JP2009151274A - Radiation-sensitive composition for red color filter, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition having a high light transmittance and enabling red pixels of high color purity to be formed without increasing the thickness of a coating film and the pigment component content of a colored radiation-sensitive composition. <P>SOLUTION: The radiation-sensitive composition includes: (A) a coloring agent; (B) an alkali-soluble resin; (C) a polyfunctional monomer; and (D) a photopolymerization initiator; wherein the coloring agent (A) includes at least one type chosen from a group consisting of C.I. Pigment Red 166, and C.I. Pigment Reds 224, 242 and 254. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive composition for a red color filter, a color filter, and a color liquid crystal display device. The present invention relates to a radiation-sensitive composition used for production, a color filter having pixels formed from the radiation-sensitive composition, and a color liquid crystal display device 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 previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and Patent Document 2).
A liquid crystal display device having such a color filter is required to have higher brightness and an expanded color reproduction region, and therefore, the color filter is also required to have higher light transmittance and higher color purity in recent years. .

Various proposals have been made for the radiation-sensitive composition for red color filters in order to achieve both high luminance and high color purity. For example, in Patent Document 3 and Patent Document 4, C.I. I. It is disclosed that Pigment Red 254 and various yellow pigments or orange pigments are used in combination. However, C.I. I. Pigment red 254 and C.I. I. A combination with a yellow pigment such as CI Pigment Yellow 139 is insufficient for obtaining a red color filter with high luminance. In addition, C.I. I. Pigment red 254 and C.I. I. Combination with orange pigments such as CI Pigment Orange 38 is insufficient for obtaining a red color filter with high color purity, and the film thickness of the formed coating must be increased to expand the color reproduction area of the color filter. In other words, the in-plane uniformity of the coating film is remarkably deteriorated, resulting in a lack of productivity.
On the other hand, in Patent Document 5 and Patent Document 6, C.I. I. Pigment red 254 and C.I. I. It is disclosed that Pigment Red 242 is used in combination. Such a combination of pigments is suitable for obtaining a red color filter having high luminance, but is not satisfactory for obtaining a red color filter having high color purity.
From the background as described above, there is a strong demand for the development of a radiation-sensitive composition for red color filters that can form pixels that satisfy the requirements of higher light transmittance and high color purity.

JP-A-2-144502 JP-A-3-53201 JP-A-10-227911 JP 11-217514 A Japanese Patent Laid-Open No. 11-14824 JP-A-2002-372618

An object of the present invention is to form red pixels with high color purity without increasing the light transmittance and without increasing the coating film thickness and without increasing the content of the pigment component in the radiation-sensitive composition. The object is to provide a radiation-sensitive composition for color filters.
Another object of the present invention is to provide a color filter having pixels formed from the radiation-sensitive composition for a color filter, and a color liquid crystal display device having the color filter.

  As a result of intensive studies, the present inventors have determined that C.I. I. It has been found that the above problems can be solved by introducing Pigment Red 166, and the present invention has been completed.

That is, the present invention firstly
A 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, As a colorant, (A1) C.I. I. Pigment red 166, and (A2) C.I. I. Pigment red 224, C.I. I. Pigment red 242 and C.I. I. A radiation-sensitive composition for a red color filter, comprising at least one selected from the group consisting of CI Pigment Red 254.
The “radiation” as used in the present invention means a substance containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

The present invention secondly,
A color filter provided with a red color filter formed using the radiation-sensitive composition.
Third, the present invention
A color liquid crystal display device comprising the color filter;

