TWI430027B - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Description

Radiation-sensitive composition for forming a dyed layer, color filter and color liquid crystal display device

The present invention relates to a radiation-sensitive composition, a color filter, and a color liquid crystal display device for forming a dye layer. In particular, it relates to a radiation-sensitive composition for forming a dyed layer which can be used for the manufacture of color filters for use in transmissive and reflective color liquid crystal displays and color and color imaging devices. A color filter of a dye layer prepared by the radiation sensitive composition and a color liquid crystal display device comprising the color filter.

As a method of manufacturing a color filter using a color radiation-sensitive composition, a substrate in which a color radiation-sensitive composition is applied to a substrate or a light-shielding layer having a desired pattern is known, dried, and then the dried coating film is exposed. A method of irradiating a desired pattern (hereinafter referred to as "exposure") and developing to obtain a color pixel (refer to JP-A 2-144502 and JP-A 3-53201).

In the technical field of color filters, the adhesive time is currently shortened by reducing the exposure amount, and it is highly desirable to form a finer pattern to reflect the higher definition of the liquid crystal display device. However, when the adhesive time is shortened, it is difficult to obtain a satisfactory pixel pattern and a black matrix pattern from the color radiation-sensitive composition of the prior art because the edge portion of the pattern is easily lost or undercut during development. The ability of prior art radiation-sensitive compositions to form extremely fine patterns is not satisfactory.

It is an object of the present invention to provide a radiation-sensitive composition for forming a dyed layer having excellent developability, and more particularly a novel radiation-sensitive composition for forming a dyed layer which does not leave insoluble products during development or The edge of the pattern creates a floating film, providing a pixel and a black matrix with no missing or side etching of the edge portion of the pattern even when the amount of exposure is low, and a fine pattern can be formed.

Another object of the present invention is to provide a color filter having a dyed layer and a color liquid crystal display device including the color filter.

Other objects and advantages of the invention will be apparent from the description.

According to the present invention, the foregoing objects and advantages are first attained by a radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photosensitive film. a radical generating agent, wherein the alkali-soluble resin (B) comprises a polyester having an alicyclic hydrocarbon skeleton in a main chain and a polymerizable unsaturated bond in a side chain, and the radiation-sensitive composition is used for dyeing Floor.

The term "dyed layer" as used in the present invention means a thin layer composed of a pixel and/or a black matrix for use in a color filter.

In accordance with the present invention, secondly, the foregoing objects and advantages of the present invention are achieved by a color filter having a dyed layer prepared from the aforementioned radiation-sensitive composition.

According to the present invention, third, the above objects and advantages of the present invention are achieved by a color liquid crystal display device including the above-described color filter.

The invention is described in detail below.

Detailed description of preferred embodiments Radiation sensitive composition -Component (A)-

The component (A) as the colorant is not limited to a specific color, and is appropriately selected depending on the application purpose of the produced color filter. It can be a pigment, a dye or a natural coloring matter.

Because the color development and heat resistance of high-definition color are required for color filters, coloring agents having high color rendering properties and high heat resistance, especially those having high heat decomposition resistance, are compared to the present invention. Good coloring agent. Therefore, it is preferred to use an organic pigment or an inorganic pigment, and it is particularly preferable to use an organic pigment or carbon black.

Examples of the foregoing organic pigments are compounds classified as a group of pigments according to a colorimetric index (CI; published by The Society of Dyers and Colourists), especially a compound having the following color index (CI) number: CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 180 and CI Pigment Yellow 185; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36. CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71 and CI pigment orange 73; CI pigment violet 1, CI pigment violet 19, CI pigment violet 23, CI pigment violet 29, CI pigment violet 32, CI pigment violet 36 and CI pigment violet 38; CI pigment red 1, CI pigment red 2. CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, C.1. Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 50:1, CI Pigment Red 52:1, CI Pigment Red 53:1, CI Pigment Red 57, CI Pigment Red 57:1, CI Pigment Red 57:2, CI Pigment Red 58:2 , CI Pigment Red 58:4, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81:1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90:1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, C.1. Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151 CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264 and CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6 And CI Pigment Blue 60; CI Pigment Green 7 and CI Pigment Green 36; CI Pigment Brown 23 and CI Pigment Brown 25; and CI Pigment Black 1 and CI Pigment Black 7.

These organic pigments can be purified by recrystallization of sulfuric acid, solvent washing or a combination thereof before use.

Examples of the foregoing inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chromium oxide. Green, cobalt, amber, titanium black, synthetic iron black and carbon black.

In the present invention, the aforementioned pigments may be used singly or in combination of two or more kinds, or an organic pigment and an inorganic pigment may be used in combination. For example, it is preferred to form a pixel using one or more organic pigments, and it is preferred to form a black matrix using two or more organic pigments and/or carbon black.

In the present invention, the surface of the particles of the pigment may be modified with a polymer as appropriate before use. Examples of the polymer for modifying the surface of the pigment particles include polymers disclosed in JP-A 8-259876 and polymers and oligomers commercially available for dispersing pigments.

In the present invention, the colorant may optionally be used in combination with a dispersing agent. The dispersant is, for example, a cationic, anionic, nonionic, amphoteric, or a surfactant based on polyfluorene as a substrate or a fluorine-based substrate.

Examples of the foregoing surfactant include polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether; polyethylene oxide Alkyl phenyl ethers such as polyethylene oxide n-octyl phenyl ether and polyethylene oxide n-decyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and poly Ethylene glycol distearate; sorbitan fatty acid ester; polyester modified with fatty acid; polyurethane modified with tertiary amine; and polyethylenimine. Commercially available trademarks of such surfactants are KP (Shin-Etsu Chemical, Co., Ltd.), Polyflow (Kyoeisha Kagaku Co., Ltd.), F Top (Tokem Products Co., Ltd.), Megafac (Dainippon). Ink and Chemicals, Inc.), Florade (Sumitomo 3M Limited), Asahi Guard and Surflon (Asahi Glass Co., Ltd.), BYK and Disperbyk (BYK Chemie Japan Co., Ltd.), Solsperse (Seneca Co., Ltd) .) and EFKA (EFKA Chemicals BV).

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

The amount of the surfactant is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the coloring agent.

In the present invention, the radiation-sensitive resin composition can be produced by a suitable method. When a pigment is used as the colorant, it is preferably mixed with an alkali-soluble resin (B) and a solvent in the presence of a dispersing agent, and dispersed therein, while being milled by a bead mill or a roll mill to prepare a pigment dispersion, This dispersion is then mixed with the components (B), (C) and (D) described below.

The amount of the dispersant used to prepare the aforementioned pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, based on 100 parts by weight of the pigment. It is preferably 10 to 50 parts by weight. When the amount of the dispersant is more than 100 parts by weight, the developability may be impaired.

The solvent used to prepare the aforementioned pigment dispersion can be used as a solvent for preparing a liquid radiation-sensitive resin composition as described below.

The amount of the solvent used to prepare the pigment dispersion is preferably from 500 to 1,000 parts by weight, more preferably from 700 to 900 parts by weight, based on 100 parts by weight of the pigment.

When a pigment dispersion is prepared using a bead mill, a glass pigment or a titanium oxide bead having a diameter of about 0.5 to 10 mm is mixed and dispersed with a pigment solution, preferably, with cooling water or the like. The solution contains a pigment, a solvent, and a dispersing agent.

In this case, the filling rate of the beads is preferably from 50 to 80% by volume of the mill capacity, and the injection amount of the solution in which the pigment is mixed is preferably from about 20 to 50% by volume of the mill capacity. The treatment time is preferably from 2 to 50 hours, more preferably from 2 to 25 hours.

The pigment dispersion is prepared using a roll mill, and the three-roll mill or the two-roll mill mixes and disperses the pigment-mixed solution, preferably while cooling with cooling water or the like.

The spacing between the rolls is preferably 10 microns or less, and the shear force is preferably about 10 ⁸ dynes/second. The treatment time is preferably from 2 to 50 hours, more preferably from 2 to 25 hours.

-Component (B)-

In the present invention, the component (B) is an alkali-soluble resin containing a polyester having an alicyclic hydrocarbon skeleton in its main chain and having a polymerizable unsaturated bond in its side chain (hereinafter referred to as ^" (B) alkali-soluble resin"). The component (B) is a binder as the colorant (A) and has solubility in an alkali developer used in a developing step for producing a dye layer.

Examples of the alicyclic hydrocarbon skeleton in the side chain unsaturated alicyclic polyester include a skeleton derived from a hydrocarbon having 4 to 8 membered carbon rings: cyclopentane, methylcyclopentane, ethylcyclopentane, N-propylcyclopentane, isopropylcyclopentane, 1-methyl-3-isopropylcyclopentane, cyclopentene, cyclohexene, methylcyclohexane, ethylcyclohexane, n-propyl Cyclohexane, isopropylcyclohexane, 1-methyl-3-isopropylcyclohexane, 1-methyl-4-isopropylcyclohexane, cyclohexene, cycloheptane, methyl Cycloheptane, ethylcycloheptane, n-propylcycloheptane, isopropylcycloheptane, 1-methyl-3-isopropylcycloheptane, 1-methyl-4-isopropylcycloheptane Alkane, cycloheptene, cyclooctane and cyclooctene.

Among these alicyclic hydrocarbon skeletons, a skeleton having a cyclohexane ring is preferred, and is derived from 1-methyl-3-isopropylcyclohexane and 1-methyl-4-isopropylcyclohexane. The skeleton is especially good.

In the side chain unsaturated alicyclic polyester, the alicyclic hydrocarbon skeleton may form a main chain ester structure for interconnecting the structural units of the polyester directly or via a divalent bond group.

