JP5298653B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Abstract

The present invention provides a radiation-sensitive composition for forming colored layer, color filter and color liquid crystal display device, the radiation-sensitive composition for forming a colored layer can form a color filter not causing 'burn-in' at a high product yield, and can form a coating having high solubility in a cleaning solvent even after drying and high solubility in an alkalideveloper. The radiation- sensitive composition for forming the colored layer contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, wherein the alkali-soluble resin (B) is a copolymer of an unsaturated compound containing (b1) one selected from the group consisting of unsaturated carboxylic acids and acid anhydrides thereof, and unsaturated phenol compounds, (b2) a maleimide substituted at N-position, and (b3) an unsaturated compound represented by the following formula (1).

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display element. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display element, a color imaging tube element and the like. The present invention relates to a radiation-sensitive composition used for forming a useful colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display element including the color filter.

As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance. Radiation is irradiated through a photomask having a pattern shape (hereinafter referred to as “exposure”), developed with an alkali developer to dissolve and remove unexposed portions, and then post-baked using a clean oven or hot plate. Thus, a method for obtaining pixels of each color (for example, see Patent Document 1 and Patent Document 2) is known.
In recent years, since the size of the substrate used for forming the color filter has increased, the coating method of the radiation-sensitive composition is different from the method using a central dropping type spin coater, and the liquid protrusion for coating the radiation-sensitive composition. It is being replaced by a method using a slit nozzle having a smaller diameter part. In the latter slit nozzle method, since the diameter of the liquid protrusion is small (narrow), the radiation-sensitive composition often remains around the nozzle tip after the application is completed. Since it falls on the color filter as a foreign substance and the quality of the color filter is significantly reduced, jet cleaning is usually performed by spraying a cleaning solvent on the nozzle tip before application, but the quality of the color filter due to dry foreign matter is still present. This is a major factor that the yield cannot be effectively prevented and the product yield is lowered.
Therefore, in order to cope with such problems, in recent years, there has been a demand for a radiation sensitive composition for a color filter that has a high cleaning property with a cleaning solvent, that is, a high solubility in the cleaning solvent even after drying.

  Moreover, when the density | concentration of the coloring agent contained in a colored radiation sensitive composition becomes high with high color purity of a color liquid crystal display element, there exists a tendency for the solubility with respect to the alkaline developing solution of a coating film to fall remarkably. For this reason, during development by the shower development method, the unexposed coating film that has been peeled and removed once floats without completely dissolving in the developing tank, and reattaches as a foreign matter on the color filter, resulting in a product yield. This is a major factor of decline.

Further, in recent years, a color liquid crystal display element having a color filter has been required to have a long lifetime, and accordingly, the demand for the anti-burning ability of the color filter has been increased.
By the way, “burn-in” is a kind of display failure of a color liquid crystal display element, and an image that should not be displayed is displayed on the screen, or a black or white “haze” -shaped image is over the image that is originally displayed. It is a phenomenon that is displayed overlaid on. Such a phenomenon is thought to result from the fact that the charged impurities in the liquid crystal diffuse in the liquid crystal and the potential difference applied to align the liquid crystal molecules is not maintained for a certain period of time. It has recently become clear that elution occurs not only in the molecular production but also in the formed color filter. In order to prevent “burn-in”, as disclosed in, for example, Patent Document 3, it is known that increasing the purity of the pigment is effective, but impurities are contained in the colored radiation-sensitive composition. It may be derived from components other than these pigments, and it is not always sufficient to raise the pigment purity.
Accordingly, there is a strong demand for the development of a further improved colored radiation-sensitive composition that satisfies the demand for high product yield during the production of color filters in recent years and does not cause “burn-in”.
JP-A-2-144502 JP-A-3-53201 JP 2000-329929 A

  An object of the present invention is to form a color filter that does not cause “burn-in” with a high product yield, and has a high solubility in a cleaning solvent even after drying, and a coating film that is highly soluble in an alkaline developer. It is in providing the radiation sensitive composition etc. for colored layer formation which can be formed.

The present invention, first,
In the radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The resin is represented by (b1) one kind selected from the group of unsaturated carboxylic acid, its acid anhydride and unsaturated phenol compound, (b2) N-substituted maleimide, (b3) represented by the following formula (1) A radiation-sensitive composition for forming a colored layer, which is a copolymer of an unsaturated compound (hereinafter referred to as “copolymer (B1)”). .

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon group having 7 to 20 carbon atoms. Represents an aralkyl group, and n represents an integer of 1 to 10.)

The present invention secondly,
A color filter provided with a colored layer formed using the radiation-sensitive composition for forming the colored layer.

Third, the present invention
A color liquid crystal display device comprising the color filter;

The present invention fourthly,
It consists of the said copolymer (B1).

