TWI467328B - Radiation-sensitive composition for blue color filter, color filter and liquid crystal display device - Google Patents

Description

Blue color filter with sensitive radiation linear composition, color filter and liquid crystal display element

The present invention relates to a linear composition for sensitive radiation of a blue color filter, a color filter, and a liquid crystal display element, and more particularly relates to a color filter which can be used for manufacturing a color camera element, a color liquid crystal display device, or the like. The blue color filter uses a sensitive radiation linear composition, a color filter including a coloring layer formed of the linear composition of the sensitive radiation, and a liquid crystal display element including the color filter.

A method of forming a color filter using a coloring sensitive radiation linear composition, the known method comprising forming a coating film of a pigment dispersion type color sensitive radiation linear composition on a substrate having or preliminarily forming a light shielding layer of a desired pattern, A method of irradiating radiation (hereinafter referred to as "exposure") and developing a photomask having a predetermined pattern to dissolve and remove an unexposed portion, and then performing post-baking to obtain a pixel having each color (for example, a reference patent) Document 1, Patent Document 2).

In recent years, in order to reflect the improvement in quality and use of color image sensor elements and color liquid crystal display devices, it is strongly required to increase the brightness of display panels. Therefore, it is reviewed to increase the brightness (Y value) of the linear composition of each sensitive radiation of blue, red or green. However, in particular, regarding the linear composition of the sensitive radiation which provides the blue pixel, the usable pigment is limited to copper phthalocyanine blue, and therefore the method of improving the brightness is also inevitably limited. Further, the yellowing of the photopolymerization initiator or the resin component contained in the linear composition of the radiation radiation becomes a significant cause of the decrease in the luminance of the blue color filter in the post-baking step.

As in the above background, one of the methods for increasing the brightness of the blue color filter is proposed as a blue color filter containing a blue colorant, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. In the linear composition of the radiation, the methacrylone-based compound and the benzophenone-based compound having a specific structure are used as the photopolymerization initiator (see, for example, Patent Document 3).

[Patent Document 1] JP-A-2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] JP-A-2001-147315

According to the linear color filter of the blue color filter described in Patent Document 3, a display panel having high brightness and a sufficient color reproduction range can be provided, but other photopolymerization initiators are used instead of the above specific light. When the initiator is polymerized, sufficient brightness cannot be obtained. Further, in an attempt to further improve the sensitivity and to use the above specific photopolymerization initiator and other photopolymerization initiators, the sensitivity is improved, but the brightness is remarkably lowered. Therefore, in order to achieve high luminance, the above-mentioned specific photopolymerization initiator can be used, but when the width of the photopolymerization initiator is limited, it is difficult to reduce the Takt Time and the like by reducing the exposure amount in recent years. Therefore, it has been strongly demanded to develop a linear composition for a sensitive color of a blue color filter which uses a more type of photopolymerization initiator to form an excellent blue pixel with high luminance.

An object of the present invention is to provide a linear composition for a blue color filter for a blue color filter which is capable of more widely selecting a photopolymerization initiator and forming an excellent blue pixel having a high luminance, and is formed of the linear composition of the radiation radiation. A color filter of a color layer and a liquid crystal display element having the color filter.

The present inventors have found that a more type of photopolymerization initiation is used in a sensitized radioactive composition for a blue color filter containing a blue colorant, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. In order to provide a blue pixel excellent in brightness, the composition contains a specific oxidation inhibitor and limits the content to a specific range.

In other words, the first aspect of the present invention provides a linear composition for sensitive radiation of a blue color filter, characterized by:

(A) a coloring agent containing a blue colorant,

(B) alkali soluble resin,

(C) a polyfunctional monomer,

(D) a photopolymerization initiator containing at least one selected from the group consisting of a compound represented by the following formula (3), an oxime ester compound, and a biimidazole compound;

(E) an oxidation preventing agent containing at least one selected from the group consisting of a phenolic oxidation preventing agent, a phosphorus-based oxidation preventing agent, and a sulfur-based oxidation preventing agent, and the total content of the component (E) is (D) The total amount of the components is 100 parts by mass, and is 1 to 100 parts by mass.

In the formula (3), R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The second aspect of the present invention provides a color filter formed using the aforementioned blue color filter with a radiation sensitive linear composition.

A third aspect of the present invention provides a liquid crystal display element including the color filter.

According to the present invention, even when a photopolymerization initiator which does not have sufficient brightness in the past is used, it is possible to provide a blue pixel which is excellent in luminance. Further, according to the present invention, even when a photopolymerization initiator which provides high luminance is used in combination, it is possible to suppress a decrease in luminance, and it is possible to provide a blue pixel having both an extremely high level of brightness and sensitivity. In this way, the photopolymerization initiator can be selected more widely than in the past, and the exposure amount in recent years can be reduced, and the Takt Time can be shortened.

Therefore, the linear color filter of the blue color filter of the present invention is extremely suitable for the manufacture of color filters and liquid crystal display panels for color liquid crystal display panels in the electronics industry.

[Best Mode for Carrying Out the Invention]

The invention is described in detail below.

Blue color filter with sensitive radiation linear composition - (A) colorant -

The coloring agent of the present invention is a blue coloring agent as an essential component.

The blue colorant is appropriately selected depending on the use of the color filter, and may be a pigment, a dye or a natural pigment, and may be an organic or inorganic system.

The color filter of the present invention is required to have high-definition color development and heat resistance. Therefore, the blue coloring agent of the present invention is a coloring agent having high color developability and high heat resistance, and among them, a coloring agent having high heat decomposition resistance is preferable. Such a blue colorant can usually be an organic pigment or an inorganic pigment, and particularly preferably an organic pigment.

The blue organic pigment used in the present invention is, for example, a compound having a color index (CI; issued by The Society of Dyers and Colourists, the same below) classified as Pigment Blue, specifically, for example, a CI pigment is attached. Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60 Color Index (CI) number. Among these blue organic pigments, it is particularly preferred to be C.I. Pigment Blue 15:6.

Further, the blue inorganic pigment is, for example, ultramarine blue or dark blue.

Further, in the present invention, a blue pigment and a violet pigment may be used in combination as needed.

The purple pigment is, for example, a compound classified into Pigment Violet in a color index. Specific examples include organic pigments of C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Pigment Violet 38 Color Index (C.I.). Among these purple organic pigments, C.I. Pigment Violet 23 is particularly preferred.

In the present invention, the blue colorants may be used singly or in combination of two or more. Further, an organic pigment and an inorganic pigment may be used in combination, but when a pixel is formed, it is preferred to use one or more organic pigments.

The organic pigment of the present invention can be used after being purified by a sulfuric acid recrystallization method, a solvent cleaning method, or a combination of these methods, if necessary.

Each pigment may be used by modifying the surface of its particles using a polymer as necessary. For example, a polymer described in Japanese Laid-Open Patent Publication No. Hei 8-259876 or a commercially available polymer or oligomer for dispersing various pigments is used.

- (B) alkali soluble resin -

The alkali-soluble resin of the present invention has a binder action for the (A) colorant, and when the color filter is produced, the developer used for the development process step is particularly preferably an alkali developer, and is soluble. When the resin is used, it is not particularly limited. The alkali-soluble resin is preferably an alkali-soluble resin having a carboxyl group, and particularly preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "carboxyl-containing unsaturated monomer") and can be used alone. A copolymer of another ethylenically unsaturated monomer (hereinafter referred to as "copolymerizable unsaturated monomer") (hereinafter referred to as "carboxyl-containing copolymer").

An unsaturated monomer having a carboxyl group, for example

An unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid or cinnamic acid;

An unsaturated dicarboxylic acid or an anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or mesaconic acid;

a trivalent or higher unsaturated polyvalent carboxylic acid or an anhydride thereof;

a monovalent [(2-(methyl) propylene oxyethyl) succinate, a monovalent or higher polyvalent carboxylic acid such as [2-(methyl) propylene oxyethyl] phthalic acid monoester] Methyl) propylene oxiranyl] esters;

A mono(meth)acrylate such as a ω-carboxypolycaprolactone mono(meth)acrylate or the like having a carboxyl group and a hydroxyl group at both terminals.