Examples of the aforementioned divalent bond group include a methyl group and a linear or branched alkyl group having 1 to 6 main chain carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a trimethyl group. And a tetra-butyl group; a cycloalkyl group having a carbon ring of 4 to 8 members, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; and a cycloalkyl group having a carbon ring of 4 to 8 members a group having a divalent hydrocarbon chain having 1 to 6 main chain carbon atoms (such as a methyl group, an ethyl group or a propyl group), such as a methyl group, a methyl group, a cyclopentyl group, and an exo a cyclopentyl propyl group, a cyclohexyl group methyl group, a cyclohexyl group ethyl group, and a cyclohexyl group propyl group; an extended aryl group having 6 to 10 carbon atoms, such as 1,3-phenylene group, 1, 4-phenylene and 1,4-naphthyl; having a divalent hydrocarbon chain (such as a methyl group) bonded to the aforementioned aryl group having 6 to 10 membered carbon atoms and having 1 to 6 main chain carbon atoms a group having an ethyl group or a propyl group; a aryloxy group having 6 to 10 carbon atoms, such as m-phenyleneoxy (-m-C ₆ H ₄ -O-) or p- phenylene group _{(-p-C 6 H 4 -O-} ); and having bonded to the front Extending in the aryloxy group and having from 1 to 6 carbon atoms in the main chain divalent hydrocarbon chain (such as methyl stretch, elongation or stretch ethyl propyl) group.

Among these divalent bond groups, an extended aryloxy group having 6 to 10 carbon atoms is preferred, and a p-phenyleneoxy group is particularly preferred.

The polymerizable unsaturated bond in the side chain of the side chain unsaturated alicyclic polyester is not particularly limited, and is limited in that it is as described below when a radiation-sensitive composition for forming a dye layer is to be produced. The functional monomer (C) and optionally a monofunctional monomer are copolymerized. However, from the viewpoint of the ease of synthesizing the side chain unsaturated alicyclic polyester, it is preferably a self-polymerizable unsaturated carboxylic acid (such as (meth)acrylic acid, crotonic acid, maleic acid, An unsaturated bond derived from fumaric acid or isaconic acid, especially an unsaturated bond derived from (meth)acrylic acid.

The side chain unsaturated alicyclic polyester of the present invention is particularly preferably a polyester represented by the following formula (1) (hereinafter referred to as "polyester (1)").

[In the formula (1), each of the X groups is independently a divalent group represented by the following formula (2) or (3), and each of the Y groups is independently a residue obtained by removing four carboxyl groups from the organic tetracarboxylic acid. Further, R ^{1 is} each independently a hydrogen atom or a methyl group, and R ^{2 is} each independently a hydrogen atom or a residue of a carboxyl terminal blocking agent, and n is an integer of 1 to 40. ]

The side chain unsaturated alicyclic polyester can be synthesized by synthesizing a diol compound having an alicyclic hydrocarbon skeleton in a main chain and having a polymerizable unsaturated bond in a side chain, and having two or more diol compounds An acid anhydride of a carboxyl group (preferably 2 to 4 carboxyl groups, particularly preferably a tetracarboxylic anhydride) is obtained by an esterification reaction.

The polyester (1) can be referred to as "tetracarboxylic dianhydride (8) from the diol compound containing a bis(meth) acrylonitrile group of the following formula (6) or (7) and represented by the following formula (8). The esterification reaction between the tetracarboxylic dianhydrides is obtained.

[In the formula (6), R ¹ is as defined in the formula (1). ]

[In the formula (7), R ¹ is as defined in the formula (1). ]

In the formula (8), Y is as defined in the above formula (1). ]

The method for producing a side chain unsaturated alicyclic polyester is mainly described below for polyester (1).

The diol compound containing a bis(meth) acrylonitrile group can be obtained by using a diphenol represented by the following formula (9) (hereinafter referred to as "diphenol (9)") or a formula (10) A phenol (hereinafter referred to as "diphenol (10)") diglycidyl ether is etherified to synthesize a diglycidyl etherified product represented by the following formula (11) or (12) so that acrylic acid and/or methacrylic acid are located therein. The epoxy group at both ends of the diglycidyl etherification product is subjected to an addition reaction.

Preferably, the diol compound containing the bis(meth)acrylonitrile group prepared as described above has an acid value of less than 10 mgKOH/g and an epoxy equivalent of 10,000 to 20,000.

When synthesizing the bis(meth)acrylonitrile-containing diol compound, it is desirable to use a weight ratio of preferably 80 to 60:20 to 40 bisphenol (9) and diphenol (10), which can be used alone or Two or more combinations are used.

The diglycidyl etherification reaction between diphenols for synthesizing a diol compound containing a bis(meth)acryl fluorenyl group can be carried out according to a method of synthesizing an epoxy resin in general. For example, the bis(meth)acrylonitrile-containing diol compound can be synthesized by reacting diphenol with epichlorohydrin in the presence of a basic catalyst.

The diglycidyl etherified product obtained as described above has an epoxy equivalent of from 260 to 300.

The tetracarboxylic dianhydride (8) is not particularly limited, but is preferably a compound of the following formula (8-1), a compound represented by the following formula (8-2) or a formula (8-3): Compound.

The method for carrying out the esterification reaction between the diol compound containing the di(meth)acrylonitrile group of the polyester (1) and the tetracarboxylic dianhydride (8) is not particularly limited. For example, the polyester (1) can be dissolved in an organic solvent by heating a di(meth)acrylonitrile group-containing diol compound, and a tetracarboxylic dianhydride (8) can be added to the formed solution. It is prepared by reacting with each other with stirring.

In the polyester (1) obtained by the above esterification reaction, R ² in the formula (1) is a hydrogen atom, and the residue of the tetracarboxylic dianhydride (8) has two or three carboxyl groups, so that the polyester ( 1) Excellent solubility in an aqueous alkali solution.

In the present invention, at least a part of the free carboxyl groups in the polyester (1) obtained by the esterification reaction may be blocked with a carboxyl blocking agent before use. The acid value of the polyester (1) is adjusted by changing the ratio of the blocked carboxyl group to control the alkali solubility.

The aforementioned carboxyl terminal blocking agent is not particularly limited, and a known blocking agent such as glycidyl ether or carbodiimide can be used. For example, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, and resorcinol glycidyl ether are preferred.

In the present invention, the acid value of the polyester (1) is preferably from 20 to 80 mgKOH/g, more preferably from 30 to 70 mgKOH/g. Depending on the type of the tetracarboxylic dianhydride (8), it is preferred that the total amount of all R ² in the polyester (1) is preferably 50 mol% or more, more preferably 70 mol% or more, of hydrogen. Atomic composition to determine high alkali developability.

The epoxy group equivalent of the polyester (1) after capping with a carboxyl blocking agent is preferably 60,000 or more.

Since the polyester (1) has a plurality of propylene groups or methacryl groups having a polymerization ability, it is cured by exposure to become insoluble in an aqueous alkali solution. At the same time, since it is soluble in the aqueous alkali solution when it is not cured, it is exposed in the form of a photoresist film, leaving a solidified portion, and the uncured portion has alkali developability, can be dissolved in the aqueous alkali solution and removed. The polyester (1) has high adhesion to various substrates, low curing shrinkage and excellent heat resistance, and has a high glass transition temperature (Tg), and can form a photoresist film having a high hardness. Further, when the alicyclic hydrocarbon skeleton contained in the molecular main chain forms a relatively soft structure, the polyester (1) has high flexibility.

In the present invention, the side chain unsaturated alicyclic polyester is measured by gel permeation chromatography (GPC) (dissolved solvent: tetrahydrofuran) to measure the weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw"). 3,000 to 100,000, more preferably 5,000 to 25,000. When Mw is lower than the above range, flexibility or adhesiveness may be lowered, and when Mw exceeds the above range, alkali solubility in a photosensitive curable or uncured state may be lowered. In the case of the polyester (1), Mw can be adjusted by changing the amount of the organic solvent and the reaction raw material in the aforementioned esterification reaction.

The side chain unsaturated alicyclic polyester is measured by gel permeation chromatography (GPC) (dissolved solvent: tetrahydrofuran), and the number average molecular weight (hereinafter referred to as "Mn") in terms of polystyrene is preferably 1,000 to 60,000. More preferably 2,000 to 25,000.

The side chain unsaturated alicyclic polyester preferably has an acid value of from 60 to 70 mg KOH/g to determine the high alkali solubility in the uncured state.

In the present invention, the side chain unsaturated alicyclic polyester may be used singly or in combination of two or more.

In the present invention, another alkali-soluble resin may be used in combination with the side chain unsaturated alicyclic polyester as the alkali-soluble resin.

The other alkali-soluble resin is, for example, a polymerizable unsaturated monomer having an acid functional group (such as a carboxyl group), a phenolic hydroxyl group or a sulfonic acid group, and another copolymerizable unsaturated monomer different from the aforementioned monomer (hereinafter referred to as Copolymer of "copolymerizable unsaturated monomer").

Examples of the carboxyl group-containing polymerizable unsaturated monomer (hereinafter referred to as "carboxy group-containing unsaturated monomer") include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. An unsaturated dicarboxylic acid and an anhydride thereof, such as maleic acid, maleic anhydride, fumaric acid, isaconic acid, isaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Three or more carboxyl groups of unsaturated polycarboxylic acids and anhydrides thereof; mono[(meth)acryloxyalkylalkyl]esters of polycarboxylic acids having two or more carboxyl groups, such as succinic acid mono[2- (meth)acryloyloxyethyl]ester and mono [2-(methyl)propenyloxyethyl] phthalic acid ester; and mono(methyl) polymer having a carboxyl group and a hydroxyl group at both terminals An acrylate such as ω-carboxypolycaprolactone mono(meth)acrylate.

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

Examples of the aforementioned polymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-α-methylhydroxystyrene, and m-α-methylhydroxyl group. Styrene, p-α-methylhydroxystyrene, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide and N-p-hydroxyphenyl Maleic acid imine.

These polymerizable unsaturated monomers having a phenolic hydroxyl group may be used singly or in combination of two or more.

Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprene disulfonic acid and p-styrenesulfonic acid.

