CN1922142B

CN1922142B - Oxime ester compound, photopolymerizable composition and color filter using same

Info

Publication number: CN1922142B
Application number: CN2005800056044A
Authority: CN
Inventors: 水上润二; 龟山泰弘; 浦野年由
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2004-02-23
Filing date: 2005-02-22
Publication date: 2012-05-02
Anticipated expiration: 2025-02-22
Also published as: TWI378919B; CN101805282B; CN101805282A; WO2005080337A1; KR100897224B1; TW200604172A; CN1922142A; KR20070100810A

Abstract

The invention provides an oxime ester compound having a specific structure, a photopolymerizable composition and a color filter using the photopolymerizable composition. In the photopolymerizable composition comprising the black coloring material , the organic binder (b) and the photopolymerization initiator (c), the oxime ester compound constitutes (c). The oxime ester compound can be used as a highly photosensitive photopolymerization initiator. The photopolymerizable composition containing the oxime ester compound in the form of a thin film has excellent sensitivity and resolution, has high light-shielding properties, and can form a high-quality resin Black Matrix (BM) at low cost. The color filter using the resin BM has excellent precision, flatness and durability, so that the display quality of a liquid crystal display device can be improved. The production process and the color filter itself are free of harmful substances, so that the danger to the human body can be reduced and the environmental safety can be improved. It is also suitable for use in applications where no coloring material is used, such as photo spacers or rib walls (liquid crystal division alignment protrusions).

Description

The colour filter of oxime ester compound, optical polymerism composition and use said composition

Technical field

The present invention relates to oxime ester compound and the optical polymerism composition that contains this oxime ester compound as Photoepolymerizationinitiater initiater.More particularly; The present invention is effectively to the optical polymerism composition that is used for colour filter with the colour filter that said compsn obtains, and said compsn is used for making and is used for the for example optical colour filter of CTV, liquid-crystal display, solid state image sensor and camera etc.; The present invention relates to colour filter and use optical polymerism composition, said compsn is suitable for producing the black matrix (after this black matrix abbreviates BM as) with high opacifying property and light sensitivity height and excellent in resolution; The invention still further relates to the colour filter of high precision and high opacifying property resin B M.

And; Oxime ester compound of the present invention is the Photoepolymerizationinitiater initiater of ISO; So its purposes is not limited to BM; It also can be used for not using the transparent photosensitive composite of coloured material, for example be used for light spacer (phto spacer) or rib wall (rib) (liquidcrystal divided-alignment protrusion), and it can be widely used for various technical fields.

Background technology

Usually through on the surface of for example transparent substrate such as glass or plastic sheet, forming black matrix, form at least three kinds of different form and aspect such as for example red, green and indigo plant then with bar shaped or mosaic color pattern successively, thereby form colour filter.Pattern dimension is generally the level of 5～700 μ m with the purposes and the colour-change of colour filter.In addition, overlapping bearing accuracy is from several to dozens of microns, and this colour filter is with the Micrometer-Nanometer Processing Technology preparation of high dimensional accuracy.

As the typical method of producing colour filter, can mention staining, print process, colo(u)rant dispersion method and anode process etc.In them; Especially, used following colo(u)rant dispersion method widely: coating contains the optical polymerism composition of coloured material on transparent substrate, the curing of carrying out image exposure, development and according to circumstances needing; Repeat these processes and form the colour filter image; This is because bearing accuracy and the height such as thickness precision grade of the color filter pixel that obtains of this method, and with the weather resistance such as for example photostabilization and thermotolerance etc. that obtains excellence, and for example defective such as pin hole is few.

Usually; BM is configured between red, the green and blue pattern with reticulation, strip or mosaic shape; BM plays thin film transistor (Thin Film Transistor, the effect of TFT) breaking down because of light leak or improving contrast gradient through the colour mixture that stops between shades of colour of preventing.Like this, require BM to have high opacifying property.At present, the film of metal such as general use case such as chromium forms BM.This method is a vapor deposition metal such as chromium and utilize photolithography that this chromium layer is carried out etching for example on transparent substrate.Can obtain the high opacifying property under thin thickness so accurately.On the other hand, this method comprises long production process, produces rate variance, and cost is big like this, and this method can produce environmental problem because of the waste water of etch processes etc.

Therefore, people are studying the method that forms pollution-free resin B M with the photoresist that is dispersed with Opacifying pigment or dyestuff at low cost energetically.But resin B M has the problem that the back is described, and does not therefore also have practical application.For the opacifying property (optical concentration) that makes resin B M equates with opacifying property with film formed BM of metal such as for example chromium, need to increase the content or the increase film thickness of Opacifying pigment or dyestuff etc.

In the method that increases film thickness, receive the influence of the unfairness property of BM, the flatness of the RGB that on BM, forms (red, green, blue) colored pixels will be damaged.Like this, cel-gap is with inhomogeneous, and the orientation of liquid crystal is with confusion, and display performance reduces.And, also can occur in the problems such as (planar film break) of breaking of transparency electrode ITO (indium tin oxide target) film that forms on the colour filter.

And, in the method for the content that increases Opacifying pigment or dyestuff, the variation such as light sensitivity, development property, resolving power and binding property of photoresist (black resist), not only productivity reduces, and can not obtain needed precision of colour filter and safety.That is, also do not have to realize showing with the form of high opacifying property and film the photosensitive material of photosensitivity and resolving power, this has stoped the practical application of resin B M.

At present, about for example common photosensitive property resin or be used for the photoresist that the coloring photosensitive combination etc. of colour filter has certain light transmission, the method for improving photosensitivity and resolving power is known.For example, known that the photosensitive composite conduct that contains adhesive resin, polyfunctional acrylic monomer and initiator (said initiator comprises triaizine compounds) wherein is dispersed with the color composition for color filter (patent documentation 1～4) of pigment.And, know that also initiator wherein is the similar composition (patent documentation 5 and 6) of two imidazoles.But when the disclosed compsn of these documents was exposed in the air, oxygen stoped their polymerizations, can not obtain actual light sensitivity like this.

Like the situation of resin B M, all need in the situation of opacifying property in the overall optical wavelength region may, give photobehavior and have significant obstacle: (1) is difficult to make that to have cross-linking density between exposed portion and the unexposed portion poor; (2) even at exposed portion, on film thickness direction, also exist cross-linking density poor, promptly; Even solidified fully on light-struck surface; Substrate also do not solidify and (3) owing to be mixed with a large amount of black colorant materials that is insoluble to developing solution, so development property obviously reduces.

Especially, above-mentioned phenomenon (1) and (2) are conflicting, and when having exposed portion when more being prone to solidified and forming, the cured density difference on film thickness direction becomes more remarkable, causes resolving power to reduce like this.And, if do not make the cured density of cross-linking density difference and exposed portion between exposed portion and the unexposed portion even, will be difficult to the developing solution that uses solvency power strong, so also will be difficult to improve development property.Usually the photosensitive composite of knowing that is used to form resin B M (for example patent documentation 7 and 8) is exactly to avoid this situation; But do not form the resin B M that opacifying property equates with metal BM; But form the resin B M that has photoperceptivity through printing opacity to a certain extent; Its light shielding ability is very low like this, thereby and impracticable.Therefore, also propose a kind of resin B M of form of film of high opacifying property, it is obtained by following mode: in case form the resin B M of the high thickness of low opacifying property, just make it be cured step and make film shrink (patent documentation 9).But because this method is complicated, and the distortion when shrinking because of film accumulates tack will be reduced, so this resin is difficult to practicality.Therefore, the problem of existence is, under original and the afoul shading condition of photoresponse, carrying out photoresponse, and this is obvious contradiction, so be difficult to realize the resin B M of practicality.

And, known the technology (patent documentation 10) of specific oxime ester compound of using as Photoepolymerizationinitiater initiater.But, only can't improve the needed picture characteristics of resin B M, i.e. light sensitivity and resolving power through the initiator (for example two imidazoles or triazine initiator) that is used for conventional resin B M with the oxime compound replacement.

And; The demand of the optical polymerism composition of high photosensitivity is extensive; It not only is used to have the BM of black pigment, and with compsn etc., its technical problem mainly is the selection of Photoepolymerizationinitiater initiater with compsn, rib wall but also be used to form compsn, the light spacer of red, green and blue pixel.

Patent documentation 1: the spy opens flat 1-152449 communique

Patent documentation 2: the spy opens flat 1-254918 communique

Patent documentation 3: the spy opens flat 2-153353 communique

Patent documentation 4: the spy opens flat 2-804 communique

Patent documentation 5: the spy opens flat 6-75372 communique

Patent documentation 6: the spy opens flat 6-75373 communique

Patent documentation 7: the spy opens flat 6-51499 communique

Patent documentation 8: the spy opens flat 6-3518 communique

Patent documentation 9: the spy opens flat 8-44050 communique

Patent documentation 10: the spy opens the 2000-80068 communique

Summary of the invention

The problem that the present invention solves

For overcoming the problems referred to above; The present invention provides a kind of anticorrosive additive material with sufficient light sensitivity and resolving power; Use this anticorrosive additive material can easily form the pattern of the form of film of high opacifying property, and make the resin B M that can high-precision low cost ground prepares colour filter through photolithography.And use has excellent display performance, for example contrast gradient by the liquid crystal indicator of the colour filter of above-mentioned resins.And,,, can obtain the free of contamination colour filter of high image quality through resin is used for BM according to the present invention.

And,, need to increase the coloured material concentration in the employed coloured composition in recent years in order to obtain colour filter needed " high density ".On the contrary, because the light transmission of this colored resin composition reduces, keep and improve image and form property so need have more the photopolymerizable material of ISO.The present invention will address the above problem exactly.

In addition, need the production of high-precision low cost ground to be used to make the following photosensitive composite of liquid crystal indicator day by day: be used for the photosensitive composite of light spacer or rib wall, and the photosensitive composite that uses the photopolymerizable material.Need have the more photopolymerizable Image forming material of ISO in addition.The present invention will address the above problem.

The method of dealing with problems

The inventor has carried out detailed research; The result finds; Can realize above-mentioned purpose through using following optical polymerism composition; The Epocryl that the specific oxime ester compound that comprises the structure with further improvement photopolymerization efficient in the said compsn is simultaneously made Photoepolymerizationinitiater initiater and had a carboxyl is made organic binder bond.

And the inventor finds that this specific oxime ester compound itself is new compound, no matter whether coloured material exists, it all is effectively as the Photoepolymerizationinitiater initiater of excellence, has accomplished the present invention like this.

That is to say, the purpose of this invention is to provide oxime ester compound by formula (1) or (2) expression:

In the formula, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _1-20Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Assorted aryloxy carbonyl alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1aCan form ring with R1 ', its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer);

R ^2aExpression can have substituent C separately _2-12Alkyloyl, C _3-25Enoyl-, C _3-8Cycloalkanes acyl group, C _7-20Benzoyl-, C _1-204-hetaroylpyrazol, C _2-10Carbalkoxy or C _7-20Carbobenzoxy; With

R1 ' expression contains the optional substituting group of aromatic ring or hetero-aromatic ring;

In the formula, R ^1bExpression can have substituent C separately _6-20Phenyl, C _1-20Alkyl, C _5-8Naphthenic base, C _2-20Alkyloyl, C _7-20Benzoyl-, C _2-12Carbalkoxy or carbobenzoxy, C _1-20Amido, nitro, C _2-25Alkenyl, C _1-10Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Assorted aryloxy carbonyl alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1bCan form ring with R1 ', its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer);

R ^2bExpression can have substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl, C _3-20Assorted aryloxy carbonyl alkyloyl or C _2-10Aminocarboxyl; With

R1 ' expression contains the optional substituting group of aromatic ring or hetero-aromatic ring.

Another object of the present invention provides above-mentioned oxime ester compound, wherein, and in formula (1),

R ^1aBe to have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, or R ^1aWith R1 ' formation ring, its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or they combination (n is 0～3 integer) and

R ^2aBe to have substituent C _2-12Alkyloyl.

Another object of the present invention provides above-mentioned oxime ester compound, wherein, and in formula (2),

R ^1bBe to have substituent C _1-20Alkyl and

R ^2bBe to have substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl.

Another object of the present invention provides the oxime ester compound by formula (3) or (4) expression:

In the formula, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _1-20Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Assorted aryloxy carbonyl alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1aWith R ³Or R ⁷Can form ring, in this case, R ^1aWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer);

R ³, R ⁴, R ⁵, R ⁶And R ⁷Represent Wasserstoffatoms, halogen atom independently of one another or can have substituent C separately _1-12Alkyl, C _1-12Alkoxyl group, C _5-8Naphthenic base, C _6-20Phenyl, C _7-20Benzyl, C _7-20Benzoyl-, C _2-12Alkyloyl, C _1-204-hetaroylpyrazol, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl, C _3-20Assorted aryloxy carbonyl alkyloyl, C _2-12Carbalkoxy or carbobenzoxy, perhaps-OR ⁸,-SR ⁹,-SOR ⁹,-SO ₂R ⁹Or NR ¹⁰R ¹¹, and, R ³, R ⁴, R ⁵, R ⁶And R ⁷In at least one expression-OR ⁸,-SR ⁹Or NR ¹⁰R ¹¹, R wherein ⁸The expression Wasserstoffatoms maybe can have substituent C _1-12Alkyl, C _2-8Alkyloyl, C _3-12Alkenyl, C _3-20Enoyl-, C _6-20Phenyl ,-(CH ₂CH ₂O) _mH (m is 1～20 integer) or C _3-15Trialkylsilkl, R ⁹Represent Wasserstoffatoms or can have substituent C separately _1-12Alkyl, C _2-8Alkyloyl, C _3-12Alkenyl, C _6-20Phenyl or C _3-15Trialkylsilkl, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl, and, R ³～R ⁷Bonding each other, or they each can with R ¹Bonding forms ring structure;

In the formula, R ^1bExpression can have substituent C separately _6-20Phenyl, C _1-20Alkyl, C _5-8Naphthenic base, C _2-20Alkyloyl, C _7-20Benzoyl-, C _2-12Carbalkoxy or carbobenzoxy, C _1-20Amido, nitro, C _2-25Alkenyl, C _1-10Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Assorted aryloxy carbonyl alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1bWith R ³Or R ⁷Can form ring, in this case, R ^1bWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer);

R ³, R ⁴, R ⁵, R ⁶And R ⁷Identical with in the formula (3).

