JP2007219499A - Photosetting composition, color filter using the same and method for producing the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting composition which suppresses clogging of a slit nozzle, generation of a dry foreign substance and uneven slit coating, and ensures high contrast when used for a color filter. <P>SOLUTION: The photosetting composition comprises a colorant, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant has an average particle diameter of ≤150 nm, the alkali-soluble resin and/or the polymerizable compound has an alkylene oxide, and the solvent comprises at least one solvent species having a boiling point of ≥200°C and at least one solvent species having a boiling point of <200°C, wherein summation (ΣT×X) of the product (T×X) of the boiling point T(°C) of each solvent species and a content X (wt.%) thereof to the total amount of the solvent is 120×10<SP>2</SP>-190×10<SP>2</SP>(°C×%). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocurable composition suitable for producing a color filter for use in a liquid crystal display device or a solid-state imaging device, a color filter using the same, and a method for producing the same.

  A color filter is an indispensable component for a liquid crystal display. A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device.

In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen is relatively small in area to TV applications where the screen is large and high image quality is required.
With the increase in screen size and substrate size, the application of the photocurable composition to the substrate is mainly based on the technology of slit coating (die coating method), which is superior in liquid-saving and manufacturing efficiency, from conventional spin coating. It has moved.

  In slit coating, fluidity higher than spin coating is required as a liquid property from the viewpoint of uniformity of a coating film. In order to improve slit coating suitability, it is known that it is effective to use an alkali-soluble resin having an alkylene oxide chain such as an ethylene oxide chain in the molecular side chain (see, for example, Patent Documents 1 to 3). .

Another problem with slit coating is drying of the liquid at the tip of the coating head that discharges the coating liquid. That is, since the coating liquid is exposed to the outside air at the slit opening at the tip of the coating head, the coating liquid is dried and solidified, resulting in slit coating unevenness due to clogging of the slit nozzle, or a coating film coated on the substrate Solidified material was brought in as a foreign substance, causing quality defects. In order to solve this problem, a technique in which solvent types having different boiling points are used in combination is known (see, for example, Patent Documents 4 to 6).
In addition, a technique for controlling the boiling point of a solvent in order to impart die coating (slit coating) suitability to a coating solution is also known (see, for example, Patent Documents 6 to 8).

On the other hand, in TV applications, higher image quality is required compared to conventional monitor applications. That is, improvement in contrast and color purity. Further, in order to impart process suitability centering on the exposure / development process, there is a high market demand for a photocurable composition for color filters having high sensitivity, wide development latitude, and no development residue. In order to improve contrast, a finer particle size is required for the colorant (organic pigment or the like) used in the photocurable composition for color filters. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of this photocurable composition for color purity improvement.
JP 2003-241368 A JP-A-2005-70152 JP 2000-194132 A JP 2003-55566 A JP 2004-346218 A JP 2004-246340 A JP 2004-292722 A JP 2004-354601 A

However, when the particle size of the pigment as the colorant is reduced and the content is increased, there is a problem that the coating liquid (photocurable composition) is liable to be dried and solidified.
Under such circumstances, a photocurable composition capable of obtaining sufficient contrast when used for a color filter while sufficiently suppressing clogging of a slit nozzle, generation of dry foreign matter, and slit coating unevenness is still provided. The current situation is not.
Further, although it is required to shorten the development time in order to improve the throughput on a large substrate, if the content of the colorant (organic pigment or the like) is increased for high color purity, the development latitude tends to be narrowed. Therefore, it has been awaited to provide a photocurable composition having a development latitude while ensuring an appropriate development speed.

The present invention has been made in view of the above, and has good fluidity, slit nozzle clogging, generation of dry foreign matter, and slit coating unevenness, and high contrast and color purity when used in a color filter. Providing a photocurable composition that can be obtained, and a color filter having high contrast and color purity that can suppress generation of quality defects and display unevenness due to dry foreign matter and slit coating unevenness, and production thereof The object is to provide a method and to achieve the object.
Another object of the present invention is to provide a photocurable composition having both a proper development speed and development latitude even on a large substrate.