These polymerizable unsaturated monomers having a sulfonic acid group may be used singly or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include a macromonomer having a mono(meth)acrylonitrile group at the end of the polymer chain (hereinafter referred to as "macromonomer"), such as polystyrene, poly(meth)acrylic acid. Ester, n-butyl poly(meth)acrylate and polyoxyalkylene; N-aryl maleimide, such as N-phenyl maleimide, N-o-hydroxyphenyl cis Butylene diimide, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl maleic acid Imine, N-m-methylphenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl-butylene Amine, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide, and N-substituted maleimide, such as N - cyclohexyl maleimide; an aromatic vinyl compound such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorobenzene Ethylene, o-methoxy styrene, -methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl Glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; hydrazine, such as hydrazine and 1-methyl hydrazine; unsaturated carboxylic acid esters such as (methyl) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (A) Base) butyl acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate , cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxybisethylene Alcohol ) Acrylate, methoxy reference glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, (meth) acrylate Ester, dicyclopentadienyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate and glycerol mono(meth)acrylate; unsaturated alkyl amide of carboxylic acid, such as 2-Aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-dimethylamine (meth)acrylate Propyl propyl ester, 3-aminopropyl (meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; unsaturated glycidyl carboxylate such as glycidyl (meth)acrylate; Vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether Vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; unsaturated decylamines such as (meth) acrylamide, α-chloropropenylamine and N-2- Hydroxyethyl (meth) acrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

In the present invention, the other alkali-soluble resin is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter referred to as a "carboxy group-containing copolymer"), and more preferably a monomer below. Copolymer of the mixture: (a) a carboxyl group-containing unsaturated monomer containing (meth)acrylic acid and (b) at least one selected from the group consisting of polystyrene macromonomers, polymethylmethacrylate macromonomers, N-phenyl groups Maleimide, N-cyclohexylmethyleneimine, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, and glycerol (meth)acrylate, and optionally (c) at least one selected from the group consisting of styrene, α-methylstyrene, methyl (meth)acrylate, allyl (meth)acrylate, and phenyl (meth)acrylate.

The Mw of the other alkali-soluble resin is preferably from 2,000 to 300,000, more preferably from 3,000 to 100,000. Mn is preferably from 1,000 to 60,000, more preferably from 2,000 to 25,000.

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

In the present invention, the total amount of the alkali-soluble resin is preferably from 10 to 1,000 parts by weight, more preferably from 20 to 500 parts by weight, per 100 parts by weight of the coloring agent (A). When the total amount of the alkali-soluble resin is less than 10 parts by weight, alkali developability may be lowered, or contamination or film residue may be generated on the substrate or the light-shielding layer of the unexposed portion. When the total amount is more than 1,000 parts by weight, the concentration of the colorant becomes relatively low, and it may be difficult to achieve the target color density of the film.

The amount of the side chain unsaturated alicyclic polyester in the alkali-soluble resin is preferably from 10 to 100% by weight, more preferably from 20 to 100% by weight. When the amount of the side chain unsaturated alicyclic polyester is less than 10% by weight, the effects to be achieved by the present invention may be impaired.

-Component (C)-

The component (C) of the present invention is a polyfunctional monomer having two or more polymerizable unsaturated bonds in the molecule.

Examples of the polyfunctional monomer include alkanediols such as di(meth)acrylates of ethylene glycol and propylene glycol; polyalkylene glycols such as di(meth)acrylates of polyethylene glycol and polypropylene glycol a poly(meth) acrylate having a polyhydric alcohol having 3 or more hydroxyl groups and a dicarboxylic acid-modified product thereof such as glycerin, trimethylolpropane, isovaerythritol and diisopentaerythritol; (Meth) acrylates, such as polyesters, epoxies, urethane resins, alkyds, polyoxyxides, and spiro resins; polymers having hydroxyl groups at both ends, such as at both ends Hydroxy poly-1,3-butadiene, polyisoprene with hydroxyl groups at both ends, and di(meth)acrylate of polycaprolactone having hydroxyl groups at both ends; and phosphoric acid tri[ 2-(Methyl)propenyloxyethyl]ester.

Among these polyfunctional monomers, polyhydric alcohols having 3 or more hydroxyl groups and poly(meth)acrylates thereof modified by dicarboxylic acid are preferred, and examples thereof include trimethylolpropane triacrylate. Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, diisoamyl Tetraol pentaacrylate, diisopentyl alcohol pentamethacrylate, diisopentyl alcohol hexaacrylate, diisopentyl alcohol hexamethacrylate, and represented by the following formulas (13) and (14) Compound.

Among these compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate and diisopentyl alcohol hexaacrylate are particularly preferred because they provide excellent strength and surface smoothness, and are extremely less than unexposed. A dyed layer of stained or film residue is formed on a portion of the substrate or light-shielding layer.

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

The amount of the polyfunctional monomer of the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). When the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the dye layer may be lowered, and when the amount is more than 500 parts by weight, the alkali developability may be lowered, or the unexposed portion may be Contamination or film residue may form on the substrate or light-shielding layer.

In the present invention, the polyfunctional monomer can be used in combination with a monofunctional monomer having a polymerizable unsaturated bond in the molecule.

Examples of the aforementioned monofunctional monomer include the carboxyl group-containing unsaturated monomer and the compound represented by the copolymerizable unsaturated monomer in the other alkali-soluble resin, N-(methyl)propenylmorpholine, N- Vinylpyrrolidone, N-vinyl-ε-caprolactam, and commercially available M-5600 (trademark of Toagosei Chemical Industry Co., Ltd.).

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

The amount of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. When the amount of the monofunctional monomer is more than 90% by weight, the strength and surface smoothness of the resulting dyed layer may become unsatisfactory.

The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 300 parts by weight, per 100 parts by weight of the alkali-soluble resin (B). When the total amount is less than 5 parts by weight, the strength and surface smoothness of the dye layer may be lowered, and when the total amount is more than 500 parts by weight, the alkali developability may be lowered, or the unexposed portion of the substrate or the light shielding layer may be Contamination or film residue may form on the surface.

- (D) Photosensitive free radical generator -

The photoactive radical generating agent (D) of the present invention is a compound which forms a radical upon exposure to radiation such as visible light radiation, ultraviolet radiation, far ultraviolet radiation, charged particle radiation or X-radiation, and the radical can initiate the aforementioned multiple Polymerization of a functional monomer (C) and optionally a monofunctional monomer.

The photoactive radical generator of the present invention is preferably a compound represented by the following formula (4) or (5) (hereinafter referred to as "carbazole-based compound (D1)").

[In the formulae (4) and (5), each R ³ is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ⁴ is independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and R ⁵ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R ⁶ , R ⁷ and R ⁸ are independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, which is limited by each of R ³ , R ⁴ , R ⁵ , R ^6. The alkyl group represented by R ⁷ and R ⁸ may be substituted by a substituent selected from a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. The phenyl group represented by R ³ and R ⁴ may be a linear, branched or cyclic alkane having from 1 to 6 carbon atoms selected from a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. The substituents of the oxy group and the halogen atom are substituted. ]

In the formulae (4) and (5), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms represented by R ³ , R ⁴ and R ⁵ include a methyl group, an ethyl group, and the like. N-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, positive Eleven carbon, n-dodecyl, cyclopentyl and cyclohexyl.

Examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by R ⁶ , R ⁷ and R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl Base, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl and cyclohexyl.

And having 1 to 6 carbons in the alkyl group represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ and the substituent on the phenyl group represented by R ³ and R ⁴ The linear, branched or cyclic alkoxy group of the atom includes, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group and a third butoxy group, and the halogen atom system includes For example, a fluorine atom and a chlorine atom.

Among the substituents on the phenyl group represented by R ³ and R ⁴ , a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms includes, for example, a methyl group, an ethyl group, a n-propyl group or a different alkyl group. Propyl, n-butyl and tert-butyl. One or more substituents of the same or different type may be present on the alkyl group and the phenyl group.

In the formulae (4) and (5), R ^{3 is} preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or phenyl, and R ^{4 is} preferably a hydrogen atom, a methyl group or a methyl group. Base, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl, R ^{5 is} preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl Or a n-butyl group, and each of R ⁶ , R ⁷ and R ^{8 is} preferably a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group.

Preferred examples of the carbazole-based compound (D1) include 1-[9-ethyl-6-benzamide-9.H.-oxazol-3-yl]-decane-1,2 -decane-2-indole-O-benzoate, 1-[9-ethyl-6-benzoguanidine-9.H.-oxazol-3-yl]-nonane-1,2-anthracene Alkan-2-indole-O-acetate, 1-[9-ethyl-6-benzamide-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2 -肟-O-acetate, 1-[9-ethyl-6-benzamide-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1- [9-Ethyl-6-(2-methylbenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9- Ethyl-6-(1,3,5-trimethylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate and 1- [9-n-Butyl-6-(2-ethylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate.

1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane in the carbazole-based compound (D1) 1- Ketone oxime-O-acetate is particularly preferred.

In the present invention, the carbazole-based compound (D1) may be used singly or in combination of two or more.

In the present invention, a photoradical generating agent other than the carbazole-based compound (D1) (hereinafter referred to as "another photoradical generating agent") can be used. The other photoactive radical generating agent is, for example, a compound based on biimidazole, a compound based on benzoin, a compound based on acetophenone, and a compound based on benzophenone. A compound of α-diketone as a substrate, a compound having a polycyclic oxime as a substrate, a compound having a xanthone as a substrate, a compound having a phosphine as a substrate or a compound A compound which is a substrate having at least one main skeleton represented by the following formula (15-1), (15-2) or (15-3).

Examples of the aforementioned biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. , 2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-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'-biimidazole, 2 , 2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole and 2,2'-bis(2,4,6- Tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Among these compounds which are based on biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole, 2,2 '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole and 2,2'-bis(2,4,6-trichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferred, and 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-Tetraphenyl-1,2'-biimidazole is preferred.

- Hydrogen donor -

When a biimidazole-based compound is used as the photoradical generating agent of the present invention, it is preferably used in combination with the following hydrogen donor to further improve the sensitivity.

The term "hydrogen donor" as used in the present invention means a compound which can provide a radical in which a hydrogen atom is supplied from the biimidazole-based compound upon exposure.

The hydrogen donor is preferably a thiol-based compound or an amine-based compound as defined below.

The above-mentioned thiol-based compound is a benzene ring or a heterocyclic ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 or 2 thiol groups directly bonded to the mother nucleus. Compound (hereinafter referred to as "thiol-based hydrogen donor").

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

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

These hydrogen donors are described in detail below.

The thiol-based hydrogen donor may have at least one benzene ring or heterocyclic ring or both. When it has two or more of such rings, a fused ring can be formed.

When the thiol-based hydrogen donor has two or more thiol groups, at least one of the other thio groups may be alkyl, aralkyl or aryl as long as at least one free thiol group is retained. Substituted by the base. Further, as long as at least one free thiol group is retained, the thiol-based hydrogen donor may have a structural unit in which two sulfur atoms are bonded via a divalent organic group (such as an alkylene group) or two of them A structural unit in which an atom is bonded in the form of a disulfide.

