-butoxy ethoxy) the carbitol class such as ethanol, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, the glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, the diethylene glycol monomethyl ether acetate, diethylene glycol ether acetate alone, the diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, ethylene diacetate, PGDA, ethyl-3-ethoxy-c acid esters, cyclohexanol acetic ester, butyl lactate, gamma-butyrolacton, 3-methyl-3-methoxyl butylacetic acid ester, ethyl lactate, n-butyl lactate, gamma-butyrolacton, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, the ester classes such as triacetin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, TRIGLYME, tetraethyleneglycol dimethyl ether, Propylene Glycol Dimethyl Ether, dipropylene glycol dimethyl ether, butyl oxide, diethylene glycol ethylmethyl ether etc.

As polymerization initiator, can list known organic peroxide, inorganic peroxide, azo-compound etc.Organic peroxide, inorganic peroxide also can combine with reductive agent, as the redox series catalysts, use.

As organic peroxide, can list benzoyl peroxide, lauroyl peroxide, peroxidating isobutyryl, tert-butyl hydroperoxide, the tert-butyl group-α-cumyl peroxide etc.As inorganic peroxide, can list ammonium persulfate, sodium peroxydisulfate, potassium persulfate, hydrogen peroxide, percarbonate etc.As azo-compound, can list 2,2 '-azoisobutyronitrile, 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2, two (4-methoxyl-2 of 2 '-azo, the 4-methyl pentane nitrile), 2, the two isobutyric acid dimethyl esters, 2 of 2 '-azo, two (2-amidine propane) dihydrochlorides of 2 '-azo etc.

As chain-transferring agent, can list the thio-alcohols such as normal-butyl mercaptan, n-dodecyl mercaptan, tert-butyl mercaptan, mercapto-ethyl acetate, thioglycolic acid-2-Octyl Nitrite, 2 mercapto ethanol; The alkyl halides such as chloroform, phenixin, carbon tetrabromide.

In addition, refuse black agent (A ¹) while thering is olefinic double bond, make to operate as described above and the multipolymer that obtains with having and can reacting with the functional group of reactive group bonding and the compound of olefinic double bond (z1), obtain thus refusing black agent (A ¹).

As with respect to reactive group, with have can with the combination of the functional group of this reactive group bonding and the compound of olefinic double bond (z1), for example can list following combination.

(1) with respect to hydroxyl, have olefinic double bond acid anhydrides,

(2) with respect to hydroxyl, have isocyanate group and olefinic double bond compound,

(3) with respect to hydroxyl, have acid chloride group and olefinic double bond compound,

(4) with respect to acid anhydrides, have hydroxyl and olefinic double bond compound,

(5) with respect to carboxyl, have epoxy radicals and olefinic double bond compound,

(6), with respect to epoxy radicals, there is the compound of carboxyl and olefinic double bond.

After epoxy radicals and the compound with carboxyl and olefinic double bond are reacted, make to have in generated hydroxyl and 1 molecule the anhydride reaction of the compound of 2 above carboxyls, also can be to refusing black agent (A ¹) the middle acidic-group that imports.

As the object lesson of the acid anhydrides with olefinic double bond, can list above-mentioned example.As the object lesson of the compound with isocyanate group and olefinic double bond, can list the 2-(methyl) acryloxy ethyl isocyanate, 1, two ((methyl) acryloyl-oxy ylmethyl) ethyl isocyanates of 1-.As the object lesson of the compound with acid chloride group and olefinic double bond, can list (methyl) acryloyl chloride.As the object lesson of the compound with hydroxyl and olefinic double bond, can list the above-mentioned example with monomer of hydroxyl.As the object lesson of the compound with epoxy radicals and olefinic double bond, can list the above-mentioned example with monomer of epoxy radicals.As the object lesson of the compound with carboxyl and olefinic double bond, can list the above-mentioned example with monomer of carboxyl.In addition, as the object lesson of the acid anhydrides of the compound that there are 2 above carboxyls in 1 molecule, can list the example of the acid anhydrides with olefinic double bond shown in above-mentioned monomer (a5).

Make the multipolymer can be with the functional group of reactive group bonding and the compound of olefinic double bond (z1) while reacting with having, as the solvent used in reaction, can use the solvent exemplified in above-mentioned multipolymer synthetic.

In addition, preferred compounding polymerization inhibitor.As polymerization inhibitor, for example can list BHT, tert-butyl group 1,4-benzoquinone.

In addition, also can add catalyzer, neutralizing agent.For example, when the multipolymer that makes to have hydroxyl reacts with the compound with isocyanate group and olefinic double bond, can use the tin compound such as dibutyl tin laurate etc.When the multipolymer that makes to have hydroxyl reacts with the compound with acid chloride group and olefinic double bond, can use base catalyst.

With respect to the preferred ratio of each monomer of the monomer gross mass of wanting copolymerization as described below.The ratio of monomer (a1) or monomer (a2) is preferably 20～80 quality %, is particularly preferably 30～60 quality %.When the lower limit that this ratio is above-mentioned scope is above, refuse black agent (A ¹) can reduce the surface tension by the curing film formed partition wall formed, can give height to partition wall and refuse China ink.When the higher limit that this ratio is above-mentioned scope is following, it is good that the adaptation of partition wall and base material becomes.

While comprising monomer (a3), its ratio is preferably 2～20 quality %, is particularly preferably 4～12 quality %.During for above-mentioned scope, it is good that the developability of negative light-sensitive resin combination becomes.

While comprising monomer (a4), its ratio is preferably 5～70 quality %, and more preferably 10～60 quality %, be particularly preferably 15～50 quality %.During for above-mentioned scope, even in the situation that improve pressure in developing procedure, also can maintain liquid-repellant.And then, can prevent residual film.

While comprising monomer (a5), its ratio is preferably 20～70 quality %, is particularly preferably 30～50 quality %.While by the polymerized unit that is derived from the monomer (a5) comprised with above-mentioned scope, importing olefinic double bond, refuse black agent (A ¹) immobilization and the developability on partition wall surface become to good.

While comprising other monomer (a6), its ratio is preferably below 70 quality %, is particularly preferably below 50 quality %.During for above-mentioned scope, alkali dissolubility, developability are good.

Refuse black agent (A ¹) manufacture in the preferred compositions of monomer as follows.

(combining 1)

Monomer (a1): be selected from (methyl) acrylic acid-2-(perfluoro butyl) ethyl ester and (methyl) acrylic acid-2-(perfluoro hexyl) in the group that forms of ethyl ester at least a kind,

Monomer (a3): be selected from least a kind in the group that acrylic acid and methacrylic acid form,

Monomer (a4): be selected from least a kind in the group that BLEMMER PME-400 and BLEMMER PME-1000 form,

Monomer (a5): (methyl) 2-Hydroxy ethyl acrylate.

Make above-mentioned monomer copolymerization and after obtaining multipolymer, with be selected from the 2-(methyl) at least a kind of compound that reacts and import olefinic double bond in the group that forms of two ((methyl) acryloyl-oxy ylmethyl) ethyl isocyanates of acryloxy ethyl isocyanate and 1,1-.

(combining 2)

Monomer as required (a6): be selected from (methyl) glycidyl acrylate, methacrylic acid 3, in the group that 4-epoxy radicals cyclohexyl, (methyl) methyl acrylate, (methyl) isobornyl acrylate and (methyl) cyclohexyl acrylate form at least a kind.

(combining 3)

Monomer (a5): (methyl) glycidyl acrylate

Monomer (a6): be selected from methacrylic acid-3, in the group that 4-epoxy radicals cyclohexyl, (methyl) methyl acrylate, (methyl) isobornyl acrylate and (methyl) cyclohexyl acrylate form at least a kind.

Make above-mentioned monomer copolymerization and after obtaining multipolymer, with be selected from the group that acrylic acid and methacrylic acid form at least a kind react, then, with be selected from 3,4,5,6-tetrabydrophthalic anhydride and cis-1, at least a kind of compound that has reacted and imported acidic-group and olefinic double bond in the group that 2,3,6-tetrabydrophthalic anhydride forms.

(combining 4)

Monomer (a2): be selected from least a kind in the group that X-22-174DX, X-22-2426 and X-22-247 form,

Monomer (a5): (methyl) 2-Hydroxy ethyl acrylate.

(combining 5)

Monomer (a5): (methyl) 2-Hydroxy ethyl acrylate.

Refuse black agent (A ¹) while having olefinic double bond, multipolymer and compound (z1) preferably reach 0.5～2.0 mode with the value of the equivalent proportion of [functional group of compound (z1)]/[reactive group of multipolymer] and drop into, and are particularly preferably 0.8～1.5.When above, refuse black agent (A for the lower limit of above-mentioned scope ¹) immobilization of partition wall is become to good.For the higher limit of above-mentioned scope when following, it is many that unreacted compound (z1) is that impurity becomes, and appearance of film worsens.It should be noted that, when both all use the monomer with carboxyl as monomer (a3) and monomer (a4), regulate the input amount of multipolymer and compound (z1) and make and refuse black agent (A ¹) acid number reach setting and get final product.

Refuse black agent (A ¹) while thering is group (1), refuse black agent (A ¹) in the containing ratio of fluorine atom be preferably 5～50 quality %, more preferably 10～40 quality %, be particularly preferably 20～35 quality %.When above, refuse black agent (A for the lower limit of above-mentioned scope ¹) reduce the capillary effect excellence of partition wall, can obtain refusing the partition wall of China ink excellence.For the higher limit of above-mentioned scope, when following, it is good that the adaptation of partition wall and base material becomes.

Refuse black agent (A ¹) while thering is group (2), refuse black agent (A ¹) in the containing ratio of silicon atom be preferably 0.1～25 quality %, be particularly preferably 0.5～10 quality %.When above, refuse black agent (A for the lower limit of above-mentioned scope ¹) give the capillary effect that reduces formed partition wall and the effect that improves black deciduous.For the higher limit of above-mentioned scope, when following, it is good that the adaptation of partition wall and base material becomes.

Refuse black agent (A ¹) acid number be preferably below 150mgKOH/g, be particularly preferably 10～100mgKOH/g.During for above-mentioned scope, can take into account the dissolubility of negative light-sensitive resin combination in developer solution and refuse manifesting of China ink.

Refuse black agent (A1) while comprising olefinic double bond, its amount is preferably 0.5 * 10 ^-3～5 * 10 ^-3mol/g, be particularly preferably 1 * 10 ^-3～4.5 * 10 ^-3mol/g.During for above-mentioned scope, refuse black agent (A ¹) immobilization and the developability of partition wall become to good.

Refuse black agent (A ¹) number-average molecular weight (Mn) be preferably 5 * 10 ³～10 * 10 ⁴, more preferably 8 * 10 ³～9 * 10 ⁴, be particularly preferably 1 * 10 ⁴～7 * 10 ⁴.During for above-mentioned scope, alkali dissolubility, developability are good.

Refuse black agent (A ¹) matter average molecular weight (Mw) be preferably 1.2 * 10 ⁴～20 * 10 ⁴, more preferably 2 * 10 ⁴～15 * 10 ⁴, be particularly preferably 3 * 10 ⁴～12 * 10 ⁴.During for above-mentioned scope, alkali dissolubility, developability are good.

As refusing black agent (A), also preferably at side chain, there is the compound that group (1), main chain are the organopolysiloxane chain in addition.Below, by main chain, be also that the black agent (A) of refusing of organopolysiloxane chain is called and " refuses black agent (A ²) ".

Refuse black agent (A as this ²), preferably the partial hydrolysis condensation product by water-disintegrable silane compound potpourri or this potpourri forms, described water-disintegrable silane compound potpourri comprise the water-disintegrable silane compound shown in following formula (14) (below, also referred to as silane compound (a7).) or its partial hydrolysis condensation product and following formula (15) shown in water-disintegrable silane compound (below, also referred to as silane compound (a8).) or its partial hydrolysis condensation product.

R ^f-CFX-Q ¹-SiX ¹ ₃…（14）

R ^H1 _p-SiX ² _（4-p）…15）

(symbol in formula (14) and (15) as described below.

X and R ^fit is same as described above,

Q ¹: the divalent organic group that does not comprise fluorine atom of carbon number 1～10,

R ^h1: the alkyl of carbon number 1～6,

X ¹, X ²: hydrolization group,

P:0,1 or 2,

Wherein, 3 X in formula (14) ¹, (4-p) the individual X in formula (15) ², a p R ^h1respectively can be different, also can be identical.）

Refuse black agent (A ²) in the containing ratio of fluorine atom be preferably 10～55 quality %, 12～40 quality % more preferably, be particularly preferably 15～30 quality %, when the containing ratio of fluorine atom is above-mentioned scope, can give the excellent ultra-violet resistance/ozone resistance of refusing China ink and refusing China ink to the partition wall obtained by negative light-sensitive resin combination.

Refuse black agent (A ²) preferably there is the silanol group hydroxyl of silicon atom bonding (that is, with).As the quantity of silanol group, with respect to each silicon atom, be preferably 0.2～3.5, more preferably 0.2～2, be particularly preferably 0.5～1.5.When above, when using negative light-sensitive resin combination to form partition wall, can prevent from refusing black agent (A for the lower limit of above-mentioned scope ²) from substrate surface, break away from.When following, refuse black agent (A for the higher limit of above-mentioned scope ²) in negative light-sensitive resin combination with the compatibility excellence of solvent, other composition.

It should be noted that, refuse black agent (A ²) in the quantity of silanol group can be by utilizing ²⁹the Si base with silanol group that Si-NMR measures is calculated with the ratio of the peak area of the Si base that does not have silanol group.