The radiation-sensitive composition for forming a colored layer of the present invention can form a color filter that does not cause “burn-in” with a high product yield, and has high solubility in a cleaning solvent even after drying. It is also suitable for application. Further, even when the concentration of the colorant contained in the colored radiation-sensitive composition is high, the coating film has high solubility in an alkaline developer, and is suitable for development by, for example, a shower development method.
Moreover, the copolymer (B1) of the present invention is useful as an alkali-soluble resin for use in a radiation-sensitive composition for forming a colored layer.
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer- (A) Colorant-
The colorant in the present invention is not particularly limited, and may be any of a pigment, a dye, or a natural pigment, but the color filter has a high purity and high light transmission color, or high light shielding properties and heat resistance. Therefore, a pigment is preferable, and an organic pigment or carbon black is particularly preferable.
Examples of the organic pigment include compounds classified as pigments in the color index, and specifically those having the following color index (CI) numbers.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

Among these organic pigments, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58; C.I. I. Pigment violet 23, C.I. I. Pigment blue 60 and C.I. I. At least one selected from the group of CI Pigment Blue 80 is preferred.
The organic pigments can be used alone or in admixture of two or more, and can also be used as a mixture of organic pigments and carbon black. It is preferable to use, and when forming a black matrix, it is preferable to use two or more organic pigments and / or carbon black.

  The radiation-sensitive composition for forming a colored layer of the present invention is a coating having high solubility in an alkali developer even when the content of the colorant is 30% by weight or more in the total solid content of the composition. A film can be formed. In the present invention, the upper limit of the content of the colorant is preferably 70% by weight or less, particularly preferably 60% by weight or less, in the total solid content of the radiation-sensitive composition, from the viewpoint of ensuring developability. . Here, solid content is components other than the solvent mentioned later.

  In the composition of the present invention, when the colorant is a pigment, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, for example, using a bead mill, a roll mill or the like while being pulverized to obtain a pigment dispersion. It is preferable to prepare this by adding (B) component, (C) component and (D) component described later, and further adding an additional solvent and other additives described later as necessary. .

As the dispersant used for the preparation of the pigment dispersion, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, but a compound having a urethane bond (hereinafter, “ Dispersants containing “urethane-based dispersants”) are preferred.
The urethane bond is generally of the formula R—NH—COO—R ₄ where R and R ₄ are aliphatic, alicyclic or aromatic monovalent or polyvalent organic groups, The group is further bonded to a group having another urethane bond or to another group.) And can be present in a lipophilic group and / or a hydrophilic group in the urethane-based dispersant. It can be present in the main chain and / or side chain of the dispersant, and more than one can be present in the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, each urethane bond may be the same or different.

Examples of such urethane dispersants include reaction products of diisocyanates and / or triisocyanates with polyesters having a hydroxyl group at one end and / or polyesters having a hydroxyl group at both ends. be able to.
Examples of the diisocyanates include benzene diisocyanates such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene-2,4-diisocyanate, toluene-2 , 5-diisocyanate, toluene-2,6-diisocyanate, toluene diisocyanates such as toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1, 2-xylene-3,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-4,6- Other aromatics such as xylene diisocyanates such as diisocyanate, 1,4-xylene-2,5-diisocyanate, 1,4-xylene-2,6-diisocyanate Mention may be made of an isocyanate, and the like.

Examples of the triisocyanates include benzene such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, and benzene-1,3,5-triisocyanate. Triisocyanates; toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-tri Toluene isocyanates such as isocyanate; 1,2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2, 4,5-triisocyanate, 1,3-xylene-2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-chi Other aromatic triisocyanates such as xylene triisocyanates such as len-2,3,5-triisocyanate and 1,4-xylene-2,3,6-triisocyanate can be mentioned. .
These diisocyanates and triisocyanates can be used alone or in admixture of two or more.

Examples of the polyester having a hydroxyl group at one end and the polyester having a hydroxyl group at both ends include polycaprolactone having a hydroxyl group at one end or both ends, polyvalerolactone having a hydroxyl group at one end or both ends, and one end Or polylactones having a hydroxyl group at one or both ends, such as polypropiolactone having a hydroxyl group at both ends; polyethylene terephthalate having a hydroxyl group at one or both ends, polybutylene terephthalate having a hydroxyl group at one or both ends, etc. Examples thereof include polycondensed polyesters having a hydroxyl group at one or both ends.
These polyesters having a hydroxyl group at one end and polyesters having a hydroxyl group at both ends can be used alone or in admixture of two or more.

The urethane-based dispersant in the present invention is preferably a reaction product of an aromatic diisocyanate and a polylactone having a hydroxyl group at one end and / or a polylactone having a hydroxyl group at both ends, particularly toluene diisocyanate. A reaction product of a polycaprolactone having a hydroxyl group at one end and / or a polycaprolactone having a hydroxyl group at both ends is preferred.
Specific examples of such urethane-based dispersants are trade names such as Disperbyk161 and Disperbyk170 (above, manufactured by BYK Chemy (BYK)), EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disparon (Enomoto) Series products such as Kasei Co., Ltd.) can be mentioned.
The Mw of the urethane-based dispersant in the present invention is usually 5,000 to 50,000, preferably 7,000 to 20,000.
The said urethane type dispersing agent can be used individually or in mixture of 2 or more types.