The carboxyl group-containing unsaturated monomer may be used singly or in combination of two or more.

In the present invention, the carboxyl group-containing unsaturated monomer is preferably (meth)acrylic acid, succinic acid mono [2-(methyl)acryloxyethyl ester], ω-carboxy polycaprolactone mono(methyl). Acrylate or the like is particularly preferably (meth)acrylic acid.

The copolymerizable unsaturated monomer is, for example, the following.

Such as N-phenyl maleimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl Maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-methylenebisimidobenzoic acid Ester, N-succinimido-4-methyleneimine butyrate, N-succinimido-6-maleimide hexanoate, N-succinimide-3 N-substituted maleimide, such as maleimide propionate or N-(acridinyl) maleimide;

Such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene , p-methoxystyrene, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, p-hydroxy α-methyl styrene,

Such as o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- An aromatic vinyl compound of vinyl benzyl glycidyl ether;

Such as 茚, 1-methyl 茚 茚;

Such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylate Butyl ester, second butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methyl) 2-hydroxypropyl 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, (methyl ) 2-phenoxyethyl acrylate, methoxy di(ethylene glycol) (meth) acrylate, methoxy tri(ethylene glycol) (meth) acrylate, methoxy propylene glycol (methyl) Acrylate, methoxybis(propylene glycol)(meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-ester, (methyl) ) 2-hydroxy-3-phenoxypropyl acrylate, glycerol mono(meth)acrylate, (methyl) 4-hydroxyphenyl acrylate, ethylene oxide modified (meth) acrylate unsaturated carboxylic acid ester of p-cumylphenol;

2-Aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylamine (meth)acrylate Alkyl propyl esters of unsaturated carboxylic acids such as propyl propyl ester, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate;

An unsaturated carboxylic acid glycidyl ester such as glycidyl (meth)acrylate;

a vinyl cyanide compound such as (meth)acrylonitrile, α-chloroacrylonitrile or ethylene dicyandiamide;

(Methyl) acrylamide, α-chloropropenylamine, N-2-hydroxyethyl (meth) acrylamide, and the like;

a vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate or vinyl benzoate;

An unsaturated ether such as vinyl methyl ether, vinyl ethyl ether or allyl glycidyl ether;

An aliphatic conjugated diene such as 1,3-butadiene, isoprene, chloroprene or isoprene sulfonic acid;

A macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate or polyoxyalkylene.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

In the present invention, it is preferred that the copolymerizable unsaturated monomer is an N-position substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a terminal of the polymer molecular chain contains a single (methyl) group. A propylene monomer-based megamonomer, etc., particularly preferably N-phenyl maleimide, N-cyclohexyl maleimide, styrene, α-methylstyrene, p-hydroxy- Α-methylstyrene, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) Alkenyl acrylate, benzyl (meth) acrylate, glycerol mono(meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol Ester, polystyrene megamonomer, poly(methyl) methacrylate megamonomer, and the like.

Specific examples of the copolymer containing a carboxyl group include the following.

(meth)acrylic acid/methyl (meth) acrylate copolymer,

(meth)acrylic acid/benzyl (meth) acrylate copolymer,

(meth)acrylic acid/2-hydroxyethyl (meth) acrylate copolymer,

(meth)acrylic acid/2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(meth)acrylic acid/methyl (meth) acrylate/polystyrene mega monomer copolymer,

(meth)acrylic acid/methyl (meth) acrylate/polymethyl methacrylate mega monomer copolymer,

(meth)acrylic acid/benzyl (meth) acrylate/polystyrene mega monomer copolymer,

(meth)acrylic acid/benzyl (meth) acrylate/polymethyl (meth) acrylate macromonomer copolymer,

(meth)acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(meth)acrylic acid/styrene/2-hydroxyethyl (meth) acrylate copolymer,

(meth)acrylic acid/2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(meth)acrylic acid/2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / styrene / benzyl (meth) acrylate copolymer,

(meth)acrylic acid/N-m-hydroxyphenyl maleimide/styrene/benzyl (meth) acrylate copolymer,

(meth)acrylic acid/N-p-hydroxyphenyl maleimide/styrene/benzyl (meth) acrylate copolymer,

(meth)acrylic acid/N-cyclohexylmethyleneimine/styrene/benzyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / α-methyl styrene / benzyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / styrene / n-butyl (meth) acrylate copolymer,

(meth)acrylic acid/N-phenylmaleimide/styrene/2-ethylhexyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / p-hydroxy-α-methylstyrene / benzyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / styrene / n-butyl (meth) acrylate copolymer,

Ethylene oxide modified (meth) acrylate copolymer of (meth)acrylic acid/N-phenylbutyleneimine/styrene/p-cumylphenol,

(Meth)acrylic acid / N-phenyl maleimide / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (methyl Acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / styrene / 2 - hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(meth)acrylic acid / N-phenyl maleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(meth)acrylic acid / N-p-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth)acrylic acid / N-phenyl maleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene mega monomer copolymer ,

(meth)acrylic acid / N-phenyl maleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate giant single Copolymer,

(meth)acrylic acid/succinic acid mono [2-(methyl) propylene oxiranyl] ester / N-phenyl maleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth)acrylic acid/succinic acid mono [2-(methyl) propylene oxiranyl] ester / Np-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate copolymer ,

(Meth)acrylic acid/succinic acid mono [2-(methyl) propylene oxiranyl] ester / N-phenyl maleimide / styrene / allyl (meth) acrylate copolymer ,

(Meth)acrylic acid / succinic acid mono [2-(methyl) propylene oxiranyl] ester / N-cyclohexyl maleimide / styrene / allyl (meth) acrylate copolymer ,

(meth)acrylic acid/succinic acid mono [2-(methyl) propylene oxiranyl] ester / N-cyclohexyl maleimide / styrene / benzyl (meth) acrylate copolymer,

(meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-m-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate copolymer,

(meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-p-hydroxyphenyl maleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / N-phenyl maleimide / styrene / benzyl (meth) acrylate / glycerol mono (methyl Acrylate copolymer,

(Meth)acrylic acid / ω-carboxy polycaprolactone mono (meth) acrylate / Np - hydroxy phenyl maleimide / styrene / benzyl (meth) acrylate / glycerol single (A Acrylate copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. When the copolymerization ratio is less than 5% by mass, the solubility of the linear radiation composition obtained to the alkali developing solution tends to be lowered. On the other hand, when the amount is more than 50% by mass, the solubility in the alkali developing solution is too large, and when the alkali developing solution is developed, the colored layer tends to fall off from the substrate or the film on the surface of the colored layer tends to be rough.

The alkali-soluble resin of the present invention is measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene is usually 3,000 to 300,000, more preferably It is 5,000 to 100,000.

The alkali-soluble resin of the present invention is measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the average molecular weight in terms of polystyrene (hereinafter referred to as "Mn") is usually 3,000 to 60,000, more preferably It is 5,000 to 25,000.

In the present invention, by using an alkali-soluble resin having such a specific Mw and Mn, a linear composition of sensitive radiation having excellent developability can be obtained, thereby forming a pixel having a sharp pattern edge while being developed. Residues, texture contamination, residual film, and the like are less likely to occur on the unexposed portion of the substrate and on the light shielding layer.

Further, the ratio (Mw/Mn) of Mw to Mn of the alkali-soluble resin of the present invention is preferably from 1 to 5, more preferably from 1 to 4.

In the present invention, the alkali-soluble resin may be used singly or in combination of two or more.

The content of the alkali-soluble resin (in terms of solid content) in the present invention is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. When the content of the alkali-soluble resin is less than 10 parts by mass, for example, alkali developability may be lowered, or texture contamination or residual film may be generated on the unexposed portion of the substrate and on the light shielding layer. When the amount is more than 1,000 parts by mass, the concentration of the colorant is lowered, so that it is difficult to achieve the color density as a target of the film.

-(C) Polyfunctional monomer -

The polyfunctional single system of the present invention is composed of a monomer having two or more polymerizable unsaturated bonds.