Aforementioned water-disintegrable silane compound potpourri comprises silane compound (a7) or its partial hydrolysis condensation product and silane compound (a8) or its partial hydrolysis condensation product.

The partial hydrolysis condensation product of water-disintegrable silane compound refers to multi-functional water-disintegrable silane compound hydrolysis, the heavy polymer of degree in the oligomer (polymer) then generated by dehydrating condensation, that be dissolved in solvent.In addition, the lower polymer of 2～4 aggressiveness equimolecular quantitys of water-disintegrable silane compound is also the partial hydrolysis condensation product in the present invention.The partial hydrolysis condensation product sometimes also has that hydrolysis occurs hydrolization group and the silanol group that generates, has unreacted hydrolization group.The partial hydrolysis condensation product that molecular weight is higher mainly has silanol group, and the partial hydrolysis condensation product that molecular weight is lower also has hydrolization group sometimes.

The result that the partial hydrolysis condensation product has further condensation, a hydrolysis finally becomes the character of the high molecular solidfied material that is insoluble to solvent.The partial hydrolysis condensation product can be also the potpourri of the oligomer that the degree of polymer is different.

The partial hydrolysis condensation product can by such as by water-disintegrable silane compound under the existence of acid catalyst and water, stir stipulated time etc. manufacture under the temperature of reaction condition of regulation.The degree of the polymer of resulting partial hydrolysis condensation product can suitably be adjusted by acid concentration, temperature of reaction, reaction time etc.

It should be noted that, mol ratio about the ratio that means following water-disintegrable silane compound, in the situation that in following water-disintegrable silane compound at least any one is the partial hydrolysis condensation product, above-mentioned mol ratio is the quantity ratio that is derived from the silicon atom of each water-disintegrable silane compound.

(the water-disintegrable silane compound shown in formula (14))

As shown in aforementioned formula (14), silane compound (a7) is for having the water-disintegrable silane compound of group (1).In aforementioned formula (14), Q ¹for linking group (1) and water-disintegrable silicyl (SiX ¹ ₃) the divalent organic group, be the divalent organic group that does not comprise fluorine atom of carbon number 1～10.Q ¹with the atomic link bonding Si on right side, at the atomic link bonding R in left side ^fwhen the form of-CFX-means, particularly, be preferably-(CH ₂) _i1-(the integer that i1 is 1～5.) ,-CH ₂o(CH ₂) _i2-(the integer that i2 is 1～4.) ,-SO ₂nR ¹-(CH ₂) _i3-(R ¹for hydrogen atom, methyl or ethyl, i3 is more than 1, with R ¹the summation of carbon number be the integer below 4.) ,-(C=O)-NR ¹-(CH ₂) _i4-(R ¹same as described above, i4 is more than 1, with R ¹the summation of carbon number be the integer below 4.) represented group.As Q ¹, more preferably i1 be 2 or 3-(CH ₂) _i1-, be particularly preferably-(CH ₂) ₂-.

During perfluoroalkyl that group (1) is carbon number 1～6, as above-mentioned Q ¹, be preferably-(CH ₂) _i1the represented group of-(i1 is same as described above).I1 is preferably 2～4 integer, particularly preferably i1 be 2-(CH ₂) ₂-.

During perfluoroalkyl that group (1) is the carbon number 4～9 that comprises etheric oxygen atom, as above-mentioned Q ¹, be preferably-(CH ₂) _i1-,-CH ₂o(CH ₂) _i2-,-SO ₂nR ¹-(CH ₂) _i3-,-(C=O)-NR ¹-(CH ₂) _i4-represented group (i1～i4 and R ¹same as described above).Now, be particularly preferably-(CH ₂) ₂-.

In formula (14), X ¹mean the hydrolization group with silicon atom bonding.As X ¹, can list the group that alkoxy, halogen atom, acyl group, isocyanate group, amino and amino hydrogen are replaced by alkyl.Be preferably the alkoxy or halogen atom of carbon number 1～4, be particularly preferably methoxyl, ethoxy, chlorine atom.This group becomes hydroxyl (silanol group) by hydrolysis reaction, and then easily successfully carries out in the intermolecular reaction of carrying out condensation reaction and forming the Si-O-Si key.

As the object lesson of silane compound (a7), can list following compound.

F（CF ₂） ₄CH ₂CH ₂Si（OCH ₃） ₃、F（CF ₂） ₄CH ₂CH ₂Si（OCH ₂CH ₃） ₃、F（CF ₂） ₄CH ₂CH ₂SiCl ₃、F（CF ₂） ₆CH ₂CH ₂Si（OCH ₃） ₃、F（CF ₂） ₆CH ₂CH ₂Si（OCH ₂CH ₃） ₃、F（CF ₂） ₆CH ₂CH ₂SiCl ₃。

CF ₃OCF ₃CF ₂CF ₂CH ₂CH ₂Si（OCH ₃） ₃、F（CF ₂） ₂OCF ₂CF ₂OCF ₂CF ₂OCF ₂CF ₂OCF ₂CH ₂CH ₂Si（OCH ₂CH ₃） ₃、CF ₃OCF（CF ₃）CF ₂CH ₂CH ₂CH ₂Si（OCH ₃） ₃。

F（CF ₂） ₂OCF ₂CF ₂OCF ₂CH ₂CH ₂CH ₂Si（OCH ₃） ₃、F（CF ₂） ₂O（CF ₂） ₂O（CF ₂） ₂CH ₂CH ₂Si（OCH ₃） ₃。

F（CF ₂） ₃OCF ₂CF ₂CH ₂CH ₂SiCl ₃、F（CF ₂） ₃OCF（CF ₃）CF ₂O（CF ₂） ₂CH ₂CH ₂Si（OCH ₃） ₃。

As silane compound (a7), wherein, be particularly preferably F(CF ₂) ₆cH ₂cH ₂si(OCH ₃) ₃, F(CF ₂) ₆cH ₂cH ₂si(OCH ₂cH ₃) ₃, F(CF ₂) ₆cH ₂cH ₂siCl ₃, F(CF ₂) ₃oCF(CF ₃) CF ₂o(CF ₂) ₂cH ₂cH ₂si(OCH ₃) ₃deng.

As the water-disintegrable silane compound comprised in water-disintegrable silane compound potpourri, silane compound (a7) can be used singly or in combination of two or more.

In addition, aforementioned water-disintegrable silane compound potpourri also can contain the partial hydrolysis condensation product of silane compound (a7).But, with the partial hydrolysis condensation product, compare, more preferably silane compound (a7) monomer.

(the water-disintegrable silane compound shown in formula (15))

Silane compound (a8) shown in aforementioned formula (15) is used as with above-mentioned silane compound (a7) the water-disintegrable silane compound comprised in water-disintegrable silane compound potpourri jointly.

In formula (15), R ^h1be preferably the alkyl of carbon number 1～4, more preferably methyl or ethyl, be particularly preferably methyl.As the R beyond alkyl ^h1, can list the thiazolinyls such as vinyl, allyl; The alkyl of the band such as phenyl, naphthenic base.

X ²for hydrolization group, comprise the X in optimal way and above formula (15) ¹identical.P is 0,1 or 2.Wherein, 2 R that p is 2 o'clock ^h1with (4-p) individual X ²each other can be different, also can be identical.

The 3 functionality compounds that silane compound (a8) the 4 functionality compounds that preferably p is 0 or p are 1.

Refuse black agent (A ²) by the group (1) that is derived from silane compound (a7) and the R that is derived from silane compound (a8) ^h1and show water repellency, mainly by group (1), show oil repellent.In addition, in order to make to refuse black agent (A ²) solidfied material show sufficient oil repellent, preferably, group (1) is with respect to refusing black agent (A ²) in group (1) and R ^h1the ratio of summation high.During p=0, refuse black agent (A ²) in the ratio of group (1) uprise, oil repellent improves, and makes in addition the film excellence., by there is R to a certain degree in p=1 or 2 o'clock ^h1, refuse black agent (A ²) becoming easily is dissolved in the hydrocarbon system solvent, while on the surface of substrate, forming filming of negative light-sensitive resin combination, can select more cheap solvent.

As silane compound (a8), be preferably following compound.In addition, can use the partial hydrolysis condensation product of silane compound (a8) to replace silane compound (a8).As the partial hydrolysis condensation product, be preferably the compound that molecular weight is lower.As the partial hydrolysis condensation product, for example can list following material.

Si（OCH ₃） ₄、Si（OCH ₂CH ₃） ₄、CH ₃Si（OCH ₃） ₃、

CH ₃Si（OCH ₂CH ₃） ₃、CH ₃CH ₂Si（OCH ₃） ₃、

CH ₃CH ₂Si（OCH ₂CH ₃） ₃、（CH ₃） ₂Si（OCH ₃） ₂、

（CH ₃） ₂Si（OCH ₂CH ₃） ₂、（C ₆H ₅）Si（OCH ₂CH ₃） ₃、

Si(OCH ₃) ₄partial hydrolysis condensation product (for example, COLCOAT CO., the Methyl Silicate51(trade name of Ltd system)),

Si(OCH ₂cH ₃) ₄partial hydrolysis condensation product (for example, COLCOAT CO., Ethyl Silicate40, the Ethyl Silicate48(of Ltd system are trade name)).

As the water-disintegrable silane compound comprised in water-disintegrable silane compound potpourri of the present invention, silane compound (a8) can be used singly or in combination of two or more.While being used in combination two or more, can also be by 4 functionality compounds and/or 3 functionality compounds and the use of 2 functionality compound combinations.

The content of the silane compound (a8) in water-disintegrable silane compound potpourri is preferably 0.1～9 mole of silane compound (a8) with respect to 1 mole of silane compound (a7), is particularly preferably 0.5～9 mole.And then the water-disintegrable silane compound that also can comprise except silane compound (a7) and silane compound (a8) is (following also referred to as silane compound (a9).), the partial hydrolysis condensation product of silane compound (a9).

(silane compound (a9))

As silane compound (a9), so long as there is 2 functionalities of hydrolization group or the silane compound of 3 functionalities, be and the compound of silane compound (a7) and silane compound (a8) cocondensation just can use known silane compound.

As silane compound (a9), be preferably the alkyl that there is in aforementioned formula (15) with carbon number the alkyl more than 7, replaced by reactive group and replace R ^h1the silane compound of structure.Wherein, the p in formula (15) is 2 o'clock, 2 R ^h1in 1 can be R ^h1.As reactive group, be preferably (methyl) acryloxy, amino, alkyl substituted-amino, epoxy radicals etc.Be particularly preferably (methyl) acryloxy etc. and there is the reactive group of olefinic double bond.

Preferred silane compound (a9) is the water-disintegrable silane compound that possesses the reactive group with olefinic double bond, is particularly preferably trialkoxy silane, dialkoxy silicane with (methyl) acryloxy substituted alkyl.The silane compound (a9) that has olefinic double bond by use, can access the black agent (A that refuses with olefinic double bond ²).

Object lesson as particularly preferred compound silane compound (a9), can be listed below.

CH ₂=C（CH ₃）COO（CH ₂） ₃Si（OCH ₃） ₃、

CH ₂=C（CH ₃）COO（CH ₂） ₃Si（OCH ₂CH ₃） ₃、

CH ₂=CHCOO（CH ₂） ₃Si（OCH ₃） ₃、

CH ₂=CHCOO（CH ₂） ₃Si（OCH ₂CH ₃） ₃、

[CH ₂=C（CH ₃）COO（CH ₂） ₃]CH ₃Si（OCH ₃） ₂、

[CH ₂=C（CH ₃）COO（CH ₂） ₃]CH ₃Si（OCH ₂CH ₃） ₂、

（C ₆H ₅）NH（CH ₂） ₃Si（OCH ₃） ₃。

As the water-disintegrable silane compound comprised in water-disintegrable silane compound potpourri of the present invention, silane compound (a9) can be used singly or in combination of two or more.

The compounding amount of the silane compound (a9) in water-disintegrable silane compound potpourri of the present invention, with respect to 1 mole of the total amount of silane compound (a7) and silane compound (a8), is preferably below 5 moles, is particularly preferably below 4 moles.

In water-disintegrable silane compound potpourri, as water-disintegrable silane compound, silane compound that can the compounding simple function.The silane compound of simple function works as molecular weight regulator while making water-disintegrable silane compound potpourri be hydrolyzed condensation, making the partial hydrolysis condensation product.That is, for the purpose of manufacturing the partial hydrolysis condensation product that molecular weight is lower, prevent that the excessive macromolecule of partial hydrolysis condensation product from quantizing and become the insoluble purpose of solvent etc. and use.The molecular weight that is preferably based on target partial hydrolysis condensation product is suitably regulated its consumption.

As the silane compound of simple function, the compound of the structure that the p in preferred aforementioned formula (15) is 3, six alkyl disiloxane.The preferred carbon number of alkyl in these compounds is below 4, is particularly preferably methyl or ethyl.

That in negative light-sensitive resin combination of the present invention, uses refuses black agent (A ²) be preferably water-disintegrable silane compound potpourri or its partial hydrolysis condensation product of above-mentioned raw materials, and be the potpourri of the partial hydrolysis condensation product that formed by different multiple condensation products such as the degree of polymerization.That is, refuse black agent (A ²) be preferably and use silane compound (a7) and silane compound (a8) as essential component, at random use silane compound (a9) and the partial hydrolysis condensation product of manufacture.This partial hydrolysis condensation product is preferably silane compound (a7), silane compound (a8), silane compound (a9) mixes arbitrarily, then makes this potpourri carry out the partial hydrolysis condensation and the condensation product manufactured.It should be noted that, also can replace with partial hydrolysis condensation product separately silane compound (a7), silane compound (a8), silane compound (a9).