The radiation-sensitive composition for a red color filter of the present invention has a high light transmittance, and has a high color purity without increasing the coating thickness or increasing the content of the pigment component in the composition. Can be formed.
Therefore, the radiation-sensitive composition of the present invention is extremely preferably used for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. Can do.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for red color filter- (A) Colorant-
The colorant in the present invention is a color index (CI; The Society of Dyers and
Published by Colorists. The same applies below. ) In (A1) C.I. I. Pigment Red 166 is essential, and (A2) C.I. I. Pigment red 224, C.I. I. Pigment red 242 and C.I. I. It contains at least one selected from the group consisting of CI Pigment Red 254 (hereinafter, these may be collectively referred to as “colorant (A2)”). By appropriately adjusting the color in such a combination of pigments, it is possible to obtain a radiation sensitive composition for a color filter that can form red pixels with high light transmittance and high color purity.
The radiation-sensitive composition of the present invention is used to form a red pixel, and can further contain a red, yellow or orange pigment other than the pigment. Such a red, yellow or orange pigment is not particularly limited, but an organic pigment is preferred because the color filter is required to have high purity and high light transmission color development and heat resistance.

  Examples of the other red organic pigments include compounds classified as pigments in the color index, specifically, those having the following color index (CI) numbers. Can do.

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 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, 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 243, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment Red 272.

  The other yellow organic pigments include, for example, compounds classified as pigments in the color index, specifically those having the following color index (CI) numbers. Can be mentioned.

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.

  The other orange organic pigments include, for example, compounds classified as pigments in the color index, specifically those having the following color index (CI) numbers. Can be mentioned.

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.

Among these other organic pigments, a yellow organic pigment or an orange organic pigment is preferable from the viewpoint of light transmittance and color purity. 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 orange 38, C.I. I. Pigment Orange 71 is preferable.
The other organic pigments can be used alone or in admixture of two or more.

In the colorant in the present invention, (A1) C.I. I. Although the content rate of Pigment Red 166 is not particularly limited, it is preferably 20 to 95% by mass, and particularly preferably 30 to 90% by mass in the total colorant. Moreover, the content rate of a coloring agent (A2) is although it does not specifically limit, Preferably it is 1-80 mass% in all the coloring agents, Most preferably, it is 5-70 mass%. By using such a colorant, a red pixel having high light transmittance and color purity and excellent solvent resistance can be obtained.
When other organic pigments are contained, the content of the other organic pigments is preferably 1 to 60% by mass, particularly preferably 5 to 40% by mass, based on the total colorant.
In the present invention, C.I. I. Pigment red 166 and C.I. I. Pigments other than CI Pigment Red 166 can be used after purification by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, combinations thereof, or the like, if necessary.

  In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876 and various commercially available pigment-dispersing polymers or oligomers.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method, for example, by mixing the components (A) to (D) with a solvent and an additive as described below depending on the case. be able to. When a pigment is used as the colorant, for example, a bead mill, a roll mill or the like is used in the presence of a dispersant and, if necessary, a dispersion aid to be added, optionally together with a part of the component (B). Mixing and dispersing while pulverizing to obtain a pigment dispersion, which can be prepared by adding and mixing components (B) to (D) and, if necessary, additional solvents and additives. preferable.

As a 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, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, an alkyl ammonium salt or a phosphate ester salt of a high molecular copolymer, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include polymers composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethanes, and cationic comb graft polymers are preferable.
Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), a cationic comb-type graft polymer Solsperse 24000, Solsperse 37500 (manufactured by Lubrizol Corporation), Addisper PB821, Addispar PB822, Addisper PB880 (Ajinomoto Fine Techno Co., Ltd.) And the like can be given.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by mass or less, preferably 0.5 to 100 parts by mass, more preferably 1 to 70 parts by mass, particularly 100 parts by mass of the pigment. Preferably it is 10-50 mass parts. In this case, when the usage-amount of a dispersing agent exceeds 100 mass parts, there exists a possibility that developability etc. 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 mass, preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment.

  Examples of the dispersion aid used for the preparation of the pigment dispersion include a pigment derivative.