The polyfunctional monomer is, for example, a di(meth)acrylate of an alkanediol such as ethylene glycol or propylene glycol;

a di(meth)acrylate of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol;

a poly(meth) acrylate of a trivalent or higher polyvalent alcohol such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol; or a dicarboxylic acid modified product thereof;

Oligo (meth) acrylates of polyesters, epoxy resins, urethane resins, alkyd resins, polyoxyxylene resins, spiro resins, and the like;

a di(meth)acrylate of two terminal hydroxylated polymers of poly-1,3-butadiene having two terminal hydroxyl groups, polyisoprene of both terminal hydroxyl groups, polycaprolactone of both terminal hydroxyl groups, and the like;

Tris[2-(methyl)propenyloxyethyl]phosphate and the like.

Among these polyfunctional monomers, poly(meth)acrylates of polyvalent or higher polyvalent alcohols or modified dicarboxylic acids thereof are preferred. Specific examples are trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate. The ester, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, a compound represented by the following formula (4), a compound represented by the following formula (5), and the like are preferred.

Among them, in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the compounds represented by the above formulas (4) and (5) have a high strength of the colored layer, and the surface of the colored layer is smooth. It is excellent in the properties, and it is preferable that the unexposed portion of the substrate and the light shielding layer are less likely to cause texture contamination, film residue, and the like.

The polyfunctional monomer may be used singly or in combination of two or more.

In the present invention, a part of the polyfunctional monomer may be substituted with a monofunctional monomer having one polymerizable unsaturated bond.

Such a monofunctional monomer is, for example, the same compound as the carboxyl group-containing unsaturated monomer or copolymerizable unsaturated monomer exemplified in (B) the alkali-soluble resin, or N-(methyl)propenylmorpholine, N. -vinylpyrrolidone, N-vinyl-ε-caprolactam, and commercial product M-5600 (trade name, manufactured by Toagosei Co., Ltd.).

These monofunctional monomers may be used singly or in combination of two or more.

The ratio of use of the monofunctional monomer is 90% by mass or less, and more preferably 50% by mass or less, based on the total mass of the polyfunctional monomer and the monofunctional monomer. When the use ratio of the monofunctional monomer exceeds 90% by mass, the strength and surface smoothness of the resulting colored layer may be insufficient.

In the present invention, the content of the polyfunctional monomer is usually 5 to 500 parts by mass, preferably 20 to 300 parts by mass, per 100 parts by mass of the (B) alkali-soluble resin (calculated as solid content). When the content is less than 5 parts by mass, the strength and surface smoothness of the colored layer tend to be lowered, and when it exceeds 500 parts by mass, for example, alkali developability may be lowered, or on the unexposed portion of the substrate or the light shielding layer. There is a tendency to cause texture contamination, residual film, and the like. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

-(D) Photopolymerization initiator -

The photopolymerization initiator is a compound which emits an active species which starts polymerization of a (C) polyfunctional monomer and, if necessary, a monofunctional monomer, by exposure to visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays.

The photopolymerization initiator of the present invention is at least one selected from the group consisting of the compound represented by the above formula (3) (hereinafter sometimes referred to as "acetophenone-based compound"), an oxime-based compound, and a biimidazole-based compound. . Thereby, the sensitivity can be further improved, so that even with a low exposure amount, a pixel having a good edge shape which does not cause undercut can be obtained.

In the present invention, the total content of the photopolymerization initiator is usually from 0.01 to 200 parts by mass, preferably from 1 to 120 parts by mass, particularly preferably from 1 to 100% by mass based on 100 parts by mass of the (C) polyfunctional monomer. Share. When the total content of the photopolymerization initiator is less than 0.01 parts by mass, the hardening by exposure is insufficient, and it is sometimes difficult to obtain a pattern array in which pixel patterns are regularly arranged. When the amount is more than 200 parts by mass, the colored layer formed is liable to fall off from the substrate during development, or texture contamination, residual film, or the like is likely to occur on the unexposed portion of the substrate or on the light shielding layer. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

The definition of the symbols in the above formula (3) will be explained.

The alkyl group having 1 to 4 carbon atoms of R ⁶ , R ⁷ and R ⁸ may be linear or branched, and may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. Second butyl, tert-butyl.

In the formula (3), R ⁶ is a methyl group or an ethyl group, particularly preferably a methyl group, and further preferably R ⁷ and R ⁸ are a hydrogen atom, a methyl group or an ethyl group.

Specific examples of the acetophenone-based compound represented by the formula (3) include

2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-benzyl-2-diethylamino-1-(4-morpholine Phenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2- (4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-n-propylbenzyl)-2 -(dimethylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-n-butylbenzyl)-2-(dimethylamino)-1 -(4-morpholinylphenyl)ethane-1-one, 2-(4-methylbenzyl)-2-(diethylamino)-1-(4-morpholinylphenyl)ethane- 1-ketone, 2-(4-ethylbenzyl)-2-(diethylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-n-propyl Benzyl)-2-(diethylamino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-n-butylbenzyl)-2-(diethyl) Amino)-1-(4-morpholinylphenyl)ethane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine Phenyl)butan-1-one, 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2- (4-i-propylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(4-n-butylbenzyl) -2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(4 -i-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(4-i-propylbenzyl)-2 -[(n-butyl)(methyl)amino]-1-(4-morpholinylphenyl)butan-1-one, 2-(4-n-butylbenzyl)-2-[(正Butyl)(methyl)amino]-1-(4-morpholinylphenyl)butan-1-one, 2-(4-i-propylbenzyl)-2-(dimethylamino) 1-(4-morpholinylphenyl)pentan-1-one, 2-(4-i-butylbenzyl)-2-[(n-butyl)(methyl)amino]]-1- (4-morpholinylphenyl)pentan-1-one and the like.

Among these acetophenone-based compounds, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one and 2-(4-methylbenzyl group are preferred. -2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one and the like.

The acetophenone-based compound may be used singly or in combination of two or more.

In the present invention, when the acetophenone-based compound is used as the photopolymerization initiator, the content thereof is usually 0.01 to 80 parts by mass, preferably 1 to 70 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. More preferably, it is 1 to 60 mass parts. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

The oxime ester compound means a compound having an oxime ester structure (>C=N-O-CO-). The oxime ester compound is, for example, a compound represented by the following formula (1) or (2).

In the formulae (1) and (2), R ¹ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group.

R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted or a monovalent alicyclic group having 7 to 20 carbon atoms ( But the aforementioned cycloalkyl group),

R ⁴ independently of each other represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a cycloalkoxy group having 3 to 8 carbon atoms.

R ⁵ independently of each other represents a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms.

k is an integer from 1 to 5,

j, m, and n are independent of each other to represent an integer from 0 to 5,

p is an integer of 0 to 6.

But (n+j)≦5,(m+k)≦5]

The definitions of the symbols in the above formulas (1) and (2) will be described.

The alkyl group having 1 to 20 carbon atoms of R ¹ , R ² and R ³ may be a linear or branched alkyl group having 1 to 12 carbon atoms (more preferably 1 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, Positive 癸 base, positive eleven base, positive twelve base, etc.

The cycloalkyl group having 3 to 8 carbon atoms of R ¹ to R ⁴ is preferably a cycloalkyl group having 5 to 6 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group.

The substituent of the phenyl group of R ² and R ^{3 may} , for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or n-hexyl. a C1-C6 alkyl group; a cycloalkyl group having a carbon number of 3 to 6 such as a cyclopentyl group or a cyclohexyl group: a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, Alkoxy group having 1 to 6 carbon atoms such as a third butoxy group; a cycloalkoxy group having 3 to 6 carbon atoms such as a cyclopentyloxy group or a cyclohexyloxy group; a phenyl group; a halogen atom such as a fluorine atom or a chlorine atom; Atoms, etc.

The monovalent alicyclic group having 7 to 20 carbon atoms of R ² and R ³ (except for the aforementioned cycloalkyl group) has, for example, a group having a 1-alkylcycloalkane skeleton, a group having a bicycloalkane skeleton, and a tricyclic ring. a group of an alkane skeleton, a group having a helical alkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like.

The alkyl group having 1 to 12 carbon atoms of R ⁴ may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms).

The alkoxy group having 1 to 12 carbon atoms of R ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). Specific examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy , n-decyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy and the like.