The partial hydrolysis condensation product that uses silane compound (a7) and silane compound (a8) to manufacture has the structure of the average group accepted way of doing sth shown in following formula (16).But it is actually hydrolization group or the residual product formed of silanol group (partial hydrolysis condensation product), therefore be difficult to this product is meaned with chemical formula.An average group accepted way of doing sth shown in formula (16) is hydrolization group in the partial hydrolysis condensation product of manufacturing as described above or the whole complete hydrolysis of silanol group, condensation and chemical formula while becoming siloxane bond.

[R ^f-CFX-Q ¹-SiO _3/2] _s·[R ^H1 _p-SiO _(4-p)/2] _t (16)

In formula (16), R ^f, R ^h1, Q ¹same as described above with the preferable range of p.S, t be each unit in a plurality of partial hydrolysis condensation products that the degree of polymerization is different on average have a molal quantity.

Supposition is in the partial hydrolysis condensation product of the structure with the average group accepted way of doing sth shown in formula (16), and the unit that is derived from respectively silane compound (a7) and silane compound (a8) is arranged randomly.It should be noted that the s/t(mol ratio in the average group accepted way of doing sth (16) when having used silane compound (a7) and silane compound (a8)), as refusing black agent (A ²) whole mean value, the content as the silane compound (a7) in water-disintegrable silane compound potpourri with respect to silane compound (a8), be preferably above-mentioned scope, i.e. 10/1～90(mol ratio), be particularly preferably 10/5～90(mol ratio).

Refuse black agent (A ²) be to use silane compound (a7), silane compound (a8) and silane compound (a9) and in the situation of manufacture, there is the structure of the average group accepted way of doing sth that the further cocondensation in unit that is derived from silane compound (a9) forms in formula (16).

As refusing black agent (A ²), be preferably the partial hydrolysis condensation product of the potpourri of following silane compound.

(combining 6)

Silane compound (a7): be selected from the 2-(perfluoro hexyl) ethyl trimethoxy silane and 2-(perfluoro butyl) in ethyl trimethoxy silane at least a kind,

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyl triethoxysilane.

(combining 7)

Silane compound (a8): tetraethoxysilane or tetraethoxysilane and methyl triethoxysilane,

The silane compound of simple function: HMDO or trimethyl methoxy silane.

(combining 8)

Silane compound (a9): 3-acryloxy propyl trimethoxy silicane or 3-methacryloxypropyl trimethoxy silane.

(combining 9)

Silane compound (a9): 3-acryloxy propyl trimethoxy silicane or 3-methacryloxypropyl trimethoxy silane,

The silane compound of simple function: HMDO or trimethyl methoxy silane.

(combining 10)

Silane compound (a9): the 3-glycidoxypropyltrime,hoxysilane,

The silane compound of simple function: HMDO or trimethyl methoxy silane.

Can think: in negative light-sensitive resin combination of the present invention, refuse black agent (A ²) in exposure, the process such as solidifying, the further condensation of the silanol group comprised, irradiate also can form and show the excellent partition wall of refusing China ink even carry out ultraviolet ray/ozone.

Refuse black agent (A in negative light-sensitive resin combination of the present invention ²) number-average molecular weight (Mn) be preferably more than 500, preferably lower than 1000000, particularly preferably lower than 10000.When the lower limit that number-average molecular weight (Mn) is above-mentioned scope is above, when using negative light-sensitive resin combination to form partition wall, can prevent from refusing black agent (A ²) from substrate surface, break away from.Number-average molecular weight (Mn) is during lower than the higher limit of above-mentioned scope, the favorable solubility in solvent, operability excellence.Refuse black agent (A ²) number-average molecular weight (Mn) can be regulated by selecting reaction conditions etc.

(refuse black agent (A ²) manufacture)

Refuse black agent (A in negative light-sensitive resin combination of the present invention ²) when the partial hydrolysis condensation product, can by making the hydrolysis of said hydrolyzed silane compound potpourri, the part condensation be (following also referred to as reaction process.) manufacture.Hydrolysis and part condensation are the reactions that the hydrolysis reaction by hydrolization group generates silanol group and dehydration condensation each other generates siloxane bond by silanol group as described above.Can apply without particular limitation in reaction process and be generally used for making the be hydrolyzed reaction conditions of reaction of condensation of water-disintegrable silane compound, for example, can make water, catalyzer, organic solvent etc.

While in reaction process, making water, its amount is preferably 25～9900 mass parts with respect to 100 mass parts of water-disintegrable silane compound potpourri, is particularly preferably 100～1900 mass parts.Be made as above-mentioned scope by the amount by water, the control of hydrolysis and condensation reaction becomes easy.

As the catalyzer for reaction process, preferably use the mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; The organic acids such as acetic acid, oxalic acid, maleic acid.The amount of the catalyzer used is preferably 0.01～10 mass parts with respect to 100 mass parts of water-disintegrable silane compound potpourri, is particularly preferably 0.1～1 mass parts.

Also can be with an organic solvent in above-mentioned reaction process.As this organic solvent, can use water-disintegrable silane compound is hydrolyzed, normally used organic solvent during condensation reaction, particularly for (to refuse black agent (A ¹) manufacture) in the organic solvent enumerated.Organic solvent can be used singly or in combination of two or more.

In reaction process, the amount of organic solvent is preferably 25～9900 mass parts with respect to 100 mass parts of water-disintegrable silane compound potpourri, is particularly preferably 100～1900 mass parts.

The common compounding of the solvent used in gained partial hydrolysis condensation product and reaction process is in negative light-sensitive resin combination.Therefore, as the solvent used in reaction process, preferably use will be refused black agent (A ²) in the solvent of silanol group stabilization.As the solvent by the silanol group stabilization, can list there is hydroxyl, the compound of scope that the relative dielectric constant (ε) under 25 ℃ is 5～20.

Particularly, can list glycol that carbon number is 2～8 is that monoalky lether acetate solvent, glycol are monoalky lether solvent, glycol dimethyl ether (glyme) series solvent, carbon number hydrocarbon system alcohol that is 2～4 etc.More specifically, as glycol, be monoalky lether acetate solvent, can list propylene glycol monomethyl ether acetate (ε: 8.3); Be the monoalky lether solvent as glycol, can list propylene glycol monomethyl ether (ε: 12.3); As hydrocarbon system alcohol, can list 2-propyl alcohol (ε: 19.92) etc.The high viewpoint from the stabilization effect of silanol group, particularly preferably propylene glycol monomethyl ether.

Reaction process preferably with the temperature of room temperature～solvent boiling point, implement under suitable stirring condition.Reaction time is different because of the amount of the material composition that uses, temperature of reaction, stirring condition etc., can list and be roughly 0.5～24 hour, be preferably 1～10 hour.Reaction also can make gained refuse black agent (A after finishing ²) be included in negative light-sensitive resin combination of the present invention and do not remove organic solvent.Can also after utilize usual way to remove organic solvent, isolate and refuse black agent (A ²), then make it be included in negative light-sensitive resin combination.

The ratio that contains of refusing black agent (A) in negative light-sensitive resin combination of the present invention is preferably 0.01～10 quality % in the total solid composition of negative light-sensitive resin combination.

Black agent (A is refused in use ¹) when refusing black agent (A), its content is 0.05～5 quality % more preferably, is particularly preferably 0.2～1 quality %.That refuses black agent (A) contains lower limit that ratio is above-mentioned scope when above, and the capillary effect of the formed partition wall that can be reduced is excellent, refuse the partition wall of China ink excellence.For the higher limit of above-mentioned scope, when following, it is good that the adaptation of partition wall and base material becomes.

Black agent (A is refused in use ²) when refusing black agent (A), its content is 0.1～6 quality % more preferably, is particularly preferably 0.2～3 quality %.Refuse black agent (A ²) content when above-mentioned scope, the bin stability excellence of negative light-sensitive resin combination, the partition wall of the optical element obtained by this negative light-sensitive resin combination in addition refuse the China ink excellence, there is smooth surface.

Of the present invention refuse black agent (A) also can in 1 molecule, possess there is group (1) side chain and have group (2) side chain the two.In addition, in negative light-sensitive resin combination of the present invention, can also comprise possess there is group (1) side chain refuse black agent (A) and possess there is group (2) side chain refuse black agent (A) the two.In these situations, negative light-sensitive resin combination can show height and refuse China ink and black deciduous.

[Photoepolymerizationinitiater initiater (B)]

Comprise Photoepolymerizationinitiater initiater (B) in negative light-sensitive resin combination of the present invention, it for having the oxime ester compound of nitro in 1 molecule.

Photoepolymerizationinitiater initiater (B) is preferably the compound shown in following formula (3).

In formula (3), R ³¹mean the alkyl of carbon number 1～20, the aryl of carbon number 6～30, aralkyl or the cyano group of carbon number 7～30.R ³²mean R ⁴¹or OR ⁴², this R ⁴¹and R ⁴²mean respectively the alkyl of carbon number 1～20, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30.R ³³the alkyl, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30 that mean carbon number 1～20.R ³⁴and R ³⁵mean independently of one another R ⁴¹, OR ⁴², cyano group or halogen atom.R ⁴¹and R ⁴²same as described above.A and b are 0～3 integer independently of one another, the integer that c is 1～3.

As R ³¹, the hydrogen atom of alkyl, aryl and aralkyl can be further by OR ⁴³, COR ⁴⁴, SR ⁴⁵, NR ⁴⁶r ⁴⁷,-NCOR ⁴⁸-OCOR ⁴⁹, cyano group, halogen atom ,-CR ⁵⁰=CR ⁵¹r ⁵²or-CO-CR ⁵³=CR ⁵⁴r ⁵⁵replace R ⁴³, R ⁴⁴, R ⁴⁵, R ⁴⁶, R ⁴⁷, R ⁴⁸, R ⁴⁹, R ⁵⁰, R ⁵¹, R ⁵², R ⁵³, R ⁵⁴and R ⁵⁵mean independently of one another the alkyl of hydrogen atom, carbon number 1～20, the aryl of carbon number 6～30, the aralkyl of carbon number 7～30 or the heterocyclic radical of carbon number 2～20.

As R ³², the hydrogen atom of alkyl, aryl and aralkyl can further be replaced by halogen atom.

Above-mentioned R ³¹, R ³³, R ⁴³～R ⁵⁵the methylene of represented substituent alkylene moiety can be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond, above-mentioned substituent moieties can have branched building block, can be also cyclic alkyl, above-mentioned substituent alkyl end can also be unsaturated link.R ³³also can with the common Cheng Huan of adjacent phenyl ring.

Oxime ester compound of the present invention is because there is geometric isomeride in two keys of oxime, but they are as broad as long, formula (3) and exemplary compounds described later mean both potpourri or any one, be not limited to the structure that means isomeride.

As above-mentioned R ⁴¹～R ⁵⁵shown alkyl, can list methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, iso-octyl, the 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexyl methyl, vinyl, allyl, butenyl group, ethinyl, propinyl, methoxy ethyl, ethoxyethyl group, the propoxyl group ethyl, the amoxy ethyl, the octyloxy ethyl, methoxyethoxyethyl, the ethoxy ethoxy ethyl, the propoxyl group ethoxyethyl group, methoxy-propyl, 2-methoxyl-1-Methylethyl etc.

As R ⁴¹～R ⁵⁵shown aryl, can list phenyl, tolyl, xylyl, ethylphenyl, chlorphenyl, naphthyl, anthryl, phenanthryl, by abovementioned alkyl, be replaced phenyl more than 1 place, xenyl, naphthyl, anthryl etc.

As R ⁴¹～R ⁵⁵shown aralkyl, can list benzyl, chlorobenzyl, α-methylbenzyl, alpha, alpha-dimethylbenzyl, phenylethyl, styryl etc.

As R ⁴³～R ⁵⁵shown heterocyclic radical, can preferably list 5～7 yuan of heterocycles such as pyridine radicals, pyrimidine radicals, furyl, thienyl, tetrahydrofuran base, dioxolanyl, benzoxazole-2-base, THP trtrahydropyranyl, pyrrole radicals, imidazolidine base, pyrazolyl, thiazolidinyl, isothiazole alkyl, oxazole alkyl, isoxazole alkyl, piperidyl, piperazinyl, morpholinyl.

As R ³³the ring that can jointly form with adjacent phenyl ring, can list 5～7 rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, phenyl ring, piperidine ring, morpholine ring, lactonic ring, lactam nucleus.

As replacing R ⁴¹～R ⁵⁵halogen atom and R ³⁴, R ³⁵shown halogen atom, can list fluorine, chlorine, bromine, iodine.

The methylene of above-mentioned substituent alkylene moiety can be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond, for the binding groups interrupted, can be now one kind or two or more group, during for the group that can interrupt continuously, also can more than 2, interrupt continuously.In addition, it can be also cyclic alkyl that above-mentioned substituent moieties can have branched building block, and above-mentioned substituent alkyl end can also be unsaturated link.