-(B) Alkali-soluble resin-
The alkali-soluble resin in the present invention is (A) a developer that acts as a binder for the pigment and that is soluble in a developer, preferably an alkali developer, used in the development step when producing a color filter. As long as there is no particular limitation, (b1) (meth) acrylic acid, (b2) N-substituted maleimide, (b3) styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, Succinic acid mono [2- (meth) acryloyloxyethyl], ω- (B1) comprising a group of ruboxypolycaprolactone mono (meth) acrylate, polystyrene macromonomer and polymethylmethacrylate macromonomer (hereinafter referred to as “unsaturated compound (b3)”) alone or a mixture of two or more thereof. It is preferable to contain a copolymer with a polymerizable unsaturated compound other than the component and the component (b2).

Examples of the N-substituted maleimide include:
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- Examples thereof 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 N-substituted maleimides can be used alone or in admixture of two or more.

  In the present invention, together with (meth) acrylic acid, N-substituted maleimide and unsaturated compound (b3), other unsaturated compounds copolymerizable therewith (hereinafter referred to as “unsaturated compound (b4)”). Further copolymerization is possible.

Examples of the unsaturated compound (b4) include:
Maleic acid, maleic anhydride, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, acenatylene, isobornyl (meth) acrylate , Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxyphenyl (meth) acrylate , 2-dimethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, and the like.

As a preferable specific example of the carboxyl group-containing copolymer (B1),
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / p-hydroxy-α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / n-butyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / n-butyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / n-butyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / glycerol mono (meth) acrylate copolymer and the like.

In the copolymer (B1), the copolymerization ratio of (meth) acrylic acid is preferably 5 to 30% by mass, particularly preferably 10 to 25% by mass, and the copolymerization ratio of N-substituted maleimide is preferably 5-30% by mass, particularly preferably 10-25% by mass, and the copolymerization ratio of the unsaturated compound (b3) is preferably 40-90% by mass, particularly preferably 50-80% by mass. The copolymerization ratio of the compound (b4) is preferably 0 to 30% by mass, particularly preferably 0 to 20% by mass.
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (B1) within the above range, a radiation-sensitive composition for forming a colored layer exhibiting light transmittance and excellent developability is obtained. Can do.

In the present invention, other alkali-soluble resins can be used in combination with the copolymer (B1). As other alkali-soluble resins, for example,
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer and the like.

  In the present invention, for example, 2- (meth) acryloyl is added to a copolymer (B1) obtained by copolymerizing an unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and / or other alkali-soluble resin. By reacting an unsaturated isocyanate compound such as oxyethyl isocyanate, a polymerizable unsaturated bond can be introduced into the side chain of the copolymer (B1) and / or other alkali-soluble resin.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (B1) and other alkali-soluble resins in the present invention is usually. 1,000 to 45,000, preferably 3,000 to 30,000.
In addition, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (B1) and other alkali-soluble resins in the present invention is as follows. Usually, it is 1,000 to 45,000, preferably 3,000 to 30,000.
In this case, if the Mw is less than 1,000, the remaining film ratio of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. If it exceeds 000, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.
In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

  Examples of the copolymer (B1) and other alkali-soluble resins include (meth) acrylic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be produced by polymerization in the presence of a radical polymerization initiator.

The copolymer (B1) and other alkali-soluble resins may be purified through a reprecipitation method using two or more organic solvents having different polarities after radical polymerization of the polymerizable unsaturated compound as described above. it can. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitant (poor) Purification by pouring into the solvent) and reprecipitation of the copolymer. At that time, of the impurities remaining in the polymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified copolymer (B1) and the like.
Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, and methyl ethyl ketone / n-heptane. Can be mentioned.

  The copolymer (B1) and other carboxyl group-containing alkali-soluble resins may be prepared by, for example, converting each unsaturated compound as a constituent component to 2,2′-azobisisobutyronitrile, 2,2′-azobis. Radical polymerization initiators such as (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester , Pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazole -1-ylthiocarbonyl) disulfide, bis (5-methyl-pi Iniferters such as sol-1-ylthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide It can be produced by living radical polymerization at a reaction temperature of usually 0 to 150 ° C., preferably 50 to 120 ° C. in an inert solvent in the presence of an acting molecular weight control agent.