The cycloalkyloxy group having 3 to 8 carbon atoms of R ⁴ is preferably a cycloalkyloxy group having 5 to 6 carbon atoms. Specific examples are a cyclopentyloxy group, a cyclohexyloxy group and the like.

a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms of R ⁵ , a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, for example, tetrahydrothiophene Base, azepine, dihydroazepine, dioxolane, triazinyl, oxazinyl, thiazolinyl, oxadiazinyl, dioxaindanyl, dithionaphthyl, Furanyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furyl, pyranyl, pyrrolyl, pyridazinyl, pyrimidinyl, pyrazinyl , pyrrolidinyl, morpholinyl, piperazinyl, quinuclidinyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, indolizinyl, chromenyl, quinolyl, Isoquinolyl, indenyl, quinazolinyl, porphyrinyl, pyridazinyl, acridinyl, oxazolyl, acridinyl, phenanthryl, thioxanthyl, phenazinyl, phenothiazine, Phenothiazyl, thiophenethio, thioxyl, tetrahydrofuranyl, tetrahydropyranyl and the like.

In the formulae (1) and (2), R ^{1 is} particularly preferably a methyl group or an ethyl group, and R ² and R ^{3 are} particularly preferably a hydrogen atom, a methyl group or an ethyl group. Further, R ^{4 is} particularly preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a methoxy group or an ethoxy group, and R ^{4 is} preferably substituted at the o-position of the aromatic ring. R ^{5 is} preferably a tetrahydrofuranyl group, a tetrahydropyranyl group or the like.

In the formula (1), n is preferably 0, 1, or 2, and particularly preferably 1. j is preferably 0 or 1, and particularly preferably 0.

In the formula (2), m is preferably 0, 1, or 2, and particularly preferably 1. Further, k is preferably 1, and p is preferably 0, 1 or 2, and particularly preferably 1.

Specific examples of the oxime ester compound represented by the formula (1) include the following.

1-[9-ethyl-6-benzoquinone-9H-carbazol-3-yl]-1,2-decane-2-indole-O-benzoate, 1-[9-ethyl-6 -phenylhydrazine-9H-carbazol-3-yl]-1,2-decane-2-indole-O-acetate, 1-[9-ethyl-6-benzoquinone-9H-carbazole-3 -yl]-1,2-pentane-2-indole-O-acetate, 1-[9-ethyl-6-benzoquinone-9H-indazol-3-yl]-octane-1-one肟-O-acetate,

1-[9-ethyl-6-(2-methylphenylhydrazine)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-B 5--6-(2-methylphenylhydrazine)-9H-oxazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-n-butyl-6-( 2-ethylphenylhydrazine)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate,

Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoquinone)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), B Ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylphenylhydrazone)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), Ethylketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenylhydrazone)-9H-indazol-3-yl]-, 1-(O-ethylindenylhydrazine Ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)phenylhydrazine}-9H-咔Zin-3-yl]-, 1-(O-ethylindenyl),

Further, specific examples of the oxime ester compound represented by the formula (2) include, for example, the following.

Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenylhydrazine)-9H-indazol-3-yl]-, 1-(O -Ethyl hydrazide), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoquinone)-9H-indazol-3-yl]-, 1- (O-acetyl hydrazine), ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl methoxybenzoquinone)-9H-carbazol-3-yl ]-, 1-(O-acetylhydrazine), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxo) Heterocyclic amyl)methoxybenzoquinone}-9H-carbazol-3-yl]-, 1-(O-ethylindenyl).

Examples of the oxime ester compound other than the compound represented by the formula (1) or (2) include the following.

1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoquinone), 1,2-butanedione, 1-[4-(benzene Thio)phenyl]-, 2-(O-benzoquinone), 1,2-butanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-ethenyl)肟), 1,2-octanedione, 1-[4-(methylthio)phenyl]-, 2-(O-benzoquinone), 1,2-octanedione, 1-[ 4-(phenylthio)phenyl]-, 2-(O-(4-methylphenylhydrazine)).

Among these oxime ester-based compounds, a compound represented by the formula (1) or (2) is preferred, and 1-[9-ethyl-6-(2-methylbenzoquinone)-9H-carbazole-3 is particularly preferred. -yl]-ethane-1-ketooxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9H- Oxazol-3-yl]-, 1-(O-acetamidoxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl- 1,3-Dioxalanyl methoxybenzoquinone}-9H-carbazol-3-yl]-, 1-(O-ethenylhydrazine) and the like.

These oxime ester compounds are very sensitive, and can form a pattern without edge defects and undercuts even at low exposure levels.

The oxime ester compound can be used singly or in combination of two or more.

In the present invention, when the oxime ester compound is used as the photopolymerization initiator, the content thereof is preferably 0.01 to 60 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. It is particularly preferably from 1 to 40 parts by mass. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

The biimidazole-based compound means a compound having at least one skeleton represented by the following formula (6), formula (7) or formula (8).

Specific examples thereof, for example

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis ( Bis(halo-substituted phenyl)tetra(alkoxycarbonylbenzene) of 2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole Bismuthimide;

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene -4,4',5,5'-tetraphenyl-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'-tetraphenyl-1,2'-linked Imidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, Bis(halo-substituted phenyl)tetraphenylbiimidazole such as 4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Among these biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2' is preferred. - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc., particularly preferably 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole.

The biimidazole-based compound is excellent in solubility in a solvent, and does not cause foreign matter such as an undissolved matter or a precipitated substance, and has high sensitivity. The biimidazole compound is sufficiently hardened by exposure with a small amount of energy, and at the same time, the contrast is high, and the unexposed portion does not cause a hardening reaction. Therefore, the film after exposure can be clearly distinguished into a hardened portion which is insoluble to the developing liquid and an unhardened portion which has high solubility to the developing liquid. Thereby, a high-definition pattern array in which the undercut pixel patterns are arranged in a predetermined arrangement can be formed.

The biimidazole compound can be used singly or in combination of two or more.

In the present invention, when the photopolymerization initiator is a biimidazole compound, the content thereof is usually 0.01 to 40 parts by mass, preferably 1 to 30 parts by mass, per 100 parts by mass of the (C) polyfunctional monomer. Preferably, it is 1 to 20 parts by mass. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

In the present invention, when the photopolymerization initiator is a biimidazole compound, it is preferred to further improve the sensitivity by using the following hydrogen donor.

The "hydrogen donor" means a compound which radicals are generated by supplying a hydrogen atom to a biimidazole compound by exposure.

The hydrogen donor of the present invention is preferably a thiol compound or an amine compound as defined below.

The thiol compound is a compound having a benzene ring or a heterocyclic ring as a core and containing one or more, preferably 1 to 3, more preferably 1 to 2 thiol groups directly bonded to the core ( Hereinafter, it is referred to as "thiol-based hydrogen donor").

The amine compound is a compound having a benzene ring or a heterocyclic ring as a core and containing one or more, preferably 1 to 3, more preferably 1 to 2 amine groups directly bonded to the core (hereinafter It is called "amine-based hydrogen donor").

These hydrogen donors may contain both a thiol group and an amine group.

The hydrogen donor will be described more specifically below.

The thiol-based hydrogen donor may have one or more benzene rings or heterocyclic rings, and may contain both a benzene ring and a hetero ring. When two or more of these rings are contained, a condensed ring may be formed.

When the thiol-based hydrogen donor contains two or more thiol groups, when at least one of the free thiol groups remains, one or more of the remaining thiol groups may be substituted with an alkyl group, an aralkyl group or an aryl group. When at least one of the free thiol groups remains, it may have two structural units in which a sulfur atom is bonded to a divalent organic group such as an alkyl group, or a structural unit in which two sulfur atoms are bonded in a disulfide form. .

The thiol-based hydrogen supply system may be substituted at a position other than the thiol group by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such a thiol-based hydrogen donor are 2-thiolbenzothiazole, 2-thiolbenzoxazole, 2-thiol benzimidazole, 2,5-dithiol-1 A thiol group-substituted heterocyclic compound such as 3,4-thiadiazole or 2-thiol-2,5-dimethylaminopyridine.

Among these thiol-based hydrogen donors, 2-thiol benzothiazole and 2-thiol benzoxazole are preferred, and 2-thiol benzothiazole is particularly preferred.