A (meth) acrylic dispersant composed of a (co) polymer of (meth) acrylic monomers is also preferred as the dispersant.
Specific examples of such (meth) acrylic dispersants include Disperbyk 2000 and Disperbyk 2001 (above, manufactured by BYK Corporation) as trade names.
The said (meth) acrylic-type dispersing agent can be used individually or in mixture of 2 or more types.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of the pigment. Preferably it is 10-50 weight part. In this case, if the amount of the dispersant used exceeds 100 parts by weight, developability and the like may be impaired.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the solvent illustrated about the liquid composition of the radiation sensitive composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 200 to 1,200 parts by weight, preferably 300 to 1,000 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent and a dispersant is used. Preferably, it can be carried out by mixing and dispersing while cooling with cooling water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixed solution is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.
Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 10 ⁸ dyn / sec. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(B) Alkali-soluble resin-
The alkali-soluble resin in the present invention is a copolymer (B1), that is, (b1) a group of unsaturated carboxylic acid, its acid anhydride and unsaturated phenol compound (hereinafter, these compounds are collectively referred to as “unsaturated compound (b1 And (b2) N-substituted maleimide (hereinafter referred to as “unsaturated compound (b2)”), and (b3) an unrepresented by the formula (1). An alkaline developer used in a development processing step for forming a colored layer, comprising a copolymer of an unsaturated compound containing a saturated compound (hereinafter referred to as "unsaturated compound (b3)"). And is a soluble component.

Among the unsaturated compound (b1), as the unsaturated carboxylic acid or acid anhydride thereof, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Of these unsaturated carboxylic acids or acid anhydrides thereof, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively light ester HOA-MS and light ester HOA-MPE ( As mentioned above, it is marketed under the trade name of Kyoeisha Chemical Co., Ltd.

Moreover, as an unsaturated phenol compound, for example,
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols.

  In the present invention, as the unsaturated compound (b1), (meth) acrylic acid, p-vinylphenol and the like are preferable, and (meth) acrylic acid is particularly preferable.

As the unsaturated compound (b2), for example,
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- Examples include succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide, and the like.
Of these N-substituted maleimides, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable, and N-phenylmaleimide is particularly preferable.
In the copolymer (B1), the unsaturated compound (b2) can be used alone or in admixture of two or more.

  In the present invention, the unsaturated compound (b3) represented by the formula (1) is copolymerized in the alkali-soluble resin, so that the solubility in the washing solvent is high even after drying and the solubility in the developer is high. A radiation-sensitive composition for forming a colored layer capable of forming a coating film can be obtained.

In the formula (1), examples of the alkyl group having 1 to 20 carbon atoms of R ₃ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopentyl group And a linear, branched or cyclic alkyl group such as a cyclohexyl group.
In the formula (1), the aralkyl group having 7 to 20 carbon atoms of R ₃ is phenyl C _1-6 such as benzyl group, phenethyl group, α-methylbenzyl group, 2-phenylpropan-2-yl group, etc. An alkyl group can be mentioned.

In the formula (1), R ₃ is preferably an aralkyl group having 7 to 20 carbon atoms, particularly preferably a 2-phenylpropan-2-yl group.
In the formula (1), examples of the alkylene group having 2 to 4 carbon atoms of R ₂ include an ethylene group, a propylene group, a trimethylene group, a butylene group, and a tetramethylene group. preferable.
In the formula (1), n is preferably 1 to 6, and particularly preferably 1 to 4.

As the unsaturated compound (b3), for example,
Examples thereof include ethylene oxide (EO) modified (meth) acrylate of phenol, EO modified (meth) acrylate of paracumylphenol, EO modified (meth) acrylate of nonylphenol, and propylene oxide (PO) modified (meth) acrylate.
Of these unsaturated compounds (b3), phenol EO-modified acrylates are Aronix M-101A (n = about 2) and M-102 (n = about 4), and paracumylphenol EO-modified acrylate is Aronix M-110. (N = about 1), EO-modified acrylate of nonylphenol is Aronix M-111 (n = about 1), M-113 (n = about 4), PO modified acrylate of nonylphenol is Aronix M-117 (above, Toagosei ( The product name is “commercially available”.

In the present invention, the unsaturated compound used for the synthesis of the copolymer (B1) can be copolymerized with these in addition to the unsaturated compound (b1), the unsaturated compound (b2), and the unsaturated compound (b3). And other unsaturated compounds (hereinafter referred to as “unsaturated compound (b4)”).
As the unsaturated compound (b4), for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;
A macromonomer having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane or the like (hereinafter simply referred to as “macromonomer”). Class:

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Examples thereof include aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene and isoprenesulfonic acid.

Of these unsaturated compounds (b4), styrene, macromonomers, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, glycerol mono (meth) acrylate, etc. Of the macromonomers, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers are particularly preferred.
In the copolymer (B1), the unsaturated compound (b4) can be used alone or in admixture of two or more.