Another object of the present invention provides a kind of oxime ester compound, wherein, and in formula (3),

R ^1aBe to have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, or R ^1aWith R ³Or R ⁷Form ring together, in this case, R ^1bWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer),

R ^2aBe to have substituent C _2-12Alkyloyl and

R ³, R ⁴, R ⁵, R ⁶And R ⁷Represent Wasserstoffatoms, halogen atom independently of one another or can have substituent C separately _1-12Alkyl, C _6-20Phenyl, C _1-204-hetaroylpyrazol or NR ¹⁰R ¹¹, and, R ³, R ⁴, R ⁵, R ⁶And R ⁷In at least one expression-NR ¹⁰R ¹¹(wherein, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl), and, R ³～R ⁷Bonding each other, or each and R in them ^1aBonding forms ring structure.

Another object of the present invention provides above-mentioned oxime ester compound, wherein, and in formula (4),

R ^1bExpression can have substituent C _1-20Alkyl,

R ^2bExpression can have substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl; With

R ³, R ⁴, R ⁵, R ⁶And R ⁷Represent Wasserstoffatoms, halogen atom separately independently of each other or can have substituent C separately _1-12Alkyl, C _6-20Phenyl, C _1-204-hetaroylpyrazol or-NR ¹⁰R ¹¹, R ³, R ⁴, R ⁵, R ⁶And R ⁷In at least one expression-NR ¹⁰R ¹¹(wherein, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl), and, R ³～R ⁷Bonding each other, or can with R ^1bBonding forms ring structure.

Another object of the present invention provides the oxime ester compound by any expression in formula (5)～(7):

In the formula, R ^1aAnd R ^2aIdentical with in the defined aforementioned formula of claim 4 (3); With

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Each is Wasserstoffatoms, halogen atom or can have substituent C separately naturally _1-12Alkyl, C _2-12Enoyl-, C _6-20Phenyl, C _7-20Benzyl or benzoyl-or-NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding forms ring structure each other:

In the formula, R ^1bAnd R ^2bIdentical with in the following formula (4); With

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Identical with in the following formula (5);

In the formula, R ^1bIdentical with in the following formula (4);

R ²R in the expression following formula (3) ^2aOr the R in the following formula (4) ^2bWith

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Each is Wasserstoffatoms, halogen atom or can have substituent C separately naturally _1-12Alkyl, C _2-12Enoyl-, C _6-20Phenyl, C _7-20Benzyl or benzoyl-or-NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding forms ring structure each other, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶In at least one contains and is selected from by having substituent C separately _1-20Heteroaralkyl, assorted aralkanoyl and 4-hetaroylpyrazol and C _3-15At least a group in the group that trialkylsilkl is formed.

Another object of the present invention provides oxime ester compound, wherein, and in formula (5),

R ^1aBe to have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, or R ^1aWith R ³Or R ⁷Can form ring together, in this case, R ^1aWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer),

R ^2aBe to have substituent C _2-12Alkyloyl; With

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Each is Wasserstoffatoms, halogen atom or can have substituent C separately naturally _1-12Alkyl, C _2-12Enoyl-, C _6-20Phenyl, C _7-20Benzyl or benzoyl-or-NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding forms ring structure each other.

Another object of the present invention provides oxime ester compound, wherein, and in formula (6),

R ^1bBe to have substituent C _1-20Alkyl,

R ^2bBe to have substituent C separately _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl; With

Another object of the present invention provides the oxime ester compound by formula (8) or (9) expression:

In the formula, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _1-20Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Heteroaryloxy carbonylic alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1aWith Ar ₁Can form ring together, its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer),

R ^2aIdentical with in the defined formula of claim 1 (1);

Ar ₁Expression can have substituent aromatic ring, hetero-aromatic ring, fused aromatic rings or fused heteroaromatic ring separately; With

P representes 2～5 integer.

In the formula, R ^1bExpression can have substituent C separately _6-20Phenyl, C _1-20Alkyl, C _5-8Naphthenic base, C _2-20Alkyloyl, C _7-20Benzoyl-, C _2-12Carbalkoxy or carbobenzoxy, C _1-20Amido, nitro, C _2-25Alkenyl, C _1-10Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-20Assorted aryloxy carbonyl alkyl or heteroarylthio alkyl, C _0-20Amino or C _1-20Aminoalkyl group, and, R ^1bWith Ar ₁Can form ring together, its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer);

R ^2bIdentical with in the defined formula of claim 1 (2);

P representes 2～5 integer.

Another object of the present invention provides oxime ester compound, wherein, and in formula (8),

R ^1aExpression can have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, and, R ^1aWith Ar ₁Can form ring together, in this case, R ^1aWith Ar ₁Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or they combination (n is 0～3 integer) and

R ^2aExpression can have substituent C _2-12Alkyloyl.

Another object of the present invention provides oxime ester compound, wherein, and in formula (9),

R ^1bExpression can have substituent C _1-20Alkyl and

R ^2bExpression can have substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl.

Another object of the present invention provides a kind of optical polymerism composition that comprises organic binder bond (b) and Photoepolymerizationinitiater initiater (c), and wherein component (c) contains above-mentioned oxime ester compound.

Another object of the present invention provides above-mentioned photopolymerizable composition, and wherein organic binder bond (b) is the Epocryl with carboxyl.

Another object of the present invention provides above-mentioned photopolymerizable composition, wherein organic binder bond (b) epoxy acrylate that to be novolac epoxy obtain with (methyl) acrylic acid reaction product and (hydrogenation) phthalic anhydride.

Another object of the present invention provides above-mentioned photopolymerizable composition, and said photopolymerizable composition also contains photopolymerization monomer (d).

Another object of the present invention provides above-mentioned photopolymerizable composition, and said photopolymerizable composition also contains the macromolecule dispersing agent (e) with basic functionality.

Another object of the present invention provides above-mentioned photopolymerizable composition, and said photopolymerizable composition also contains coloured material (a).

Another object of the present invention provides a kind of colour filter, and said colour filter has the image that forms with above-mentioned optical polymerism composition.

Another object of the present invention provides a kind of liquid crystal indicator, and said liquid crystal indicator has the image that forms with above-mentioned optical polymerism composition.

The invention effect

Oxime ester compound of the present invention can be as the Photoepolymerizationinitiater initiater of new high photosensitivity.It is combined with organic binder bond and coloured material, can be configured for the optical polymerism composition of colour filter.Particularly when combining, when the optical polymerism composition that obtains or even the form of film of high opacifying property, also have excellent light sensitivity and resolving power, can form high-quality resin B M at low cost like this with the black colorant material.Use the colour filter of resin B M of the present invention to have excellent accuracy, flatness and weather resistance, it can improve the display quality of liquid crystal cell like this.And, because production process and colour filter itself do not use deleterious material, thus danger can be reduced to human body, and improve environmental safety.And the present invention is not limited to and is used for BM, also is applicable to the transparent photosensitive composite that does not use coloured material, for example is used for light spacer or rib wall (liquidcrystal divided-alignment protrusion), and is widely used for various technical fields.

Description of drawings

Fig. 1 is the synoptic diagram that the explanation contact angle receives the state of thermal distortion.

Nomenclature

W1: the contact angle that the side of heating preleptonema image and substrate plane form.

W2: the contact angle that the side of heating back fine rule image and substrate plane form.

Embodiment

(a) coloured material

In the present invention, the optional component of coloured material, but coloured material is used in combination in many purposes.Here, coloured material is to the painted material of photosensitive composite.As coloured material, can mention dyestuff and pigment, but from thermotolerance, photostabilization equal angles, preferred pigments.As pigment, can use versicolor pigment, for example blue pigments, veridian, red pigment, yellow ultramarine, violet pigment, orange pigments, brown pigments and black pigment.And; About their structure, for example also can use pigment dyestuff such as azo-type, phthalocyanine type, quinacridone type, benzimidazolone type, isoindolinone type 、 dioxazine (dioxadine) type, indanthrene type and perylene type and various mineral dyes etc.With the pigment sequence number object lesson of operable pigment is represented as follows.For example following terms such as " C.I. Pigment reds 2 " is represented pigment index (C.I.).

As red pigment, can mention C.I. Pigment red 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275 and 276.In them, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242 and 254, more preferably the C.I. Pigment red 177,209,224 and 254.

As blue pigments, can mention C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78 and 79.In them, preferred C.I. pigment Blue 15,15:1,15:2,15:3,15:4 and 15:6, more preferably C.I. pigment Blue 15: 6.

As veridian, can mention C.I. Pigment green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54 and 55.In them, preferred C.I. pigment Green 7 and 36.

As yellow ultramarine, can mention C.I. Pigment Yellow 73 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207 and 208.In them, preferred C.I. pigment yellow 83,117,129,138,139,150,154,155,180 and 185, more preferably C.I. pigment yellow 83,138,139,150 and 180.

As orange pigments, can mention C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79.In them, preferred C.I. pigment orange 38 and 71.

As violet pigment, can mention C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49 and 50.In them, preferred C.I. pigment violet 19 and 23, more preferably C.I. pigment Violet 23.

As the black colorant material, can use independent black material or with blended black colorant materials such as red, green or indigo plant.This black colorant material can be selected from inorganic and pigment dyestuff and dyestuff arbitrarily, can use individually or use with the mixture of several types.

Single black colorant material for example is carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine, cyanines are black or titanium is black.In them, from the angle of shading ratio and picture characteristics, preferred especially carbon black and titanium are black.Can mention that following commodity are as commercially available sooty example.

Product by the production of Mitsubishi Chemical society: MA7, MA8, MA11, MA100, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900 etc.

Product by DEGGUSA production: Printex 95, Printex 90, Printex 85, Printex75, Printex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 550, Special Black 350, Special Black 250, SpecialBlack 100 etc.

Product by Cabot Corporation production: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, BLACK PEARLS 480, PEARLS 130 etc.

Product by Columbian Chemicals production: RAVEN 11, RAVEN 15, RAVEN30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040 etc.

Explain the black colorant material that obtains through mixing now.6), Lionogen Red GD (Pigment red 168), the green 2YS of Li Nuoer (pigment green 36) (the numeral pigment index (C.I.) in the top bracket) as the object lesson of the coloured material that is used for the blended base material, can mention that Victoria's ethereal blue (42595), auramine O (41000), card are for dragon (catilon) lucidin (alkalescence 13), rhodamine 6G CP (45160), rhodamine B (45170), safranine OK 70:100 (50240), Erio Grawsin X (42080), the sharp Nore of No.120/ (lionol) yellow (21090), the yellow GRO (21090) of Li Nuoer, the fast yellow 8GF of Simla (Shimilor) (21105), diarylide yellow 4T-564D (21095), Simla's fast red 4015 (12355), the red 7B4401 of Li Nuoer (15850), strong turquoise (Fast Gen Blue) TGR-L (74160), the blue SM (26150) of Li Nuoer, the blue ES of Li Nuoer (pigment Blue 15:.

And; As example through operable other pigment of mixing; With reference to the C.I. sequence number, can mention C.I. yellow ultramarine 20,24,86,93,109,110,117,125,137,138,147,148,153,154 and 166, C.I. orange pigments 36,43,51,55,59 and 61, C.I. red pigment 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228 and 240, C.I. violet pigment 19,23,29,30,37,40 and 50, C.I. blue pigments 15,15:1,15:4,22,60 and 64, C.I. veridian 7 and C.I. brown pigments 23,25 and 26.

Above-mentioned carbon black can use with other black or colored inorganic or pigment dyestuff.Other pigment have opacifying property or the picture characteristics lower than carbon black, so its blending ratio receives himself to limit.

As producing the black method of titanium; The mixture that for example can mention in reducing atmosphere heating titanium oxide and metal titanium carries out reductive method (spy opens clear 49-5432 communique), in containing the reducing atmosphere of hydrogen and also the method (spy opens clear 57-205322 communique) of the superfine titanic oxide that reason titanium tetrachloride pyrohydrolysis obtains, in the presence of ammonia high temperature reduction titanium oxide or titanium hydroxide method (spy opens clear 60-65069 communique, the spy opens clear 61-201610 communique) and vanadium compound adhered on titanium oxide or the titanium hydroxide; Then the method (spy opens clear 61-201610 communique) of high temperature reduction in the presence of ammonia still is not limited to these methods.

The example that commercially available titanium is black can be mentioned the black 10S of titanium, 12S, 13R, 13M, the 13M-C that Mitsubishi Material Corporation produces.

(b) organic binder bond

In the present invention, when constituting optical polymerism composition, use organic binder bond (b).Do not limit organic binder bond especially, still, preferred especially the Epocryl that uses with carboxyl.

With α, β-unsaturated monocarboxylic acid or have the α of carboxyl at ester moiety, β-unsaturated monocarboxylic acid ester adds on the epoxy resin, makes multi-anhydride and its reaction again, thereby obtains described Epocryl.See that from chemical structure this reaction product does not have epoxy group(ing) basically, and be not limited to " propenoate ", still, epoxy resin is its raw material, and " propenoate " be its exemplary, therefore so name of custom.

As raw material epoxy resin, for example preferably use (adjacent,, to)-the cresols phenol aldehyde type epoxy resin, phenol phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, tris-phenol type epoxy resin or the epoxy resin (No. 2878486 communique of Japanese Patent) that is expressed from the next:

In the weight-average molecular weight that GPC measures, the molecular weight of epoxy resin is generally 200～200, and 000, preferred 300～100,000.If molecular weight is less than above-mentioned scope, film forms the property existing problems in many cases.On the other hand,,, be easy to take place gelationization during the addition reaction of β-unsaturated monocarboxylic acid, will be difficult to produce this resin at α if it surpasses above-mentioned scope.