Further, the amine-based hydrogen donor may contain one or more of a benzene ring or a hetero ring, or both a benzene ring and a hetero ring. When two or more of these rings are contained, a condensed ring can be formed.

One or more amine groups of the amine-based hydrogen supply system may be substituted by an alkyl group or a substituted alkyl group, and may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, or a substituted position other than the amine group. A phenoxycarbonyl group, a nitrile group or the like is substituted.

Specific examples of such an amine-based hydrogen donor include amine groups such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. Substituted benzophenones; 4-diethylaminobenzophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylamine Benzoic acid, 4-dimethylaminobenzonitrile, and the like.

Among these amine-based hydrogen donors, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are preferred. 4,4'-bis(diethylamino)benzophenone.

When the amine-based hydrogen donor is a photopolymerization initiator other than the biimidazole-based compound, it is also a person having a sensitizer.

In the present invention, the hydrogen donor may be used singly or in combination of two or more. In particular, it is preferable to combine one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogens from the viewpoint that the formed color layer is less likely to fall from the substrate during development, and the color layer has high strength and high sensitivity. The supplier is used.

Specific examples of the combination of the thiol-based hydrogen donor and the amine-based hydrogen donor include 2-thiolbenzothiazole/4,4'-bis(dimethylamino)benzophenone and 2-thiol group. Benzothiazole/4,4'-bis(diethylamino)benzophenone, 2-thiol benzoxazole/4,4'-bis(dimethylamino)benzophenone, 2-thiol benzoxazole/4,4'-bis(diethylamino)benzophenone. A preferred combination thereof is 2-thiol benzothiazole/4,4'-bis(diethylamino)benzophenone, 2-thiol benzoxazole/4,4'-bis (two) Ethylamino)benzophenone, particularly preferably 2-thiolbenzothiazole/4,4'-bis(dimethylamino)benzophenone.

The mass ratio of the thiol-based hydrogen donor to the amine-based hydrogen donor in the combination of the thiol-based hydrogen donor and the amine-based hydrogen donor is usually 1:1 to 1:4, preferably 1:1 to 1: 3.

In the present invention, when the hydrogen donor and the biimidazole compound are used in combination, the amount of the hydrogen donor is preferably 0.01 to 40 parts by mass, more preferably 1 to 30, based on 100 parts by mass of the (C) polyfunctional monomer. The mass fraction is particularly preferably from 1 to 20 parts by mass. When the amount of the hydrogen donor is less than 0.01 parts by mass, the effect of improving the sensitivity tends to be lowered. When it exceeds 40 parts by mass, the formed coloring layer tends to fall from the substrate at the time of development. When a polyfunctional monomer and a monofunctional monomer are used together, the mass of the monofunctional monomer is contained within the mass of the polyfunctional monomer.

Further, in the present invention, the photopolymerization initiator and other photopolymerization initiators (hereinafter sometimes referred to as "other photopolymerization initiators") may be used in combination as the (D) photopolymerization initiator. Other photopolymerization initiators include, for example, an acetophenone-based compound, a benzoin-based compound, an α-diketone-based compound, a polynuclear oxime-based compound, a xanthone-based compound, and a phosphine-based compound other than the compound represented by the formula (3). a compound, a triazine compound, or the like.

In the present invention, these other photopolymerization initiators may be used singly or in combination of two or more.

An acetophenone-based compound other than the compound represented by the formula (3), for example, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy- 2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2- In addition to diphenylethane-1-one, etc., there are phenyl groups having a morpholinyl group such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. An ketone compound.

Among these acetophenone-based compounds, 2-methyl-(4-methylthiophenyl)-2-morpholinyl-1-propan-1-one and 4-(2-hydroxyethoxy) are preferred. Phenyl-(2-hydroxy-2-propyl) ketone and the like.

The benzoin-based compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzimidazole or the like.

Examples of the α-diketone compound include butanedione, biphenyl ketone, and methotrexate.

The polynuclear lanthanide compound is, for example, hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, 1,4-naphthoquinone or the like.

Examples of the xanthone-based compound include xanthone ketones such as xanthone, thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone.

Examples of the phosphine-based compound include bis(2,4,6-trimethylbenzhydrazide)phenylphosphine oxide and 2,4,6-trimethylbenzimidium diphenylphosphine oxide.

The triazine-based compound is, for example, 2,4,6-para(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(Furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl] -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis (three Chloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2- (4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl) a compound containing a halogen methyl group such as -s-triazine or 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Among these triazine-based compounds, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine or the like is preferable.

-(E) Oxidation inhibitor -

In the present invention, the (E) oxidation preventing agent is an oxidation preventing agent containing at least one selected from the group consisting of a phenolic oxidation preventing agent, a phosphorus-based oxidation preventing agent, and a sulfur-based oxidation preventing agent. The combination of the specific oxidation preventing agent and the specific photopolymerization initiator described above can suppress the problem of lowering the brightness when the above-mentioned specific photopolymerization initiator is used, and the pixel formed by using the specific photopolymerization initiator can be used. Show maximum brightness. This is because the specific oxidation preventing agent inhibits the yellowing of the specific photopolymerization initiator due to the post-baking step. The present inventors have found that such an effect is effective when these specific oxidation preventing agents are combined with the above specific photopolymerization initiator, and have no effect on brightness or the like when combined with the above other photopolymerization initiators. .

As the phenolic oxidation inhibitor, a known compound can be used. Specifically, for example, there is 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1-dimethylethyl Oxy]-2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol ‧tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate a phenolic compound having a spiro skeleton;

1,3,5-trimethyl-2,4,6-tris(3'5'-di-t-butyl-4-hydroxybenzyl)benzene, triethylene glycol-bis[3-(3- T-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-3-methylphenol), tris-(3,5- Di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-trimerization Isocyanate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-sulfur-diethylene bis[3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamin Amine), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,4-bis[(octylsulfide) )methyl]-O-cresol, 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl -[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene bis(4-methyl-6-t-butylphenol), 4 , 4'-butyl fork-bis(3-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) Alkane, 1,3,5-tris(4-hydroxybenzyl)benzene and tetrakis[methyl-3-(3,5'-di-t-butyl-4'-hydroxyphenylpropionate)]methane Wait.

Among these, from the viewpoint of heat resistance and prevention of heat discoloration, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propenyloxy group is preferred. ]-1,1-dimethylethoxy]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5,-trimethyl-2,4,6, -Tris(3'5'-di-t-butyl-4-hydroxybenzyl)benzene, pentaerythritol ‧ tetra[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl- 3-methylphenol), tris-(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate, 1,3,5-tris(4-t-butyl-3-hydroxyl -2,6-dimethylbenzyl)-trimeric isocyanate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , 2,2-thio-diethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis (3,5- Di-t-butyl-4-hydroxy-hydrocinnacinamine, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Base) Benzene, 2,4-bis[(octylthio)methyl]-O-cresol, and the like.

The phenolic oxidation inhibitor may be used singly or in combination of two or more.

As the phosphorus-based oxidation preventing agent, a known compound can be used. Specifically, for example, there is 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphate. a phosphite compound having a spiro ring skeleton such as spiro[5.5]undecane, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite;

2,2'-Methylene bis(4,6-di-t-butyl-1-phenoxy)(2-ethylhexyloxy)phosphorus, 6-[3-(3-t-butyl- 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphine Phosphine), triphenylphosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, 4,4'-butylidene-bis(3-methyl-6-t-butyl Phenyl di-tridecyl phosphite, octadecyl phosphite, tris(nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-Oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,4-di-t-butylphenyl)phosphite, cyclic Pentaerythritol bis(2,4-di-t-butylphenyl) phosphite, cyclic pentaerythritol bis(2,6-di-t-butylphenyl) phosphite, 2,2-methylene bis ( 4,6-di-t-butylphenyl)octyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butyl Phenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, bis[2,4-bis(1,1-dimethylethyl)-6-methylbenzene Ethyl ester , phosphonic acid, etc.

Among these phosphorus-based oxidation inhibitors, 2,2'-methylenebis(4,6-di-t-butyl-1-phenoxy)(2) is preferred from the viewpoint of heat resistance and prevention of heat discoloration. Ethylhexyloxy)phosphorus, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9- Spiro[5.5]undecane,6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t -butyldibenzo[d,f][1,3,2]phosphinepine or the like.