Among oxime ester compound of the present invention, following compound is easily synthetic and sensitivity is also high, during in addition as Photoepolymerizationinitiater initiater, dissolve 1 quality % in solvent more than, meets the requirement as Photoepolymerizationinitiater initiater, thereby preferably.Described compound is: in formula (3), and R ³¹compound for the aralkyl of the aryl of the alkyl of carbon number 11～20, carbon number 6～30, carbon number 7～30; R ³³compound for the alkyl of the alkyl of the carbon number 1～12 that interrupted forming for 1～5 time by ehter bond or ester bond, carbon number 13～20; Especially R ³¹compound for the aryl of the alkyl of carbon number 11～20 or carbon number 6～30; Perhaps R ³³for the methylene of the alkylene moiety of alkyl can be interrupted 1～5 time, the compound branched alkyl of carbon number more than 8 by ehter bond or ester bond; R ³³for the methylene of the alkylene moiety of alkyl can be interrupted 1～5 time, the compound alkyl of carbon number more than 13 by ehter bond or ester bond; R ³³for interrupted the compound of the alkyl of 1～5 time by ehter bond; R ³³for interrupted the compound of the alkyl of 1～5 time by ester bond.The mensuration of its solubleness is preferably carried out under 20～30 ℃.As above-mentioned solvent, be preferably propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone.

Oxime ester compound of the present invention also can as shown in the formula shown in (4) and following formula (5) like that, pass through R ³¹or R ³²carry out Dimerized.

Object lesson as the oxime ester compound shown in formula (3), can list the compound shown in following compound N o.1～71.

Oxime ester compound shown in formula (3) for example according to the following formula the reaction equation of (6) manufacture by the following method.At first, make nitrocarbazole compound 1 and acyl chlorides 2 react under the existence of zinc chloride and obtain acyl body 3.Then, make acyl body 3 and hydrochloric acid hydramine react under the existence of DMF and obtain oxime compound 4.Then, make oxime compound 4 and acid anhydrides 5 or acyl chlorides 5 ' react and obtain the oxime ester compound shown in formula (3).

The ratio that contains of the Photoepolymerizationinitiater initiater in negative light-sensitive resin combination of the present invention (B) is preferably 1～15 quality % in the total solid composition of negative light-sensitive resin combination, and more preferably 2～10 quality %, be particularly preferably 3～6 quality %.During for above-mentioned scope, curing property is good, in exposure process, developing procedure, can form the pattern close with mask pattern, live width.Even especially the surface of cured film is in the situation that block the exposure light below 330nm by cut-off filter etc., and then, under low exposure, refuses China ink also good.

In negative light-sensitive resin combination of the present invention, also can be used in combination Photoepolymerizationinitiater initiater (B) Photoepolymerizationinitiater initiater in addition.

As the Photoepolymerizationinitiater initiater that can be used in combination, can list benzil, biacetyl, aminomethyl phenyl glyoxylic ester, 9, the α-diones of 10-phenanthrenequione etc.; The acyloin classes such as benzoin; The acyloin ethers such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether; Thioxanthones, CTX, 2-methyl thioxanthones, 2,4-dimethyl thioxanthones, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-bis-clopenthixal ketones, 2,4-diisopropyl thioxanthones, thioxanthones-thioxanthene ketones such as 4-sulfonic acid; Benzophenone, 4, the benzophenones such as 4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone; Acetophenone, 2-(4-tosyloxy)-2-phenyl acetophenone, to dimethylamino benzoylformaldoxime, 2,2 '-dimethoxy-2-phenyl acetophenone, acetanisole, 2-methyl-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-acetophenones such as 1-ketone; The quinones such as anthraquinone, 2-EAQ, camphorquinone, 1,4-naphthoquinone; The aminobenzoic acids of 2-dimethylaminobenzoic acid ethyl ester, EDMAB, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-Octyl Nitrite etc.; The halogen compounds such as phenacyl chloride, trihalomethyl group benzene sulfone; The acylphosphine oxide class; The superoxide such as di-tert-butyl hydrogen peroxide; 1-[4-(thiophenyl) phenyl]-1,2-octane diketone 2-(O-benzoyl oxime), acetaldehyde 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime) etc. oxime ester class; The aliphatics amines such as triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N methyldiethanol amine, diethylamino ethyl-methyl acrylate; The mercaptan compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, two (3-sulfydryl butyric ester), three (the 2-sulfydryl propionyloxy ethyl) isocyanuric acid esters of Isosorbide-5-Nitrae-butanols, pentaerythrite four (3-sulfydryl butyric ester) etc.

Wherein, when benzophenone, aminobenzoic acids, aliphatics amine and mercaptan compound and other Photoepolymerizationinitiater initiater are used jointly, showing sometimes the sensitization effect, is preferred.

While containing the Photoepolymerizationinitiater initiater except Photoepolymerizationinitiater initiater (B) in negative light-sensitive resin combination, it contains ratio is preferably below 20 quality % in the total solid composition of negative light-sensitive resin combination, more preferably 1～15 quality %, be particularly preferably 2～10 quality %.

[alkali soluble resin (C)]

As alkali soluble resin (C), be not particularly limited, can list: possess side chain with acidic-group and there is the resin (C1-1) of the side chain of olefinic double bond, to the resin (C1-2) that has imported acidic-group and olefinic double bond in epoxy resin, possess the side chain with acidic-group and there is the monomer (C1-3) etc. of the side chain of olefinic double bond.They can be used singly or in combination of two or more.

Resin (C1-1) can synthesize by the following method: make to possess side chain with reactive group and have acidic-group side chain multipolymer with have and can carry out the functional group of bonding and the compound of olefinic double bond is dissolved in solvent and is reacted to reactive group, the described multipolymer that possesses the side chain with reactive group and there is the side chain of acidic-group be by making to there is hydroxyl, the monomer of carboxyl, epoxy radicals isoreactivity group and monomer with acidic-group carry out copolymerization and obtain.

As the monomer with hydroxyl, can list (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-3-hydroxypropyl acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, (methyl) acrylic acid-5-hydroxy pentane ester, (methyl) acrylic acid-own ester of 6-hydroxyl, (methyl) acrylic acid-4-hydroxyl cyclohexyl, neopentyl glycol single (methyl) acrylate, the chloro-2-hydroxypropyl acrylate of (methyl) acrylic acid-3-, glycerine list (methyl) acrylate, 2-hydroxyethyl vinethene, 4-hydroxyl butyl vinyl ether, cyclohexanediol list vinethene, 2-hydroxyethyl allyl ether, N-methylol (methyl) acrylamide, N, two (methylol) (methyl) acrylamides of N-etc.

As the monomer with carboxyl, can list acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt etc.It should be noted that, these monomers also can be as the monomer with acidic-group.

As the monomer with epoxy radicals, can list (methyl) glycidyl acrylate, acrylic acid-3,4-epoxy radicals cyclohexyl methyl esters etc.

Monomer as having acidic-group, be not particularly limited, and except the above-mentioned monomer with carboxyl, as the monomer with phosphate, also can list the 2-(methyl) acryloxy ethane phosphoric acid etc.

The copolymerization of the above-mentioned monomer with reactive group and the monomer with acidic-group can be carried out according to known method in the past.

As thering is the monomer of hydroxyl as reactive group, can list acid anhydrides, the compound with isocyanate group and olefinic double bond with olefinic double bond, thering is the compound of acid chloride group and olefinic double bond etc.

As the acid anhydrides with olefinic double bond, can list maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norborene-2,3-dicarboxylic anhydride, 3,4,5,6-tetrabydrophthalic anhydride, cis-1,2,3,6-tetrabydrophthalic anhydride, 2-butene-1-Ji succinic anhydride etc.

As the compound with isocyanate group and olefinic double bond, can list the 2-(methyl) acryloxy ethyl isocyanate, 1, two ((methyl) acryloyl-oxy ylmethyl) ethyl isocyanates of 1-etc.

As the compound with acid chloride group and olefinic double bond, can list (methyl) acryloyl chloride etc.

As thering is the monomer of carboxyl as reactive group, can list the compound with epoxy radicals and olefinic double bond.As this compound, can list (methyl) glycidyl acrylate, acrylic acid-3,4-epoxy radicals cyclohexyl methyl esters etc.The acid anhydrides that also can make the dehydrating condensation of the hydroxyl that generates and carboxylic acid partly become the part of ring texture herein reacts to importing carboxyl in resin (C1-1).

As thering is the monomer of epoxy radicals as reactive group, can list the compound with carboxyl and olefinic double bond.As the object lesson of this compound, can list acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt etc.The acid anhydrides that also can make the dehydrating condensation of the hydroxyl that generates and carboxylic acid partly become the part of ring texture herein reacts to importing carboxyl in resin (C1-1).

Resin (C1-2) can be by after making epoxy resin and the compound with carboxyl and olefinic double bond reacting, then synthesize with polybasic carboxylic acid or its anhydride reaction.

Particularly, by making epoxy resin react in epoxy resin and import olefinic double bond with the compound with carboxyl and olefinic double bond.Then, by making to have imported epoxy resin and polybasic carboxylic acid or its anhydride reaction of olefinic double bond, can import carboxyl.

As epoxy resin, be not particularly limited, can list the epoxy resin shown in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, tris-phenol type epoxy resin, the epoxy resin with naphthalene skeleton, the epoxy resin with the biphenyl backbone shown in following formula (C1-2a), following formula (C1-2b), there is the epoxy resin of the biphenyl backbone shown in following formula (C1-2c) etc.

(in formula (C1-2a), v is 1～50, is preferably 2～10.In addition, the hydrogen atom of phenyl ring can maybe can be had substituent phenyl by the alkyl of carbon number 1～12, halogen atom independently of one another and replaces.）

(in formula (C1-2b), R ⁶¹, R ⁶², R ⁶³and R ⁶⁴the alkyl that is 1～5 for hydrogen atom, chlorine atom or carbon number independently of one another, w is 0～10.）

(in formula (C1-2c), the hydrogen atom of phenyl ring can maybe can be had substituent phenyl by the alkyl of carbon number 1～12, halogen atom independently of one another and replace.U is 0～10.）

It should be noted that, after making the epoxy resin shown in formula (C1-2a)～(C1-2c) and the compound with carboxyl and olefinic double bond reacting, during again with the polybasic carboxylic acid anhydride reactant, as polybasic acid anhydride, preferably use dicarboxylic anhydride and tetracarboxylic dianhydride's potpourri.By change dicarboxylic anhydride and tetracarboxylic dianhydride's ratio, can control molecular weight.

Resin (C1-2) can be used commercially available product.As commercially available product, can list KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H, the ZCR-1761H of following arbitrary trade name, more than ZAR-2001H(, Nippon Kayaku K. K's system), EX1010(Nagase ChemteX Corporation system) etc.

As monomer (C1-3), can list 2,2,2-, tri-acryloxy Methylethyl phthalic acids (trade name: NK ESTER CBX-1 ,Xin Zhong village chemical industry Co., Ltd. system.) etc.

As alkali soluble resin (C), filming when developing peel off the viewpoint that is suppressed, can accesses high-resolution pattern, from the rectilinearity of line good viewpoint, from cure the viewpoint that outward appearance after operation was maintained, was easy to obtain level and smooth film coated surface, preferably use resin (C1-2).

As resin (C1-2), particularly preferably be: to the resin that has imported acidic-group and olefinic double bond in bisphenol A type epoxy resin, to the resin that has imported acidic-group and olefinic double bond in bisphenol f type epoxy resin, to the resin that has imported acidic-group and olefinic double bond in phenol novolak type epoxy resin, to the resin that has imported acidic-group and olefinic double bond in the cresols phenolic resin varnish type epoxy resin, to the resin that has imported acidic-group and olefinic double bond in tris-phenol type epoxy resin, to the resin that has imported acidic-group and olefinic double bond in the epoxy resin shown in formula (C1-2a)～(C1-2c).

The matter average molecular weight (Mw) of alkali soluble resin (C) is preferably 1.5 * 10 ³～30 * 10 ³, be particularly preferably 2 * 10 ³～15 * 10 ³.In addition, number-average molecular weight (Mn) is preferably 500～20 * 10 ³, be particularly preferably 1.0 * 10 ³～10 * 10 ³.When the lower limit that matter average molecular weight (Mw) and number-average molecular weight (Mn) they are above-mentioned scope is above, solidifying fully during exposure, and for the higher limit of above-mentioned scope, when following, developability is good.

The preferred average out to of the quantity of the olefinic double bond that alkali soluble resin (C) has in 1 molecule, more than 3, is particularly preferably more than 6.When the lower limit that the quantity of olefinic double bond is above-mentioned scope is above, the alkali solubility of exposed portion and unexposed portion easily there are differences, and can form with exposure still less fine pattern.

The acid number of alkali soluble resin (C) is preferably 10～200mgKOH/g, and more preferably 30～150mgKOH/g, be particularly preferably 50～100mgKOH/g.Acid number is when above-mentioned scope, and it is good that the bin stability of negative light-sensitive resin combination and developability become.

The alkali soluble resin comprised in negative light-sensitive resin combination (C) can be a kind, can be also potpourri of more than two kinds.

The ratio that contains of the alkali soluble resin in negative light-sensitive resin combination of the present invention (C) is preferably 10～50 quality % in the total solid composition of negative light-sensitive resin combination, and more preferably 12～40 quality %, be particularly preferably 15～30 quality %.Contain ratio when above-mentioned scope, developability is good.

[negative light-sensitive resin combination]

Negative light-sensitive resin combination of the present invention contains refuses black agent (A), Photoepolymerizationinitiater initiater (B), alkali soluble resin (C), black colorant as required (D), macromolecule dispersing agent (E), dispersing aid (F), crosslinking chemical (G) and solvent (H).And then, can also contain following thermal cross-linking agent (I), silane coupling agent (J), particulate (K), phosphate cpd (L) and other adjuvant.

The negative light-sensitive resin combination of the application of the invention, even block the following exposure light of 330nm, also can manufacture the good negative light-sensitive resin combination of the reproduction of the live width of refusing the good and mask of China ink and use said composition and the partition wall of the homogeneous that obtains.Therefore, can also tackle the situation that requires to form fine pattern.Its reason is considered as follows.