α, β-unsaturated monocarboxylic acid for example are methylene-succinic acid, Ba Dousuan, styracin, acrylic or methacrylic acid, are preferably acrylic or methacrylic acid, see from the angle of hyperergy, preferred especially vinylformic acid.Have the α of carboxyl at ester moiety, β-unsaturated monocarboxylic acid ester for example is vinylformic acid-2-amber acyloxy ethyl ester, vinylformic acid-2-Malaysia acyloxy ethyl ester, vinylformic acid-2-O-phthalic acyl-oxygen base ethyl ester, vinylformic acid-2-six hydrogen O-phthalic acyl-oxygen base ethyl esters, methylacrylic acid-2-amber acyloxy ethyl ester, methylacrylic acid-2-Malaysia acyloxy ethyl ester, methylacrylic acid-2-O-phthalic acyl-oxygen base ethyl ester, methylacrylic acid-2-six hydrogen O-phthalic acyl-oxygen base ethyl esters or Ba Dousuan-2-amber acyloxy ethyl ester.Preferred vinylformic acid-2-Malaysia acyloxy ethyl ester or vinylformic acid-2-O-phthalic acyl-oxygen base ethyl ester, preferred especially vinylformic acid-2-Malaysia acyloxy ethyl ester.

Can carry out α with known method, the addition reaction of β-unsaturated monocarboxylic acid or its ester and epoxy resin.For example, can in the presence of esterifying catalyst, under 50～150 ℃ temperature, react.Esterifying catalyst for example is a tertiary amine, for example triethylamine, Trimethylamine 99, benzyl dimethyl amine or benzyl DIETHANOL AMINE, or quaternary ammonium salt, for example tetramethylammonium chloride, tetraethylammonium chloride or chlorination dodecyl trimethyl ammonium.

Based on 1 normal epoxy group(ing) in the raw material epoxy resin, α, the amount of β-unsaturated monocarboxylic acid or its ester is preferably 0.5～1.2 equivalent, more preferably 0.7～1.1 equivalent.If α, the amount of β-unsaturated monocarboxylic acid or its ester is little, and the amount of the unsaturated group of introducing is insufficient, subsequently with the reaction of multi-anhydride with insufficient.And residual a large amount of epoxy group(ing) is disadvantageous.On the other hand, if should amount big, α then, β-unsaturated monocarboxylic acid or its ester left behind as unreacted product.In every kind of situation, curing characteristics is all with variation.

The α that further added to addition, the multi-anhydride on the epoxy resin of beta-unsaturated carboxylic acid or its ester can be for example maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, PMA acid anhydride, trimellitic acid 1,2-anhydride, benzophenone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, interior methylene radical Tetra Hydro Phthalic Anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, methyl tetrahydrophthalic anhydride or BPDA.Preferred maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, PMA acid anhydride, trimellitic acid 1,2-anhydride or BPDA, preferred especially Tetra Hydro Phthalic Anhydride or BPDA.

Also can carry out the addition of multi-anhydride with known method, can with α, react continuously under the same terms of the addition of beta-unsaturated carboxylic acid or its ester.The addition amount of preferred multi-anhydride makes the acid number of the Epocryl that forms in the scope of 10～150mgKOH/g, more preferably 20～140mgKOH/g.If the acid number of resin is lower than above-mentioned scope, alkali-developable is with variation so, if it surpasses above-mentioned scope, curing characteristics is with variation.

As organic binder bond (b), except Epocryl, can also use following resin with carboxyl.Following resin comprises the resin that belongs to Epocryl, and said resin must not range diverse material.

That is to say; For example, preferably for example can mention homopolymer or multipolymer, carboxylic Vinylite and polymeric amide, polyester, polyethers, urethane, polyvinyl butyral acetal, Z 150PH, PVP K120 and the ethanoyl Mierocrystalline cellulose of (methyl) vinylformic acid, (methyl) propenoate, (methyl) vinyl cyanide ((meth) acrylonitrole), (methyl) acrylic amide, toxilic acid, vinylbenzene, vinyl-acetic ester, vinylidene chloride or maleimide.In them, form the angle of property from alkali-developable and image, preferred above-mentioned Epocryl and carboxylic Vinylite with carboxyl more preferably has the Epocryl of carboxyl.

Carboxylic Vinylite can be the multipolymer of for example unsaturated carboxylic acid and vinyl compound; Said unsaturated carboxylic acid for example is (methyl) vinylformic acid, Ba Dousuan, iso-crotonic acid, toxilic acid, maleic anhydride, methylene-succinic acid or citraconic acid; Said vinyl compound for example is vinylbenzene, alpha-methyl styrene, hydroxy styrenes, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) vinylformic acid pentyl ester, (methyl) NSC 11786, (methyl) vinylformic acid dodecyl ester, (methyl) ethyl acrylate, (methyl) vinylformic acid hydroxyl methyl esters, (methyl) Hydroxyethyl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid DCPA, (methyl) benzyl acrylate, (methyl) vinylformic acid-N; N-dimethylamino ethyl ester, N-(methyl) acryloyl morpholine, (methyl) vinyl cyanide, (methyl) acrylic amide, N-formyl radical (methyl) acrylic amide, N; N-dimethyl-(methyl) acrylic amide, N, N-dimethyl aminoethyl (methyl) acrylic amide or vinyl-acetic ester.

In above-mentioned multipolymer; Optimization styrene/(methyl) propenoate/(methyl) PEMULEN TR2 more preferably comprises (methyl) propenoate of the vinylbenzene of 3 moles of %～30 mole %, 10 moles of %～70 mole % and (methyl) acrylic acid multipolymer of 10 moles of %～60 mole %.Especially, preferably comprise (methyl) propenoate of the vinylbenzene of 5 moles of %～25 mole %, 20 moles of %～60 mole % and (methyl) acrylic acid multipolymer of 15 moles of %～55 mole %.And this carboxylic Vinylite has 30～250mg-KOH/g, preferred 50～200mg-KOH/g, the more preferably acid number of 70～150mg-KOH/g.

And above-mentioned carboxylic Vinylite is preferably the resin that has the ethylenic unsaturated link(age) in the side chain.It can be following reaction product: for example; The unsaturated compound of carboxylic polymkeric substance and fatty family epoxy group(ing) or contain the reaction product that the unsaturated compound reaction of alicyclic epoxy base obtains; 5 moles of %～90 mole % of the carboxyl that this carboxylic polymkeric substance had, preferred about 30 moles of %～about 70 moles of % participate in reaction; The unsaturated compound of said fatty family epoxy group(ing) for example is glycidyl allyl ether, (methyl) glycidyl acrylate, (methyl) vinylformic acid-α-ethyl glycidyl ester, Ba Dousuan glycidyl ester, iso-crotonic acid glycidyl ester, crotonyl glycidyl ether, an alkyl one glycidyl itaconic ester, an alkyl one glycidyl fumarate or an alkyl one glycidyl maleic acid ester; The said unsaturated compound that contains the alicyclic epoxy base for example is (methyl) vinylformic acid-3; 4-epoxycyclohexyl methyl esters, (methyl) vinylformic acid-2; 3-oxirane ring amyl group methyl esters or (methyl) vinylformic acid-7, the 8-epoxy [three the ring [5.2.1.0] last of the ten Heavenly stems-the 2-yl] the oxygen methyl esters; Or below the reaction product that has unsaturated carboxylic acid such as the compound of at least two kinds of unsaturated groups and for example (methyl) vinylformic acid or obtain with the esters of unsaturated carboxylic acids copolymerization again; Make aforementioned 10 moles of all %～90 mole % of compound with unsaturated group; Copolymerization takes place in preferred about 30 moles of %～about 80 moles of %; Said compound for for example (methyl) allyl acrylate, (methyl) vinylformic acid-3-allyloxy-2-hydroxypropyl acrylate, (methyl) vinylformic acid cinnamic ester, (methyl) vinylformic acid crotons ester, (methyl) vinylformic acid first for allyl ester or N; N-diallyl (methyl) acrylic amide etc. has the compound of at least two kinds of unsaturated groups, or for example (methyl) vinyl acrylate, (methyl) vinylformic acid-1-vinylchlorid ester, (methyl) vinylformic acid-2-phenyl vinyl acetate, (methyl) vinylformic acid-1-propylene ester, Vinyl crotonate or vinyl (methyl) acrylic amide etc. have the compound of at least two kinds of unsaturated groups.

And, when optical polymerism composition is used to form liquidcrystal divided-alignment protrusion, especially, in the situation of Epocryl with carboxyl; The weight-average molecular weight of measuring with GPC (GPC) of calculating by PS is generally at least 1,000, and preferably at least 1,500; And usually at the most 30,000, preferably at the most 20,000; More preferably at the most 10,000, especially preferably at the most 5,000.In the situation of carboxylic Vinylite, it is generally at least 1,000, and preferably at least 1,500, more preferably at least 2,000, and usually at the most 100,000, preferably at the most 50,000, more preferably at the most 20,000, especially preferably at the most 10,000.When comprising the organic binder bond with the molecular weight in the above-mentioned scope, the distortion of optical polymerism composition will be significant during heating, therefore, possibly form arc-shaped protrusions, and this arc-shaped protrusions has the favourable shape as liquidcrystal divided-alignment protrusion.

(c) Photoepolymerizationinitiater initiater

Optical polymerism composition of the present invention contains by the oxime ester compound of formula (1) or (2) expression as Photoepolymerizationinitiater initiater:

In the formula, the definition in the implication of symbol such as the following formula (1).

In formula (1), preferably, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, R ^1aCan form ring with R1 ', its linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer), and R ^2aExpression can have substituent C separately _2-12Alkyloyl, and R1 ' expression contains the optional substituting group of aromatic ring or hetero-aromatic ring;

In the formula, the definition in the implication of symbol such as the following formula (2).

In formula (2), preferably, R ^1bExpression C _1-20Alkyl, R ^2bExpression can have substituent C separately _1-20Heteroaryl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl; And R1 ' expression contains the optional substituting group of aromatic ring or hetero-aromatic ring.

In oxime ester compound by formula (1) and (2) expression, the compound of preferably representing by formula (3) or (4):

In the formula, the definition in the implication of symbol such as the following formula (3).

In formula (3), preferably, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, and R ^1aWith R ³Or R ⁷Can form ring.In this case, R ^1aWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer), R ^2aExpression can have substituent C _2-12Alkyloyl, R ³, R ⁴, R ⁵, R ⁶And R ⁷Represent Wasserstoffatoms, halogen atom independently of one another or can have substituent C separately _1-12Alkyl, C _6-20Phenyl, C _1-204-hetaroylpyrazol or-NR ¹⁰R ¹¹, and R ³, R ⁴, R ⁵, R ⁶And R ⁷In at least one expression-NR ¹⁰R ¹¹, and, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl, R ³～R ⁷Bonding or each and R in them each other ¹Bonding forms ring structure.

In the formula, the definition in the implication of symbol such as the following formula (4).

In formula (4), preferably, R ^1bFor having substituent C _1-20Alkyl, R ^2bFor having substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl; R ³, R ⁴, R ⁵, R ⁶And R ⁷Represent Wasserstoffatoms, halogen atom independently of one another or can have substituent C separately _1-12Alkyl, C _6-20Phenyl, C _1-204-hetaroylpyrazol or-NR ¹⁰R ¹¹, and R ³, R ⁴, R ⁵, R ⁶And R ⁷In at least one expression-NR ¹⁰R ¹¹(wherein, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl), and, R ³～R ⁷Each other bonding or in them each can with R ^1bBonding forms ring structure.

More preferably, oxime ester compound is the compound by any expression in following formula (5)～(7):

In the formula, the definition in the implication of symbol such as the following formula (5).

Preferably, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _1-10Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-15Heteroarylthio alkyl, C _2-12Dialkylamino, C _1-15Dialkylaminoalkyl or C _3-15N-acyloxy-N-amidoalkyl, or R ^1aWith R ³And/or R ⁷Bonding forms and can have substituent C separately each other _1-15Alkylidene group ,-(CH=CH) _n-or their combination.

More preferably, R ^1aExpression can have substituent C separately _2-12Alkenyl, C _3-12Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-10Heteroarylthio alkyl or C _2-8Amino, or R ^1aWith R ³And/or R ⁷Bonding forms and can have substituent C separately each other _1-10Alkylidene group ,-(CH=CH) _n-or their combination.

In above-mentioned, n is 0～3 integer, preferred 1 or 2.

Preferably, R ^2aExpression can have substituent C separately _2-12Alkyloyl, C _3-12Enoyl-, C _3-8Cycloalkanes acyl group, C _7-15Benzoyl-, C _1-154-hetaroylpyrazol, C _2-10Carbalkoxy or C _7-20Carbobenzoxy, C _3-12Dialkylamino carbonyl or C _7-15The phenylamino carbonyl.

Preferably, R ³, R ⁶, R ⁷And R ¹²～R ¹⁵Represent Wasserstoffatoms, halogen atom independently of one another or can have substituent C separately _1-12Alkyl, C _2-12Alkenyl, C _2-12Enoyl-, C _5-8Naphthenic base, C _6-12Phenyl, C _3-20Heteroaryl, C _7-12Benzoyl-, C _2-12Alkyloyl, C _3-204-hetaroylpyrazol, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl, C _3-20Assorted aryloxy carbonyl alkyloyl, C _3-20Assorted aryloxy carbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _3-20Assorted aryloxy carbonyl alkyl, C _2-12Carbalkoxy or carbobenzoxy or-OR ⁸Or NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁵Bonding or each and R in them each other ^1aBonding forms ring structure.