Further, the thiol-based hydrogen donor may be substituted at a position other than the thiol group (etc.) by a carboxy group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. Substituted phenoxycarbonyl or nitrile group.

Examples of such thiol-based hydrogen donors include 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2,5-dihydrogen. Thio-1,3,4-thiadiazole and 2-hydrothio-2,5-dimethylaminopyridine.

Among these hydrogen donors having a thiol as a substrate, 2-hydrothiobenzothiazole and 2-hydrothiobenzoxazole are preferred, and 2-hydrothiobenzothiazole is particularly preferred.

The amine-based hydrogen donor may have at least one benzene ring or heterocyclic ring or both. When it has two or more of such rings, a fused ring can be formed.

At least one amine group of the amine-based hydrogen donor may be substituted with an alkyl group or a substituted alkyl group. The amine-based hydrogen donor may be substituted at a position other than the amine group (etc.) by a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted benzene group. Oxycarbonyl or nitrile group.

Examples of the aforementioned amine-based hydrogen donor include 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. 4-Diethylaminoethenylbenzene, 4-dimethylaminopropyl phenyl benzene, ethyl-4-dimethylamino benzoate, 4-dimethylaminobenzoic acid isoprene Ester, 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile.

Among these amine-based hydrogen donors, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are preferred. And 4,4'-bis(diethylamino)benzophenone is particularly preferred. 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone can be used alone as a photoradical generator, even when bi-imidazole When the compound as a substrate is not present.

In the present invention, the aforementioned hydrogen donors may be used singly or in combination of two or more. It is preferred to use at least one thiol-based hydrogen donor and at least one amine-based hydrogen donor composition because the resulting dyed layer hardly detaches from the substrate during development and has High strength and sensitivity.

Preferred examples of the composition of the thiol-based hydrogen donor and the amine-based hydrogen donor include 2-hydrothiobenzothiazole and 4,4'-bis(dimethyl Composition of amino)benzophenone, composition of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone, 2-hydrothiobenzoxazole And a composition of 4,4'-bis(dimethylamino)benzophenone and 2-hydrothiobenzoxazole and 4,4'-bis(diethylamino)benzophenone combination. Compositions of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone and 2-hydrothiobenzoxazole and 4,4' in such compositions A compound of bis(diethylamino)benzophenone is preferred, and a combination of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone is particularly preferred.

In the composition of the thiol-based hydrogen donor and the amine-based hydrogen donor, the weight of the thiol-based hydrogen donor relative to the amine-based hydrogen donor The preferred system is 1:1 to 1:4, preferably 1:1 to 1:3.

Examples of the aforementioned benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, and methyl 2-benzoin benzoate.

Examples of the above-mentioned acetophenone-based compound include 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, and 2,2-dimethoxy-2-phenyl. Ethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-(4-methylthiophenyl-2-morpholine-1-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl) Ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl)butan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1 , 2-diphenylethan-1-one.

Examples of the aforementioned diphenyl ketone as a substrate compound include 4,4'-bis(dimethylamino)diphenyl ketone and 4,4'-bis(diethylamino)diphenyl. Ketone.

Examples of the aforementioned α-diketone as a substrate compound include diethyl fluorenyl, diphenylmethyl decyl and methyl benzhydrylcarboxylate.

Examples of the above-mentioned polycyclic guanidine as a substrate compound include hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and 1,4-naphthoquinone.

Examples of the aforementioned xanthone as a substrate compound include xanthone, thioxanthone, and 2-chloroxanthone.

Examples of the aforementioned phosphine-based compound include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and 2,4,6-trimethylbenzhydryldiphenylphosphine oxide. .

The aforementioned three Examples of the substrate compound include a halogenated methyl group a compound such as 2,4,6-tris(trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three A compound of the following formulas (16) and (17).

In the present invention, the photoradical generating agent may be used singly or in combination of two or more.

In the present invention, the photo-sensitive radical generating agent may be used together with at least one sensitizer, a curing accelerator, and a polymer photocrosslinking/sensitizer as needed.

In the present invention, the amount of the photoradical generating agent is preferably 0.01 to 200 parts by weight based on 100 parts by weight of the polyfunctional monomer (C) or the total of the polyfunctional monomer and the monofunctional monomer. The number is more preferably from 1 to 120 parts by weight, particularly from 1 to 100 parts by weight. When the amount of the photoradical generating agent is less than 0.01 parts by weight, the curing by exposure is incomplete, and it may be difficult to obtain a pattern array having a predetermined pixel pattern or a black matrix pattern. When the amount is more than 200 parts by weight, the formed dye layer is liable to be detached from the substrate during development or to cause substrate contamination or residual film or the like on the substrate or the light-shielding layer of the unexposed portion.

When the carbazole-based compound (D1) and another photoradical generating agent are combined as a photoradical generating agent in the present invention, the amount of the other photoradical generating agent is based on the carbazole The total amount of the compound (D1) and the other photoradical generating agent is preferably 50% by weight or less, more preferably 30% by weight or less.

-additive-

The radiation-sensitive composition of the present invention for forming the dyed layer of the present invention may optionally contain various additives.

The aforementioned additives include organic acids or organic amine-based compounds (excluding the aforementioned hydrogen donors) to further improve the solubility of the radiation-sensitive composition in the alkali developer and further suppress the generation of insoluble products remaining after development.

The above organic acid is preferably an aliphatic carboxylic acid having at least one carboxyl group in the molecule or a carboxylic acid having a phenyl group.

Examples of the aforementioned aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; dicarboxylic acids such as oxalic acid. , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, azelaic acid, basic acid, methylmalonic acid, ethylmalonic acid, dimethyl Malonic acid, methyl succinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, isaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; and tricarboxylic acid Such as glycerol tricarboxylic acid, aconitic acid and camphorone acid.

The phenyl group-containing carboxylic acid is, for example, a compound having a carboxyl group directly bonded to a phenyl group or a carboxylic acid having a phenyl group bonded via a carbon chain.

Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, lauric acid, benzotricarboxylic acid, and dimethylbenzoic acid; aromatic dicarboxylic acids such as phthalic acid, Isophthalic acid and terephthalic acid; aromatic polycarboxylic acids having 3 or more carboxyl groups, such as trimellitic acid, trimellitic acid, pyromellitic acid and pyromellitic acid; and phenylacetic acid, hydrogenated Oleic acid, hydrogenated cinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamic acid, coumaric acid and umbrella acid.

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

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

The amount of the organic acid is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total radiation-sensitive composition. When the amount of the organic acid is more than 15% by weight, the adhesion of the formed dye layer to the substrate may be lowered.

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

Examples of the aforementioned aliphatic amines include mono(cyclo)alkylamines such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, tert-butylamine, positive Amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methyl Cyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, and 4-ethylcyclohexylamine; di(cyclo)alkyl An amine such as a methyl group. Ethylamine, diethylamine, methyl. N-propylamine, ethyl. N-propylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-isobutylamine, di-secondbutylamine, di-t-butylamine, two - n-pentylamine, d-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and dicyclohexylamine; tri(cyclo)alkylamines such as dimethyl. Ethylamine, methyl. Diethylamine, triethylamine, dimethyl. N-propylamine, diethyl. N-propylamine, methyl. Di-n-propylamine, ethyl. Di-n-propylamine, tri-n-propylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-tert-butylamine, tri-tert-butylamine , tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, and tricyclohexylamine; Alkanolamines, such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentane Alcohol, 6-amino-1-hexanol and 4-amino-1-cyclohexanol; di(cyclo)alkanolamines, such as diethanolamine, di-n-propanolamine, di-isopropanolamine, two - n-butanolamine, di-isobutanolamine, di-n-pentanolamine, di-n-hexanolamine and bis(4-cyclohexanol)amine; tri(cyclo)alkanolamines, such as triethanolamine, tri- N-propanolamine, tri-isopropanolamine, tri-n-butanolamine, tri-isobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine and tris(4-cyclohexanol)amine; amine Alkane (cyclo)alkane, such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amine -1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexane Alkanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propane Alcohol and 2-diethylamino-1,3-propanediol; amine-containing cycloalkane methanol, such as 1-aminocyclopentane methanol, 4-aminocyclopentane methanol, 1-amino ring Hexane methanol, 4-aminocyclohexane methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexane methanol and 4 - diethylaminocyclohexane methanol; and an aminocarboxylic acid such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutylene Acid, 3-aminoisobutyric acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid and 4- Aminocyclohexanecarboxylic acid.

The phenyl group-containing amine is, for example, a compound having an amine group directly bonded to a phenyl group or a compound having an amine group bonded to a phenyl group via a carbon chain.

Examples of the phenyl group-containing amine include aromatic amines such as aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4- Isopropylaniline, 4-n-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, N,N-dimethylaniline, N,N-diethylaniline and 4-methyl-N,N-dimethylaniline; aminobenzyl alcohol such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethyl Aminobenzyl alcohol and 4-diethylaminobenzyl alcohol; and aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol and 4-Diethylaminophenol.

Among these organic amine-based compounds, mono(cyclo)alkanolamines and amines from the viewpoints of solubility in a solvent described below and prevention of contamination or film residue on a substrate or a light-shielding layer of an unexposed portion Alkyl (cyclo)alkane is preferred, and 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-Amino-1,3-propanediol and 4-amino-1,2-butanediol are particularly preferred aliphatic amines. Aminophenol is preferred, and 2-aminophenol, 3-aminophenol and 4-aminophenol are particularly preferred phenylamine-containing amines.

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

The amount of the organic amine-based compound is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total radiation-sensitive composition. When the amount of the organic amine-based compound is more than 15% by weight, the adhesion of the formed dye layer to the substrate may be lowered.