As Photoepolymerizationinitiater initiater, need to effectively absorb over the exposure light of 330nm the highly sensitive compound be activated, can selective light polymerization initiator (B).

According to the inventor's opinion, while blocking the following exposure light of 330nm, exist the curing property on the surface of partition wall extremely to reduce, surface refuse the tendency that the China ink part easily comes off, refuses the China ink reduction.If the negative light-sensitive resin combination that comprises Photoepolymerizationinitiater initiater (B) can improve the curing property on the surface of partition wall.For comprising the compound poor to the animal migration on partition wall surface as for the negative light-sensitive resin combination of refusing black agent, when the partition wall surface occurs to solidify, refuse black agent and move to the partition wall surface not yet fully, but well to the animal migration on partition wall surface refuse black agent by using, refuse China ink and become good.

Refuse the combination of black agent and Photoepolymerizationinitiater initiater (B) except the above-mentioned curing property of needs, surface migration, also needing is that negative light-sensitive resin combination is the viscosity that can be coated with, stable combination.According to the inventor's research, found to refuse the combination of black agent (A) and Photoepolymerizationinitiater initiater (B).

[black colorant (D)]

Negative light-sensitive resin combination of the present invention also comprises black colorant (D).

For the cancellate black of the pixel of the R, the G that form the color filter that surrounds liquid crystal display cells, these three kinds of colors of B is partly black matrix" and while using negative light-sensitive resin combination, preferably comprise black colorant (D).

It is that black pigment, perylene is black pigment that black colorant (D) can list carbon black, nigrosine, anthraquinone, particularly, can list C.I. pigment black 1,6,7,12,20,31 etc.Also can use the organic pigments such as red pigment, blue pigment, viridine green, yellow uitramarine or azomethine is the potpourri of black pigment, inorganic pigment.As black colorant (D), from price, light-proofness size, be preferably carbon black, carbon black also can carry out surface treatment with resin etc.In addition, in order to regulate tone, can be used in combination blue pigment, violet pigment.About color filter, the organic EL of black matrix" array type (black matrix on array), require low-k, high-resistancely film, partition wall.In order to obtain, foregoingly film, partition wall, preferably using potpourri, the azomethine of above-mentioned organic pigment is black pigment.

As carbon black, from the viewpoint of the shape of black matrix", the specific surface area be preferably based on the BET method is 50～200m ²the carbon black of/g.Specific surface area is 50m ²when/g is above, the black matrix" shape is difficult to deteriorated.For 200m ²when/g is following, in carbon black, can exceedingly not adsorb dispersing aid, need to be in order not show each physical property a large amount of dispersing aid of compounding.

In addition, as carbon black, from the viewpoint of sensitivity, the oil absorption that is preferably dibutyl phthalate is the following carbon black of 120cc/100g, and oil absorption is more few more preferred.

And then average 1 particle diameter of observing based on transmission electron microscope of carbon black is preferably 20～50nm.Average 1 particle diameter is 20nm when above, and easily acquisition can be with the negative light-sensitive resin combination that high concentration is disperseed in negative light-sensitive resin combination, ageing stability is good.For 50nm, when following, the black matrix" shape is difficult for deteriorated.In addition, average 2 particle diameters as observing based on transmission electron microscope, be preferably 80～200nm.

Make in negative light-sensitive resin combination of the present invention to contain black colorant (D) and during for formation of black matrix" etc., the ratio that contains of the black colorant in this negative light-sensitive resin combination (D) is preferably 15～80 quality % in the total solid composition of negative light-sensitive resin combination, more preferably 20～70 quality %, be particularly preferably 25～65 quality %.During for above-mentioned scope, the sensitivity of gained negative light-sensitive resin combination is good, in addition, and the light-proofness excellence of formed partition wall.

[macromolecule dispersing agent (E)]

When negative light-sensitive resin combination contains above-mentioned black colorant (D) isodispersity material, in order to make its dispersed raising, preferably contain macromolecule dispersing agent (E).As macromolecule dispersing agent (E), be not particularly limited, carbamate system, polyimide system, alkyd system, epoxy system, polyester system, melamine series, phenol system, acrylic acid series, polyethers system, vinyl chloride, vinyl chloride vinyl acetate based copolymer system, polyamide-based, polycarbonate-based etc. be can list, carbamate system or polyester system are preferably.In addition, macromolecule dispersing agent (E) can also have the structural unit that is derived from oxirane and/or epoxypropane.

While in order to disperse black colorant (D), using macromolecule dispersing agent (E), consider the compatibility to black colorant (D), preferably use the macromolecule dispersing agent (E) with basic group.As basic group, be not particularly limited, can list primary amino radical, secondary amino group or tertiary amino.

As macromolecule dispersing agent (E), also can use commercially available product.As commercially available product, can list DISPARLON DA-7301(trade name, nanmu originally changes into Co., Ltd.'s system); BYK161, BYK162, BYK163, BYK182(are above is all trade name, BYK-Chemie K.K. system), more than SOLSPERSE5000, SOLSPERSE17000(, be all trade name, Zeneca Inc. system) etc.

The ratio that contains of macromolecule dispersing agent (E) is preferably 5～30 quality % with respect to black colorant (D), is particularly preferably 10～25 quality %.For the lower limit of above-mentioned scope, when above, the dispersiveness of black colorant (D) improves, and for the higher limit of above-mentioned scope, when following, it is good that the developability of negative light-sensitive resin combination becomes.

[dispersing aid (F)]

Negative light-sensitive resin combination can also contain phthualocyanine pigment derivant, metal phthalocyanine sulfonamide compounds as dispersing aid (F).Can think: dispersing aid (F) is adsorbed in black colorant (D) isodispersity material and macromolecule dispersing agent (E), has the function that improves dispersion stabilization.

[crosslinking chemical (G)]

In negative light-sensitive resin combination of the present invention, as promoting radical-cured any composition, can also comprise crosslinking chemical (G).As crosslinking chemical (G), be preferably in 1 molecule the compound that there are 2 above olefinic double bonds and do not there is acidic-group.By making negative light-sensitive resin combination comprise crosslinking chemical (G), the curing property raising of the above-mentioned alkali soluble resin (C) during exposure, can reduce the exposure while forming partition wall.

As thering are 2 above olefinic double bonds in 1 molecule and not thering is the crosslinking chemical (G) of acidic-group, so long as there is the compound of this condition, just be not particularly limited, can list diethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, ethoxylation isocyanuric acid triacrylate, 6-caprolactone modification three-(2-acryloxy ethyl) isocyanuric acid ester, two 4-(allyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide) and phenyl } methane, N, a N '-xylylene-bis-(allyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide), urethane acrylate etc.They can be used singly or in combination of two or more.

As crosslinking chemical (G), can use commercially available product.As commercially available product, can list KAYARAD DPHA(trade name, Nippon Kayaku K. K's system, the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate), NK ESTER A-9530(trade name, Xin Zhong village chemical industry Co., Ltd. system, the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate)), the V#802(trade name, Osaka Organic Chemical Industry Co., Ltd.'s system, the dipentaerythritol acrylate, the tripentaerythritol acrylate, the potpourri of four pentaerythritol acrylates), NK ESTER A-9300(trade name, Xin Zhong village chemical industry Co., Ltd. system, ethoxylation isocyanuric acid triacrylate), NK ESTER A-9300-1CL(trade name, Xin Zhong village chemical industry Co., Ltd. system, 6-caprolactone modification three-(2-acryloxy ethyl) isocyanuric acid ester), the BANI-M(trade name, Maruzen Petrochemical Co., Ltd.'s system, two 4-(allyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide) and phenyl } methane), the BANI-X(trade name, Maruzen Petrochemical Co., Ltd.'s system, N, a N '-xylylene-bis-(allyl dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide)) etc.As urethane acrylate, can list the KAYARAD UX SERIES of Nippon Kayaku K. K's system, as concrete trade name, can list UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20 etc.

The reason of the sensitivity of the cured film that wherein, KAYARAD DPHA and NK ESTER A-9530 are obtained by negative light-sensitive resin combination from raising is preferred.NK ESTER A-9300, BANI-M and BANI-X are preferred from the viewpoint of cured film being given to hardness, inhibition hot-fluid extension.NK ESTER A-9300-1CL is preferred from the viewpoint of cured film being given to flexibility.Urethane acrylate can be realized appropriate development time, and developability becomes well, thereby preferably.

The ratio that contains of the crosslinking chemical in negative light-sensitive resin combination of the present invention (G) is preferably 3～30 quality % in the total solid composition of negative light-sensitive resin combination, and more preferably 5～20 quality %, be particularly preferably 7～15 quality %.During for above-mentioned scope, it is good that the alkali-developable of negative light-sensitive resin combination becomes.

[solvent (H)]

Negative light-sensitive resin combination of the present invention contains solvent (H) as required.While containing solvent (H), the reduced viscosity of negative light-sensitive resin combination, therefore the easy substrate to negative light-sensitive resin combination is coated with.Can form filming of uniform negative light-sensitive resin combination.It should be noted that, when negative light-sensitive resin combination does not comprise solvent (H), filming of negative light-sensitive resin combination is identical with the film of negative light-sensitive resin combination.

As long as the solvent (H) that negative light-sensitive resin combination of the present invention is contained have makes contained above-mentioned of negative light-sensitive resin combination refuse black agent (A), Photoepolymerizationinitiater initiater (B), alkali soluble resin (C), black colorant as required (D), macromolecule dispersing agent (E), dispersing aid (F) and crosslinking chemical (G), and then any composition described later dissolves equably or disperses, thereby make the coating even and easy function of negative light-sensitive resin combination to the base material of formation partition wall, and do not there is the reactivity with these compositions, just be not particularly limited, for example can use the solvent phase that uses when refusing black agent (A) synthetic with solvent.

The solvent comprised in negative light-sensitive resin combination (H) to contain ratio different because of the composition of negative light-sensitive resin combination, purposes etc., preferred compounding 50～99 quality % in negative light-sensitive resin combination, more preferably 60～95 quality %, be particularly preferably 65～90 quality %.

Negative light-sensitive resin combination of the present invention contains refuses black agent (A), Photoepolymerizationinitiater initiater (B), alkali soluble resin (C), black colorant as required (D), macromolecule dispersing agent (E), dispersing aid (F), crosslinking chemical (G) and solvent (H).And then can also contain following thermal cross-linking agent (I), silane coupling agent (J), particulate (K), phosphate cpd (L) and other adjuvant.

[thermal cross-linking agent (I)]

Thermal cross-linking agent (I) be have more than 2 can with the compound of the group of carboxyl and/or hydroxyl reaction.Thermal cross-linking agent (I) is in the situation that alkali soluble resin (B) has carboxyl and/or hydroxyl, have with alkali soluble resin (B) react, increase cured film cross-linking density, improve stable on heating effect.

As thermal cross-linking agent (I), can preferably list at least a kind in the group of selecting free amino resins, epoxy compound, oxazoline compound, polyisocyanate compound, poly-carbodiimide compound to form.These compounds may be used singly or in combination of two or more.

The ratio that contains of the thermal cross-linking agent in negative light-sensitive resin combination of the present invention (I) is preferably 1～50 quality % in the total solid composition of negative light-sensitive resin combination, is particularly preferably 5～30 quality %.During for above-mentioned scope, it is good that the developability of gained negative light-sensitive resin combination becomes.

[silane coupling agent (J)]

If use silane coupling agent (J), the base material adaptation of the cured film formed by the gained negative light-sensitive resin combination improves.

As the object lesson of silane coupling agent (J), triethoxysilane that can list tetraethoxysilane, 3-glycidoxypropyltrime,hoxysilane, methyltrimethoxy silane, vinyltrimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, APTES, 17 fluorine octyl group ethyl trimethoxy silanes, contains the polyoxy alkylidene chain etc.They may be used singly or in combination of two or more.

As silane coupling agent (J), can use commercially available product.As commercially available product, can list KBM5013(trade name, KCC of SHIN-ETSU HANTOTAI system, 3-acryloxy propyl trimethoxy silicane) etc.

The ratio that contains of the silane coupling agent in negative light-sensitive resin combination of the present invention (J) is preferably 0.1～20 quality % at the total solid composition of negative light-sensitive resin combination, is particularly preferably 1～10 quality %.For the lower limit of above-mentioned scope, when above, the base material adaptation of the cured film formed by negative light-sensitive resin combination improves, and for the higher limit of above-mentioned scope, when following, refuses China ink good.

[particulate (K)]

Negative light-sensitive resin combination can also comprise particulate (K) as required.By compounding particulate (K), can prevent that the hot-fluid of the partition wall that obtained by negative light-sensitive resin combination from hanging.

Particulate (K) is not particularly limited, and can list silicon dioxide, zirconia, magnesium fluoride, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO) etc. inorganic is particulate; The organic system particulates such as tygon, polymethylmethacrylate (PMMA), if consider thermotolerance, being preferably inorganic is particulate, if consider, obtains easiness, dispersion stabilization, is particularly preferably silicon dioxide or zirconia.In addition, when negative light-sensitive resin combination contains black colorant (G) and macromolecule dispersing agent (E), if consider the adsorptive power of this macromolecule dispersing agent (E), preferably particulate (K) is electronegative.And then, if consider the exposure sensitivity of negative light-sensitive resin combination, preferably particulate does not absorb irradiated light when exposure, and the main light emission wavelength that does not particularly preferably absorb ultrahigh pressure mercury lamp is i ray (365nm), h ray (405nm), g ray (436nm).