Preferably, R ¹⁶Expression can have substituent C separately _1-12Alkyl, C _2-12Alkenyl, C _2-12Enoyl-, C _5-8Naphthenic base, C _6-12Phenyl, C _3-20Heteroaryl, C _7-12Benzyl, C _7-12Benzoyl-, C _2-12Alkyloyl, C _3-204-hetaroylpyrazol, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _3-20Assorted aryloxy carbonyl alkyl, C _2-12Carbalkoxy or carbobenzoxy, C _3-15Trialkylsilkl or C _2-4Hydroxyalkyl, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding or each and R in them each other ^1aBonding forms ring structure.

Here, R ⁸Represent Wasserstoffatoms or can have substituent C separately _1-12Alkyl, C _2-8Alkyloyl, C _3-12Alkenyl, C _3-20Enoyl-, C _6-12Phenyl ,-(CH ₂CH ₂O) _mH (m is 1～20 integer, preferred 1～5) or C _3-15Trialkylsilkl, R ⁹Represent Wasserstoffatoms or can have substituent C separately _1-12Alkyl, C _2-8Alkyloyl, C _3-12Alkenyl or C _6-12Phenyl, R ¹⁰And R ¹¹Represent Wasserstoffatoms independently of one another or can have substituent C separately _1-12Alkyl, C _2-4Hydroxyalkyl, C _3-5Alkenyl or C _6-20Phenyl.

In the formula, the definition in the implication of symbol such as the following formula (6).

Preferably, R ^1bExpression can have substituent C separately _6-15Phenyl, C _1-10Alkyl, C _5-8Naphthenic base, C _2-15Alkyloyl, C _7-15Benzoyl-, C _2-12Carbalkoxy or C _7-12Carbobenzoxy, C _1-15Amido, nitro, C _2-15Alkenyl, C _1-10Heteroaralkyl, C _3-20Alkoxycarbonyl alkyl, C _1-15Heteroarylthio alkyl, C _2-12Dialkylamino, C _1-15Dialkylaminoalkyl or C _3-15N-acryloxy-N-acrylamido alkyl, or R ^1aWith R ³And/or R ⁷Bonding forms and can have substituent C separately each other _1-15Alkylidene group ,-(CH=CH) _n-or their combination.

More preferably, R ^1bExpression can have substituent C separately _6-15Phenyl, C _1-10Alkyl, C _5-8Naphthenic base, C _2-12Alkyloyl, C _7-12Benzoyl-, C _2-12Carbalkoxy or C _7-12Carbobenzoxy, C _1-10Amido, nitro, C _2-12Alkenyl, C _3-12Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl, C _1-10Heteroarylthio alkyl or C _2-8Amino, or R ^1aWith R ³And/or R ⁷Bonding forms and can have substituent C separately each other _1-10Alkylidene group ,-(CH=CH) _n-or their combination.

In above-mentioned, n is 0～3 integer, preferred 1 or 2.

Preferably, R ^2aExpression can have substituent C separately _1-15Heteroaryl, C _1-15Heteroaryl alkyloyl, C _3-15Carbalkoxy alkyloyl, C _8-15Carbobenzoxy alkyloyl, C _3-15Assorted aryloxy carbonyl alkyloyl or C _2-10Aminocarboxyl.

Preferred R ³, R ⁶, R ⁷And R ¹²～R ¹⁵And preferred R in the following formula (6) ³, R ⁶, R ⁷And R ¹²～R ¹⁵Identical.

Wherein, R ^1bWith middle define identical of following formula (4);

R ²R in the expression following formula (3) ^2aOr the R in the following formula (4) ^2b

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Respectively do for oneself Wasserstoffatoms, halogen atom or can have substituent C separately _1-12Alkyl, C _2-12Enoyl-, C _6-20Phenyl, C _7-20Benzyl or benzoyl-or-NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding forms ring structure, R each other ³, R ⁶, R ⁷And R ¹²～R ¹⁶In at least one group contain and be selected from by having substituent C separately _1-20Heteroaralkyl, assorted aralkanoyl and 4-hetaroylpyrazol and C _3-15At least a group in the group that trialkylsilkl is formed.

In the chemical formula of expression oxime ester compound of the present invention, separate R ^1a, R ^1b, R ^2a, R ^2bAnd R ²～R ¹⁶" can have substituent substituting group separately " be for example halogen atom, for example fluorine atom, chlorine atom, bromine atoms or iodine atom independently of one another; Hydroxyl; Nitro; Cyanic acid; Or optional organic group, this optional organic group for example is C _1-18Straight or branched alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, tert-pentyl, n-hexyl, n-heptyl, n-octyl or uncle's octyl group; C _1-18Naphthenic base, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl; C _2-18Straight or branched alkenyl, for example vinyl, propenyl or hexenyl; C _3-18Cycloalkenyl group, for example cyclopentenyl or cyclohexenyl; C _1-18The straight or branched alkoxyl group, for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec.-butoxy, tert.-butoxy, pentyloxy, uncle's pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy or uncle's octyloxy; C _1-18The straight or branched alkylthio, for example methylthio group, ethylmercapto group, positive rosickyite base, iprotiazem base, positive butylthio, secondary butylthio, uncle's butylthio, penta sulfenyl, uncle's penta sulfenyl, just own sulfenyl, positive heptan sulfenyl, positive hot sulfenyl or the hot sulfenyl of uncle; C _6-18Aryl, for example phenyl, tolyl, xylyl or mesityl; C _7-18Aralkyl, for example benzyl or styroyl; C _2-18Straight or branched alkene oxygen base, for example vinyloxy group, propenyloxy group or hexene oxygen base; C _2-18Straight or branched alkenylthio group, for example ethene sulfenyl, propylene sulfenyl or hexene sulfenyl; By-COR ¹⁷The acyl group of expression; Carbonyl; By-OCOR ¹⁸The acyloxy of expression; By-NR ¹⁹R ²⁰The amino of expression; By-NHCOR ²¹The amido of expression; By-NHCOOR ²²The carbamate groups of expression; By-CONR ²³R ²⁴The carbamyl of expression; By-COOR ²⁵The carboxylic acid ester groups of expression; By-SO ₃NR ²⁶R ²⁷The sulfamyl of expression; By-SO ₃R ²⁸The sulfonate ester group of expression; Saturated or unsaturated heterocycle group; For example 2-thienyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino base, pyrrolidyl or titanium dioxide THTP group; Or trialkylsilkl, for example trimethylsilyl.

And,,, for example can mention=N-OC (=O) R as the substituting group among the present invention except above-mentioned ²Deng substituting group.As such compound, R ^1aAnd R ^1bCan be to have=N-OC (=O) R separately ²Substituent C _1-20Alkyl, C _5-8Naphthenic base, C _2-20Alkyloyl, C _7-20Benzoyl-, C _2-12Carbalkoxy or carbobenzoxy or C _1-20Amido.

In above-mentioned, a plurality of substituting groups can bonding form ring, and formed ring can be saturated or unsaturated aromatic nucleus or heterocycle and the substituting group that can also have loop type, and substituting group can also form ring.

R ¹⁷～R ²⁸Represent Wasserstoffatoms separately, can have substituent alkyl, can have substituent alkenyl, can have substituent aryl and maybe can have substituent aralkyl.Position relation to them does not have special qualification, and when they had a plurality of substituting group, substituting group can be identical or different.

Described the compound by formula (5)～(7) expression above in detail, the compound with preferred substituted combination is summarized as follows.

The compound of formula (5), wherein

R ^1aBe to have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C ^1-20Aminoalkyl group, or R ^1aWith R ³Or R ⁷Form ring together, in this case, R ^1aWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer),

R ^2aExpression can have substituent C _2-12Alkyloyl and

The compound of formula (6), wherein

R ^1bExpression can have substituent C _1-20Alkyl,

R ^2bFor having substituent C separately _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl and

The compound of formula (7), wherein

R ^1bExpression can have substituent C _1-20Alkyl, C _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, or R ^1aWith R ³Or R ⁷Form ring together, in this case, R ^1aWith R ³And/or R ⁷Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer),

R ²For having substituent C separately _2-12Alkyloyl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl and

R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Each is Wasserstoffatoms, halogen atom or can have substituent C separately naturally _1-12Alkyl, C _2-12Enoyl-, C _6-20Phenyl, C _7-20Benzyl or benzoyl-or-NR ¹⁰R ¹¹, and, R ³, R ⁶, R ⁷And R ¹²～R ¹⁶Bonding forms ring structure, R each other ³, R ⁶, R ⁷And R ¹²～R ¹⁶In at least one group contain at least a group that is selected from following group, described group by having substituent C separately _1-20Heteroaralkyl, assorted aralkanoyl and 4-hetaroylpyrazol and C _3-15Trialkylsilkl is formed.

In addition, by the compound of following formula (8) or (9) expression preferably as oxime ester compound:

The wherein definition in symbol such as the following formula (8).

In formula (8), preferably, R ^1aExpression can have substituent C separately _2-25Alkenyl, C _3-20Alkoxycarbonyl alkyl, C _8-20Carbobenzoxy alkyl or C _1-20Aminoalkyl group, and, R ^1aWith Ar ₁Can form ring together, in this case, R ^1aWith Ar ₁Bonding forms divalence or trivalent linking group each other, and this linking group is can have substituent C separately _1-10Alkylidene group ,-(CH=CH) _n-,-(C ≡ C) _n-or their combination (n is 0～3 integer), and R ^2aExpression can have substituent C _2-12Alkyloyl.

The wherein definition in symbol such as the following formula (9).

In formula (9), preferably, R ^1bExpression can have substituent C _1-20Alkyl, R ^2bExpression can have substituent C separately _1-20Heteroaryl, C _1-20Assorted aralkanoyl, C _3-20Carbalkoxy alkyloyl, C _8-20Carbobenzoxy alkyloyl or C _2-10Aminocarboxyl.

And, Ar ₁Be the part that needs for compound absorb light of the present invention, preferably use absorbing wavelength to be 200nm at least, preferred 200～500nm, the more preferably compound of the light of 250～500nm.Particularly, Ar ₁It for example is the ring that phenyl ring, phenanthrene ring, azulene, fluorenes ring, acenaphthylene ring, indenes ring or aromatic nucleus, furan nucleus, thiphene ring, pyrrole ring 、 oxazole ring 、 isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazoles ring, furazan ring, triazole ring, pyranoid ring, thiadiazoles Huan 、 oxadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, the pyrazine ring that contains their condensed ring contain their condensed ring; Or comprise aromatic nucleus and heterocyclic condensed ring, for example acridine ring, phenanthridines ring, xanthene ring, carbazole ring, azophenlyene ring, thiodiphenylamine ring 、 phenoxazine ring or benzothiazole ring.

P corresponding be selected from above-mentioned aromatic nucleus, assorted aromatic nucleus, condense aromatic nucleus and condense the Ar of assorted aromatic nucleus ₁The middle commutable Wasserstoffatoms number that exists, P is generally 2～5, and preferred 2～3.

According to substituent combination, the object lesson of preferred compound of the present invention is illustrated in the following table 1 (1)～1 (6).

And,, can use above-mentioned oxime ester compound in combination individually or with other Photoepolymerizationinitiater initiaters as Photoepolymerizationinitiater initiater of the present invention.Be used in combination other Photoepolymerizationinitiater initiaters and can expect to obtain high light sensitivity.For example can mention following compounds.

The pyrrolotriazine derivatives of halomethylation; 2-(4-methoxyphenyl)-4 for example; Two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxy-naphthyl)-4; Two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxy naphthyl)-4, two (trichloromethyl)-s-triazine of 6-or 2-(4-ethoxycarbonyl naphthyl)-4, two (the trichloromethyl)-s-triazine of 6-; Halomethylation De oxadiazole verivate, for example 2-trichloromethyl-5-(2 '-benzofuryl)-1,3; 4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-benzofuryl) vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuryl) vinyl)-1; 3; 4-oxadiazole or 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Imdazole derivatives; 2-(2 '-chloro-phenyl-)-4 for example; 5-diphenyl-imidazole dimer, 2-(2 '-chloro-phenyl-)-4, two (3 '-methoxyphenyl) imidazoles dimers of 5-, 2-(2 '-fluorophenyl)-4,5-diphenyl-imidazole dimer, 2-(2 '-methoxyphenyl)-4; 5-diphenyl-imidazole dimer or (4 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer; Benzoin alkylether, for example benzoin methylether, bitter almond oil camphor phenylate, bitter almond oil camphor ethyl isobutyl ether or benzoin iso-propylether; Anthraquinone derivative, for example 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone or 1-chloroanthraquinone; The benzanthrone verivate; Benzophenone derivates, for example UVNUL MS-40, Michler's keton, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine UVNUL MS-40 or 2-carboxyl benzophenone; Acetophenone derivs; For example 2; 2-dimethoxy-2-phenyl methyl phenyl ketone, 2; 2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-(methyl sulfenyl) phenyl)-2-morpholino-1-acetone or 1,1,1-trichloromethyl-(to butyl phenyl) ketone; Thioxanthone derivates, for example thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone or 2,4-di-isopropyl thioxanthone; Benzoate derivatives, for example (dimethylamino)-ethyl benzoate or to the diethylin ethyl benzoate; Acridine derivatives, for example 9-phenylacridine or 9-(p-methoxyphenyl) acridine; The azophenlyene verivate, for example 9,10-dimethylbiphenyl azophenlyene; Or two luxuriant titanium derivative, for example titanocene dichloride, phenylbenzene two luxuriant titaniums, two (2,3,4; 5,6-penta fluoro benzene-1-yl) two luxuriant titaniums, two (2,3,5; 6-tetra fluoro benzene-1-yl) two luxuriant titaniums, two (2,4,6-trifluoro-benzene-1-yl), two luxuriant titaniums, 2,6-two fluorobenzene-1-base two luxuriant titaniums, 2; 4-two fluorobenzene-1-base two luxuriant titaniums, two (2,3,4,5; 6-penta fluoro benzene-1-yl) dimethyl-cyclopentadienyltitanium, two (2,6-two fluorobenzene-1-yl) dimethyl-cyclopentadienyltitanium or 2,6-two fluoro-3-(pyrroles-1-yl)-benzene-1-base two luxuriant titaniums.