The additives other than the aforementioned organic acid and organic amine-based compound include a dispersing aid such as a blue pigment derivative or a yellow pigment derivative such as a copper phthalocyanine derivative; a filler such as glass or alumina; a polymer compound , such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or poly(fluoroalkyl acrylate); nonionic, cationic or anionic surfactant; adhesion accelerators, such as vinyl trimethoxy decane, Vinyl triethoxy decane, vinyl tris(2-methoxyethoxy)decane, N-(2-aminoethyl)-3-aminopropyl. methyl. Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Baseline, 3-glycidoxypropyl. methyl. Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl. methyl. Dimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-hydrothiopropyltrimethoxynonane; antioxidants such as 2,2 '-Thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; UV absorbers such as 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; adhesion inhibitors such as sodium polyacrylate; and thermal radical generators such as 1,1'-azo Bis(cyclohexane-1-carbonitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent

The radiation-sensitive composition for forming a dye layer of the present invention comprises the above components (A) to (D) as a basic component and optionally the aforementioned additives, usually mixed with a solvent to prepare a liquid composition.

A suitable solvent may be selected and used as long as it disperses or dissolves the components (A) to (D) and additives constituting the radiation-sensitive composition, does not react with such components, and has appropriate volatility.

Examples of the solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl Ether, bisethylene glycol monomethyl ether, bisethylene glycol monoethyl ether, bisethylene glycol mono-n-propyl ether, bisethylene glycol mono-n-butyl ether, ginseng ethylene monomethyl Ether, propylene 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 monomethyl ether, dipropylene glycol single B Ethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetate, such as Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, bisethylene glycol monomethyl ether acetate, bisethylene glycol monoethyl ether acetate, propylene glycol monomethyl Ether acetate and propylene glycol monoethyl ether acetate; other ethers such as bisglycol dimethyl ether, bisethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketone, Such as Methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactate such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycol Ester, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate , n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid Isopropyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate and ethyl 2-oxybutyrate; Aromatic hydrocarbons such as toluene and xylene; and decylamine and decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidinone.

From the viewpoints of solubility, pigment dispersibility, and coatability, among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl Ethyl acetate, diethylene glycol dimethyl ether, bisethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionic acid Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, formic acid N-amyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate are particularly preferred.

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

In addition, high boiling solvents such as benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, caproic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl b Acid ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate or ethylene glycol monophenyl ether acetate It can be used in combination with the aforementioned solvent.

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

The amount of the solvent is not particularly limited, but from the viewpoint of the coatability and stability of the resulting radiation-sensitive composition, it is desirable to determine the total amount of all components except the solvent of the composition to be preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight.

Color filter

The color filter of the present invention has a dyed layer formed from the radiation-sensitive composition of the present invention for forming a dyed layer.

A method of forming a dyed layer in the color filter of the present invention is described below.

Forming a light-shielding layer on the surface of the substrate as appropriate to define a portion for forming a pixel, applying a liquid radiation-sensitive composition (including, for example, a red pigment dispersed therein) to the substrate, pre-baking to evaporate the solvent, A coating film is formed. The coating film is then exposed to radiation via a reticle, developed with an alkali developer, dissolved and removed from the unexposed portions of the coating film, and post-baked to form a pixel array having a predetermined red pixel pattern.

Thereafter, the same method is applied to apply, pre-baking, exposing, developing, and post-baking the liquid radiation-sensitive composition containing the green and blue pigment dispersed therein to form a green pixel array and blue on the same substrate in sequence. The color pixel array is used to obtain a color filter having an array of red, green, and blue pixels on the substrate. The order in which the present invention forms a color pixel is not limited to the foregoing.

The black matrix can likewise be formed using a liquid radiation-sensitive composition comprising, for example, a black pigment dispersed therein.

The substrate used to form the pixel and/or black matrix is made of glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamido-imine or polyimine.

The substrate may optionally be pretreated, such as by chemical treatment with a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction or vacuum deposition.

When the liquid radiation-sensitive composition is applied to the substrate, a suitable coating technique such as spraying, roll coating, spin coating (spin coating), slit extrusion coating, bar coating or spraying may be employed. Ink coating method. Among these methods, a spin coating method and a slit extrusion coating method are preferred.

The thickness of the coating film after drying is preferably from 0.1 to 10 μm, more preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm.

The radiation used to form the pixel and/or black matrix is selected from the group consisting of visible radiation, ultraviolet radiation, far ultraviolet radiation, electron beams, and X-rays. Among such radiations, radiation having a wavelength of 190 to 450 nm is preferred.

The radiation dose is preferably from 10 to 10,000 J/m ² .

The alkali developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene or An aqueous solution of 1,5-diazabicyclo-[4.3.0]-5-pinene.

A suitable amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the aforementioned alkali developer. The coating film is preferably washed with water after alkali development.

Spray development, spray development, dip (immersion) development or retort development can be employed. As the developing conditions, the coating film is preferably developed at room temperature for 5 to 300 seconds.

The obtained color filter of the present invention can be extremely effectively used for a transmissive and reflective type color liquid crystal display device, a color photographing device, a color sensor, and the like.

Color liquid crystal display device

The color liquid crystal display device of the present invention comprises the color filter of the present invention.

As an example of the color liquid crystal display device of the present invention, a radiation-sensitive composition for forming a dye layer of the present invention can be used to form a pixel and/or a black matrix on a thin film transistor substrate array as described above to produce an excellent characteristic. Color liquid crystal display device.

The radiation-sensitive composition for forming a dye layer of the present invention comprises the aforementioned components (A) to (D) as a basic component. Particularly preferred examples of compositions (i) through (iv) are described below.

(i) a radiation-sensitive composition for forming a dye layer comprising an esterification reaction between a diol compound containing a di(meth)acrylonitrile group and a tetracarboxylic dianhydride (8) and having 3,000 to 100,000 Mw of polyester (1) as alkali-soluble resin (B) (ii) radiation-sensitive composition (i) for forming a dye layer, which comprises a solvent selected from trimethylolpropane triacrylate, isoprene Alcohol triacrylate and diisopentaerythritol hexaacrylate as the polyfunctional monomer (C) (iii) used to form the dye-sensitive layer of the radiation-sensitive composition (i) or (ii), which comprises 1-[ 9-ethyl-6-(2-methylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-acetate as a substrate with carbazole a compound (D1) which is a photo-sensitive radical generating agent (D) (iv) for forming a dye-sensitive layer of the radiation-sensitive composition (i), (ii) or (iii), which comprises an organic pigment and/or Carbon black as a coloring agent (A).

Preferably, the color filter (v) of the present invention has a pixel and/or a black matrix prepared from the radiation-sensitive composition (i), (ii), (iii) or (iv) used to form the dye layer.

Preferably, the color liquid crystal display device (vi) of the present invention comprises the aforementioned color filter (v), and more preferably, the color liquid crystal display device (vii) of the present invention comprises the aforementioned color filter (on the thin film transistor substrate array) ( v).

As described above, the radiation-sensitive composition for forming a dyed layer of the present invention can form an excellent pixel pattern and a black matrix pattern at a low exposure dose even when a high-concentration pigment is contained, without being exposed at the time of development. A portion of the substrate or the light-shielding layer leaves an insoluble product and a floating film is formed on the edge of the pixel pattern and the black matrix pattern.

Further, the pixel and the black matrix obtained by the radiation-sensitive composition for forming a dye layer of the present invention have high surface smoothness and are excellent in adhesion to a substrate.

Accordingly, the radiation-sensitive composition of the present invention for forming a dyed layer is highly advantageous for the manufacture of various types of color filters, such as color filters for use in color liquid crystal display devices in the electronics industry.

Example

The following examples are intended to further illustrate the invention but are not to be construed as limiting. The "parts" used in the present invention means parts by weight.

<Manufacture of alkali soluble resin> Synthesis Example 1 (Synthesis of diglycidyl etherified product of diphenol)

1,070 g of diphenol (9) and diphenol (10) in a weight ratio of 70:30 (trademark: YP-90, manufactured by Yasuhara Chemical Co., Ltd.), 1,520 g of epichlorohydrin, and 1,700 g of dimethyl The argon feed device was placed in a flask equipped with a cooling tube and a stirrer, heated to dissolve at 50 ° C under agitation, and 290 g of caustic soda was added to carry out a reaction at 65 to 90 ° C for 10 hours. The progress and the end of the reaction were confirmed by measuring the epoxy equivalent. After the epoxy equivalent reached the target value, the solvent was distilled off under reduced pressure at 90 to 100 °C. Thereafter, the reaction product was again dissolved in toluene at 50 to 70 ° C, distilled water was added to rinse the reaction product, and the mixture was separated, and then the solvent was removed from the organic layer under reduced pressure to obtain 1,260 g of a reaction product. The resulting reaction product had 260 epoxy equivalents.

When the ¹ H-NMR spectrum of the reaction product (solvent: CDCl ₃ , based on tetramethylnonane, the same applies hereinafter), the peak was found at the following chemical shift: δ (ppm) 6.8 to 7.3 (self-bonded to the cyclohexane skeleton) Derivatized by a benzene ring; 8H), 3.3 and 3.9 to 4.2 (derived from an epoxy group; 6H) and 0.7 to 0.9 (derived from a bis group bonded to an isopropyl group of a cyclohexyl skeleton).

When the infrared absorption spectrum (IR) was measured, the absorption was found to be 1,241 cm ^-1 (derived from an aromatic ether structure and an epoxy group) and 1,036 and 828 cm ^-1 (derived from an aromatic ether structure).

From the foregoing results, it was confirmed that the reaction product was a mixture of the diglycidyl etherification product represented by the above formula (11) and the diglycidyl etherification product represented by the above formula (12).

Synthesis Example 2 (Synthesis of a diol compound containing a dimethyl methacrylate group)

1,000 g of a mixture of the diglycidyl etherified product obtained in Synthesis Example 1, 1,350 g of methacrylic acid and 1.0 g of hydroquinone monomethyl ether were fed into a flask equipped with a cooling tube and a stirrer under agitation After heating to dissolve at 60 ° C, 8 g of tetraethylammonium bromide was added to carry out the reaction at 70 to 90 ° C with stirring until the acid value and epoxy equivalent of the reaction product became 8 mg KOH / gram and 17,000 each. Thereafter, the end of the reaction was confirmed by the acid value and the epoxy group equivalent, and then cooled to room temperature to obtain 1,300 g of a reaction product. The resulting reaction product had an acid value of 8 mg KOH/g, a hydroxyl value of 165 mg KOH/g and an epoxy equivalent of 17,000.

When the ¹ H-NMR spectrum of the reaction product was measured, peaks were found at the following chemical shifts: δ (ppm) 5.6 and 6.1 (derived from a double bond of methacrylic acid; 4H), and 3.9 to 4.4 (diglycidyl etherified product) The peaks of the mixture at 3.3 and 3.9 to 4.2 are displaced by the ring opening of the epoxy group; 10H).