In this invention, a copolymer (B1) can be used individually or in mixture of 2 or more types, Moreover, other alkali-soluble resin is also the same.
In this invention, the total usage-amount of alkali-soluble resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. In this case, if the total use amount of the alkali-soluble resin is less than 10 parts by mass, for example, the alkali developability may be lowered, or a residue or background stain may occur on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by mass, the colorant concentration is relatively lowered, 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 mass%, Most preferably, it is 30-100 mass%. In this case, when the proportion of the copolymer (B1) used is less than 10% by mass, the intended effect of the present invention may be impaired.

-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional 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 of diethylene glycol or higher, polypropylene glycol of dipropylene glycol or higher;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Polymer di (meth) acrylates having hydroxyl groups at both ends, such as poly-1,3-butadiene having hydroxyl groups at both ends, polyisoprene having hydroxyl groups at both ends, polycaprolactone having hydroxyl groups at both ends,
And tris [2- (meth) acryloyloxyethyl] phosphate.

  Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate and di Pentaerythritol hexaacrylate is preferred because it has high pixel strength, excellent pixel surface smoothness, and is less likely to cause scumming or film residue on the unexposed substrate and the light shielding layer. 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 mass parts normally with respect to 100 mass parts of (B) alkali-soluble resin, Preferably it is 20-300 mass parts. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by mass, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, if it exceeds 500 parts by mass, for example, alkali developability may be reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the substrate or on 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 the carboxyl group-containing unsaturated monomer, copolymerizable unsaturated monomer, N-vinyl succinimide, and N-vinyl exemplified for the (B) alkali-soluble resin. Pyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N -N-vinyl-containing heterocyclic compounds such as vinylindoline, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpiperidine, N-vinylpiperazine, N-vinylmorpholine, N-vinylphenoxazine; In addition to N- (meth) acryloylmorpholine, commercially available products include M-5300 and M-54. 0, M-5600 can be mentioned (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 mass or less, preferably 50% by mass or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by mass, the strength and surface smoothness of the pixel tend to be lowered.

-(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 capable of initiating 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.

  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 mass normally with respect to a total of 100 mass parts of (C) polyfunctional monomer and a monofunctional monomer. Part, preferably 1 to 100 parts by weight. In this case, when the amount of the photopolymerization initiator used is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 120 parts by mass, the formed colored layer tends to be 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-based compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by mass of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by mass, preferably 1 to 70 parts by mass, and more preferably 1 to 60 parts by mass. In this case, if the amount of the acetophenone-based compound is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when it exceeds 80 parts by mass, the formed colored layer tends to be detached 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 ′, 5,5′-tetraphenyl-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 mass of the polyfunctional monomer and the monofunctional monomer, 0.01-40 mass parts, Preferably it is 1-30 mass parts, More preferably, it is 1-20 mass parts. In this case, if the amount of the biimidazole compound used is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by mass, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

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.
The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound defined below.

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 one or more, preferably 1 to 3, 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.
Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are 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.
Further, 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.
Of these amine-based 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 hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

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, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0 with respect to 100 parts by mass of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. In this case, if the use amount of the hydrogen donor is less than 0.01 parts by mass, the effect of improving the sensitivity tends to be reduced. On the other hand, if it exceeds 40 parts by mass, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

  The amine-based hydrogen donor can function as a sensitizer when used in combination with a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound. When an amine hydrogen donor is used as a sensitizer, the amount used is usually 300 parts by mass or less, preferably 200 parts by mass or less, based on 100 parts by mass of a photopolymerization initiator other than a biimidazole compound. The amount is preferably 100 parts by mass or less, but if the amount used is too small, it is difficult to obtain a sufficient effect. Therefore, the lower limit of the amount used is preferably 2 parts by mass, and more preferably 5 parts by mass.

  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 cistyryl) -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 a photopolymerization initiator is preferably 0 with respect to 100 parts by mass of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. In this case, if the amount of the triazine compound used is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by mass, the formed colored layer tends to be easily detached from the substrate during development.