In the copolymer (B1), the copolymerization ratio of the unsaturated compound (b1) is preferably 10 to 40% by weight, particularly preferably 10 to 25% by weight, and the copolymerization ratio of the unsaturated compound (b2) is The copolymerization ratio of the unsaturated compound (b3) is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight. The copolymerization ratio of the unsaturated compound (b4) is preferably 5 to 70% by weight, particularly preferably 10 to 60% by weight.
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (B1) to the above range, sensitivity, adhesion to the substrate, washability with an organic solvent, solubility in an alkaline developer, and the like are achieved. An excellent radiation-sensitive composition for forming a colored layer can be obtained.

In the present invention, other alkali-soluble resins can be used in combination with the copolymer (B1).
The other alkali-soluble resin is not particularly limited as long as it is soluble in an alkali developer used in the development processing step when forming the colored layer. For example, the unsaturated compound (b1) And a copolymer of at least one selected from the group consisting of the unsaturated compound (b2) and the unsaturated compound (b4).

In the present invention, Mw of the copolymer (B1) and other alkali-soluble resins is preferably 1,000 to 25,000, more preferably 3,000 to 20,000, and particularly preferably 3,000 to 12,000. It is.
Further, Mw / Mn of the copolymer (B1) and other alkali-soluble resins is preferably 1.0 to 2.2, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 1, respectively. .8.
In the present invention, the copolymer (B1) having the specific Mw and / or Mw / Mn is used, or the copolymer (B1) and another copolymer having the specific Mw and / or Mw / Mn are used. By using in combination with an alkali-soluble resin, a radiation-sensitive composition having excellent developability can be obtained, whereby a pixel and a black matrix having sharp pattern edges can be formed, and washing with an organic solvent is possible. Therefore, it is possible to realize a high product yield without generating dry foreign matters during the production of the color filter, and to effectively prevent “burn-in” of the color filter.

  Further, according to the present inventors, when the unsaturated compound (b3) represented by the formula (1) is to be copolymerized in the (B) alkali-soluble resin, the polymerization conversion rate tends to decrease. . If the polymerization conversion rate decreases and an unreacted unsaturated compound remains, the electrical characteristics of the resulting colored layer may be deteriorated, and this must be controlled. In the production of the copolymer (B1), the polymerization conversion rate is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. Here, the polymerization conversion rate refers to the ratio of the weight of the copolymer (B1) obtained by the polymerization reaction to the total weight of each component constituting the copolymer (B1) subjected to the polymerization reaction.

  A living radical polymerization can be mentioned as a manufacturing method which controls Mw, Mn, and a polymerization conversion rate of a copolymer (B1) to the above-mentioned range. In the living radical polymerization, each unsaturated compound is converted into 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy- 2,4-dimethylvaleronitrile) and other radical polymerization initiators, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazole-1- Ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (5-methyl-pyrazol-1-ylthio) Carbonyl) disulfide, bis (3,4,5-trimethyl- Razol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide, bis (n-octylmercapto-thiocarbonyl) disulfide, bis (n-dodecylmercapto-thiocarbonyl) disulfide In the presence of a molecular weight controlling agent that acts as an iniferter such as bis (benzylmercapto-thiocarbonyl) disulfide (addition), the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C. in an inert solvent. Can be carried out by polymerization.

In this invention, a copolymer (B1) can be used individually or in mixture of 2 or more types, and other alkali-soluble resin is also the same.
In this invention, the total usage-amount of alkali-soluble resin is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the total use amount of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may decrease, or there is a possibility that background stain or film residue may occur on the unexposed part of the substrate or on the light shielding layer. On the other hand, when the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.
Moreover, the usage-amount of the copolymer (B1) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Most preferably, it is 30-100 weight%. In this case, if the proportion of the copolymer (B1) used is less than 10% by weight, the intended effect of the present invention may be impaired.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,

A compound represented by the following formula (2):

Compound represented by the following formula (3)

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is too small, the strength and surface smoothness of the colored layer may be reduced. On the other hand, if the amount is too large, for example, the alkali developability may be reduced or the unexposed area may be reduced. There is a risk that background contamination, film residue, etc. are likely to occur on the substrate or the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include those similar to the compounds exemplified for the unsaturated compound (b1) or unsaturated compound (b4) in (B) the alkali-soluble resin, and N- (meth) acryloylmorpholine. In addition to N-vinylpyrrolidone and N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.
The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, if the usage ratio of the monofunctional monomer is too large, the strength and surface smoothness of the resulting colored layer may be insufficient.

  The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is too small, the strength and surface smoothness of the colored layer may be lowered. On the other hand, if the total amount is too large, for example, alkali developability may be lowered, the substrate on the unexposed area or light shielding. There is a risk that soiling, film residue, etc. are likely to occur on the layer.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species that can initiate polymerization of the body.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferred.

  In this invention, the general usage-amount of a photoinitiator is 0.01-120 weight normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer. Parts, preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while too much. Then, the formed colored layer may be easily detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 70 parts by weight, and more preferably 1 to 60 parts by weight. In this case, if the amount of the acetophenone-based compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. The formed colored layer may be easily removed from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrafe 1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is preferred.
These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the biimidazole compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while too much. When developing, there is a possibility that the formed colored layer may easily fall off from the substrate or the colored layer surface may come off.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is too small, the effect of improving the sensitivity tends to be lowered. On the other hand, if the amount is too large, the formed colored layer may be easily detached from the substrate during development.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the amount of triazine compound used as the photopolymerization initiator is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is too small, curing due to exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, while if too large, The formed colored layer may be easily removed from the substrate during development.