As particulate (K), be preferably silicon dioxide.As silicon dioxide, be preferably cataloid and be preferably.In general, as cataloid, there are the silica hydrosol, the Jiang Shui that are dispersed in water to replace with organic silicon dioxide gel of organic solvent, are preferably with an organic solvent the organic silicon dioxide gel as dispersion medium.

As this organic silicon dioxide gel, can use commercially available product, as commercially available product, can list commodity PMA-ST(silicon dioxide particle diameter: 10～20nm by name, the silica solid composition of following arbitrary Nissan Chemical Ind Ltd system: 30 quality %, propylene glycol monomethyl acetate: 70 quality %.), NPC-ST(silicon dioxide particle diameter: 10～20nm, silica solid composition: 30 quality %, n-pro-pyl cellosolve: 70 quality %.), IPA-ST(silicon dioxide particle diameter: 10～20nm, silica solid composition: 30 quality %, IPA:70 quality %.) etc.

The ratio that contains of the particulate in negative light-sensitive resin combination of the present invention (K) is preferably 3～40 quality % in the total solid composition of negative light-sensitive resin combination, is particularly preferably 5～30 quality %.More than most preferably being 7 quality % and lower than 25 quality %.Contain ratio when above-mentioned scope, refuse China ink good, the bin stability of negative light-sensitive resin combination is good.

[phosphate cpd (L)]

Negative light-sensitive resin combination can also comprise phosphate cpd (L) as required.By making negative light-sensitive resin combination comprise phosphate cpd (L), can improve the adaptation of negative light-sensitive resin combination and substrate.As phosphate cpd (L), can list list (methyl) acryloxy ethyl phosphonic acid ester, two (methyl) acryloxy ethyl phosphonic acid ester, three (methyl) acryloxy ethyl phosphonic acid ester etc.

[other adjuvant]

Can also contain as required curing accelerator, thickening agent, plastifier, defoamer, levelling agent, anti-repellents, ultraviolet light absorber etc. in negative light-sensitive resin combination of the present invention.

[preferred compositions of negative light-sensitive resin combination]

Negative light-sensitive resin combination of the present invention preferably according to purposes, require characteristic to select to form and the compounding ratio.

The preferred composition of the various compounding compositions in negative light-sensitive resin combination of the present invention is as follows.

Refuse black agent (A): aforementionedly refuse black agent (A ¹) preferred compositions 1～5 or aforementionedly refuse black agent (A ²) preferred compositions 6～10, in the total solid composition of negative light-sensitive resin combination, be 0.01～10 quality %;

Photoepolymerizationinitiater initiater (B): in No. 2008/078678th, International Publication, o.1～58 the compound N of record, is 0.01～10 quality % in the total solid composition of negative light-sensitive resin combination;

Alkali soluble resin (C): choosing, at least a kind in the group of the resin composition that has imported acidic-group and olefinic double bond in (C1-2a), (C1-2b), (C1-2c) and cresols phenolic resin varnish type epoxy resin, is freely 12～40 quality % in the total solid composition of negative light-sensitive resin combination;

Solvent (H): in the group of selecting free 2-propyl alcohol, gamma-butyrolacton, 3-methoxyl butylacetic acid ester, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone and butyl lactate to form at least a kind is 50～99 quality % in negative light-sensitive resin combination.

[manufacture method of negative light-sensitive resin combination]

As the method for manufacturing negative light-sensitive resin combination, contain and refuse black agent (A), Photoepolymerizationinitiater initiater (B), alkali soluble resin (C), black colorant as required (D), macromolecule dispersing agent (E), dispersing aid (F), crosslinking chemical (G) and solvent (H), and then, the method of preferably, mixing with following thermal cross-linking agent (I), silane coupling agent (J), particulate (K), phosphate cpd (L) and other adjuvant.

Negative light-sensitive resin combination of the present invention and common negative light-sensitive resin combination be similarly as the material of photoetching process etc., makes the curing of coating of said composition and the cured film that obtains can be as the parts of the optical element of the cured film of using common negative light-sensitive resin combination.

[manufacture method of used for optical elements partition wall]

Be applied to be manufactured on substrate the used for optical elements partition wall that there are a plurality of pixels and be positioned at the partition wall between neighbor.

Negative light-sensitive resin combination of the present invention is coated on aforesaid substrate and forms film (film and form operation), then, by the above-mentioned heating of filming (prebake operation), then, only the part that becomes above-mentioned partition wall of filming is exposed and made its photocuring (exposure process), then, remove except above-mentioned filming and form the partition wall (developing procedure) partly formed by above-mentioned photocuring of filming through the part of photocuring, then, by the partition wall of above-mentioned formation heating (curing afterwards operation), can manufacture the partition wall of used for optical elements thus.

It should be noted that, when negative light-sensitive resin combination of the present invention contains black colorant (D), the partition wall of used for optical elements forms with the form of black matrix".

Material to substrate is not particularly limited, and for example can use various glass plates; The thermoplastic plastic sheets such as polyester (polyethylene terephthalate etc.), polyolefin (tygon, polypropylene etc.), polycarbonate, polymethylmethacrylate, polysulfones, polyimide, poly-(methyl) acrylic resin; The cured sheets of the thermoset resin such as epoxy resin, unsaturated polyester (UP) etc.Especially from stable on heating viewpoint, be preferably the heat-resistant plastics such as glass plate, polyimide.

Fig. 1 means the diagrammatic cross-section of having used Production Example negative light-sensitive resin combination of the present invention, the used for optical elements partition wall.(I) of Fig. 1 means the figure of the section that is formed with 2 the state of filming formed by negative light-sensitive resin combination of the present invention on substrate 1.(II) mean the schematic diagram of exposure process.(III) mean the sectional view of the partition wall 6 formed on substrate 1 after developing procedure and substrate.

Below, specifically describe the manufacture method of the used for optical elements partition wall that has used negative light-sensitive resin combination of the present invention with Fig. 1.

(film and form operation)

Section as shown in Fig. 1 (I) is such, the negative light-sensitive resin combination of coating the invention described above on substrate 1, and what formation was formed by negative light-sensitive resin combination films 2.It should be noted that, form filming before 2 of negative light-sensitive resin combination on substrate 1, preferably the cleaning of the coated face utilization of the negative light-sensitive resin combination of substrate 1 alcohol, ultraviolet ray/ozone clean etc. are cleaned.

Coating process as negative light-sensitive resin combination, so long as can form the method for filming of uniform film thickness, just be not particularly limited, can list spin-coating method (spin coat method), spraying process, slot coated method, rolling method, method of spin coating, excellent Tu Fa etc. for the film formed method of common painting.

2 the thickness of filming decides according to the height of the partition wall finally obtained.2 the thickness of filming be preferably the partition wall finally obtained height 100～3000%, be particularly preferably 100～2000%.2 the thickness of filming is preferably 0.3～325 μ m, is particularly preferably 1.3～65 μ m.

(prebake operation)

Above-mentioned filming formed to 2 heating of filming that form on substrate 1 in operation, obtain film 2.By heating, form volatile ingredient that comprise, that comprise solvent in the negative light-sensitive resin combination of filming and volatilize and be removed, obtain not having fusible film.In addition, refusing black agent (A) moves near film coated surface.As the heating method, can list heating arrangements such as utilizing hot plate, baking oven under 250～120 ℃ by substrate 1 and the method for common heat treated about 10～2000 seconds of filming.

It should be noted that, also can remove the volatile ingredients such as solvent by the heating in the prebake operation as described above, but the drying processes such as vacuum drying except heating (drying) can also be set separately in order to remove the volatile ingredient such as solvent before the prebake operation.In addition, for the inequality that do not produce appearance of film, carry out drying efficiently, more preferably be used in combination the heating dry based on having concurrently of above-mentioned prebake operation and vacuum drying.Vacuum drying condition is also different because of the kind of each composition, compounding ratio etc., preferably, can carry out with 500～10Pa, broad scope about 10～300 seconds.

(exposure process)

As shown in Fig. 1 (II), across 4 pairs of films of mask, the 2 irradiation light 5 of predetermined pattern.Light 5 only sees through the predetermined pattern be divided into by above-mentioned mask 4 and partly arrives the film on substrate 1, and only this part is carried out photocuring.Therefore, when carrying out the formation of partition wall, the afore mentioned rules pattern setting is the shape that is suitable for the partition wall shape.

For example, after cure the partition wall after operation on average being preferably below 100 μ m of width, be particularly preferably below 20 μ m.In addition, on average being preferably below 500 μ m of the distance between adjacent partition wall, be particularly preferably below 300 μ m.Preferably use the mask that forms pattern in the mode that reaches above-mentioned scope.

In Fig. 1 (II), the exposed portion 3 that irradiated the film of light is formed by the cured film of negative light-sensitive resin combination, on the other hand, and the residual state of film that unexposed portion is uncured negative light-sensitive resin combination 2 itself.

As irradiated light 5, can list visible ray; Ultraviolet ray; Far ultraviolet; KrF excimer laser, ArF excimer laser, F ₂excimer laser, Kr ₂excimer laser, KrAr excimer laser, Ar ₂the excimer laser such as excimer laser; X ray; Electron ray etc.In addition, as irradiating light 5, be preferably the electromagnetic wave of wavelength 100～600nm, more preferably in the scope of 300～500nm, there is the light of distribution, be particularly preferably i ray (365nm), h ray (405nm) and g ray (436nm).It should be noted that, for example, while using the exposure method in mirror surface projection (MPA) mode, block the following electromagnetic wave of 330nm and irradiate exposure light.Like this, in manufacture method of the present invention, also can have been blocked as required the following electromagnetic exposure of 330nm.

As irradiation unit, can use known ultrahigh pressure mercury lamp etc.The i ray benchmark of exposure when utilizing cut-off filter etc. to block the electromagnetic wave below 330nm, be preferably 5～1000mJ/cm ², 5～200mJ/cm more preferably ², 10～100mJ/cm more preferably ², be particularly preferably 15～50mJ/cm ².When the lower limit that exposure is above-mentioned scope is above, the negative light-sensitive resin combination that becomes partition wall solidifies fully, is difficult for producing in development thereafter dissolving, peeling off from substrate 1.When following, can obtain high resolving power for the higher limit of above-mentioned scope.Even China ink, utilizing cut-off filter etc. to block in the electromagnetic situation below 330nm, is refused also good especially in the surface of the cured film obtained by negative light-sensitive resin combination of the present invention.

Time shutter also because of exposure, for minus, the composition of photosensitive composition, the thickness of filming etc. are different, are preferably for 1～60 second, are particularly preferably for 5～20 seconds.

(developing procedure)

Use developer solution to be developed, the unexposed portion 2 on the substrate 1 shown in removal Fig. 1 (II).Obtain thus sectional view as shown in Fig. 1 (III) such, substrate 1 and forming by the curing film formed partition wall 6 of negative light-sensitive resin combination on aforesaid substrate.In addition, the part surrounded by partition wall 6 and substrate 1 forms pixel, is called as a little 7 part by China ink injection etc.Gained substrate 10 becomes the substrate that can be used in the optical element of manufacturing ink-jetting style via after described later, curing operation.

As developer solution, can use the aqueous alkali of bases such as comprising inorganic base, amine, alcamines, quaternary ammonium salt.In addition, in order to improve dissolubility, to remove residue, can in developer solution, add the organic solvents such as surfactant, alcohol.

Development time (time contacted with developer solution) was preferably for 5～180 seconds.In addition, developing method can list stirring method, infusion process, spray process etc.By in the laggard horizontal high voltage washing of developing, flowing water cleans and utilize pressurized air, compressed nitrogen to make it air-dry, can remove the moisture on substrate 1 and partition wall 6.

In addition, the Thickness Variation of the cured film of part before and after developing procedure, that become partition wall is preferably below 60nm, and more preferably 50nm, be particularly preferably below 45nm.Thickness Variation is 60nm when following, surface can be fully residual for show cured film top layer after exposure refuse China ink refuse the China ink layer, after the China ink of refusing of cured film after curing become good.

(curing afterwards operation)

By partition wall 6 heating on substrate 1.As the heating method, can list heating arrangements such as utilizing hot plate, baking oven under 150～250 ℃ by substrate 1 and the partition wall 6 common heat treated method of 5～90 minutes.By heat treated, the curing film formed partition wall 6 by negative light-sensitive resin combination on substrate 1 further solidifies, the also immobilization more of shape of the point 7 that partition wall 6 and substrate 1 surround.It should be noted that, above-mentioned heating-up temperature is particularly preferably more than 180 ℃.When heating-up temperature is too low, partition wall 6 curing insufficient, therefore can't obtain sufficient chemical reagent resistance, in ink-jet application operation thereafter when injecting China ink in point 7, the worry that has the solvent because comprising in this China ink to cause partition wall 6 swellings or China ink to be spread and sunk in out.On the other hand, when heating-up temperature is too high, there is partition wall 6 that the worry of thermal decomposition occurs.

On average being preferably below 100 μ m of the width of the partition wall of negative photosensitive composition of the present invention, be particularly preferably below 20 μ m.In addition, on average being preferably below 500 μ m of the distance between adjacent partition wall (width of point), be particularly preferably below 300 μ m.In addition, the height of partition wall on average be preferably 0.05～50 μ m, be particularly preferably 0.2～10 μ m.

The curing of coating film formed by negative light-sensitive resin combination of the present invention refuse China ink can utilize water and propylene glycol-1-monomethyl ether-2-acetate (below, also referred to as PGMEA.) contact angle estimate, more than the contact angle of water is preferably 90 degree, more preferably 95 the degree more than.In addition, more than the contact angle of PGMEA is preferably 30 degree, more preferably more than 35 degree, more than being particularly preferably 40 degree.The curing of coating film refuse China ink particularly preferably the contact angle of water be that 90 degree contact angle above and PGMEA is more than 30 degree.