  Specific examples of the O-acyloxime compound include 1,2-heptanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (benzoyl) phenyl]-, 2- (O-benzoyloxime), ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (3- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl)-, 1- O- acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl Ruben benzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl } -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

Among these O-acyloxime compounds, in particular, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -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 this invention, the usage-amount in the case of using an O-acyl oxime type compound as a photoinitiator is (C) 100 mass parts in total of a polyfunctional monomer and a monofunctional monomer, Preferably it is 0.01-60 mass parts, More preferably, it is 1-50 mass parts, Most preferably, it is 1-40 mass parts. In this case, when the amount of the O-acyloxime compound used is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 60 parts by mass, the formed colored layer tends to fall off from the substrate during development.

-Other additives-
Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it can also contain another additive as needed.
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-t-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 Examples thereof include an aggregation inhibitor such as sodium acrylate.

Solvent The radiation-sensitive composition of the present invention contains the components (A) to (D) and other additives that are optionally added. Usually, a solvent is added as a liquid composition. Prepared.
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,
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as 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, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
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, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, etc. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate I-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methyl Xylbutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl pyruvate and the like are preferable.
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 acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The amount of solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferable from the viewpoints of applicability and storage stability of the resulting radiation-sensitive composition. Is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

Method of forming a color filter Then, using a 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 of this invention on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) A step of post-baking the developed coating film.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, if necessary, a light shielding layer is formed on the surface of the substrate so as to divide a portion where pixels are to be formed, and the sensitivity of the present invention containing, for example, a red (A) pigment is formed on the substrate. Usually, after apply | coating a radiation composition as a liquid composition, a coating film is formed by prebaking and evaporating and removing a solvent.
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 applying the liquid composition to the substrate, an appropriate coating method such as a spin coating method, a casting coating method, a roll coating method, or a coating method using a slit die coater can be employed. A coating method using a slit die coater is preferred.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C.
The coating thickness is usually 1.0 to 10 μm, preferably 1.0 to 6.0 μm, particularly preferably 1.0 to 4.0 μm as the film thickness after removal of the solvent.

-(2) Process-
Thereafter, at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is usually 10~10,000J / m ^2.

-(3) Process-
Then, it develops using a developing solution, Preferably an alkaline developing solution, The unexposed part of a coating film is dissolved and removed.
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 a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 10 to 300 seconds at room temperature.

-(4) Process-
Thereafter, a post-baked coating film after development can provide a substrate on which red 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 1.0 to 3.0 μm.

  Moreover, a green pixel pattern is formed on the same board | substrate by repeating the said (1)-(4) process using the green radiation sensitive composition containing a green (A) pigment, and also blue color By forming the blue pixel pattern on the same substrate by repeating the steps (1) to (4) using the blue radiation-sensitive composition containing the pigment, the three primary colors of red, green and blue are formed. A pixel array in which pixel patterns are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.

Color filter The color filter of the present invention has red pixels formed from the radiation-sensitive composition for red color filter of the present invention.
The color filter of the present invention is extremely useful for a liquid crystal display application having a wide color reproduction region represented by TV.

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 with a liquid crystal layer interposed therebetween. In addition, 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 are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Red 166 at 13.5 parts by mass, C.I. I. 1.5 parts by weight of Pigment Red 254, 5 parts by weight of Ajisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a dispersant, and 80 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill. A pigment dispersion (M-1) was prepared.

Preparation Examples 2-12
Pigment dispersions (M-2) to (M-12) were prepared in the same manner as in Preparation Example 1 except that the colorant was changed as shown in Table 1 in Preparation Example 1.

  In Table 1, for example, “R166” means C.I. I. Pigment Red 166, “O38” means C.I. I. Pigment Orange 38, “Y83” is C.I. I. Each means CI Pigment Yellow 83.