Except above-mentioned initiator component, can also in optical polymerism composition of the present invention, add sensitizing dye.In order to make optical polymerism composition under high shading condition, experience photopolymerization reaction, preferably add sensitizing dye.This sensitizing dye is for example opened and disclosedly in the flat 5-289335 communique is had a heterocyclic coumarin compound for the spy opens flat 3-239703 communique or spy; The spy opens disclosed 3-ketone coumarin compound in the clear 63-221110 communique; Te Kaiping 4-221958 communique or spy open the flat disclosed xanthene dye of 4-219756 communique; The disclosed pyromethene dyestuff of Te Kaiping 6-19240 communique; The spy opens clear 47-2528 communique; The spy opens clear 54-155292 communique; The spy opens clear 56-166154 communique or the spy opens clear 59-56403 communique disclosed (right-the dialkylamino tolylene) ketone; The styryl type dye; The sensitizing dye or the spy of the disclosed julolidyl of the having base of Te Kaiping 6-295061 communique open the flat disclosed diaminobenzene compound of 11-326624 communique.

In these sensitizing dyves, especially preferably contain amino sensitizing dye or xanthene dye.

(d) photopolymerization monomer

As photopolymerization monomer of the present invention, use compound (after this being called ethylenic compound) with at least one ethylenic unsaturated group.The terminal compound of reaction product, styryl, the unsaturated compound of phosphoric acid or the adduct of polyepoxide and unsaturated carboxylic acid of ester, polyvalent alcohol and the poly-hydroxy isocyanic ester and the unsaturated carboxylic acid of the esterification reaction product of the esterification reaction product of the ester that can obtain particularly,, ethylene oxide, propylene oxide adduct and the unsaturated carboxylic acid of aromatic polyhydroxy compounds, ethylene oxide, propylene oxide adduct and the unsaturated carboxylic acid of aliphatic polyhydroxy compound, the polyvalent alcohol of caprolactone modification and unsaturated carboxylic acid for the ester of ester, aromatic series (many) oxy-compound and the unsaturated carboxylic acid of for example aliphatics (many) oxy-compound and unsaturated carboxylic acid, by unsaturated carboxylic acid, multi-hydroxy carboxy acid and aliphatic polyhydroxy compound.

In them; Particularly; The ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid can be for for example: propenoate, for example glycol diacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate, hexanediyl ester, Viscoat 295, trimethylolethane trimethacrylate propenoate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol five propenoate, dipentaerythritol acrylate or vinylformic acid glyceryl ester; Or similar methacrylic ester, itaconic ester, crotonate or maleic acid ester.

The ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid can be for example quinhydrones diacrylate, quinhydrones dimethacrylate, Resorcinol diacrylate, Resorcinol dimethacrylate or pyrogallol triacrylate.The ester that unsaturated carboxylic acid, multi-hydroxy carboxy acid and polyol esterification obtain needs not to be one matter, and its typical object lesson comprises the condenses of condenses, (methyl) vinylformic acid, hexanodioic acid, butyleneglycol and glycerine of condenses, (methyl) vinylformic acid, terephthalic acid and tetramethylolmethane of condenses, (methyl) vinylformic acid, toxilic acid and the Diethylene Glycol of (methyl) vinylformic acid, phthalic acid and terepthaloyl moietie.

As the example that is used for other ethylenic compound of the present invention, can also use for example acrylic amide such as ethylene acrylic amide; Allyl ester such as Phthalic acid, diallyl ester for example; For example phthalic acid divinyl ester etc. contains the compound of vinyl.

In above-mentioned ethylenic compound, preferably have the compound of (methyl) acryl, more preferably have the compound of acryl.This compound for example can be Viscoat 295, trimethylolethane trimethacrylate propenoate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol five propenoate or dipentaerythritol acrylate.

Combined amount as the said components in the optical polymerism composition of the present invention; With respect to per 100 weight part organic binder bonds (b); Photoepolymerizationinitiater initiater (c) is generally 0.1～50 weight part; Preferred 1～45 weight part, photopolymerization monomer (d) is generally 0～200 weight part, preferred 3～180 weight parts.And in the total solids composition outside desolventizing, black colorant material (a) is generally 30 weight %～70 weight %, preferred 35 weight %～65 weight %.And with respect to per 1 00 weight part organic binder bonds (b), sensitizing dye is generally 0～30 weight part, preferred 0～10 weight part.

If Photoepolymerizationinitiater initiater is lower than above-mentioned scope, then optical polymerism composition will have the operation efficiency of low light sensitivity and difference, if surpass above-mentioned scope, then film forming function is with variation.If photopolymerization monomer (ethylenic compound) is lower than above-mentioned scope, then cross-linking density will reduce, and produce problems such as weather resistance, thermotolerance thus, if surpass above-mentioned scope, then development property can reduce.If the black colorant material is lower than above-mentioned scope, then opacifying property will reduce, and will be difficult to form the resin B M with sufficient optical concentration like this.On the other hand, if surpass above-mentioned scope, then light sensitivity, resolving power, development property etc. will reduce significantly, will be difficult to imaging like this.

Usually the state that is dissolved in the solvent with black colorant material (a), organic binder bond (b) (Epocryl with carboxyl), Photoepolymerizationinitiater initiater (c) (oxime ester compound) and the photopolymerization monomer (d) (ethylenic compound) that according to circumstances needs uses optical polymerism composition of the present invention.

It is desirable to, said solvent is selected from the component and the solvent of boiling point in 100 ℃～200 ℃ scopes that can dissolve or disperse to constitute compsn.Better is the solvent with boiling point of 120 ℃～170 ℃.

This solvent can be; For example divalent alcohol monoalky lether, for example ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxyl methyl amylalcohol, dihydroxypropane single-ether, dipropylene glycol list ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol or tripropylene glycol methyl ether;

Divalent alcohol dialkyl ether, for example glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol dipropyl ether or dibutyl ethylene glycol ether;

Divalent alcohol alkyl oxide acetic ester, for example ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, methoxy butylacetic acid ester, methoxycarbonyl pentyl yl acetate, dipropylene glycol monomethyl ether acetic ester or 3-methyl-3-methoxy butylacetic acid ester;

Ethers, for example ether, propyl ether, isopropyl ether, butyl ether, amyl ether, ethyl isobutyl ether or hexyl ether;

Ketone, for example acetone, methylethylketone, methyl amylketone, MIPK, methyl isoamyl ketone, DIBK, MIBK, pimelinketone, EAK, methyl butyl ketone, methyl hexyl ketone or methyl nonyl ketone;

Monobasic or polyvalent alcohol, for example ethanol, propyl alcohol, butanols, hexanol, hexalin, terepthaloyl moietie, Ucar 35, Diethylene Glycol, dipropylene glycol or USP Kosher;

Aliphatic hydrocarbon, for example Skellysolve A, octane, diisobutylene, normal hexane, hexene, isoprene, limonene or dodecyl;

Cycloaliphates, for example hexanaphthene, methylcyclohexane, tetrahydrotoluene or couplet hexanaphthene;

Aromatic hydrocarbon, for example benzene,toluene,xylene or cumene;

Chain or cyclic ester, for example pentyl formate, ethyl formate, ETHYLE ACETATE, butylacetate, propyl acetate, pentyl acetate, ethylene glycol ethyl ethers acid esters, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octylate, butyl stearate, ethyl benzoate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-methoxy propyl propionate, 3-methoxy butyl propionate or gamma-butyrolactone;

Alkoxyl group carboxylic acid, for example 3-methoxypropionic acid or 3-ethoxy-propionic acid;

Halohydrocarbon, for example chlorobutane or chloropentane;

Ether ketone, for example methoxyl methyl pentanone; Or

Nitrile, for example acetonitrile or benzonitrile.

Corresponding above-mentioned solvent can be the commodity of following trade(brand)name: mineral sprit; Varsol#2; The Apco#18 solvent; The Apco solvent or diluent; Socal solvent No.1 and No.2; Solvesso#150; The ShellTS28 solvent; Trivalin SF (Carbitol); Ethyl carbitol (Ethyl Carbitol); Diethylene glycol monobutyl ether (Butyl Carbitol); Methylcyclohexane (Methyl Cellosolve); Ethyl cellosolve (EthylCellosolve); Ethyl cellosolve acetate (Ethyl Cellosolve Acetate) and diglime.

These solvents can be individually or are used with several kinds mixture.Preferred these solvents that use are prepared into the solid component concentration of 5 weight %～50 weight %, the solid component concentration of preferred 10 weight %～30 weight % with optical polymerism composition of the present invention.

In the present invention, add essential component (a) and (b) with (c) with in case of necessity optional components (d), in addition, can preferably add pigment dispersing agent, binding property improving agent, coating improving agent, development property improving agent etc.Especially, from stay-in-grade angle, preferred hybrid pigment dispersion agent in the compsn of the present invention, this is owing to it is important for fine disperseing black colorant material and stable dispersion state.

Said pigment dispersing agent is the pigment dispersing agent that black colorant material (a) and organic binder bond (b) are all had avidity, for example is nonionic, positively charged ion or AS or macromolecule dispersing agent.In them, preferred macromolecule dispersing agent, particularly advantageous ground uses the macromolecule dispersing agent (e) with basic functionality, said basic functionality for for example primary, the second month in a season or uncle's amino or nitrogen heterocyclic rings such as pyridine, pyrimidine or pyrazine for example.

As the object lesson of the preferred chemical structure of the macromolecule dispersing agent with basic functionality (e), can mention the compound that has 1 or 2 hydroxyl in polyisocyanate compound, the molecule with having the dispersion resin that the amino compound reaction of active hydrogen and uncle obtains in a part.

Above-mentioned polyisocyanate compound can be for example aromatic diisocyanate; For example to phenylene vulcabond, 2; 4-tolylene vulcabond, 2; 6-tolylene vulcabond, 4,4 '-diphenylmethanediisocyanate, naphthalene-1,5-vulcabond or tolidine vulcabond; Aliphatic diisocyanate, for example hexamethylene diisocyanate, lysine methyl ester vulcabond, 2,4,4-trimethyl hexamethylene diisocyanate or dimer acid diisocyanate; Alicyclic diisocyanate, isophorone diisocyanate, 4 for example, 4 '-methylene-bis (cyclohexyl isocyanate) or ω, ω '-vulcabond dimethyl cyclohexane; Aliphatic diisocyanate with aromatic nucleus, for example eylylene diisocyanate or α, α, α ', α '-tetramethyl-eylylene diisocyanate; Triisocyanate; Methionin ester triisocyanate, 1 for example; 6,11-undecane triisocyanate, 1,8-vulcabond-4-isocyanic ester methyloctane, 1; 3,6-hexa-methylene triisocyanate, norbornane triisocyanate, three (isocyanate benzene methylmethane) or three (isocyanate phenyl) thiophosphatephosphorothioate; Or its tripolymer or water adduct or its polyvalent alcohol adduct.The tripolymer of organic diisocyanate is preferably as POLYMETHYLENE POLYPHENYLISOCYANATE, and the most preferably tripolymer of methylene phenylene diisocyanate or Trimerization of Isophorone Diisocyanate body can be individually or use them in combination.

The trimerical method of producing isocyanic ester can be for example following method: handle above-mentioned POLYMETHYLENE POLYPHENYLISOCYANATE with for example suitable catalyst for trimerization such as tertiary amine, phosphine, alkoxide, MOX or carboxylate salt; Make partly trimerization of isocyanate groups; Add anticatalyzer and stop trimerization reaction; Remove unreacted POLYMETHYLENE POLYPHENYLISOCYANATE with SX and thin film distillation, thereby obtain containing the POLYMETHYLENE POLYPHENYLISOCYANATE title product of isocyanate groups.

Can be for example polyether Glycols, polyester diol, PCDL or polyolefine divalent alcohol with the compound that has 1 or 2 hydroxyl in a part, or the hydroxyl of these compound one ends is by C _1-25The compound of alkyl alkoxide, or two or more mixture in them.

Polyether Glycols can be polyether glycol, polyether ester glycol or two or more mixture in them.Polyether glycol can be the polyether glycol that oxyalkylene homopolymerization or copolymerization obtain, for example polyoxyethylene glycol, W 166, polyoxyethylene glycol-Ucar 35, polyoxy tetramethylene glycol, polyoxy hexamethylene glycol, polyoxy eight methylene glycols or two or more mixture in them.

The polyether ester glycol can be mixture and di-carboxylic acid or the polyether ester glycol that its anhydride reaction obtains that contains the glycol of ether or contain glycol and other divalent alcohol of ether; Or the polyether ester glycol that obtains of polyester glycol and reactions of alkylene oxide, for example gather (polyoxy tetramethylene) adipic acid ester.As polyether glycol, most preferably the hydroxyl of polyoxyethylene glycol, W 166, polyoxy tetramethylene glycol or these compounds one end is by C _1-25The compound of alkyl alkoxide.