[manufacture method of optical element]

After forming partition wall by above-mentioned manufacture method on substrate, the substrate surface exposed in the zone surrounded by aforesaid substrate and above-mentioned partition wall is carried out to ink-receptiveization processing (ink-receptiveization treatment process), then, utilize ink-jet method to inject China ink and form above-mentioned pixel (black injection process) to above-mentioned zone.It should be noted that, in the manufacture of optical element, ink-receptiveization treatment process is operation not necessarily, according to the optical element of manufacturing, does not sometimes also carry out ink-receptiveization treatment process.

(ink-receptiveization treatment process)

As the method for ink-receptiveization processing, can list the methods such as the cleaning treatment of utilizing aqueous alkali, ultraviolet cleaning treatment, ultraviolet ray/ozone clean processing, quasi-molecule cleaning treatment, Corona discharge Treatment, oxygen plasma treatment.

The cleaning treatment of utilizing aqueous alkali is to use the wet processed on aqueous alkali (potassium hydroxide, tetramethylammonium hydroxide aqueous solution etc.) cleaning base plate surface.

The ultraviolet ray cleaning treatment is to use the dry process on ultraviolet cleaning base plate surface.

It is the dry process of using the low pressure mercury lamp cleaning base plate surface of the light that sends 185nm and 254nm that ultraviolet ray/ozone clean is processed.

The quasi-molecule cleaning treatment is to use the dry process on the xenon excimer lamp cleaning base plate surface of the light that sends 172nm.

Corona discharge Treatment is to utilize high-frequency high-voltage to make to occur in air the dry process on corona discharge cleaning base plate surface.

Oxygen plasma treatment is main with take in a vacuum high frequency electric source etc. as triggering excites oxygen, to make its " plasmoid " high in reactivity, carrys out the dry process on cleaning base plate surface.

As the method for ink-receptiveization processing, from easy viewpoint, be preferably ultraviolet ray/dry treatment methods such as ozone clean processing.Ultraviolet ray/ozone can occur with commercially available device.At the inner substrate that is formed with partition wall of placing of ultraviolet ray/ozone equipment, in air, under room temperature, carry out the processing about 1～10 minute in the scope of the oil repellent that does not damage partition wall, can carry out ink-receptiveization processing thus.It should be noted that, about the processing time, the time that coordinates each ultraviolet ray/ozone equipment to be adjusted into the scope of the oil repellent that does not damage partition wall gets final product.

Utilize this ink-receptiveization processing, remove fully impurity in remaining in a little etc. after forming above-mentioned partition wall, thereby can realize fully ink-receptiveization a little, can prevent from using the white dot phenomenon of the colour display device etc. of gained optical element.

(black injection process)

The China ink injection process is to utilize ink-jet method to form the operation of pixel to injecting China ink in the point after ink-receptiveization treatment process.This operation can be used normally used ink discharge device and usual way in ink-jet method similarly to carry out.The ink discharge device used in formation as this pixel, be not particularly limited, and can use the ink discharge device that has utilized following method: spray continuously charged China ink the method for utilizing magnetic field to be controlled; Use piezoelectric element intermittently to spray black method; China ink is heated and utilize it to foam to carry out the intermittent the whole bag of tricks such as method that spray.

Optical element as using negative light-sensitive resin combination of the present invention to manufacture, can list color filter, organic EL display element, organic tft array etc.

[manufacture of color filter]

The ink-receptiveization processing of the formation of partition wall, point, the China ink based on ink-jet method inject as mentioned above.In color filter, what also can make formed pixel is shaped as the known arbitrary arrangements such as stripe, mosaic type, triangle type, 4 pixel arrangement types.

The China ink that is used to form pixel mainly comprises coloring components, resin glue composition and solvent.As coloring components, preferably use pigment and dyestuff that thermotolerance, photostability etc. are excellent.As the resin glue composition, be preferably the resin of transparent and excellent heat resistance, can list acrylic resin, melamine resin, carbamate resins etc.The China ink of water-based comprises water and water-miscible organic solvent as required is used as solvent, comprises water soluble resin or water-dispersed resin and is used as the resin glue composition, and comprise various auxiliary agents as required.In addition, the China ink of oiliness comprises organic solvent and is used as solvent, comprises the resin that dissolves in organic solvent and is used as the resin glue composition, and comprise various auxiliary agents as required.

In addition, preferably, after utilizing ink-jet method to inject China ink, then carry out as required drying, be heating and curing, ultraviolet curing.

After forming pixel, form as required protective film.Arrive the purpose of liquid crystal layer from the leachable in the China ink of partition wall, pixel section for the purpose that improves surface and blocking-up, be preferably formed protective film.While forming protective film, preferably remove in advance the China ink of refusing of partition wall.Do not remove and refuse Mo Xingshi, can repel the external coating coating fluid, can't obtain uniform thickness, thus not preferred.The method of refusing China ink as removing partition wall, can list plasma ashing processing, light ashing processing etc.

Preferably, further as required, for the high-grade of using the liquid crystal panel that color filter manufactures, form photic sept on the black matrix" formed with partition wall.

[manufacture of organic EL display element]

Before forming partition wall, the transparency electrode of tin-doped indium oxide (ITO) etc. is filmed on the transparent bases such as glass by sputtering method etc., and as required transparency electrode is etched into to the pattern of expectation.Then, use negative light-sensitive resin combination of the present invention to form partition wall, after carrying out ink-receptiveization processing a little, use ink-jet method be coated with successively the solution of hole mobile material, luminescent material and carry out drying point, form hole transmission layer, luminescent layer., utilize vapour deposition method etc. form the electrode of aluminium etc., obtain thus the pixel of organic EL display element thereafter.

[manufacture of organic tft array]

Can manufacture the organic tft array via following (i)～(iii) operation.

(i) use negative light-sensitive resin combination of the present invention to form partition wall on the transparent bases such as glass.After the ink-receptiveization processing of point, use ink-jet method to a solution of coating gate material, form gate electrode.

(ii), after forming gate electrode, form gate insulating film thereon.Use negative light-sensitive resin combination of the present invention to form partition wall on gate insulating film, after carrying out ink-receptiveization processing a little, use ink-jet method to a solution of coating source-drain electrode material, formation source-drain electrode.

(iii) after formation source-drain electrode, in the mode that surrounds the zone that comprises pair of source-drain electrode, use negative light-sensitive resin combination of the present invention to form partition wall, after the ink-receptiveization processing of point, use ink-jet method to be coated with the semi-conductive solution of machine to point, form organic semiconductor layer between source-drain electrode.

It should be noted that, (i)～(iii) can only in 1 operation separately, utilize the partition wall that has used negative light-sensitive resin combination of the present invention, also can in plural operation, utilize the partition wall that has used negative light-sensitive resin combination of the present invention.

[manufacture of organic EL illuminating element]

Can with the manufacture of organic EL display element, similarly operate to manufacture.It is stacked that luminescent layer can will send by ink-jet the versicolor luminophor such as red, green, blue, also aforementioned luminophor can be distinguished to coating in the plane.

Embodiment

Below further describe the present invention with embodiment, but the present invention is not limited to these embodiment.It should be noted that, example 1～21 is that embodiment, example 31～33 are comparative example.

Each is measured and carries out in accordance with the following methods.

Number-average molecular weight (Mn) is usingd polystyrene by gel permeation chromatography and is measured as standard substance.

The containing ratio of refusing the fluorine atom in black agent (A) is to using Isosorbide-5-Nitrae-bis-(trifluoromethyl) benzene as standard substance, utilization ¹⁹f NMR measures and calculates.The amount of refusing the olefinic double bond in black agent (A) is to using Isosorbide-5-Nitrae-bis-(trifluoromethyl) benzene as standard substance, utilization ¹h NMR measures and calculates.

The quantity of the olefinic double bond in acid number (mgKOH/g) and 1 molecule is the theoretical value of being calculated by the compounding ratio of starting monomer.

The abbreviation of the compound used in synthesis example and embodiment is as follows.

(refuse black agent (A ¹) synthetic in the compound that uses)

The MEK:2-butanone.

C6FMA：CH ₂=C（CH ₃）COOCH ₂CH ₂（CF ₂） ₆F。

MAA: methacrylic acid.

MMA: methyl methacrylate.

PME400:BLEMMER PME-400(NOF Corp system.Alpha-Methyl-ω-methacryloxy gathers (oxygen ethene).CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kcH ₃: the k in formula means intermolecular mean value, and the value of k is about 9.）。

PME1000:BLEMMER PME-1000(NOF Corp system.Alpha-Methyl-ω-methacryloxy gathers (oxygen ethene).CH ₂=C(CH ₃) COO(CH ₂cH ₂o) _kcH ₃: the k in formula means intermolecular mean value, and the value of k is 23.）。

V-65: trade name (Wako Pure Chemical Industries, Ltd.'s system.Two (2, the 4-methyl pentane nitriles of 2,2'-azo.））。

2-HEMA: 2-hydroxyethyl methacry-late.

GMA: glycidyl methacrylate.

AOI:2-acryloxy ethyl isocyanate (Showa Denko K. K's system, trade name: Karenz AOI.）。

DBTDL: dibutyl tin laurate.

TBQ: tert-butyl group 1,4-benzoquinone.

(refuse black agent (A ²) synthetic in the compound that uses)

Compound (a7-1): CF ₃(CF ₂) ₅cH ₂cH ₂si(OCH ₃) ₃(Asahi Glass Co., Ltd's system).

Compound (a8-1): Si(OC ₂h ₅) ₄(COLCOAT CO., Ltd system).

Compound (a9-1): CH ₂=CHCOO(CH ₂) ₃si(OCH ₃) ₃(East capital changes into Industrial Co., Ltd's system).

TMMS: trimethyl methoxy silane [(CH ₃) ₃si(OCH ₃)] (East capital changes into Industrial Co., Ltd's system).

PGME: propylene glycol monomethyl ether.

PGMEA: propylene glycol monomethyl ether acetate.

(Photoepolymerizationinitiater initiater (B))

Above-claimed cpd No.1～3, compound N o.7, compound N o.10, compound N o.12, compound N o.20, compound N o.33, the compound shown in compound N o.45～51 and compound N o.53～58.

(Photoepolymerizationinitiater initiater (B) Photoepolymerizationinitiater initiater in addition)

OXE02: acetaldehyde 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime) (Ciba Specialty Chemicals Corp. system, trade name: OXE02.）。

IR907: trade name; IRGACURE907, BASF Co., Ltd. system, 2-methyl isophthalic acid-[the 4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone.

EAB:4,4 '-bis-(diethylamino) benzophenone (Tokyo HuaCheng Industry Co., Ltd's system).

(alkali soluble resin (C))

EX1010: the resin (Nagase ChemteX Corporation system, trade name: the EX-1010 that import olefinic double bond and acidic-group in the epoxy resin shown in upper quadrant (C1-2b).Solid constituent: 60 quality %, PGMEA:40 quality %.）。

ZCR1761: the resin (Nippon Kayaku K. K's system, the trade name: ZCR-1761H that import olefinic double bond and acidic-group in the epoxy resin with xenyl skeleton shown in upper quadrant (C1-2a).Solid constituent: 60 quality %, PGMEA:40 quality %.）。

ZCR1642: the resin (Nippon Kayaku K. K's system, the trade name: ZCR-1642H that import olefinic double bond and acidic-group in the epoxy resin with xenyl skeleton shown in upper quadrant (C1-2a).Solid constituent: 60 quality %, PGMEA:40 quality %.）。

C-1: the cresols phenolic resin varnish type epoxy resin is reacted, then with 1,2 with acrylic acid; 3; the 6-tetrabydrophthalic anhydride reacts and imports acryloyl group and carboxyl, by the refining resin formed of hexane for the gained resin, and solid constituent 70%, acid number 60mgKOH/g, PGMEA:30 quality %.

ZAR2002: trade name; KAYARAD ZAR-2002, Nippon Kayaku K. K's system, to the resin, solid constituent 70%, acid number 60mgKOH/g, the PGMEA:30 quality % that import carboxyl and olefinic double bond in bisphenol A type epoxy resin.

(black colorant (D))

CB: carbon black dispersion liquid (average 2 particle diameter: 120nm, carbon black: the polyurethane series macromolecule dispersing agent that 20 quality %, amine value are 18mgKOH/g: 5 quality %, PGMEA:75 quality %.）。

Mix organic pigment: the potpourri of the 10:5:5:5 of C.I. pigment blue 15 6, C.I. paratonere 254, C.I. pigment yellow 13 9 and macromolecule dispersing agent (solid constituent: 25 quality %, PGMEA:75 quality %.）。

(crosslinking chemical (G))

UX5002: polyfunctional carbamate, acrylate oligomer (Nippon Kayaku K. K's system, trade name: KAYARAD UX-5002D-P20.Solid constituent: 80 quality %, PGMEA:20 quality %.）。

A9300CL: 6-caprolactone modification three-(2-acryloxy ethyl) isocyanuric acid ester (Xin Zhong village chemical industry Co., Ltd. system, trade name: NK ESTER A-9300-1CL.）。

A9530: the melange of dipentaerythritol acrylate and dipentaerythritol five acrylate (Xin Zhong village chemical industry Co., Ltd. system, trade name: NK ESTER A-9530.）。

(solvent (H))

PGMEA: propylene glycol-1-monomethyl ether-2-acetate.

The IPA:2-propyl alcohol.