  Specific examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio). Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole -3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetate) Oxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9 -Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2- Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl) -1,3-dioxolanyl) benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) ) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9H-carbazole-3 -Yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O -Acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9H-cal Basol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

Of these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using an O-acyloxime compound as a photopolymerization initiator is based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-80 weight part, More preferably, it is 1-70 weight part, Most preferably, it is 1-60 weight part. In this case, if the amount of the O-acyloxime compound used is too small, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. If the amount is too large, the formed colored layer may be easily removed from the substrate during development.

-Other additives-
The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) as essential components, but may further contain other additives as necessary.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulation agents such as sodium acrylate; residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

Preparation of liquid composition The radiation-sensitive composition for forming a colored layer of the present invention is usually prepared as a liquid composition by blending a solvent.
As the solvent, components (A) to (D) constituting the radiation-sensitive composition and other additive components are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is, it can be selected and used as appropriate.

As such a solvent, for example,
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;
(Poly) alkylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether;
Other ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, ethyl ethoxy acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as Le;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono -N-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether Cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, Preferred are n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferably 5 to 5 from the viewpoints of applicability, stability and the like of the obtained liquid composition. An amount of 50% by weight, particularly preferably 10 to 40% by weight, is desirable.

Method of forming a color filter Then, using a colored layer forming radiation-sensitive composition of the present invention, a method for forming a color filter of the present invention.
The method for forming a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the radiation sensitive composition for colored layer formation of this invention on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) A step of developing the coated film after exposure.
(4) A step of heat-treating (hereinafter referred to as “post-bake”) the coated film after development.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming a pixel, and a radiation-sensitive composition for forming a colored layer containing, for example, a red pigment is formed on the substrate. After applying the liquid composition of the product, pre-baking is performed to evaporate the solvent and form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When the liquid composition is applied to the substrate, an appropriate application method such as spin coating, cast coating, roll coating, or slit nozzle coating can be employed. The composition has high solubility in a cleaning solvent even after drying, and is suitable for application by a slit nozzle.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, and more preferably 0.2 to 6.0 μm as the film thickness after removal of the solvent.

-(2) Process-
Thereafter, at least a part of the formed coating film is exposed. When exposing a part of the coating film, it is usually exposed through a photomask having an appropriate pattern.
As the radiation used in this step, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is usually, 10~10,000J / m ² approximately.

-(3) Process-
Thereafter, the exposed coating film is preferably developed using an alkali developer, and an unexposed portion of the coating film is dissolved and removed to form a pattern.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method, and the like can be applied. The radiation-sensitive composition in the present invention is an alkaline developer. Therefore, it is suitable for development by shower development.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-(4) Process-
Then, the post-baking of the developed coating film can provide a substrate on which pixel patterns made of a cured product of the radiation-sensitive composition are arranged in a predetermined arrangement.
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.5 to 3.0 μm.

Furthermore, by repeating the steps (1) to (4) using each liquid composition of the colored layer forming radiation-sensitive composition containing a green or blue pigment, a green pixel pattern and a blue By forming the pixel pattern on the same substrate, a colored layer in which pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors in the present invention is not limited to the order described above.
Further, the black matrix can be formed by processing in the same manner as in the formation of the pixel pattern except that a liquid composition of the radiation-sensitive composition for forming a colored layer containing a black pigment is used.

Color filter The color filter of the present invention comprises a colored layer formed using the radiation-sensitive composition for forming a colored layer of the present invention.
The color filter of the present invention is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other through the liquid crystal layer. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed include a liquid crystal layer. It is also possible to adopt a structure facing each other. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition color liquid crystal display element can be obtained.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis of alkali-soluble resin Synthesis Example 1
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 200 parts by weight of dipropylene glycol dimethyl ether Then, 20 parts by weight of methacrylic acid, 30 parts by weight of N-phenylmaleimide, 30 parts by weight of EO-modified acrylate of paracumylphenol (Aronix M-110 manufactured by Toagosei Co., Ltd.) and 20 parts by weight of styrene were charged with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another 2 hours to obtain a copolymer solution (polymerization conversion rate 99%). Got. This copolymer had Mw = 6,000 and Mw / Mn = 1.4. This copolymer is referred to as “copolymer (S-1)”.
Here, the polymerization conversion rate indicates how much of the components other than the solvent subjected to the polymerization reaction was consumed in the polymerization reaction, and was specifically calculated by the following formula.
Polymerization addition rate (%) = solid content concentration of copolymer solution (%) × total charge of all components / total charge of components other than solvent The solid content concentration of the copolymer solution is determined by comparing the copolymer solution with aluminum. When weighed in a dish and heated on a hot plate at 180 ° C. for 1 hour, the weight before and after heating was measured and calculated by (weight after heating × 100 / weight before heating).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3.5 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid and 30 parts by weight of N-phenylmaleimide. , 30 parts by weight of EO-modified acrylate of paracumylphenol, 20 parts by weight of styrene, and 10 parts by weight of α-methylstyrene dimer (molecular weight control agent) were charged with nitrogen, and then the reaction solution was stirred while gently stirring. The temperature was raised to 0 ° C., and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1.5 parts by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another 2 hours to obtain a copolymer solution (polymerization conversion rate). 87%). This copolymer had Mw = 17,000 and Mw / Mn = 2.1. This copolymer is referred to as “copolymer (S-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 3.5 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid and 30 parts by weight of N-phenylmaleimide. , 30 parts by weight of EO-modified acrylate of paracumylphenol, 20 parts by weight of styrene, and 10 parts by weight of α-methylstyrene dimer (molecular weight control agent) were charged with nitrogen, and then the reaction solution was stirred while gently stirring. The temperature was raised to 0 ° C., and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 3.5 parts by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was continued for another 2 hours to obtain a copolymer solution (polymerization conversion rate). 92%). This copolymer had Mw = 22,000 and Mw / Mn = 1.9. This copolymer is referred to as “copolymer (S-3)”.