Polyester glycol can be to make di-carboxylic acid (for example succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, fumaric acid, toxilic acid or phthalic acid) or its acid anhydrides and divalent alcohol (for example, aliphatic dihydroxy alcohol, for example terepthaloyl moietie, Diethylene Glycol, triethylene glycol, Ucar 35, dipropylene glycol, tripropylene glycol, 1,2-butyleneglycol, 1; 3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, NSC 6366,2-methyl isophthalic acid; Ammediol, 2-methyl-2-propyl group-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 1,5-pentanediol, 1; 6-pinakon, 2-methyl-2,4-pentanediol, 2,2,4-trimethylammonium-1; 3-pentanediol, 2-ethyl-1,3-pinakon, 2,5-dimethyl--2,5-pinakon, 1; 8-eight methylene glycols, 2-methyl isophthalic acid, 8-eight methylene glycols or 1,9-nonanediol; Alicyclic divalent alcohol, for example two methylol hexanaphthenes; Aromatic diol, for example xylylene glycol or two hydroxy ethoxy benzene; Or N-alkyl dioxane hydramine; N methyldiethanol amine for example) polyester glycol that obtains of polycondensation; For example polyethylene glycol adipate, poly adipate succinic acid ester, gather hexanodioic acid hexamethylene glycol ester or gather adipate glycol/propylene glycol ester, or use above-mentioned divalent alcohol or C _1-25Polylactone glycol or polylactone one alcohol that monohydroxy-alcohol obtains as initiator, for example polycaprolactone glycol, gather the methylpent lactone or two or more mixture in them.As polyester glycol, most preferably use polycaprolactone glycol or with C _1-25The polycaprolactone that alcohol obtains as initiator.

Polycarbonate diol can be for for example gathering carbonic acid (hexamethylene glycol) ester or gathering carbonic acid (3-methyl isophthalic acid, 5-pentamethylene glycol) ester, and polyolefin diols can be for example polybutadiene diol, hydrogenated butadiene polymer glycol or hydrogenated polyisoprene glycol.Number-average molecular weight with the compound that has 1 or 2 hydroxyl in a part is 300～10,000, and is preferred 500～6,000, more preferably 1,000～4,000.

Has the amino compound of active hydrogen and uncle in same a part that explained later the present invention uses.It can be the Wasserstoffatoms in the functional groups such as hydroxyl, amino or thiol group for example that active hydrogen promptly is bonded directly to Wasserstoffatoms on Sauerstoffatom, nitrogen-atoms or the sulphur atom, in them, and the Wasserstoffatoms in the Wasserstoffatoms, particularly primary amino in the preferred amino.Uncle's amino there is not special qualification.Uncle's amino can be to have C _1-4The amino of alkyl or heterocycle structure, more specifically, said heterocycle structure can be imidazole ring or triazole ring.

As with the example that has the amino compound of active hydrogen and uncle in a part, can mention for example N, N-dimethyl--1,3-tn, N, N-diethylammonium-1; 3-tn, N, N-dipropyl-1,3-tn, N, N-dibutyl-1,3-tn, N; N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dipropyl quadrol, N, N-dibutyl quadrol, N; N-dimethyl--1,4-tetramethylenediamine, N, N-diethylammonium-1,4-tetramethylenediamine, N; N-dipropyl-1,4-tetramethylenediamine or N, N-dibutyl-1,4-tetramethylenediamine.

And; As uncle amino contain the N heterocycle for example for containing the N five-membered ring, for example pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzoglyoxaline ring, benzotriazole ring, benzoxazole ring, benzothiazole ring or diazosulfide ring; Or contain the hexa-member heterocycle of N, for example pyridine ring, pyrrole acridine ring (pyridadine), pyrimidine ring, triazine ring, quinoline ring, acridine ring or isoquinoline 99.9 ring.Imidazole ring or triazole ring are preferably as containing the N heterocycle.

As having the object lesson of imidazole ring, can mention for example 1-(3-aminopropyl) imidazoles, Histidine, 2-aminooimidazole and 1-(2-amino-ethyl) imidazoles with the compound of amino.And,, can mention for example 3-amino-1,2 as having the object lesson of triazole ring with the compound of amino; 4-triazole, 5-(2-amino-5-chloro-phenyl-)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2; 4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1; 4-phenylbenzene-1,2,3-triazoles and 3-amino-1-benzyl-1H-2, the 4-triazole.

In them, preferred N, N-dimethyl--1,3-tn, N, N-diethylammonium-1,3-tn, 1-(3-aminopropyl) imidazoles or 3-amino-1,2,4-triazole.Preferred blending ratio as dispersant material; With respect to per 100 weight part polyisocyanate compounds, be 10～200 weight parts with the compound that has 1 or 2 hydroxyl in a part and have a number-average molecular weight of 300～10,000; Preferred 20～190 weight parts; More preferably 30～180 weight parts are 0.2～25 weight part with having the amino compound of active hydrogen and uncle in a part, preferred 0.3～24 weight part.

The weight-average molecular weight of measure calculating with GPC (GPC) with macromolecule dispersing agent (e) of basic functionality is 1,000～200,000, and is preferred 2,000～100,000, more preferably 3,000～50,000.If molecular weight is 1,000 to the maximum, then dispersiveness and dispersion stabilization are poor, if its minimum is 200,000, then solvability will reduce, bad dispersibility, and simultaneously, reaction is difficult to control.Currently known methods according to producing urethane resin carries out the production of macromolecule dispersing agent.Solvent during as production for example can use: ketone, for example acetone, methylethylketone, MIBK, ketopentamethylene, pimelinketone or isophorone usually; Ester class, for example ETHYLE ACETATE, butylacetate or cellosolve acetate; Hydro carbons, for example benzene,toluene,xylene or hexane; Part alcohol, for example Pyranton, Virahol, sec-butyl alcohol or the trimethyl carbinol; Muriate, for example methylene dichloride or chloroform; Ether, for example THF or ether; Or aprotic polar solvent, for example N, N-Methyl pyrrolidone or DMSO 99.8MIN..

For above-mentioned production, use the urethane catalysts usually.For example can be tin type catalyzer, for example dibutyl tin dilaurate, two LAURIC ACID 99 MIN, two hot tin, two sad two fourth tin or stannous octoates; Swage catalyzer, for example ferric acetyl acetonade or iron(ic)chloride; Or tertiary amine-type catalyzer, for example triethylamine or Triethylene Diamine.

In reacted amine value, preferably be controlled in the scope of 1～100mgKOH/g with the introducing amount that has the amino compound of active hydrogen and uncle in a part.More preferably in the scope of 5～95mgKOH/g.The amine value is when alkalescence amino carries out neutralization titration with acid and the corresponding value of showing with the mg numerical table of KOH of acid number.When the amine value is lower than above-mentioned scope, dispersing property will reduce, if surpass above-mentioned scope, development property will reduce.When isocyanate groups remains in the macromolecule dispersing agent that above-mentioned reaction obtains, preferably make the isocyanate groups inactivation with alcohol or amine compound, thus the lasting stability and will improve of product, this is favourable.In the situation of using macromolecule dispersing agent, with respect to black colorant material (a), the ratio of macromolecule dispersing agent is preferably 0.1 weight %～30 weight %, preferred especially 0.5 weight %～25 weight %.

The preparation method of explained later optical polymerism composition of the present invention.In the present invention, coloured material uses preferably usually that for example paint regulator, sand mill, ball mill, roller mill, stone mill, jet mill or homogenizer carry out dispersion treatment.Through dispersion treatment coloured material is formed fine particle, thereby will improve the coating of resist.And when the black colorant material is used as coloured material, this processing will promote the improvement of light shielding ability.

Preferably in following system, carry out dispersion treatment: wherein, combination use black colorant material and solvent or organic binder bond, or and then the above-mentioned pigment dispersing agent of combination use with divergent function.Especially preferably use macromolecule dispersing agent to obtain excellent dispersion stability with time.And because the heat that produces when disperseing can make hyperergy component generation sex change, to carry out dispersion treatment in the liquid of whole components to be mixed be disadvantageous so in as resist liquid, mixed.

Carrying out in the dispersive situation with sand mill, preferably using the granulated glass sphere or the zirconium oxide bead of 0.1～8mm diameter.As for dispersion condition, temperature is generally 0～100 ℃, preferred room temperature to 80 ℃.Because the optimum dispersion time is with the composition (coloured material, solvent, dispersion agent) of ink, the variations such as equipment size of sand mill, so suitably regulate jitter time.The dispersive standard is that the gloss of control ink makes 20 of resist spend gloss numbers in 100～200 scope.If resist gloss is low, then dispersion treatment is insufficient, can stay thick granules of pigments in many cases, sees that from development property, adhesivity, resolving power equal angles this is inadequate.And, surpass above-mentioned scope if carry out dispersion treatment up to gloss number, then can form a large amount of ultra-fine grains, can damage dispersion stabilization so on the contrary.

Then, add the ink that obtains by above-mentioned dispersion treatment and, mix obtaining homogeneous solution as above-mentioned other component of necessity of resist component.In many cases, in process of production, fine dust is blended in the photosensitive solution, and therefore, the resist photosensitive solution that obtains preferably filters with for example strainer.

Explained later uses optical polymerism composition of the present invention to produce the method for colour filter.

The application examples of explained later optical polymerism composition of the present invention.

(I) colour filter

At first, be coated with apparatus for coating such as machine (die coater), roller coating machine or spraying machine, optical polymerism composition of the present invention be coated on the transparent substrate drying with for example spinner, the excellent spreader that winds the line, flow coating machine, mould.Then, photomask is placed on the sample, carries out image exposure, development, and according to circumstances need carry out thermofixation or photocuring, thereby be formed for the BM image of shading through photomask.Repeat this operation for three look RGB (red, green, blue), thereby form the colour filter image.

(I-1) coating of optical polymerism composition and drying

When using optical polymerism composition of the present invention to form the pixel of colour filter because it has high light sensitivity and high resolving power, so can be under the situation of the oxygen barrier layers that is not equipped with Z 150PH for example etc. through exposure with develop and form image.The transparent substrate that uses is the transparent substrate that is used for colour filter; Its material there is not special qualification; For example be like polyester such as polyethylene terephthalates, like polyolefine or thermoplastic plastic sheets such as polycarbonate, polymethylmethacrylate or polysulfones such as Vestolen PP 7052 or Vilaterm, perhaps for like epoxy resin, vibrin or gather thermosetting resin sheet material or various sheet glass such as (methyl) vinyl resin.Especially, from stable on heating angle, preferably use sheet glass or heat-resistant plastic.

Can or for example form that the processing of polymeric film such as silane coupling agent or mephenesin Carbamate polymkeric substance is applied on the transparent substrate in advance with Corona discharge Treatment, ozonize, to improve physicalies such as lip-deep for example adhesivity.Coating process is not had special qualification, and the film thickness at the bottom of coating and the dried resin black is 0.1～2 μ m suitably, preferred 0.1～1.5 μ m, more preferably 0.1～1 μ m.Here, from the angle of opacifying property, the optical concentration of colour filter of the present invention is preferably at least 3.0/1 μ m thickness.And as the index of the dispersion state of solids components such as for example pigment, the 20 degree gloss numbers of BM are 100～200th, and are favourable.

(I-2) exposure and development

Can hot plate, IR bake or convection oven etc. be used for drying, preferred drying conditions is 40～150 ℃, and be 10 seconds to 60 minutes time of drying.And the light source that is used to make public can be for example light source, for example xenon lamp, halogen lamp, tungsten lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp or low pressure mercury lamp; Or LASER Light Source, for example Argon, YAG laser apparatus, excimer laser or nitrogen laser.When use only has the irradiates light of specific wavelength, can use spectral filter.

Development treatment there is not special qualification, as long as use the solvent of the resist film that can dissolve unexposed portion just passable.For example, can be with an organic solvent, for example acetone, methylene dichloride, trieline or pimelinketone.But many organic solvents produce environmental pollution, and are harmful, have fire hazard, the therefore preferred alkaline-based developer that does not have said danger that uses.This alkaline-based developer can be for for example containing the aqueous solution of inorganic alkaline agents or organic basic reagent; Said inorganic alkaline agents for example is yellow soda ash, salt of wormwood, water glass, potassium silicate, sodium hydroxide or Pottasium Hydroxide, and said organic basic reagent for example is diethylolamine, trolamine or tetraalkylammonium hydroxide.According to circumstances need, alkaline-based developer can contain tensio-active agent, water-miscible organic solvent, or have the low-molecular weight compound etc. of hydroxyl or carboxyl.Especially, many tensio-active agents have the effect of improving development property and resolving power and reduction scum silica frost, the therefore preferred tensio-active agent that adds.

For example, the tensio-active agent that is used for developing solution can be AS with sodium naphthalene sulfonate base or Supragil GN base, have the nonionogenic tenside of polyalkylene oxide groups or have the cats product of tetra-allkylammonium group.Developing method is not had special qualification, use immersion development, spray developing, brushing development or UW development etc. usually, develop under preferred 15～45 ℃ development temperature at 10～50 ℃.

(II) liquid crystal indicator (plate)

Can use above-mentioned colour filter to produce liquid crystal indicator of the present invention as follows.At first, on colour filter, form alignment films, then spacer is arranged on this alignment films, opposed substrate is fitted forms liquid crystal cell on it.Then, liquid crystal is injected in the formed liquid crystal cell, then is wired on the counter electrode.

As alignment films, for example resin molding such as pi is suitable.In order to form alignment films, use woodburytype or flexographic printing method usually.The thickness of alignment films is generally 10～100nm.Alignment films is cured processing through thermal bake-out, carries out surface treatment with uviolizing or friction cloth then, it is formed can regulate the condition of surface that liquid crystal tilts.

As spacer, use the spacer have with the corresponding size in gap of opposed substrate, the spacer of common 2～8 μ m is suitable.Can use photolithography on color filter substrate, to form the light spacer (PS) of transparent resin film, and be used for replacing spacer.As opposed substrate, it is suitable using array substrate, particularly TFT (thin film transistor) substrate usually.

The gap of fitting after the opposed substrate changes with the purposes of liquid crystal indicator, and this gap is selected in the scope of 2～8 μ m usually.After spacer fits on the opposed substrate, except that with the corresponding part of liquid crystal injecting port, rest part is with the sealing of sealing materials such as epoxy resin for example.Sealing material shines and/or is heating and curing through ultraviolet ray (UV), thereby with sealing around the liquid crystal cell.