The phosphorus-based oxidation inhibitors may be used singly or in combination of two or more.

As the sulfur-based oxidation preventing agent, a known compound can be used. Specifically, for example, there are 2,2-bis({[3-(dodecylthio)propenyl)oxy}methyl)-1,3-propanediyl-bis[3-(dodecane) Base thio)propionate], 2-hydrothiobenzimidazole, dilauryl-3,3'-thiodipropionate, tetracosyl-3,3'-thiodipropionate, di-hard a compound having a thioether structure such as a lipid-3,3'-thiodipropionate or pentaerythritol-tetrakis(3-laurylthiopropionate); 2-hydrothiobenzimidazole or the like.

Among these sulfur-based oxidation inhibitors, from the viewpoint of heat resistance and heat-resistant discoloration prevention, it is preferred.

2,2-bis({[3-(dodecylthio)propenyl)oxy)methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate ), 2-hydrothiobenzimidazole, and the like.

The sulfur-based oxidation inhibitors may be used singly or in combination of two or more.

In the present invention, from the viewpoint of suppressing the decrease in brightness and the combination of brightness and sensitivity, it is preferred to use the following (E-1) or (E-2) as the oxidation preventing agent.

(E-1) is at least one selected from the group consisting of a phosphorus-based oxidation inhibitor and a sulfur-based oxidation inhibitor.

(E-2) A combination of a phosphorus-based oxidation inhibitor or a sulfur-based oxidation inhibitor and a phenolic oxidation inhibitor.

The total content of the oxidation preventing agent of the present invention is usually from 1 to 100 parts by mass, preferably from 2 to 80 parts by mass, particularly preferably from 4 to 60 parts by mass, per 100 parts by mass of the total of (D) photopolymerization initiator. . When the total content is less than 1 part by mass, the desired effect cannot be obtained. On the other hand, when it exceeds 100 parts by mass, there may be insoluble matter or residue after development.

-additive-

The sensitive radiation linear composition of the present invention may be added with various additives as necessary.

The aforementioned additives are, for example, organic acids or organic amine based compounds (excluding the aforementioned hydrogen donor) and the like. These compounds further improve the solubility characteristics of the linear composition of the radiation sensitive agent to the alkali imaging solution, and exhibit a function of further suppressing the residual action of the undissolved substance after the development.

The organic acid is preferably an aliphatic carboxylic acid having one or more carboxyl groups in the molecule or a carboxylic acid having a phenyl group.

The aliphatic carboxylic acid is, for example, an aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid or octanoic acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malonic acid, methylmalonic acid, ethylmalonic acid, two Methylmalonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, isaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid, etc. Carboxylic acid; glycerin tricarboxylic acid, aconitic acid, tricarboxylic acid of camphoric acid, and the like.

Further, the phenyl group-containing carboxylic acid may, for example, be a compound in which a carboxyl group is directly bonded to a phenyl group, or a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain.

a phenyl group-containing carboxylic acid such as an aromatic monocarboxylic acid having benzoic acid, toluic acid, cumic acid, benzotricarboxylic acid or dimethylbenzoic acid;

An aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid or cinnaminoic acid;

An aromatic polycarboxylic acid having a trivalent or higher valence of trimellitic acid, trimellitic acid, pyromellitic acid or pyromellitic acid;

Phenylacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamyl acetic acid, coumaric acid, umbrella acid, and the like.

Among these organic acids, an aliphatic carboxylic acid is preferred from the viewpoints of alkali solubility, solubility in a solvent to be described later, prevention of texture contamination on a substrate on an unexposed portion or on a light shielding layer, and film retention. The dicarboxylic acid is particularly preferably malonic acid, adipic acid, isaconic acid, citraconic acid, fumaric acid, mesaconic acid or the like. The phenyl group-containing carboxylic acid is preferably an aromatic dicarboxylic acid, particularly preferably phthalic acid.

The above organic acids may be used singly or in combination of two or more.

The content of the organic acid is usually 15% by mass or less, preferably 10% by mass or less, based on the total mass (calculated as solid content) of the linear composition of the radiation. When the content of the organic acid exceeds 15% by mass, the adhesion of the colored layer to the substrate tends to be lowered.

The organic amine-based compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amine groups in the molecule.

The above aliphatic amine is, for example, the following.

The aliphatic amines are, for example, n-propylamine, i-propylamine, n-butylamine, i-butylamine, second-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine. , n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine a mono(cyclo)alkylamine such as 3-ethylcyclohexylamine or 4-ethylcyclohexylamine;

Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-second-butylamine a di(cyclo)alkylamine such as di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine or dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i - propylamine, tri-n-butylamine, tri-i-butylamine, tri-second-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, two a tri(cyclo)alkylamine such as ethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine or tricyclohexylamine;

2-Aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino group a mono(cyclo)alkanolamine such as 1-hexanol or 4-amino-1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di(4- a bis(cyclo)alkanolamine such as cyclohexanol)amine;

Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tris(4- a tri(cyclo)alkanolamine such as cyclohexanol)amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4- Amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2- Amino (cyclo)alkanediols such as propylene glycol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;

1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-aminocyclohexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane methanol, 4-di An amine group-containing cycloalkane methanol such as ethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol, 4-diethylaminocyclohexane methanol;

--alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5 An aminocarboxylic acid such as aminolevulinic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid or 4-aminocyclohexanecarboxylic acid.

Further, the phenyl group-containing amine is, for example, a compound in which an amine group is directly bonded to a phenyl group, a compound in which an amine group is bonded to a phenyl group, and the like.

Phenyl-containing amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4- n-Butylaniline, 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline, 4-methyl-N,N- An aromatic amine such as dimethylaniline;

Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;

Aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, 4-diethylaminophenol, and the like.

Among these organic amine-based compounds, the aliphatic amine is preferably a mono(cyclo)alkanolamine from the viewpoints of solubility to a solvent to be described later, prevention of texture contamination on a substrate or an unexposed portion or a film residue on an unexposed portion. And amino (cyclo)alkanediols, particularly preferably 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2- Propylene glycol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, and the like. The phenyl group-containing amine is preferably an aminophenol, and particularly preferably a 2-aminophenol, a 3-aminophenol, a 4-aminophenol or the like.

The organic amine-based compounds may be used singly or in combination of two or more.

The content of the organic amine-based compound is usually 15% by mass or less, preferably 10% by mass or less, based on the total mass of the linear composition of the radiation radiation (in terms of solid content). When the content of the organic amine-based compound exceeds 15% by mass, the adhesion of the colored layer to the substrate tends to be lowered.

Additive ingredients other than the foregoing, for example:

a dispersing aid such as a blue pigment derivative or a yellow pigment derivative of a copper phthalocyanine derivative;

Filler for glass, alumina, etc.;

a polymer compound such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or poly(fluoroalkyl acrylate);

a surfactant such as a nonionic, cationic or anionic surfactant;

Vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy a adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane;

Ultraviolet absorbers such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone;

An agglomeration preventing agent such as sodium polyacrylate;

A thermal radical generator such as 1,1'-azobis(cyclohexane-1-carbonitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

- solvent -

The sensitive radiation linear composition of the present invention contains the above components (A) to (E) as essential components, and sometimes contains the above additives, and is usually mixed with a solvent to prepare a liquid composition.

The solvent may be appropriately selected as long as it can disperse or dissolve each component constituting the linear composition of the radiation radiation and does not react with these components, and has appropriate volatility.

Such a solvent is, for example, the following.

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 single positive Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol single (poly)alkylene glycol monoalkyl ether acetates such as diethyl ether acetate;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Ketones;

a lactate alkyl ester such as methyl lactate or ethyl lactate;

Ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, propionic acid Butyl ester, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, B Other esters such as ethyl acetate and ethyl 2-oxobutanoate;

An aromatic hydrocarbon such as toluene or xylene;

A decylamine or an indoleamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether B are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. Acid ester, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, 3-ethyl Methyl oxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, acetic acid I-amyl ester, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

The solvent may be used singly or in combination of two or more.