Synthesis example 4
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 200 parts by weight of dipropylene glycol dimethyl ether Then, 20 parts by weight of methacrylic acid, 30 parts by weight of N-phenylmaleimide, 30 parts by weight of benzyl methacrylate, and 20 parts by weight of styrene were charged, and after replacing with nitrogen, the reaction solution was brought to 80 ° C. while gently stirring. The temperature was raised and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another 2 hours to obtain a copolymer solution (polymerization conversion rate 99%). Got. This copolymer had Mw = 6,500 and Mw / Mn = 1.5. This copolymer is referred to as “copolymer (S-4)”.

Synthesis example 5
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, and 200 parts by weight of dipropylene glycol dimethyl ether Then, 20 parts by weight of methacrylic acid, 30 parts by weight of benzyl methacrylate, 30 parts by weight of EO-modified acrylate of paracumylphenol (Aronix M-110 manufactured by Toagosei Co., Ltd.) and 20 parts by weight of styrene were added, The reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisovaleronitrile was added, and the polymerization was continued for another 2 hours to obtain a copolymer solution (polymerization conversion rate 99%). Got. This copolymer had Mw = 7,000 and Mw / Mn = 1.5. This copolymer is referred to as “copolymer (S-5)”.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobisisovaleronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid, 30 parts by weight of N-phenylmaleimide, and benzyl. After charging 30 parts by weight of methacrylate, 20 parts by weight of styrene, and 10 parts by weight of α-methylstyrene dimer (molecular weight control agent) and replacing with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring, The polymerization was carried out for 2 hours while maintaining the temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 3 parts by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was further continued for 2 hours. A copolymer solution (polymerization conversion rate 99%) obtained by this operation was obtained. This copolymer had Mw = 6300 and Mw / Mn = 2.3. This copolymer is referred to as “copolymer (S-6)”.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 3.5 parts by weight of 2,2′-azobisisovaleronitrile and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 20 parts by weight of methacrylic acid and 30 parts by weight of N-phenylmaleimide. Then, 30 parts by weight of benzyl methacrylate, 20 parts by weight of styrene, and 5 parts by weight of α-methylstyrene dimer (molecular weight control agent) were charged, and after replacing with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring. The polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1.5 parts by weight of 2,2′-azobisisovaleronitrile was added, and polymerization was further continued for 2 hours. A copolymer solution (polymerization conversion rate 99%) obtained by this operation was obtained. This copolymer had Mw = 16,000 and Mw / Mn = 2.0. This copolymer is referred to as “copolymer (S-7)”.

[Developer immersion test]
Example 1
(A) C.I. I. Pigment red 254 and C.I. I. A mixture of 160 parts by weight of a 50/50 (weight ratio) mixture with CI Pigment Yellow 139, 40 parts by weight of Disperbyk 2001 as a dispersant (in terms of solid content), and 800 parts by weight of ethyl 3-ethoxypropionate as a solvent, A pigment dispersion was prepared by mixing and dispersing for 12 hours with a fine mill (trade name, manufactured by Mitsubishi Materials Corporation, bead mill (bead diameter: 1.0 mm)).
Next, 600 parts by weight of this pigment dispersion, (B) 70 parts by weight (in terms of solid content) of copolymer (S-1) as an alkali-soluble resin, and (C) dipentaerythritol hexaacrylate as a polyfunctional monomer 80 parts by weight, (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one as a photopolymerization initiator, and 800 parts by weight of propylene glycol monomethyl ether acetate as a solvent And 200 parts by weight of ethylene glycol mono-n-butyl ether acetate were mixed to prepare a liquid composition (r-1).
Next, the liquid composition (r-1) was spin-coated on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface, and then in a clean oven at 80 ° C. Pre-baking was performed for 10 minutes to form a 3.0 μm coating film on the substrate.
The substrate was then immersed for 2 minutes in 1000 cc of a developer composed of a 0.04 wt% aqueous potassium hydroxide solution stirred with a magnetic stirrer, whereby the coating film was completely dissolved.