The liquid crystal cell of sealing on every side is cut into the display panel unit, in Vakuumkammer, under reduced pressure above-mentioned liquid crystal injecting port is immersed in the liquid crystal then, then make this Vakuumkammer pressure release, thereby make liquid crystal inject liquid crystal cell.Decompression degree in the liquid crystal cell is generally 1 * 10 ^-2～1 * 10 ^-7Pa, preferred 1 * 10 ^-3～1 * 10 ^-6Pa.And, preferably when decompression, heating this liquid crystal cell, Heating temperature is generally 30～100 ℃, preferred 50～90 ℃.This liquid crystal cell kept heating 10～60 minutes usually when decompression, was immersed in the liquid crystal then.Ultraviolet curable resin is solidified seal the liquid crystal injecting port of the liquid crystal cell that injects liquid crystal, thereby accomplish liquid crystal indicator (plate).

Type to liquid crystal does not have special qualification, and liquid crystal can be known liquid crystal, for example aromatic series type, aliphatics type or fused ring compound, and it can be in lytropic liquid crystals and the thermotropic liquid crystal etc. any.As thermotropic liquid crystal, known nematic liquid crystal, smectic liquid crystal and cholesteric liquid crystal etc., can use in them any.

(III) light spacer

The method of (III-1) supplying to substrate

Resin combination of the present invention is usually with dissolving or be dispersed in state supply in the solvent on substrate.Can be coated with ordinary methods such as method, rolling method or spraying method and supply with for example spin-coating method, the excellent method that winds the line, flow coat method, mould.Especially, from comprehensive angle, preferred mould coating method, because the usage quantity of its coating fluid significantly reduces, for example bluring when not using spin-coating method fully waits influence, and can suppress the appearance of foreign matter.With elcometer, glue spread is generally 0.5～10 μ m, preferred 1～8 μ m, preferred especially 1～5 μ m.And importantly, the height of build or the final spacer that forms is uniform on whole substrate surface.Significantly ununiformity will make the liquid crystal board unfairness.And, can supply resin combination with pattern form with ink jet method or print process.

(III-2) drying means

Resin combination preferably carries out drying through the drying means that uses hot plate, infrared-ray oven or convection oven after supplying on substrate.And, can be combined and used in the hypobaric drying method that does not increase temperature that carries out in the Vakuumkammer.Can select drying conditions aptly according to performance of the drying machine of the type of solvent composition, use etc.According to performance of the drying machine of the type of solvent composition, use etc., under 40～100 ℃ temperature, be selected from 15 seconds to 5 minutes scope time of drying usually, preferably in 30 seconds to 3 minutes scope, selecting under 50～90 ℃.

(III-3) exposure method

Make public as follows: the minus mask pattern is overlayed on the coated film of resin combination, then through mask pattern irradiation ultraviolet radiation or visible light.And, also can use method through the laser beam flying exposure.In this case, according to circumstances need,, for example can on the photopolymerizable layer, form oxygen barrier layers such as polyvinyl alcohol layer, make public then for the light sensitivity that prevents the photopolymerizable layer reduces because of oxygen.The light source that is used to make public there is not special qualification.Light source for example is a light source, for example xenon lamp, halogen lamp, tungsten lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arcotron (carbon arcor) or luminescent lamp; Or LASER Light Source, for example Argon, YAG laser apparatus, excimer laser, nitrogen laser, helium cadmium laser, blue violet semiconductor laser or near infrared semiconductor laser.In light-struck situation, can use spectral filter with specific wavelength.

(III-4) developing method

After carrying out above-mentioned exposure, use the aqueous solution or the organic solvent that contain basic cpd and tensio-active agent, form picture pattern on the substrate through being developed in.Can also contain organic solvent, buffer reagent, complexing agent, dyestuff or pigment in this aqueous solution.

Basic cpd can be for example inorganic alkaline compound, for example sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, water glass, potassium silicate, Starso, sodium phosphate, potassiumphosphate, Sodium phosphate, dibasic, potassium hydrogenphosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate or volatile caustic; Or organic basic compound, for example monoethanolamine, diethylolamine or trolamine, single methylamine, n n dimetylaniline or Trimethylamine 99, mono aminoethane, diethylamine or triethylamine, single Isopropylamine or Diisopropylamine, n-Butyl Amine 99, monoisopropanolamine, HSDB 338 or tri-isopropanolamine, ethylene imine, second diimine, tetramethylammonium hydroxide (TMAH) or choline.Basic cpd can be two or more a mixture in them.

Tensio-active agent can be for example nonionogenic tenside, for example Voranol EP 2001, polyoxyethylene alkylaryl ether, polyxyethylated ester, sorbitanic alkyl ester or monoglyceride alkyl ester; AS, for example sulfonated alkylbenzene, sulfonated alkyl naphathalene, alkyl-sulphate, AS or sulfosuccinate; Or amphoterics, for example alkyl betaine or amino acid.

Organic solvent can be for example Virahol, phenylcarbinol, ethyl cellosolve, ethylene glycol butyl ether, phenyl cellosolve, Ucar 35 or Pyranton.Organic solvent can use separately, or uses with aqueous solution combination.

(III-5) thermofixation is handled

On the substrate after the development, preferably carrying out thermofixation handles.In this case, as the thermofixation treatment condition, temperature is selected from 100～280 ℃ scope, and preferred 150～250 ℃, the time is selected from 5～60 minutes scope.

(IV) rib wall (liquidcrystal divided-alignment protrusion)

Rib wall (liquidcrystal divided-alignment protrusion) is meant the projection in order to the visual angle of improving liquid crystal indicator that on transparency electrode, forms.Utilize the gradient of said projection that liquid crystal is tilted partly, thereby in a pixel, liquid crystal is cut apart along a plurality of directions.At length explain the method that forms the rib wall below.

(IV-1) coating and developing process

On the transparent substrate of common thick 0.1～2mm, be provided with black matrix and red, blue and green colour filter; And deposit the ITO (indium tin oxide target) of thick 150mm above that, for example using, spin coater, the excellent spreader that winds the line, flow coating machine, mould are coated with coating apparatus such as machine, roller coating machine or spraying machine and on this substrate, are coated with photosensitive composite of the present invention.The coated film thickness of compsn is generally 0.5～5 μ m.Drying comprises the coated film of said composition, then photomask is placed on the dry-coated film, then carries out image exposure through photomask.After the exposure, remove unexposed non-cured portion, thereby form pixel through development.Usually, the image that obtains after needing to develop has the reproducibility of the fine rule of wide 5～20 μ m, according to the demand of high image quality indicating meter, tends to have the line reproducibility of high-resolution.The wide angle in development leeway from the physical stimulation of development time for example, developing solution aging (aging) and development shower etc.; In order stably to reproduce the high-resolution fine rule, the cross-sectional shape of the fine rule image after the development is preferably between non-image part and the image section contrast gradient rectangle clearly.

(IV-2) heat-processed

In the present invention, the image after the development has near the orthogonal cross-sectional shape.In order to obtain the needed arc of rib wall shape, through heat-treating rectangular cross sectional shape is deformed into arc, form the rib wall of wide 0.5～20 μ m and high 0.2～5 μ m; The temperature of said heat treated is at least 150 ℃ usually, preferably at least 180 ℃, and more preferably at least 200 ℃; And at the most 400 ℃ usually, preferably at the most 300 ℃, more preferably at the most 280 ℃; The time of said heat treated is at least 10 minutes usually, preferably at least 15 minutes, and more preferably at least 20 minutes; And at the most 120 minutes usually, preferably at the most 60 minutes, more preferably at the most 40 minutes.Through suitably regulating photosensitive composite and heating condition is controlled thermal distortion; Make when the contact angle (W2) of the side surface of the fine rule image after contact angle (W1) that the side surface of the fine rule image (rectangular cross sectional shape image) before the heating and substrate plane form and the above-mentioned thermal treatment and substrate plane formation compares; W1/W2 is at least 1.2, preferably at least 1.3, more preferably at least 1.5; And usually at the most 10, preferably at the most 8.When higher or heat-up time is longer when Heating temperature, deformation extent will be more obvious, and on the other hand, deformation extent will be lower more in short-term lower or heat-up time when Heating temperature.

Embodiment

Now, explain the present invention in more detail with reference to embodiment and Comparative Examples.But, should be appreciated that in being no more than the scope of the object of the invention, the present invention is in no way limited to the following example.

Preparation example 1

The preparation of macromolecule dispersing agent solution

The tripolymer of 32g tolylene diisocyanate (is produced by Mitsubishi Chemical society; MytecGP750A; Resin solid content 50 weight %, butylacetate solution) and 0.02g do the dibutyl tin dilaurate dilution of catalyzer and be dissolved in the 47g propylene glycol methyl ether acetate (PGMEA).Under agitation; To its number-average molecular weight that dropwise adds 14.4g is 1; An end of 000 is that the number-average molecular weight of polyoxyethylene glycol (being produced UNIOX M-1000 by Japanese grease society) and the 9.6g of methoxyl group is that 1,000 W 166 (changes into the production of industrial society by Sanyo; SANNIX PP-1000) mixture then reacted under 70 ℃ 3 hours again.Then, add 1gN to it, N-dimethylamino-1, the 3-tn then reacted under 40 ℃ 1 hour again.The amine value that the solution that contains macromolecule dispersing agent that discovery obtains like this obtains through neutralization titration is 14mgKOH/g.And find that to obtain resin content be 40 weight % with parching (dry up) method (on hot plate at 150 ℃ down except that desolvating 30 minutes, by weight change amount computation tree lipid concentration).

Preparation example 2

The preparation of organic binder bond

O-Hydroxytoluene formaldehyde epoxy resin, 72g vinylformic acid, 0.2g p methoxy phenol, 0.2g chlorination dodecyl trimethyl ammonium and the 272g PGMEA of the softening temperature of the epoxy equivalent (weight) with 200g/eq of 200g and 65 ℃ are put into flask, 8 hours (1 normal vinylformic acid and 1 normal epoxy reaction) of reaction under 100 ℃ temperature.Add the 42g Tetra Hydro Phthalic Anhydride to it again, then reacted 3 hours down at 80 ℃.Reaction solution is redeposition in water, and vacuum-drying obtains having the phenolic aldehyde Epocryl of carboxyl.Carry out neutralization titration with KOH, the acid number that records resin is 50mgKOH/g.

Sooty disperses

Carbon black according to the painted usefulness of 50 weight parts (is produced by Mitsubishi Chemical society; MA-220) and the macromolecule dispersing agent that obtains of 5 weight parts preparation example 1 as the ratio of solids component; Add carbon black, macromolecule dispersing agent solution and PGMEA, make that solid component concentration is 50 weight %.The gross weight of dispersion liquid is 50g.Stir this dispersion liquid fully with whisking appliance and carry out pre-mixing.

Then, use coating vibrator under 25～45 ℃, to carry out dispersion treatment 6 hours.As ball, the zirconium white ball of the 0.5mm diameter of adding and dispersion liquid identical weight.After disperseing completion, separate ball and dispersion liquid with strainer.

Preparation example 3

The preparation of oxime ester compound C-1

(1) production of carbazole derivative (ketone)

3.9g (20 mmole) ethyl carbazole is dissolved in the 20ml methylene dichloride, adds 2.9g (22 mmole) aluminum chloride.Under the cooling of ice bath, in below 5 ℃, dropwise add 4.1g (22 mmole) o-methyl-benzene formyl chloride to it in the temperature that keeps reaction solution.When stirring, with 1 hour temperature is risen to room temperature gradually, at room temperature reacted again 3 hours.Again reaction solution is cooled off in ice bath, adds 2.9g (22 mmole) aluminum chloride to it, the ice bath cooling down the maintenance reacting liquid temperature be below 5 ℃ in, dropwise add 2.3g (22 mmole) methacrylic chloride to it.When stirring, with 1 hour temperature is risen to room temperature gradually, and then at room temperature reacted 3 hours.

Reaction solution dropwise is added in the 150ml frozen water, adds 100ml ETHYLE ACETATE to it and extract, use 50ml ethyl acetate extraction water layer again, merge organic layer, extract with the aqueous sodium carbonate of 150ml10%.Organic layer is again with 150ml water extraction, and this organic layer uses anhydrous magnesium sulfate drying, boils off solvent with vaporizer, obtains orange red oil thus.Use the silica gel column chromatography post (to launch solvent: ETHYLE ACETATE/normal hexane=1/1) purify, obtain 3.1g light yellow solid (1) and 0.7g light yellow solid (2).Solid (1) and solid (2) to obtaining carry out the NMR spectroscopic analysis, obtain following result (shift value).

Solid (1):

7.9-8.8，m，3H；7.4，m，7H；5.9(1H)，5.6，s，1H；5.6，s，1H；4.4(2H)，2.4，s，3H；2.1，2.4，d3H，1.5，t，3H

Solid (2):

8.6，dd，1H；8.0，dd，1H；7.9，d，1H；7.4，m，6H；4.5，q，2H；3.6，d，2H；2.6，s，1H；2.4，s，3H；2.2，s，3H；1.5，t，3H

According to above-mentioned NMR analytical results, light yellow solid (1) is confirmed as 3-methacryloyl-9-ethyl-6-(toluoyl base)-9H-carbazole.The ketone compound of proof light yellow solid (2) for being expressed from the next:

(II) production of oxime ester compound

Above-mentioned light yellow solid (2) (0.38g, 0.001 mole) is dissolved in the ethanol of 5ml, adds oxammonium hydrochloride (0.075g, 0.00105 mole) and pyridine (0.084g, 0.00105 mole), then refluxed 2 hours to it.After boiling off ethanol, add entry with dissolving inorganic substance, subsequent filtration.To leach thing and be dissolved in the ETHYLE ACETATE, and use dried over mgso, evaporation obtains the body of oxime.The solid that obtains is dissolved among the THF of 3ml, adds Acetyl Chloride 98Min. (0.23g, 0.0022 mole), stir then to it.At room temperature triethylamine (0.21g, 0.0023 mole) dropwise is added in the reaction solution.When dropwise adding triethylamine, confirm to be settled out salt.After stirring 2 hours, add 20ml water, then use the 40ml ethyl acetate extraction.With 20ml water washing organic layer 2 times, with 20ml salt of wormwood saturated aqueous solution washing 2 times, use the dried over mgso organic layer, evaporate.Use the silica gel column chromatography post (to launch solvent: ETHYLE ACETATE/normal hexane=1/1) purify, obtain 0.3g light yellow solid (3).