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and 20 parts by mass of N-phenylmaleimide. , 55 parts by mass of benzyl methacrylate, 10 parts by mass of styrene and 3 parts by mass of 2,4-diphenyl-4-methyl-1-pentene (trade name: NOFMER MSD manufactured by NOF Corporation) as a molecular weight regulator, Replaced. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution (solid content concentration = 33.3% by mass). The obtained resin was Mw = 16,000 and Mn = 7,000. This resin solution is referred to as “resin solution (B-1)”.

Example 1
(A) 100 parts by mass of a pigment dispersion (M-1) as a colorant, (B) 10 parts by mass (in terms of solid content) of a resin solution (B-1) as an alkali-soluble resin, (C) a polyfunctional monomer 15 parts by mass of dipentaerythritol hexaacrylate as (D) 4 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4′-bis (D) as a photopolymerization initiator Diethylamino) benzophenone (1 part by mass) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R-1) having a solid concentration of 25%.
The liquid composition (R-1) was evaluated by forming a pixel pattern according to the following procedure. The evaluation results are shown in Table 2.

Pattern formation The liquid composition (R-1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater at three rotations. After that, prebaking was performed for 4 minutes on a 90 ° C. hot plate to form three coating films with different film thicknesses.
Next, after these substrates were cooled to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² through a photomask using a high-pressure mercury lamp. Thereafter, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) on these substrates, Post baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm red dot pattern on the substrate.

Evaluation of Chromaticity and Film Thickness of the obtained red dot pattern using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured. Further, the film thickness of the obtained red dot pattern was measured using an alpha step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value y, the stimulus value (Y), and the film thickness at which the chromaticity coordinate value x becomes 0.603 were obtained. The evaluation results are shown in Table 2. A larger Y value indicates higher light transmittance (brightness), and a thinner film thickness indicates higher coloring power.

Evaluation of solvent resistance The above three substrates on which red dot patterns were formed were each immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the dot patterns before and after immersion were observed with a scanning electron microscope. ○, when the pattern having a good edge shape is formed and the film thickness ratio before and after immersion (film thickness after immersion x 100 / film thickness before immersion) is 95% or more, film thickness before and after immersion A case where the ratio was less than 95% or a portion of the pattern was found to be chipped was evaluated as Δ, and a case where the pattern was all peeled off from the substrate after immersion was evaluated as ×.

Examples 2-9 and Comparative Examples Comparative Examples 1-3
Liquid compositions (R-2) to (R-12) were prepared in the same manner as in Example 1 except that the pigment dispersion was changed as shown in Table 2 in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (R-2) to (R-12) were used in place of the liquid composition (R-1). The results are shown in Table 2.

  From Table 2, C.I. I. Pigment red 166, C.I. I. It can be seen that by using at least one selected from the group consisting of CI Pigment Reds 224, 242, and 254, red pixels having good light transmittance (luminance) and color purity can be formed. Furthermore, C.I. I. It can also be seen that by introducing Pigment Red 166, the solvent resistance is improved. C. I. It is considered that the dispersion stability was improved by co-dispersing with Pigment Red 166.

Claims (6)

  A 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, As a colorant, (A1) C.I. I. Pigment red 166, and (A2) C.I. I. Pigment red 224, C.I. I. Pigment red 242 and C.I. I. A radiation-sensitive composition for a red color filter, comprising at least one selected from the group consisting of CI Pigment Red 254.   The radiation-sensitive composition for a red color filter according to claim 1, further comprising (A) at least one of a yellow organic pigment and an orange organic pigment as a colorant.   As the yellow organic pigment and orange organic pigment, C.I. I. Pigment orange 38, C.I. I. Pigment orange 71, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139 and C.I. I. The radiation-sensitive composition for a red color filter according to claim 2, comprising at least one selected from the group consisting of CI Pigment Yellow 150.   The radiation-sensitive composition for a red color filter according to any one of claims 1 to 3, comprising 20 to 95% by mass of (A1) and 1 to 80% by mass of (A2) in all colorants.   The color filter provided with the red color filter formed using the radiation sensitive composition in any one of Claims 1-4.   A color liquid crystal display device comprising the color filter according to claim 5.