Example 2
The liquid composition (r-2) was prepared in the same manner as in Example 1 except that 70 parts by weight of the copolymer (S-2) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer comprising a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was completely dissolved.

Example 3
A liquid composition (r-3) was prepared in the same manner as in Example 1, except that 70 parts by weight of the copolymer (S-3) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer comprising a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was completely dissolved.

Comparative Example 1
The liquid composition (r-4) was prepared in the same manner as in Example 1 except that 70 parts by weight of the copolymer (S-4) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer consisting of a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was not completely dissolved, and a large amount of insoluble matter was contained in the solution. Lump was observed.

Comparative Example 2
The liquid composition (r-5) was prepared in the same manner as in Example 1 except that 70 parts by weight of the copolymer (S-5) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer comprising a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was completely dissolved.

Comparative Example 3
A liquid composition (r-6) was prepared in the same manner as in Example 1 except that 70 parts by weight of the copolymer (S-6) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer consisting of a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was not completely dissolved, and a large amount of insoluble matter was contained in the solution. Lump was observed.

Comparative Example 4
A liquid composition (r-7) was prepared in the same manner as in Example 1 except that 70 parts by weight of the copolymer (S-7) (in terms of solid content) was used instead of the copolymer (S-1). A coating film was formed on a soda glass substrate.
Then, when this substrate was immersed in 1000 cc of a developer consisting of a 0.04 wt% aqueous potassium hydroxide solution for 2 minutes in the same manner as in Example 1, the coating film was not completely dissolved, and a large amount of insoluble matter was contained in the solution. Lump was observed.
As is clear from Examples 1 to 3 and Comparative Examples 1 to 4, (B) the unsaturated compound represented by the above formula (1) is copolymerized in the alkali-soluble resin so that the solubility in the developer is increased. A high coating film can be formed.

[Solvent immersion test]
Example 4
The liquid composition (r-1) was spin-coated on a 4 inch diameter soda glass substrate having a SiO ₂ film formed on its surface to prevent elution of sodium ions, and then left in a clean room at 23 ° C. for 12 hours. Then, a coating film was formed by drying.
Next, when this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved.

Example 5
When the solvent immersion test was conducted in the same manner as in Example 4 except that the liquid composition (r-2) was used instead of the liquid composition (r-1), the coating film was completely dissolved.

Example 6
Except for using the liquid composition (r-3) in place of the liquid composition (r-1), a solvent immersion test was carried out in the same manner as in Example 4, and the coating film was not completely dissolved. A slight amount of foreign matter was observed.

Comparative Example 5
When the solvent immersion test was carried out in the same manner as in Example 4 except that the liquid composition (r-4) was used instead of the liquid composition (r-1), the coating film was completely dissolved.

Comparative Example 6
When the solvent immersion test was conducted in the same manner as in Example 4 except that the liquid composition (r-5) was used instead of the liquid composition (r-1), the coating film was completely dissolved.

Comparative Example 7
When the solvent immersion test was conducted in the same manner as in Example 4 except that the liquid composition (r-6) was used instead of the liquid composition (r-1), the coating film was completely dissolved.

Comparative Example 8
A solvent immersion test was conducted in the same manner as in Example 4 except that the liquid composition (r-7) was used instead of the liquid composition (r-1). The coating film was not completely dissolved, A large amount of foreign matter was observed.
As is clear from Examples 5 to 6 and Comparative Example 8, (B) a feeling for forming a colored layer after drying by copolymerizing the unsaturated compound represented by the formula (1) in the alkali-soluble resin. It turns out that there exists an effect which improves the solubility with respect to the washing | cleaning solvent of a radiation composition.

[Evaluation of voltage holding ratio]
Example 7
The liquid composition (r-1) is spin-coated on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After that, prebaking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 250 ° C. for 30 minutes. And the coating film was cured to form red pixels on the substrate. The film thickness of this pixel was 1.6 μm.
Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 (trade name) is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). As a result, the voltage holding ratio was 95%.
When the voltage holding ratio of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-1) has almost no risk of “burn-in”.

Example 8
A liquid crystal cell was prepared in the same manner as in Example 7 except that the liquid composition (r-2) was used instead of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, a liquid crystal display element including a color filter formed using the liquid composition (r-2) is less likely to cause “burn-in”.

Example 9
A liquid crystal cell was prepared in the same manner as in Example 7 except that the liquid composition (r-3) was used in place of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, the liquid crystal display element including the color filter formed using the liquid composition (r-3) has almost no risk of “burn-in”.

Comparative Example 9
A liquid crystal cell was prepared in the same manner as in Example 7 except that the liquid composition (r-4) was used instead of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, the liquid crystal display element including the color filter formed using the liquid composition (r-4) has almost no risk of “burn-in”.

Comparative Example 10
A liquid crystal cell was prepared in the same manner as in Example 7 except that the liquid composition (r-5) was used instead of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, the liquid crystal display element including the color filter formed using the liquid composition (r-5) has almost no possibility of causing “burn-in”.