Further, the above solvent may be combined with benzyl ether, di-n-hexyl ether, acetamidine acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate. A high boiling point solvent such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate is used in combination.

These high boiling point solvents may be used singly or in combination of two or more.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent is usually 5 to 50% by mass from the viewpoint of coatability and stability of the obtained linear composition of the radiation sensitive agent. Preferably, it is 10 to 40% by mass.

-Production method-

The sensitive radiation linear composition of the present invention can be prepared by a suitable method. For example, when a coloring agent is used, the pigment is dispersed and dispersed in a solvent, a roll mill or the like in the presence of a solvent or a dispersing agent. The pigment dispersion liquid is preferably mixed with the component (B), the component (C), the component (D), and the component (E), and a solvent or other additive added as necessary.

Examples of the dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polyethylene glycol diester dispersant. A sorbitol fatty acid ester dispersant, a fatty acid modified polyester dispersant, an acrylic dispersant, and the like.

Specific examples of such a dispersing agent include EFKA (manufactured by EFKA Chemicals (EFKA) Co., Ltd.), Disperbyk (manufactured by BYK Chemie (BYK) Co., Ltd.), Disbaron (manufactured by Nanmoto Chemical Co., Ltd.), and Solsperse (manufactured by Lubrizol Co., Ltd.). KP (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F Top (Tokem Products), Megafac (Daily Ink Chemical Industry Co., Ltd.), Florade (Sumitomo) 3M (share) system, Asahi Guard, Surflon (above is Asahi Glass Co., Ltd.).

These dispersing agents can be used individually or in combination of 2 or more types.

The amount of the dispersant used in preparing the pigment dispersion liquid 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 preferably 10 to 50 parts by mass per 100 parts by mass of the pigment. Share. When the amount of the dispersant used is too large, the development property may be affected.

Further, the solvent used in the preparation of the pigment dispersion liquid is, for example, the same as the above solvent.

The amount of the solvent to be used in the preparation of the pigment dispersion liquid is usually 200 to 1,200 parts by mass, preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

When the pigment dispersion liquid is prepared by a ball mill, the pigment dispersion liquid composed of a pigment, a solvent, and a dispersant is preferably cooled by cooling water or the like using a glass bead or a titanium oxide bead having a diameter of, for example, 0.5 to 10 mm, and mixed and dispersed at the same time. Methods.

At this time, the filling rate of the beads is preferably from 50 to 80% by volume of the mill, and the amount of the pigment mixture is preferably from 20 to 50% by volume of the mill. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

In the preparation by the roll mill, for example, a three-roll mill or a double-roll mill or the like is used, and a method in which the pigment mixed liquid is cooled by cooling water or the like is preferably used.

At this time, the interval of the drum is preferably 10 μm or less, and the shearing force is usually 10 ⁸ dyn/sec. The treatment time is usually 2 to 50 hours, more preferably 2 to 25 hours.

Color filter

The color filter of the present invention is formed by using the blue color filter of the present invention with a radiation sensitive linear composition.

The method of forming the color filter of the present invention will be described below.

First, a light-shielding layer is formed on the surface of the substrate to distinguish the portion forming the pixel, and the liquid composition of the linear composition for sensitive radiation of the blue color filter of the present invention is coated on the substrate, and then pre-baked. The solvent is evaporated to form a coating film.

Next, after the film was exposed through a photomask, it was developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, the pixel array in which the blue pixel pattern is arranged according to the predetermined arrangement is formed by post-baking.

Then, using a liquid composition of a linear composition of each sensitive radiation composed of a green or red coloring agent, coating, prebaking, exposing, developing, and post-baking the respective liquid compositions are carried out in the same manner as described above. A green pixel array and a red pixel array are sequentially formed on the same substrate, and a color filter in which pixel arrays of three primary colors of red, green, and blue are disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the foregoing.

The substrate used for forming the color filter is, for example, glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimine or the like.

Such a substrate may be subjected to an appropriate pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum vapor deposition method.

When the liquid composition of the linear composition of the radiation radiation is applied to the substrate, a suitable coating such as a spray coating method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method may be employed. The cloth method is a spin coating method or a slit die coating method.

The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, and particularly preferably 0.2 to 6.0 μm.

For the radiation for forming the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength of 190 to 450 nm is preferable.

The amount of exposure of the radiation is preferably from 10 to 10,000 J/m ² .

Further, the alkali developing solution is preferably, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- eleven An aqueous solution of carbene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developing solution. After alkali imaging, it is usually washed with water.

As the development processing method, for example, a spray-type development method, a spray-type development method, an immersion-type development method, a stirring development method, or the like can be employed. The development condition is preferably carried out at room temperature for 5 to 300 seconds.

The post-baking conditions are preferably from 180 to 230 ° C for 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.

The color filter of the present invention thus obtained is very suitable for, for example, a transmissive or reflective type color liquid crystal display element, a color image pickup tube element, a color sensor, and the like.

Liquid crystal display element

The liquid crystal display element of the present invention is provided with the color filter of the present invention.

In addition, an embodiment of one of the liquid crystal display elements of the present invention is a linear composition for a blue color filter of the present invention, and a pixel and/or a black matrix can be formed on the thin film transistor substrate array as described above. A liquid crystal display element having particularly excellent characteristics.

[Examples]

Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited to the embodiments described.

The photopolymerization initiator and the oxidation inhibitor used in the examples are as follows.

Photopolymerization initiator

(d-1): 2-methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one (trade name: Irgacure 907, manufactured by Ciba‧Speciality ‧ Chemicals)

(d-2): 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

(d-3): 2,4-diethylthioxanthone

(d-4): 2-Hydroxythiobenzothiazole

(d-5): 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (IRUGACURE 369, manufactured by Ciba‧Speciality ‧ Chemicals)

(d-6): 1-[9-Ethyl-6-(2-methylbenzoquinone)-9H-indazol-3-yl]-ethane-1-one oxime-O-acetate (IRUGACURE OXE-02, Ciba‧Speciality‧Chemicals)

Oxidation inhibitor

(e-1): 2,2'-methylenebis(4,6-di-t-butyl-1-phenoxy)(2-ethylhexyloxy)phosphorus (trade name ADK STAB HP-10 , the company ADEKA)

(e-2): 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphate Spirulina [5.5] undecane (ADK STABPEP-36, manufactured by the company ADEKA)

(e-3): 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl Oxy]-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK STABAO-80, manufactured by the company ADEKA)

(e-4): 2,2-bis({[3-(dodecylthio)propenyl)oxy}methyl}-1,3-propanediyl-bis[3-(dodecane) Base thio)propionate] (ADK STABAO-412S, manufactured by ADEKA)

(B) Production example of alkali-soluble resin Synthesis Example 1

1 part by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by loading a methyl group. 15 parts by mass of acrylic acid, 35 parts by mass of benzyl methacrylate, 10 parts by mass of glycerin monomethacrylate, 25 parts by mass of N-phenyl maleimide, and α-methylstyrene dimer ( 2.5 parts by mass of the chain transfer agent, after being substituted by nitrogen, the mixture was slowly stirred, and the reaction solution was heated to 80 ° C, and the temperature was maintained at this temperature for 3 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, 0.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and polymerization was further carried out for 1 hour to obtain (B) an alkali-soluble resin. Solution (solid content concentration = 33.0%).

This (B) alkali-soluble resin is Mw = 10,000 and Mn = 6,000. This (B) alkali-soluble resin is referred to as "resin (b)".

Example 1

(A) colorant: 12 parts by mass of a mixture of CI Pigment Blue 15:6/CI Pigment Violet 23=80/20 (mass ratio), dispersing agent: BYK2001 (Disperbyk: BYK Chemie (BYK)) 3.8 parts by mass (solid content conversion), Solsperse 12000: 0.8 parts by mass and solvent: propylene glycol monomethyl ether acetate 83.4 parts by mass was treated by a bead mill to prepare a pigment dispersion.