When the infrared absorption spectrum (IR) was measured, the absorption was found below: 1,720 cm ^-1 (derived from an aliphatic ester structure).

From the above results, it was confirmed that the reaction product was a dimethyl propylene group-containing diol compound represented by the following formula (6-1) and a dimethyl methacrylate group represented by the following formula (7-1). a mixture of alcohol compounds.

Synthesis Example 3 (Synthesis of a diol compound containing a dipropylene fluorenyl group)

1,200 g of a mixture of a diol compound containing a dipropylene fluorenyl group represented by the following formula (6-2) and a diol compound containing a dipropylene fluorenyl group represented by the following formula (7-2) is produced in the same manner as in Synthesis Example 2. In this case, 293 g of acrylic acid was used instead of methacrylic acid. The resulting mixture had an acid value of 6 mg KOH/g, a hydroxyl value of 171 mg KOH/g and an epoxy equivalent of 16,500.

Synthesis Example 4 (Manufacture of Polyester (1))

670 g of the mixture containing the dimethyl propylene decyl diol compound prepared in Synthesis Example 2 and 1,300 g of methyl isobutyl ketone were fed into a flask equipped with a cooling tube and a stirrer, and heated to dissolve at 60 ° C with stirring. 220 g of benzenetetracarboxylic anhydride (manufactured by Daicel Chemical Industries, Ltd.) represented by the above formula (8-1) was added, and the reaction was carried out under stirring at 80 ° C until the average acid value of the obtained reaction product became 67.9 mg KOH / The change in acid value is changed to 2 mg KOH/g or less. After the completion of the reaction, distilled water was added to the reaction solution to carry out rinsing, and the mixture was allowed to stand for separation. Then, the solvent was distilled off from the organic layer under reduced pressure at 50 to 70 ° C to obtain 860 g of a resin. The obtained resin had an acid value of 18,000 Mw and 61.2 mg KOH/g.

When the ¹ H-NMR spectrum of the resin was measured, the peak was found at the following chemical shift: δ (ppm) 6.9 to 7.6 (derived from a benzene ring bonded to a benzene ring of a cyclohexane skeleton and a benzenetetracarboxylic acid), 5.8 and 6.2 (derived from the double bond of methacrylic acid), 1.1 to 2.2 (derived from the cyclohexane skeleton) and 0.7 to 0.9 (derived from the dimethyl group bonded to the 2,2-propanyl group of the cyclohexyl skeleton: 6H).

When the infrared absorption spectrum (IR) was measured, the absorption was found to be 1,735 cm ^-1 (derived from an aliphatic ester structure) and 1,735 cm ^-1 , 1,241 cm ^-1 and 1,102 cm ^-1 (derived from an aromatic ester structure).

From the above results, it was confirmed that the resin was the polyester (1) represented by the following formula (1-1).

This polyester (1) is referred to as an alkali-soluble resin (B-1).

[In the formula (1-1), the X system is as defined in the above formula (1). ]

Synthesis Example 5 (manufacture of polyester (1))

840 g of the polyester (1) represented by the following formula (1-2) was obtained in the same manner as in Synthesis Example 4, except that a mixture of a dipropylene-based diol compound obtained in Synthesis Example 3 was used. A mixture of the methacryl oxime group-containing diol compound obtained in Synthesis Example 2. The obtained polyester (1) had an Mw of 15,000 and an acid value of 60.9 mgKOH/g.

This polyester (1) is referred to as an alkali-soluble resin (B-2).

[In the formula (1-2), the X system is as defined in the above formula (1). ]

Synthesis Example 6 (Manufacture of carboxyl terminated polyester (1))

275 g of the polyester (1) obtained in Synthesis Example 4 and 275 g of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, and heated to dissolve at 60 ° C with stirring, and 1.5 was added. Tetraethylammonium bromide and 30 g of phenyl glycidyl ether (Epiol P, NOF Corporation) (as a carboxyl endcapping agent) were reacted at 80 to 90 ° C with stirring until the acid value changed to 2 mg KOH. / gram or less. After the reaction was completed, the reaction product was cooled to room temperature to obtain 300 g of a resin. The resulting resin had an acid value of 21,000 Mw and 52.1 mg KOH/g.

When the ¹ H-NMR spectrum of this resin was measured, in addition to the peak of the polyester (1) obtained in Synthesis Example 4, the peak was found at the following chemical shift: δ (ppm) 6.9 to 7.6 (from phenyl glycidyl ether) Benzene ring derived).

When the infrared absorption spectrum (IR) was measured, the absorption was found below: 1,047 cm ^-1 (derived from an aromatic ester structure). This absorption was stronger than the polyester (1) obtained in Synthesis Example 4 because of the blocking of the carboxyl group.

From the foregoing results, it was confirmed that the resin was a polyester (1) having a structure in which 78% of hydrogen atoms of a carboxyl group in the above formula (1-1) were blocked (-CH ₂ CH(OH)CH ₂ OC ₆ H ₅ ) replaced.

This polyester (1) is referred to as an alkali-soluble resin (B-3).

Synthesis Example 7 (Production of Carboxyl terminated polyester (1))

340 g of the resin was obtained in the same manner as in Synthesis Example 6, except that 300 g of the polyester (1) obtained in Synthesis Example 5 was used instead of the polyester (1) obtained in Synthesis Example 4. The resin obtained from the obtained resin had an acid value of 25,000 Mw and 50.0 mg KOH/g.

This polyester (1) is referred to as an alkali-soluble resin (B-4).

Synthesis Example 8 (manufacture of polyester (1))

670 g of the mixture containing the dimethyl propylene decyl diol compound prepared in Synthesis Example 2 and 1,470 g of methyl isobutyl ketone were fed into a flask equipped with a cooling tube and a stirrer, and heated to dissolve at 60 ° C with stirring. 313 g of diphenyl ether tetracarboxylic anhydride (manac Co., Ltd.) represented by the above formula (8-2) was added, and the reaction was carried out under stirring at 80 ° C until the acid value became 53.3 mg KOH / g or Lower. After the completion of the reaction, distilled water was added to the reaction solution to carry out rinsing, and the mixture was allowed to stand for separation. Thereafter, the solvent was distilled off from the organic layer under reduced pressure at 50 to 70 ° C to obtain 800 g of a resin. The obtained resin had an acid value of 18,000 Mw and 61.2 mg KOH/g.

This polyester (1) is referred to as an alkali-soluble resin (B-5).

[In the formula (1-3), X is as defined in the above formula (1), and Y ¹ is a residue obtained by removing four carboxyl groups from diphenyl ether tetracarboxylic acid. ]

Synthesis Example 9 (manufacture of polyester (1))

670 g of the mixture containing the dimethyl propylene decyl diol compound prepared in Synthesis Example 2 and 1,660 g of methyl isobutyl ketone were fed into a flask equipped with a cooling tube and a stirrer, and heated to dissolve at 60 ° C with stirring. 434 g of ethylene glycol bis(trimellitic acid ester) dianhydride (manufactured by Nippon Rika Co., Ltd.) represented by the above formula (8-3) was added, and the reaction was carried out at 80 ° C with stirring until the acid value It became 46.2 mg KOH/g. After the completion of the reaction, distilled water was added to the reaction solution for rinsing, and the mixture was allowed to stand for separation. Then, the solvent was distilled off from the organic layer under reduced pressure at 50 to 70 ° C to obtain 900 g of a resin. The obtained resin had a Mw of 13,000 and was a polyester (1) represented by the following formula (1-4).

This polyester (1) is referred to as an alkali-soluble resin (B-6).

[In the formula (1-4), X is as defined in the above formula (1), and Y ² is a residue obtained by removing four carboxyl groups from ethylene glycol bis(trimellitic acid ester). ]

Synthesis Example 10 (Production of Control Alkali Soluble Resin)

4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, and sent to the flask. 12 parts of methacrylic acid, 18 parts of styrene, 24 parts of benzyl methacrylate, 30 parts of N-phenyl maleimide, 16 parts of 2-hydroxyethyl methacrylate and 6.5 parts of α-A The styrene dimer (as a chain transfer agent) was internally purged with nitrogen, and the mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and the temperature was maintained for 3 hours. After the completion of the polymerization, the reaction solution was heated at 100 ° C, 0.5 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and polymerization was further carried out for 1 hour to obtain a solution of an alkali-soluble resin (solid content). 33.2% by weight).

The resulting alkali-soluble resin had a MW of 8,500 and an Mn of 4,500.

This alkali-soluble resin is called an alkali-soluble resin (B-7).

Synthesis Example 11 (Production of Control Alkali Soluble Resin)

2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, and sent in a flask. 10 parts of methacrylic acid, 15 parts of styrene, 30 parts of benzyl methacrylate, 25 parts of N-phenyl maleimide, 20 parts of ω-carboxypolycaprolactone mono(meth)acrylate And 2 parts of α-methylstyrene dimer (as a chain transfer agent), the inside of the flask was purged with nitrogen, and the mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and the temperature was maintained for 3 hours. After the completion of the polymerization, the reaction solution was heated at 100 ° C, 0.5 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and polymerization was further carried out for 1 hour to obtain a solution of an alkali-soluble resin (solid content). 33.1% by weight).

The resulting alkali-soluble resin had a Mw of 20,000 and an Mn of 9,000.

This alkali-soluble resin is called an alkali-soluble resin (B-8).

Synthesis Example 12 (Production of Control Alkali Soluble Resin)

4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were fed into a flask equipped with a cooling tube and a stirrer, and sent to the flask. 10 parts of methacrylic acid, 15 parts of styrene, 40 parts of benzyl methacrylate, 25 parts of N-phenyl maleimide, 10 parts of 2-hydroxyethyl methacrylate and 6.5 parts of α-A The styrene dimer (as a chain transfer agent) was internally purged with nitrogen, and the mixture was gently stirred, and the resulting reaction solution was heated at 80 ° C, and the temperature was maintained for 3 hours. After the completion of the polymerization, the reaction solution was heated at 100 ° C, 0.5 part of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and polymerization was further carried out for 1 hour to obtain a solution of an alkali-soluble resin (solid content). 33.3% by weight).