Comparative Example 11
A liquid crystal cell was produced in the same manner as in Example 7 except that the liquid composition (r-6) was used instead of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-6) is likely to cause “burn-in”.

Comparative Example 12
A liquid crystal cell was prepared in the same manner as in Example 7 except that the liquid composition (r-7) was used instead of the liquid composition (r-1), and the voltage holding ratio was measured. %Met. Therefore, a liquid crystal display device including a color filter formed using the liquid composition (r-7) is less likely to cause “burn-in”.

  As is clear from Examples 1 to 3 and Comparative Examples 1 to 4, it is understood that the voltage holding ratio is improved by controlling the Mw, Mw / Mn and polymerization conversion rate of (B) the alkali-soluble resin.

[Evaluation of developability]
Example 10
The liquid composition (r-1) was applied to a soda glass substrate having a diameter of 4 inches on the surface of which a SiO ₂ film for preventing elution of sodium ions was formed using a spin coater, and then applied to a hot plate at 90 ° C. Was pre-baked for 2 minutes to form a coating film having a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays including 365 nm, 405 nm, and 436 nm through a photomask (slit width 90 μm) using a high pressure mercury lamp. The exposure amount at this time was 100 mJ / cm ² . Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. was discharged at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development, and then post-baked at 220 ° C. for 30 minutes. As a result, a red stripe pixel pattern was formed on the substrate.
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.

Example 11
Except for using the liquid composition (r-2) instead of the liquid composition (r-1), the evaluation of developability was carried out in the same manner as in Example 10, and on the unexposed portion of the substrate. No development residue was observed, and no chipping was observed on the edge of the pixel pattern.

Example 12
Except that the liquid composition (r-3) was used in place of the liquid composition (r-1), the developability was evaluated in the same manner as in Example 10, and on the unexposed portion of the substrate. No development residue was observed, and no chipping was observed on the edge of the pixel pattern.

Comparative Example 13
Except that the liquid composition (r-4) was used in place of the liquid composition (r-1), the developability was evaluated in the same manner as in Example 10, and on the unexposed portion of the substrate. No development residue was observed, and no chipping was observed on the edge of the pixel pattern.

Comparative Example 14
Except that the liquid composition (r-5) was used in place of the liquid composition (r-1), the developability was evaluated in the same manner as in Example 10, and on the unexposed portion of the substrate. Development residues were observed, and chipping was observed on the edge of the pixel pattern.

Comparative Example 15
Except for using the liquid composition (r-6) instead of the liquid composition (r-1), the evaluation of developability was carried out in the same manner as in Example 10, and on the unexposed portion of the substrate. No development residue was observed, and no chipping was observed on the edge of the pixel pattern.

Comparative Example 16
Except that the liquid composition (r-7) was used in place of the liquid composition (r-1), the developability was evaluated in the same manner as in Example 10 to find on the unexposed portion of the substrate. No development residue was observed, and no chipping was observed on the edge of the pixel pattern.
As is clear from Examples 10 to 12 and Comparative Examples 13 to 16, (B) a radiation sensitive material for forming a colored layer having excellent developability by copolymerizing an N-substituted maleimide in an alkali-soluble resin. A composition can be obtained.
Here, although the radiation sensitive composition using a red pigment was evaluated, similar results were obtained in the case of a radiation sensitive composition using a blue, green, yellow or black pigment.

  As apparent from the above (1) developer immersion test, (2) solvent immersion test, (3) evaluation of voltage holding ratio, and (4) evaluation of developability, (B) as an alkali-soluble resin, (b1 ), (B2), and a composition containing a copolymer containing (b3), all of these evaluation results are good, and a color filter that does not cause "burn-in" can be formed with a high product yield. It was also found that the composition was a radiation-sensitive composition for forming a colored layer, which can form a coating film having high solubility in a washing solvent and high solubility in an alkali developer even after drying.

Claims (5)

In the radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The resin is represented by (b1) one kind selected from the group of unsaturated carboxylic acid, its acid anhydride and unsaturated phenol compound, (b2) N-substituted maleimide, (b3) represented by the following formula (1) that I copolymer der unsaturated compound comprising the unsaturated compound, and the polystyrene reduced weight average molecular weight measured by gel permeation chromatography of the copolymer (GPC) (Mw) of 1,000 A radiation-sensitive composition for forming a colored layer of a color filter, which is ˜25,000 .

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon group having 7 to 20 carbon atoms. Represents an aralkyl group, and n represents an integer of 1 to 10.) (B) a copolymer which constitutes the alkali-soluble resin, the ratio between the Mw and gel permeation chromatography number average molecular weight in terms of polystyrene as measured by (GPC) (Mn) (Mw / Mn) is 1.0 to 2. The radiation-sensitive composition for forming a colored layer of a color filter according to claim 1, wherein (B) The radiation-sensitive composition for forming a colored layer of a color filter according to claim 1 or 2, wherein the alkali-soluble resin is a copolymer obtained by living radical polymerization. The color filter formed using the radiation sensitive composition for colored layer formation of the color filter of any one of Claims 1-3.   A color liquid crystal display device comprising the color filter according to claim 4.