Next, 360 parts by mass of the pigment dispersion liquid, (B) 70 parts by mass of the alkali-soluble resin: resin (b) (calculated as solid content), and (C) 80 parts by mass of polyfunctional monomer: dipentaerythritol hexaacrylate ( D) Photopolymerization initiator: (d-1) 30 parts by mass, (d-2) 3 parts by mass, (d-3) 10 parts by mass, and (d-4) 1.5 parts by mass, (E) oxidation preventing agent (e-1) 2.5 parts by mass, additive: a perfluoroalkyl group-containing oligomer (trade name: Megafac R08-MH, manufactured by Dainippon Ink Co., Ltd.) 0.3 parts by mass and 3-methacryloxypropyl group 0.4 parts by mass of trimethoxydecane (trade name: SILA-ACE S710, manufactured by Alizarin Co., Ltd.) and a solvent: 900 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a linear radiation sensitive linear composition (B1).

Formation of pixel array

The linear composition of sensitive radiation (B1) was applied to a soda-lime glass substrate on the surface of which a sodium ion-dissolving SiO ₂ film was formed using a spin coater, and after changing the number of revolutions, 3 pieces were coated in a clean oven at 80 ° C. Prebaking was carried out for 10 minutes to form a coating film having a film thickness of 1.5 to 2.5 μm and different three sheets.

Next, after cooling the substrate to room temperature, the coating film was exposed to a radiation amount of 5,000 J/m ² at a wavelength of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp. Next, the substrate was immersed in a 0.1% by mass aqueous solution of tetramethylammonium hydroxide at 25° C. for 1 minute, subjected to development treatment, washed with ultrapure water, and air-dried. Thereafter, post-baking was carried out at 230 ° C for 30 minutes to prepare a pixel array of a pixel pattern of blue having a size of 20 μm × 20 μm on each side.

Evaluation of chromaticity

For the obtained pixels, a color analyzer (TC-1800M manufactured by Tokyo Electron Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and brightness (Y) of the CIE color system using a C light source and a 2 degree field of view. , the brightness (Y) at (x, y) = (0.141, 0.089) is obtained. A larger Y value indicates a higher brightness. The evaluation results are shown in Table 1.

Example 2

A blue pixel was formed on the substrate in the same manner as in Example 1 except that 2.5 parts by mass of the oxidation preventing agent (e-2) was used instead of 2.5 parts by mass of the oxidation preventing agent (e-2). The results are shown in Table 1.

Example 3

A blue pixel was formed on the substrate in the same manner as in Example 1 except that 2.5 parts by mass of the oxidation preventing agent (e-3) was used instead of 2.5 parts by mass of the oxidation preventing agent (e-3). The results are shown in Table 1.

Example 4

A blue color was formed on the substrate in the same manner as in Example 1 except that 1.9 parts by mass of the oxidation preventing agent (e-1) and 0.6 parts by mass of the oxidation preventing agent (e-3) were used instead of the oxidation preventing agent (e-1) of 2.5 parts by mass. The pixels are evaluated. The results are shown in Table 1.

Example 5

A blue color was formed on the substrate in the same manner as in Example 1 except that 0.6 parts by mass of the oxidation preventing agent (e-3) and 1.9 parts by mass of the oxidation preventing agent (e-4) were used instead of the oxidation preventing agent (e-1) of 2.5 parts by mass. The pixels are evaluated. The results are shown in Table 1.

Example 6

The substrate was used on the substrate in the same manner as in Example 1 except that 20 parts by mass of the initiator (d-5) was used instead of the initiators (d-1), (d-2), (d-3) and (d-4). Blue pixels were formed and evaluated. The results are shown in Table 1.

Example 7

A blue color was formed on the substrate in the same manner as in Example 6 except that 0.6 parts by mass of the oxidation preventing agent (e-3) and 1.9 parts by mass of the oxidation preventing agent (e-4) were used instead of the oxidation preventing agent (e-1) of 2.5 parts by mass. The pixels are evaluated. The results are shown in Table 1.

Example 8

Except that 10 parts by mass of the initiator (d-6) was used in place of the initiators (d-1), (d-2), (d-3) and (d-4), on the substrate as in Example 5. Blue pixels were formed and evaluated. The results are shown in Table 1.

Comparative example 1

A blue pixel was formed on the substrate in the same manner as in Example 1 except that 2.5 parts by mass of the oxidation preventing agent (e-1) was not contained, and the evaluation was performed. The results are shown in Table 1.

Comparative example 2

A blue pixel was formed on the substrate in the same manner as in Example 6 except that 2.5 parts by mass of the oxidation inhibitor (e-1) was not contained, and the evaluation was performed. The results are shown in Table 1.

Comparative example 3

A blue pixel was formed on the substrate in the same manner as in Example 8 except that 1 part by mass of the oxidation preventing agent (e-3) and 1.9 parts by mass of the oxidation preventing agent (e-4) were not contained, and evaluation was performed. The results are shown in Table 1.

Reference example

A blue pixel was formed on the substrate in the same manner as in Example 1 except that 30 parts by mass of the photopolymerization initiator (d-1) and 2.5 parts by mass of the oxidation inhibitor (e-1) were not used. The results are shown in Table 1.

The reference example is a high-luminance blue pixel using the photopolymerization initiator (d-1) of Patent Document 3, and the Y value of the blue pixel is 9.6. In order to further improve the sensitivity, when the photopolymerization initiator (d-1) is combined with three kinds of photopolymerization initiators (d-2) to (d-4), it is found that the Y value is lowered to 9.4 (comparison example 1).

However, in Examples 1 to 5, in order to further improve the sensitivity, the photopolymerization initiator (d-1) is combined with three kinds of photopolymerization initiators (d-2) to (d-4), and the specific combination is combined. The oxidation inhibitor was confirmed to have a Y value (9.5 to 9.6) which is comparable to the reference example. As described above, in Examples 1 to 5, a specific photopolymerization initiator and a specific oxidation inhibitor are combined, and a blue pixel having a high level of brightness and sensitivity can be obtained.

When used alone in Comparative Examples 2 to 3, a photopolymerization initiator having a sufficient luminance (Y value) could not be obtained, and in Examples 6 to 7, a photopolymerization initiator was combined with a specific oxidation inhibitor. High-brightness blue pixels are available.

Claims (7)

A linear color filter for a blue color filter, characterized by: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, ( D) a photopolymerization initiator containing at least one selected from the group consisting of a compound represented by the following formula (3), an oxime ester compound, and a biimidazole compound, and (E) containing a phosphorus-based oxidation preventive agent An oxidation preventing agent prepared by combining at least one of a group of the agent and the sulfur-based oxidation preventing agent with a phenolic oxidation preventing agent, and the total content of the component (E) is 100 parts by mass based on the total of the component (D). Containing 1 to 100 parts by mass, Wherein R ⁶ independently of each other represents an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A linear color filter for a blue color filter, characterized by: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, ( D) a photopolymerization initiator containing a compound represented by the following formula (3), (E) an oxidation inhibitor containing a combination of a sulfur-based oxidation inhibitor and a phenolic oxidation inhibitor, and (E) component The total content is 1 to 100 parts by mass based on 100 parts by mass of the total of the component (D). Wherein R ⁶ independently of each other represents an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A linear color filter for a blue color filter, characterized in that: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator containing an oxime ester-based compound, and (E) a combination of a sulfur-based oxidation inhibitor and a phenolic oxidation inhibitor The total amount of the component (E) is from 1 to 100 parts by mass based on 100 parts by mass of the total of the component (D). A linear color filter for a blue color filter, characterized by: (A) a coloring agent containing a blue coloring agent, (B) an alkali-soluble resin, (C) a polyfunctional monomer, ( D) a photopolymerization initiator containing a biimidazole-based compound, (E) a combination of a phosphorus-based oxidation inhibitor and a phenolic oxidation inhibitor, or a sulfur-based oxidation inhibitor and a phenol-based oxidation inhibitor The oxidation inhibitor is combined, and the total content of the component (E) is 1 to 100 parts by mass based on 100 parts by mass of the total of the component (D). The sensitive linear composition for a blue color filter according to any one of claims 1 to 4, wherein the phenolic oxidation preventing agent is a phenolic compound containing a spiro ring skeleton. A color filter characterized in that the blue color filter of any one of claims 1 to 5 is formed using a linear composition of a sensitive radiation. A liquid crystal display element characterized by having a color filter of claim 6 of the patent application.