The resulting alkali-soluble resin had a Mw of 7,800 and an Mn of 4,500.

This alkali-soluble resin is called an alkali-soluble resin (B-9).

Example 1

<Preparation of liquid composition> 8 parts of CI Pigment Red 254 and CI Pigment Red 177 in a weight ratio of 80:20 (as coloring agent (A)), 4 parts (solid content) of EFKA-46 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

87 parts of the obtained pigment dispersion, 8 parts of the alkali-soluble resin (B-1) (as an alkali-soluble resin), 2 parts of diisopentyltetraol hexaacrylate, and 4 parts of isopenic alcohol tetraacrylate (as polyfunctionality) Monomer (C)), 3 parts of 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-oxazol-3-yl]-ethane-1-one oxime- O-acetate (trademark: CGI-242, Chiba Specialty Chemicals Holding Inc., hereinafter the same) (as photo-sensitive radical generator (D)) and 70 parts of methoxybutyl acetate and 96 parts of ethyl-3 Ethoxypropionate (as a solvent) is mixed to prepare a liquid composition (R1).

<Formation of Dye Layer> The liquid composition (R1) was applied to the surface of soda lime glass by a spin coater (this surface has a film of cerium oxide (SiO ₂ ) to prevent dissolution of sodium ions on the surface), and a hot plate at 90 ° C The film was prebaked for 2 minutes to form a 1.2 μm thick coating film.

Thereafter, the substrate was cooled to room temperature, and the coating film was exposed to ultraviolet radiation having a wavelength of 365 nm, 405 nm, and 436 nm through a reticle (slit width: 30 μm) with a high pressure mercury lamp. The exposure amount at this time was 100 J/m ² . The substrate was then immersed in a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C for 45 seconds to develop, rinsed with ultrapure water and air dried. The coating film was then baked in a 230 ° C clean oven for 30 minutes to form a red strip-shaped pixel pattern on the substrate.

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 1-1.

Examples 2 to 5

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (R2) to (R5) were prepared in the same manner as in Example 1, except that the dispersant was changed as shown in Table 1-1.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R2) to (R5) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 or 6 μm was formed.

The foregoing results are shown in Table 1-1.

Example 6

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (R6) was prepared in the same manner as in Example 1, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-2).

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R6) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 1-1.

Examples 7 to 10

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (R7) to (R10) were prepared in the same manner as in Example 6, except that the dispersant was changed as shown in Table 1-1.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R1) to (R10) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 8 μm or 6 μm was formed.

The foregoing results are shown in Table 1-1.

Example 11

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (R11) was prepared in the same manner as in Example 1, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-3).

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R11) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 1-2.

Examples 12 to 15

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (R12) to (R15) were prepared in the same manner as in Example 11 except that the dispersant was changed as shown in Table 1-2.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R12) to (R15) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm or 8 μm was formed.

The foregoing results are shown in Table 1-2.

Example 16

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (R16) was prepared in the same manner as in Example 1, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-4).

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R16) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 1-2.

Examples 17 to 20

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (R17) to (R20) were prepared in the same manner as in Example 16 except that the dispersing agent was changed as shown in Table 1-2.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R17) to (R20) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 8 μm or 6 μm was formed.

The foregoing results are shown in Table 1-2.

Example 21

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (R21) was prepared in the same manner as in Example 1, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-5).

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm was formed.

The foregoing results are shown in Tables 1-3.

Examples 22 to 25

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (R22) to (R25) were prepared in the same manner as in Example 21 except that the dispersing agent was changed as shown in Table 1-3.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R22) to (R25) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 8 μm or 6 μm was formed.

The foregoing results are shown in Tables 1-3.

Example 26

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (R26) was prepared in the same manner as in Example 1, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-6).

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R26) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Tables 1-3.

Examples 27 to 30

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (R27) to (R30) were prepared in the same manner as in Example 26 except that the dispersing agent was changed as shown in Table 1-3.

Thereafter, a red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (R27) to (R30) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 8 μm or 6 μm was formed.

The foregoing results are shown in Tables 1-3.

Example 31

<Preparation of liquid composition> 11 parts of a mixture of CI Pigment Green 36 and CI Pigment Yellow 150 in a weight ratio of 60:40 (as a coloring agent (A)), 4 parts (solid content) EFKA-46 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

90 parts of the obtained pigment dispersion, 8 parts of an alkali-soluble resin (B-1) (as an alkali-soluble resin (B)), 2 parts of diisoamyltetraol hexaacrylate, and 4 parts of isopenic alcohol tetraacrylate (as Polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1- Ketone oxime-O-acetate (as photo-sensitive radical generator (D)) and 70 parts of methoxybutyl acetate and 96 parts of ethyl-3-ethoxypropionate (as solvent) to prepare a liquid Composition (G1).

<Formation of Dye Layer> A green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R1) was replaced by the liquid composition (G-1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 2-1.

Examples 32 to 35

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G2) to (G5) were prepared in the same manner as in Example 31 except that the dispersing agent was changed as shown in Table 2-1.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G2) to (G5) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm or 6 μm was formed.

The foregoing results are shown in Table 2-1.

Example 36

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (G6) was prepared in the same manner as in Example 31, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-2).

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (G6) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 2-1.

Examples 37 to 40

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G7) to (G10) were prepared in the same manner as in Example 36 except that the dispersing agent was changed as shown in Table 2-1.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G7) to (G10) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), side etching was not observed, and a pattern having a line width of 6 μm, 8 μm or 5 μm was formed.

The foregoing results are shown in Table 2-1.

Example 41

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (G11) was prepared in the same manner as in Example 31, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-3).

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (G11) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 2-2.

Examples 42 to 45

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G12) to (G15) were prepared in the same manner as in Example 41 except that the dispersing agent was changed as shown in Table 2-2.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G12) to (G15) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm or 6 μm was formed.

The foregoing results are shown in Table 2-2.

Example 46

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (G16) was prepared in the same manner as in Example 31, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-4).

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (G16) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 2-2.

Examples 47 to 50

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G17) to (G20) were prepared in the same manner as in Example 46 except that the dispersing agent was changed as shown in Table 2-2.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G17) to (G20) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm, 5 μm or 8 μm was formed.

The foregoing results are shown in Table 2-2.

Example 51

<Preparation of Liquid Composition and Formation of Dyeing Layer> The liquid composition (G21) was prepared in the same manner as in Example 31 except that the alkali-soluble resin (B) became an alkali-soluble resin (B-5).

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (G21) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 2-3.

Examples 52 to 55

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G22) to (G25) were prepared in the same manner as in Example 51 except that the dispersing agent was changed as shown in Table 2-3.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G22) to (G25) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), side etching was not observed, and a pattern having a line width of 6 μm, 8 μm or 5 μm was formed.

The foregoing results are shown in Table 2-3.

Example 56

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (G26) was prepared in the same manner as in Example 31, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-6).

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (G26) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 2-3.

Examples 57 to 60

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (G27) to (G30) were prepared in the same manner as in Example 56 except that the dispersing agent was changed as shown in Table 2-3.

Thereafter, a green strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (G27) to (G30) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 6 μm or 8 μm was formed.

The foregoing results are shown in Table 2-3.

Example 61

<Preparation of liquid composition> 9 parts of CI Pigment Blue 15:6 and CI Pigment Violet 23 in a weight ratio of 95:5 (as coloring agent (A)), 4 parts (solid content) EFKA-46 (as a dispersing agent) And 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

88 parts of the obtained pigment dispersion, 8 parts of an alkali-soluble resin (B-1) (as an alkali-soluble resin (B)), 2 parts of diisopentyltetraol hexaacrylate, and 4 parts of isopentaerythritol tetraacrylate (as Polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1- Ketone oxime-O-acetate (as photo-sensitive radical generator (D)) and 70 parts of methoxybutyl acetate and 96 parts of ethyl-3-ethoxypropionate (as solvent) to prepare a liquid Composition (B1).

<Formation of Dye Layer> A blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 3-1.

Examples 62 to 65

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (B2) to (B5) were prepared in the same manner as in Example 61 except that the dispersing agent was changed as shown in Table 3-1.

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (B5) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm or 6 μm was formed.

The foregoing results are shown in Table 3-1.

Example 66

<Preparation of Liquid Composition and Formation of Dyeing Layer> The liquid composition (B6) was prepared in the same manner as in Example 61, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-2).

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B6) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 3-1.

Examples 67 to 70

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (B7) to (B10) were prepared in the same manner as in Example 66 except that the dispersing agent was changed as shown in Table 3-1.

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (B10) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), side etching was not observed, and a pattern having a line width of 8 μm or 5 μm was formed.

The foregoing results are shown in Table 3-1.

Example 71

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (B11) was prepared in the same manner as in Example 61, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-3).

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B11) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 3-2.

Examples 72 to 75

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (B12) to (B15) were prepared in the same manner as in Example 71 except that the dispersant was changed as shown in Table 3-2.

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B12) to (B15) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 6 μm or 8 μm was formed.

The foregoing results are shown in Table 3-2.

Example 76

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (B16) was prepared in the same manner as in Example 61 except that the alkali-soluble resin (B) became an alkali-soluble resin (B-4).

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B16) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 3-2.

Examples 77 to 80

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (B17) to (B20) were prepared in the same manner as in Example 76 except that the dispersant was changed as shown in Table 3-2.

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B17) to (B20) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm or 8 μm was formed.

The foregoing results are shown in Table 3-2.

Example 81

<Preparation of Liquid Composition and Formation of Dyeing Layer> The liquid composition (B21) was prepared in the same manner as in Example 61, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-5).

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B21) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The above results are shown in Table 3-3.

Examples 82 to 85

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (B22) to (B25) were prepared in the same manner as in Example 81 except that the dispersing agent was changed as shown in Table 3-3.

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (B25) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm or 8 μm was formed.

The above results are shown in Table 3-3.

Example 86

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (B26) was prepared in the same manner as in Example 61, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-6).

Thereafter, a blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B26) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm was formed.

The above results are shown in Table 3-3.

Examples 87 to 90

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (B27) to (B30) were prepared in the same manner as in Example 86 except that the dispersing agent was changed as shown in Table 3-3.

Thereafter, a blue strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B27) to (B30) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), side etching was not observed, and a pattern having a line width of 8 μm or 5 μm was formed.