(silane coupling agent (J))

KBM5013: trade name (KCC of SHIN-ETSU HANTOTAI system.3-acryloxy propyl trimethoxy silicane.）。

(particulate (K))

IPA-ST: trade name (Nissan Chemical Ind Ltd's system.Organic silicon dioxide gel, solid constituent: 30 quality %, IPA:70 quality %.）。

[synthesis example 1: refuse black agent (A ¹synthesizing-1)]

Drop into MEK(420g to possessing in autoclave stirring machine, that internal volume is 1L), C6FMA(90g), MAA(9g), PME1000(81g) and polymerization initiator V-65(0.2g), stir in nitrogen on limit, crude polymer, with 50 ℃ of polymerizations 24 hours, is synthesized in limit.Add hexane deposition and purification again in the solution of gained crude polymer, then carry out vacuum drying, obtain refusing black agent (A-1) (158.6g).Refuse black agent (A ¹-1) number-average molecular weight (Mn) is 64690, matter average molecular weight (Mw) is 92270.

[synthesis example 2: refuse black agent (A ¹synthesizing-2)]

Drop into MEK(420g to possessing in autoclave stirring machine, that internal volume is 1L), C6FMA(85g), 2-HEMA(50g), PME400(36g), MAA(9g) and polymerization initiator V-65(0.7g), stir in nitrogen on limit, limit, with 50 ℃ of polymerizations 24 hours, obtains the solution of polymkeric substance (1).

(importing of olefinic double bond)

To possessing in autoclave stirring machine, that internal volume is 1L solution (500g), the AOI(45.6g that drops into above-mentioned polymkeric substance (1)), DBTDL(0.13g), TBQ(1.6g) and MEK(17.1g), with 40 ℃ of reactions 24 hours, in polymkeric substance (1), import olefinic double bond while stirring.Add hexane deposition and purification again in gained solution, then carry out vacuum drying, obtain refusing black agent (A ¹-2) (165.0g).Refuse black agent (A ¹the amount that number-average molecular weight-2) (Mn) is 41200, matter average molecular weight (Mw) is 110800, the containing ratio of fluorine atom is 20.6 quality %, olefinic double bond (the C=C amount, * 10 ^-3mol/g) be 1.66 * 10 ^-3mol/g, acid number are 25.0mgKOH/g.

[synthesis example 3～4: refuse black agent (A ¹-3) and (A ¹synthesizing-4)]

Except refusing black agent (A ¹-1) in synthetic, by the formula change of raw material, be table 1 like that beyond, obtain refusing black agent (A by identical copolyreaction ¹-3) and (A ¹-4).Gained is refused black agent (A ¹-3) and (A ¹containing ratio (quality %), the acid number (mgKOH/g) of number-average molecular weight-4) (Mn), matter average molecular weight (Mw), fluorine atom are shown in table 1.

[synthesis example 5: refuse black agent (A ¹synthesizing-5)]

Except in polymkeric substance (1) synthetic, by the formula change of raw material, be table 1 like that, obtain polymkeric substance (2) by identical copolyreaction.Except refusing black agent (A ¹-2) in synthetic, the compounding of raw material is changed to table 1 like that beyond, import olefinic double bond by identical reaction in polymkeric substance (2), obtain refusing black agent (A ¹-5).Gained is refused black agent (A ¹the amount of the containing ratio (quality %) of weight average molecular weight-5) (Mn), number-average molecular weight (Mw), fluorine atom, acid number (mgKOH/g), olefinic double bond (the C=C amount, * 10 ^-3mol/g) be shown in table 1.

[table 1]

[synthesis example 6: refuse black agent (A ²-1) manufacture]

To the 1000cm that possesses stirring machine ³there-necked flask in drop into 11.8g compound (a7-1), 29.4g compound (a8-1), 29.4g compound (a9-1), 29.4g TMMS, obtain water-disintegrable silane compound potpourri.Then, in this potpourri, drop into 564.7g PGMEA, make solution (material solution).

Limit is stirred limit with 40 ℃ and dripped the 52.0g1.0% aqueous hydrochloric acid solution in the gained material solution.After dripping end, with 40 ℃ of stirrings 5 hours, with PGMEA solution, (refuse black agent (A ²-1) concentration: 10 quality %.Hereinafter referred to as " (A ²-1) liquid ".) form obtain refusing black agent (A ²-1).It should be noted that, use gas chromatograph to be measured reactant liquor, confirm each compound as raw material all below detectability.

Gained is refused black agent (A ²the containing ratio of number-average molecular weight-1) (Mn), matter average molecular weight (Mw), fluorine atom with refuse black agent (A ²-1) inventory form (% by mole) jointly be shown in table 2.

[synthesis example 7: refuse black agent (A ²-2) manufacture]

To the 1000cm that possesses stirring machine ³there-necked flask in drop into 16.7g compound (a7-1), 41.7g compound (a8-1), 41.7g compound (a9-1), obtain water-disintegrable silane compound potpourri.Then, to dropping into 564.7g PGME in this potpourri, make solution (material solution).

Limit is stirred limit with 40 ℃ and dripped the 65.7g1.0% aqueous solution of nitric acid in the gained material solution.After dripping end, with 40 ℃ of stirrings 5 hours, with PGME solution, (refuse black agent (A ²-2) concentration: 10 quality %.Hereinafter referred to as " (A ²-2) liquid ".) form obtain refusing black agent (A ²-2).It should be noted that, use gas chromatograph to be measured reactant liquor, confirm each compound as raw material all below detectability.

Gained is refused black agent (A ²-2) number-average molecular weight (Mn), matter average molecular weight (Mw), fluorine atom containing ratio and refuse black agent (A ²-2) input amount form (% by mole) jointly be shown in table 2.

[table 2]

[example 1～24 and example 31～33: the preparation of negative light-sensitive resin combination, the formation of partition wall and evaluation]

With the ratio shown in table 3 and table 4 (quality %), come compounding to refuse black agent (A), Photoepolymerizationinitiater initiater (B), alkali soluble resin (C), black colorant (D), crosslinking chemical (G), solvent (H), silane coupling agent (J) and particulate (K), obtain negative light-sensitive resin combination.

After using spinner be coated with negative light-sensitive resin combination on glass substrate, with 100 ℃ on hot plate dry 2 minutes, the formation thickness is filming of 2.0 μ m.Then, by mask (the clathrate patterns of light shielding part 100 μ m * 200 μ m, transmittance section 20 μ m), utilize ultrahigh pressure mercury lamp (to utilize cut-off filter to stop the wavelength that 330nm is following.The main blend formed by i ray, h ray and g ray.) to the regulation exposure shown in exposure chart 3 and table 4 of filming.

Then, unexposed portion is immersed in inorganic base developer solution (10 times of dilute aqueous solutions of horizontal creek oil prodution industry Co., Ltd. system, trade name SEMICLEAN DL-A4) and is developed, water rinses unexposed section, makes its drying.

Then, by heating 1 hour with 220 ℃, obtain forming figuratum glass substrate (1) on hot plate.In addition, being exposed, with above-mentioned same operation, obtain being formed with the glass substrate (2) of curing of coating film except not using above-mentioned mask.For glass substrate (1) or (2), according to method shown below, measure and estimate live width, development caudacoria decrement, refuse China ink (PGMEA contact angle).The results are shown in table 3 and table 4.

(live width)

For above-mentioned glass substrate (1), use super degree of depth measuring shape microscope VK-8500(KEYENCE CORPORATION system) measure the live width of the clathrate pattern that transmittance section is 20 μ m.Live width more approaches 20 μ m of the transmittance section of mask, means more can reappear the live width of mask.

(development caudacoria decrement)

For above-mentioned glass substrate (1), use high precision fine shape is measured the little slope institute system of machine SURFCORDER ET4000A() the front thickness (THK1) of development of mensuration exposed portion (cured film) and the rear thickness (THK2) that develops.Thickness from developing is deducted to thickness after development and value as development caudacoria decrement.This value is less means that the photocuring of negative light-sensitive resin combination is better.

(refusing China ink)

According to the PGMEA contact angle (degree) on the cured film surface of above-mentioned glass substrate (2), estimated.Contact angle refers to the angle that the tangent line with respect to liquid surface at the some place contacted with liquid at solid becomes with solid surface, with the angle of the side that comprises liquid, defines.This angle is larger, mean cured film to refuse China ink more excellent.

By sessile drop method, based on JIS R3257 " the wettability test method on base plate glass surface ", the 3 carrying PGMEA of place on the mensuration surface on base material drip, and each PGMEA is dripped and measured.Drop is that 2 μ L/ drip, and is determined under 20 ℃ and carries out.Contact angle means with the form of the mean value (n=3) of 3 measured values.

[table 3]

[table 4]

The photocuring of the negative light-sensitive resin combination of example 1～24 is all good.In addition, the cured film formed by said composition refuse the live width that China ink is good and can reappear mask.

On the other hand, the negative light-sensitive resin combination of example 31～33 is not used the oxime ester compound that has nitro in 1 molecule as Photoepolymerizationinitiater initiater, so exposure is 20mJ/cm ²and 40mJ/cm ²and development caudacoria decrement surpasses 60nm, and photocuring is insufficient.In addition, formed cured film refuses the live width that China ink is insufficient and can't reappear mask.

utilizability on industry

Even negative light-sensitive resin combination of the present invention in the situation that reduce exposure or the exposure light that blocks below 330nm is exposed, also can be manufactured and refuse good and live width mask of China ink and reappear good partition wall.

Negative light-sensitive resin combination of the present invention can be manufactured the formation of the partition wall of purposes, organic EL display element manufacture purposes aptly for the color filter as having utilized the ink-vapor recording technology law.

It should be noted that, the full content of instructions, claims, accompanying drawing and the summary of No. 2011-102039, the Japanese patent application of on April 28th, 2011 application is quoted so far, be incorporated to as the disclosure of instructions of the present invention.

description of reference numerals

1 ... substrate, 2 ... the filming of negative light-sensitive resin combination, 3 ... the exposed portion, 4 of filming ... mask, 5 ... light, 6 ... partition wall, 7 ... point, 10 ... the used for optical elements substrate used in ink-jetting style

Claims

1. a negative light-sensitive resin combination, is characterized in that, it contains:

Alkali soluble resin (C),

-CFXR ^f （1）

-（SiR ¹R ²-O） _n-SiR ³R ⁴R ⁵ （2）

In formula (1), X means hydrogen atom, fluorine atom or trifluoromethyl, R ^fexpression can have fluoroalkyl or the fluorine atom of at least 1 carbon number replaced by fluorine atom etheric oxygen atom, hydrogen atom below 20,

2. negative light-sensitive resin combination according to claim 1, wherein, described Photoepolymerizationinitiater initiater (B) is the compound be comprised of following formula (3),

In formula (3), R ³¹mean the alkyl of carbon number 1～20, the aryl of carbon number 6～30, aralkyl or the cyano group of carbon number 7～30, R ³²mean R ⁴¹or OR ⁴², this R ⁴¹and R ⁴²mean respectively the alkyl of carbon number 1～20, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30, R ³³the alkyl, the aryl of carbon number 6～30 or the aralkyl of carbon number 7～30 that mean carbon number 1～20, R ³⁴and R ³⁵mean independently of one another R ⁴¹, OR ⁴², cyano group or halogen atom, a and b are 0～3 integer independently of one another, the integer that c is 1～3.

3. negative light-sensitive resin combination according to claim 1 and 2, it also comprises black colorant (D).

4. according to the described negative light-sensitive resin combination of any one in claim 1～3, it also comprises crosslinking chemical (G).

5. according to the described negative light-sensitive resin combination of any one in claim 1～4, wherein, refuse black agent (A) for there is the compound that group (1) or group (2), main chain are hydrocarbon chain at side chain.

6. negative light-sensitive resin combination according to claim 5, wherein, refuse black agent (A) and have acidic-group.

7. according to the described negative light-sensitive resin combination of any one in claim 1～4, wherein, refuse black agent (A) for there is the compound that group (1), main chain are the organopolysiloxane chain at side chain.

8. according to the described negative light-sensitive resin combination of any one in claim 5～7, wherein, refuse black agent (A) and there is olefinic double bond.

9. a cured film, it is that the curing of coating of the described negative light-sensitive resin combination of any one in the claim 1～8 that makes to form on substrate forms.

10. a partition wall, its partition wall for forming for subregion is set on substrate, it is formed by cured film claimed in claim 9.

11. a black matrix", its black matrix" for forming for subregion is set on substrate, it is formed by cured film claimed in claim 9, and described cured film is formed by negative light-sensitive resin combination claimed in claim 3.

12. the manufacture method of a partition wall, is characterized in that, the method possesses following operation successively: the described negative light-sensitive resin combination of any one in claim 1～8 is coated on to the operation that on substrate, formation is filmed; By the described heating and after making film of filming, only the established part of this film is exposed and made the operation of its photocuring; Remove the operation except described film through the part of photocuring; And, the heating of the described part through photocuring is obtained to the operation of partition wall,

Remove before described film and the Thickness Variation of the described part through photocuring afterwards is below 60nm.

13. the manufacture method of a black matrix", it is in the described manufacture method of claim 12, and right to use requires 3 described negative light-sensitive resin combinations to obtain described partition wall as black matrix".

14. a color filter, is characterized in that, it possesses: a plurality of pixels on substrate, substrate and be positioned at the partition wall between neighbor, this partition wall is formed by the cured film of the described negative light-sensitive resin combination of any one in claim 1～8.

15. an organic EL, is characterized in that, it possesses: a plurality of pixels on substrate, substrate and be positioned at the partition wall between neighbor, this partition wall is formed by the cured film of the described negative light-sensitive resin combination of any one in claim 1～8.