Under following condition, the solid (3) that obtains is carried out the H-NMR spectroscopic analysis, obtain following result (shift value).

Solvent: heavy chloroform (CDCl ₃)

Frequency: 270MHz

N-compound: (CH ₃) ₄Si

8.5，dd，1H；8.1，dd，1H；7.9，dd，1H；7.4，m，6H；4.4，q，2H；3.6，d，2H，2.4，s，3H；2.3，s，3H；2.2，s，3H；2.0，s，3H；1.5，t，3H

Confirm that from above-mentioned NMR analytical results light yellow solid (3) is the oxime ester compound (after this being called the Photoepolymerizationinitiater initiater C-1 that embodiment 1 uses) that is expressed from the next:

Preparation example 4

The preparation of oxime ester compound C-2

Same way as with preparation C-1 prepares C-2, and different 3-methacryloyl-9-ethyl-6-(toluoyl the base)-9H-carbazoles that are to use replace the light yellow solid (2) in the preparation example 3.The NMR shift value is following:

8.5，d，1H；8.4，d，1H；8.1，dd，1H；7.9，dd，1H；7.4，m，6H；7.2，d，1H；5.6，s，1H；5.1，s，1H；4.4，q，2H；2.4，s，3H；2.2，s，3H；2.0，s，3H；1.5，t，3H

Preparation example 5

The preparation of oxime ester compound C-3

Same way as with preparation C-1 prepares C-3, and different is that the methacrylic chloride that will prepare in the example 3 changes crotonyl chloride into.The NMR shift value is following:

8.5，d，1H；8.4，d，1H；8.1，dd，1H；7.9，dd，1H；7.4，m，6H；4.4，q，2H；2.4，s，3H；2.2，s，3H；2.0，s，3H；1.5，t，3H

Preparation example 6

The preparation of oxime ester compound C-4

Same way as with preparation C-1 prepares C-4, and different is that the methacrylic chloride that will prepare in the example 3 changes Acetyl Chloride 98Min. into, and the Acetyl Chloride 98Min. that final step is used changes the diethyl succinate acyl chlorides into.The NMR shift value is following:

8.6，d，1H；8.5，d，1H；8.1，dd，1H；8.0，dd，1H；7.9，dd，1H；7.5，m，6H；4.5，q，2H；4.2，m，6H；2.9，t，2H；2.8，t，2H；2.7，t，2H；2.6，s，3H；2.5，s，3H；1.5，t，3H；1.3，s，3H

Preparation example 7

The preparation of oxime ester compound C-5

Same way as with preparation C-1 prepares C-5, and different is that the methacrylic chloride that will prepare in the example 3 changes Acetyl Chloride 98Min. into, and the Acetyl Chloride 98Min. that final step is used changes the morpholinyl carbonyl chloride into.

Preparation example 8

The preparation of oxime ester compound C-8

Same way as with preparation C-1 prepares C-8, and different is that the methacrylic chloride that will prepare in the example 3 changes the diethyl succinate acyl chlorides into.The NMR shift value is following:

8.5，d，1H；8.4，d，1H；8.1，dd，1H；7.9，dd，1H；7.4，m，6H；4.4，q，2H；4.1，q，2H；3.3，t，2H；2.6，s，3H；2.4，s，3H；2.3，s，3H；1.5，t，3H；1.2，d，3H

Embodiment 1～9 and Comparative Examples 1～3

(1) preparation of resist solution

Use above-mentioned carbon black dispersion ink, with solid component meter, with following ratio of mixture add each component (a) and (b), (c), (d) with (e), organic solvent and tensio-active agent, then stir and dissolving with whisking appliance, prepare black resist photosensitive solution.

(a) black colorant material

Carbon black (is produced MA-220) 50g by Mitsubishi Chemical society

(b) organic binder bond

30g as shown in table 2

(d) photopolymerization monomer: ethylenic compound

Dipentaerythritol acrylate 10g

(c) Photoepolymerizationinitiater initiater

As shown in table 2

Organic solvent

Propylene glycol methyl ether acetate 300g

(e) macromolecule dispersing agent (preparation example 1) 5g

Tensio-active agent (is produced FC-430) 100ppm by Sumitomo 3M society

(2) resist evaluation

With spinner black resist photosensitive solution is coated on the glass substrate (being produced 7059 by CorningIncorporated), following dry 1 minute at 80 ℃ on hot plate.With the film thickness of the dry back of contact pin type film thickness gauge (KLA-Tencor Corporation produces, the α rank) mensuration resist, the result is 1 μ m.Then, through changing exposure this sample is carried out image exposure through mask with high voltage mercury lamp.Under 25 ℃ temperature, working concentration is 0.8% aqueous sodium carbonate spray developing, obtains the resist pattern.

Estimate light sensitivity, resolving power and opacifying property according to standards, obtain the result shown in the table 2.

1. light sensitivity

Use the proper exposure amount (mj/cm that can form the mask pattern of 20 μ m according to arrangement ²) the expression light sensitivity.That is, owing to can form image with little exposure, so the resist of little exposure has high light sensitivity.

2. resolving power

Using magnification is the minimum pattern size of microscopic examination discernmible resist under the exposure of the mask pattern that verily reproduces 20 μ m of 200.

The minimum pattern size is at most 10 μ m: zero

The minimum pattern size surpasses 10 μ m: *

3. opacifying property

Measure the optical concentration (OD) of image section with Macbeth reflection density appearance (TR927 is produced by Gretag Macbeth (former コ Le モ Le グ Application society)).The OD value is the numerical value of expression light shielding ability, and the high more expression opacifying property of this value is high more.

4. scratch resistance

The glass substrate that will have the picture pattern that obtains is placed on untreated glass substrate and (is produced by Coming Incorporated; 7059) on; Make picture pattern contact untreated glass surface, when applying load as follows, with the speed friction of 3cm/ second 5 times.After the friction, according to standards with the naked eye the visual assessment scratch whether occur.

Load g/cm ²Scratch is estimated

60 observe △

60 do not observe zero at all

100 do not observe ◎ at all

Embodiment 10

Carry out the processing identical with embodiment 9, titanium is black (is produced by MITSUBISHIMATERIAL CORPORATION, 13M-C) replace used carbon black (to be produced by Mitsubishi Chemical society, MA-220) as the black colorant material, to obtain the black matrix pattern in different being to use.The result is illustrated in the table 2.

Comparative Examples 4

Carry out the processing identical with Comparative Examples 3, titanium is black (is produced by MITSUBISHIMATERIAL CORPORATION, 13M-C) replace used carbon black (to be produced by Mitsubishi Chemical society, MA-220) as the black colorant material, to obtain the black matrix pattern in different being to use.The result is illustrated in the table 2.

Table 2

In table 2, the connotation of symbol is following.

ACA-200M: (by DAICEL CHEMICAL INDUSTRIES, LTD. produces XPA, ACA-200M)

C-1: the compound N shown in the table 1 o.22

C-2: the compound N shown in the table 1 o.3

C-3: the compound N shown in the table 1 o.4

C-4: the compound N shown in the table 1 o.16

C-5: the compound N shown in the table 1 o.19

C-7: the compound N shown in the table 1 o.28

C-8: the compound N shown in the table 1 o.29

C-9: the compound N shown in the table 1 o.37

Triazine A:4-(-bromo-is right-p-methoxy-phenyl) and-2,6-two (trichloromethyl)-s-triazine (5g)

CGI-124: Photoepolymerizationinitiater initiater (is produced CGI-124) (5g) by Ciba Specialty Chemicals K.K.

Three kinds mixture: 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (2g)+4,4 '-two (diethylin) UVNUL MS-40 (1g)+2-mercaptobenzothiazole (1g)

Embodiment 11 and 12 with Comparative Examples 5

With spinner every kind of test soln being coated with sputter above that has on the AN100 glass substrate of the thick ITO of 150nm, on hot plate, descends dry 3 minutes at 80 ℃, obtains the coated film of 1.7 μ m dried film thicknesses.Then, from the coated film side,, use the 3kW high voltage mercury lamp at 25mJ/cm through the thread pattern mask of wide 15 μ m ^-2, 50mJ/cm ^-2, 100mJ/cm ^-2And 200mJ/cm ^-2Various conditions of exposures under carry out image exposure.Then; The photographic developer that use comprises the following aqueous solution sprays development under the hydraulic pressure of 0.25MPa and 23 ℃; The said aqueous solution contains the salt of wormwood of 1 weight % and the nonionogenic tenside of 4 weight % (by " the Emulgen A-60 " of Hua Wangshe production), makes to develop with pure water to stop.Clean substrate through the washing sprinkling.Regulating the spray development time is 10～120 seconds, and making it is dissolving and the twice of removing the time (break period) of sensitive layer.The glass substrate that is formed with image was therefrom above that heated 30 minutes down at 230 ℃, form and be deformed into arcual thread pattern.Measure the cross-sectional shape that heats front and back gained fine rule with VK9500, obtain the contact angle that substrate plane and fine rule image-side surface forms, with the velocity of variation of following method evaluation heating front and back contact angle.The result is illustrated in the table 3.

Can find out obviously that from table 3 in using the embodiment 11 and 12 of photosensitive composite of the present invention, the deformation rate of contact angle height has advantageously generated arc-shaped protrusions, and can form image is formed favourable liquidcrystal divided-alignment protrusion.

Contact angle is because of the evaluation of the velocity of variation of heating

The cross-sectional shape of measuring fine rule before and after the heating with VK9500 is to obtain contact angle; The contact angle (W2) that the side surface that obtains heating the side surface of preleptonema image and contact angle (W1) that substrate plane forms and heating back fine rule image and substrate plane form is pressed the variation of following standard evaluation contact angle because of heating with the value of the velocity of variation (W1/W2) of contact angle.See Fig. 1.

A:W1/W2 is at least 2

B:W1/W2 is at least 1.5 and less than 2

C:W1/W2 is at least 1.2 and less than 1.5

D:W1/W2 is less than 1.2

Image forms

The image that obtains by above-mentioned exposure and development treatment by following standard evaluation.

A: formed 70% the image that film thickness is at least coated film thickness

B: formed 70% the image of film thickness less than coated film thickness

C: sensitive layer dissolves fully, does not form image.

Table 3

In table 3, the connotation of symbol is following.

M-1: produce dipentaerythritol acrylate (DPHA) by Japanese chemical drug society

M-2: Xin Zhong village science society produces, difunctionality SULPHOSUCCINIC ACID ESTER " PM-21 "

S-1: produce " IRGACURE 907 " by Ciba Specialty Chemicals K.K.

S-2: produce by Japanese chemical drug society, 2, the 4-diethyl thioxanthone

P-1: have the alkali soluble resins of the acid number of 2,000 weight-average molecular weight and 100, structural formula is as follows.

F-1: by DAINIPPON INK AND CHEMICALS, INCORPORATED produces, fluorine type surfactant " F475 "

PGMA: change into society by Tokyo and produce the Isopropanediol methyl ether acetate.

In table 3, suitable light sensitivity mJ/cm ^-2Be meant the minimum exposure amount of the thread pattern that can reproduce 15 μ m.

The Me=methyl

Industrial applicibility

Optical polymerism composition of the present invention is suitable for for example colour television set, liquid-crystal display, solid state image sensor and camera with the colour filter that uses said composition.

Here with the whole whole disclosures of introducing Japanese patent application 2004-046071 number (submission on February 23rd, 2004), Japanese patent application 2004-094927 number (submission on March 29th, 2004) and Japanese patent application 2004-183593 number (submission on June 22nd, 2004) of the mode of reference, comprising specification sheets, claims and summary.

Claims

1. An oxime ester compound represented by formula (5):

In formula (5), R ^1a represents C _3-15 N-acyloxy-N-amidoalkyl;

R ^2a represents a C _2-12 alkanoyl group or a C _2-12 alkanoyl group with an alkoxycarbonyl substituent; and

Each of R ³ , R ⁶ , R ⁷ , R ¹² and R ¹⁴ to R ¹⁶ is a hydrogen atom or a C _1-12 alkyl group, and R ¹³ is a benzoyl group or a benzoyl group having a methyl substituent.

2. A photopolymerizable composition comprising an organic binder (b) and a photopolymerization initiator (c), wherein component (c) contains an oxime ester compound as defined in claim 1.

3. The photopolymerizable composition according to claim 2, wherein the organic binder (b) is an epoxy acrylate resin having a carboxyl group.

4. The photopolymerizable composition as claimed in claim 3, wherein the organic binder (b) is a reaction product of epoxy novolak resin and acrylic acid or methacrylic acid with phthalic anhydride or hydrogenated phthalic anhydride The epoxy acrylate obtained by the reaction.

5. The photopolymerizable composition according to any one of claims 2 to 4, further comprising a photopolymerizable monomer (d).

The photopolymerizable composition in any one of Claims 2-4 which further contains a coloring material (a).

7. The photopolymerizable composition according to any one of claims 2 to 4, further comprising a polymer dispersant (e) having a basic functional group.

8. The photopolymerizable composition according to claim 5, further comprising a coloring material (a).

9. The photopolymerizable composition according to claim 5, further comprising a polymer dispersant (e) having a basic functional group.

10. The photopolymerizable composition according to claim 6, further comprising a polymer dispersant (e) having a basic functional group.

11. The photopolymerizable composition according to claim 8, which also contains a polymer dispersant (e) with a basic functional group

The color filter which has the image formed with the photopolymerizable composition in any one of Claims 2-11.

The liquid crystal display device which has the image formed with the photopolymerizable composition in any one of Claims 2-11.