The above results are shown in Table 3-3.

Example 91

<Preparation of liquid composition> 20 parts of carbon black (as coloring agent (A)), 4 parts (solid content) of EFKA-46 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) A bead mill was mixed to prepare a pigment dispersion.

99 parts of the obtained pigment dispersion, 8 parts of an alkali-soluble resin (B-1) (as an alkali-soluble resin (B)), 2 parts of diisoamyltetraol hexaacrylate, and 4 parts of isopenic alcohol tetraacrylate (as Polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1- Ketone oxime-O-acetate (as a photoradical radical generator (D)) and 150 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed to prepare a liquid composition (BK1).

<Formation of Dye Layer> A black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm was formed.

The foregoing results are shown in Table 4-1.

Examples 92 to 95

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (BK2) to (BK5) were prepared in the same manner as in Example 91 except that the dispersant was changed as shown in Table 4-1.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (BK5) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm or 6 μm was formed.

The foregoing results are shown in Table 4-1.

Example 96

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (BK6) was prepared in the same manner as in Example 91, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-2).

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 4-1.

Examples 97 to 100

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (BK7) to (BK10) were prepared in the same manner as in Example 96 except that the dispersing agent was changed as shown in Table 4-1.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (BK10) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm or 5 μm was formed.

The foregoing results are shown in Table 4-1.

Example 101

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (BK11) was prepared in the same manner as in Example 91, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-3).

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 4-2.

Examples 102 to 105

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (BK12) to (BK15) were prepared in the same manner as in Example 101 except that the dispersant was changed as shown in Table 4-2.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (BK12) to (BK15) was used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm, 8 μm or 6 μm was formed.

The foregoing results are shown in Table 4-2.

Example 106

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (BK16) was prepared in the same manner as in Example 91, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-4).

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm was formed.

The foregoing results are shown in Table 4-2.

Examples 107 to 110

<Preparation of Liquid Composition and Formation of Dyeing Layer> Liquid compositions (BK17) to (BK20) were prepared in the same manner as in Example 106 except that the dispersing agent was changed as shown in Table 4-2.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid compositions (B1) to (BK20) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm or 5 μm was formed.

The foregoing results are shown in Table 4-2.

Example 111

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (BK21) was prepared in the same manner as in Example 91, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-5).

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 6 μm was formed.

The foregoing results are shown in Table 4-3.

Examples 112 to 115

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (BK22) to (BK25) were prepared in the same manner as in Example 111 except that the dispersant was changed as shown in Table 4-3.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (BK22) to (BK25) was used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 8 μm, 6 μm or 5 μm was formed.

The foregoing results are shown in Table 4-3.

Example 116

<Preparation of Liquid Composition and Formation of Dye Layer> The liquid composition (BK26) was prepared in the same manner as in Example 91, except that the alkali-soluble resin (B) became an alkali-soluble resin (B-6).

Thereafter, a black strip-shaped pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (B1) was used instead of the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), no side etching was observed, and a pattern having a line width of 5 μm was formed.

The foregoing results are shown in Table 4-3.

Examples 117 to 120

<Preparation of Liquid Composition and Formation of Dye Layer> Liquid compositions (BK27) to (BK30) were prepared in the same manner as in Example 116 except that the dispersant was changed as shown in Table 4-3.

Thereafter, a black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (BK27) to (BK30) were used instead of the liquid composition (R1).

<Evaluation> When each pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion, and no edge portion of the pixel pattern was found to be missing.

When the cross section of each pixel pattern was observed by a scanning electron microscope (SEM), side etching was not observed, and a pattern having a line width of 8 μm or 5 μm was formed.

The foregoing results are shown in Table 4-3.

Comparative Example 1

<Preparation of liquid composition> 8 parts of CI Pigment Red 254 and CI Pigment Red 177 in a weight ratio of 80:20 (as coloring agent (A)), 4 parts (solid content) of EFKA-46 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

a mixture of 87 parts of the obtained pigment dispersion, 2 parts of an alkali-soluble resin (B-7), 3 parts of an alkali-soluble resin (B-8), and 4 parts of an alkali-soluble resin (B-9) (as an alkali-soluble resin (B) ), 2 parts of diisopentyl alcohol hexaacrylate and 4 parts of pentaerythritol tetraacrylate (as polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-A) Benzobenzamide-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate (as photo-sensitizing agent (D)) and 70 parts of methoxyacetate Butyl ester and 96 parts of ethyl-3-ethoxypropionate (as a solvent) were mixed to prepare a liquid composition (CR1).

<Formation of Dye Layer> A red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (R1) was replaced by the liquid composition (CR-1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, development residue was found on the unexposed portion of the substrate.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), side etching was observed, and only a pattern having a line width of 35 μm was formed.

The foregoing results are shown in Table 5.

Comparative Example 2

<Preparation of liquid composition> 11 parts of a mixture of CI Pigment Green 36 and CI Pigment Yellow 150 in a weight ratio of 60:40 (as a coloring agent (A)), 4 parts (solid content) BYK-2000 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

a mixture of 90 parts of the obtained pigment dispersion, 2 parts of an alkali-soluble resin (B-7), 3 parts of an alkali-soluble resin (B-8), and 4 parts of an alkali-soluble resin (B-9) (as an alkali-soluble resin (B) ), 2 parts of diisopentyl alcohol hexaacrylate and 4 parts of pentaerythritol tetraacrylate (as polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-A) Benzobenzamide-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate (as photo-sensitizing agent (D)) and 70 parts of methoxyacetate Butyl ester and 96 parts of ethyl-3-ethoxypropionate (as a solvent) were mixed to prepare a liquid composition (CG1).

<Formation of Dye Layer> A green stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (CG1) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion. However, when the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), side etching was found, and only a pattern having a line width of 45 μm was formed.

The foregoing results are shown in Table 5.

Comparative Example 3

<Preparation of liquid composition> 9 parts of CI Pigment Blue 15:6 and CI Pigment Violet 23 in a weight ratio of 95:5 (as coloring agent (A)), 4 parts (solid content) BYK-2001 (as a dispersing agent) And 75 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed by a bead mill to prepare a pigment dispersion.

a mixture of 88 parts of the obtained pigment dispersion, 2 parts of an alkali-soluble resin (B-7), 3 parts of an alkali-soluble resin (B-8), and 4 parts of an alkali-soluble resin (B-9) (as an alkali-soluble resin (B) ), 2 parts of diisopentyl alcohol hexaacrylate and 4 parts of pentaerythritol tetraacrylate (as polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-A) Benzobenzamide-9.H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate (as photo-sensitizing agent (D)) and 70 parts of methoxyacetate Butyl ester and 96 parts of ethyl-3-ethoxypropionate (as a solvent) were mixed to prepare a liquid composition (CB1).

<Formation of Dye Layer> A blue stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (C1) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, no development residue was observed on the substrate of the unexposed portion. However, when the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), side etching was found, and only a pattern having a line width of 40 μm was formed.

The foregoing results are shown in Table 5.

Comparative Example 4

<Preparation of liquid composition> 20 parts of carbon black (as coloring agent (A)), 4 parts (solid content) BYK-164 (as a dispersing agent), and 75 parts of propylene glycol monomethyl ether acetate (as a solvent) A bead mill was mixed to prepare a pigment dispersion.

99 parts of the obtained pigment dispersion, 8 parts of an alkali-soluble resin (B-1) (as an alkali-soluble resin (B)), 2 parts of diisoamyltetraol hexaacrylate, and 4 parts of isopenic alcohol tetraacrylate (as Polyfunctional monomer (C)), 3 parts of 1-[9-ethyl-6-(2-methylbenzhydrazide)-9.H.-carbazol-3-yl]-ethane-1- Ketone oxime-O-acetate (as a photoradical generator (D)) and 150 parts of propylene glycol monomethyl ether acetate (as a solvent) were mixed to prepare a liquid composition (CBK1).

<Formation of Dye Layer> A black stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (C1K-1) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, development residue was found on the unexposed portion of the substrate.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), side etching was observed, and only a pattern having a line width of 50 μm was formed.

The foregoing results are shown in Table 5.

Comparative Example 5

<Preparation of Liquid Composition and Formation of Dye Layer> A liquid composition (CR2) was prepared in the same manner as in Comparative Example 1, except that the dispersant was changed to BYK-182.

<Formation of Dye Layer> A red stripe pixel pattern was formed on the substrate in the same manner as in Example 1, except that the liquid composition (CR2) was substituted for the liquid composition (R1).

<Evaluation> When the pixel array on the substrate was observed through an optical microscope, development residue was found on the unexposed portion of the substrate.

When the cross section of the pixel pattern was observed through a scanning electron microscope (SEM), side etching was observed, and only a pattern having a line width of 45 μm was formed.

The foregoing results are shown in Table 5.

Claims (4)

A radiation-sensitive composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photoradical generating agent, wherein the alkali-soluble resin (B) comprises a main a polyester having an alicyclic hydrocarbon skeleton in the chain and a polymerizable unsaturated bond in the side chain, and the radiation-sensitive composition is used to form a dye layer, wherein the component (B) is a formula (1) Show the polyester: Wherein each of X is independently a divalent group represented by the following formula (2) or (3), and each of Y is independently a residue obtained by removing four carboxyl groups from the organic tetracarboxylic acid, each of R ¹ Is independently a hydrogen atom or a methyl group, and each of R ^{2 is} independently a residue of a hydrogen atom or a carboxyl blocking agent, and n is an integer of 1 to 40, The radiation-sensitive composition of claim 1, wherein the photo-radical generating agent (D) is a compound represented by the following formula (4) or (5): Wherein each R ³ is independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ⁴ is independently a hydrogen atom and has a straight 1 to 12 carbon atoms. chain, branched or cyclic alkyl group or a phenyl group, each R ⁵ is independently a hydrogen atom lines or straight chain from 1 to 12 carbon atoms, branched or cyclic alkyl group, and each R ^6, R ^7, and R ⁸ is independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and is limited to each of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 .} The alkyl group represented may be substituted with a substituent selected from a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, and benzene represented by R ³ and R ⁴ The group may be selected from a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. Substituted by a substituent. A color filter having a dyed layer obtained from the radiation-sensitive composition of claim 1 or 2. A color liquid crystal display device comprising the color filter of item 3 of the patent application.