As a result of intensive studies to achieve the object of the present invention, the present inventors have used a colorant having an average particle diameter of 150 nm or less, and further used two or more solvent species having different boiling points in combination with photocurability. When preparing the composition, the ease of drying and solidification of the composition is determined by the product of the boiling point T (° C.) of each solvent species and the content X (mass%) relative to the total amount of the solvent (T · X). ) Was highly dependent on the sum (ΣT · X). Based on this knowledge, it discovered that the said subject could be solved by using further specific alkali-soluble resin and / or polymeric compound, and completed this invention.
That is, the object of the present invention is achieved by the following means.

<1> In a photocurable composition containing a colorant, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the colorant has an average particle size of 150 nm or less, and the alkali-soluble resin is a molecule. It has an alkylene oxide chain in the side chain, and the solvent contains at least one kind of solvent having a boiling point of 200 ° C. or more and a kind of solvent having a boiling point of less than 200 ° C., and the boiling point T (° C.) of each solvent type Photocurability characterized in that the sum (ΣT · X) of the product (T · X) with the content X (mass%) relative to the total amount of the solvent is 120 × 10 ^{2 to} 190 × 10 ² (° C.%) It is a composition.

<2> In a photocurable composition containing a colorant, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the colorant has an average particle size of 150 nm or less, and the polymerizable compound is alkylene. It has an oxide group, and the solvent contains at least one kind of solvent having a boiling point of 200 ° C. or more and a kind of solvent having a boiling point of less than 200 ° C., and the content of each solvent type with respect to the boiling point T (° C.) and the total amount of the solvent. The photocurable composition is characterized in that the sum (ΣT · X) of the product (T · X) with the rate X (mass%) is 120 × 10 ^{2 to} 190 × 10 ² (° C. ·%). .

<3> The photocurable composition according to <1> or <2>, wherein the colorant is a pigment for red (R), and a content ratio in a solid content is 30% by mass or more.

<4> The photocurable composition according to <1> or <2>, wherein the colorant is a pigment for green (G), and the content ratio in the solid content is 40% by mass or more.

<5> The photocurable composition according to <1> or <2>, wherein the colorant is a blue (B) pigment, and the content ratio in the solid content is 20% by mass or more.

<6> A color filter produced using the photocurable composition according to any one of <1> to <5>.

<7> The photocurable composition according to any one of <1> to <5> is applied on a substrate by slit coating and dried to form a coating film, and pattern coating is applied to the coating film. Next, the color filter manufacturing method is characterized by performing alkali development.

According to the present invention, photocuring has good fluidity, clogging of slit nozzles, generation of dry foreign matter, slit coating unevenness, and high contrast and color purity when used in a color filter. Sex compositions can be provided.
Furthermore, according to the present invention, it is possible to provide a color filter having a high contrast and color purity, and a method for manufacturing the same, in which generation of quality defects and display unevenness due to dry foreign matter and slit coating unevenness is suppressed.
Furthermore, it is possible to provide a photocurable composition having good development characteristics even when the substrate is large and having both an appropriate development speed and development latitude.

≪Photocurable composition≫
Hereinafter, the colorant, solvent, alkali-soluble resin, polymerizable compound, photopolymerization initiator, and other components of the photocurable composition of the present invention will be described in detail.
In the present specification, the photocurable composition used for forming the red (R) pixel of the color filter may be referred to as “red (R) photocurable composition”. In addition, the photocurable composition used to form the green (G) pixel of the color filter is used as the “green (G) photocurable composition” and the blue (B) pixel of the color filter. The resulting photocurable composition is sometimes referred to as “blue (B) photocurable composition”.

<Colorant>
The colorant contained in the photocurable composition of the present invention is characterized in that the average particle size is 150 nm or less, and the lower limit is preferably 5 nm or more, more preferably 10 nm or more. In the present invention, the average particle size means a light scattering particle size distribution analyzer (trade name: Microtrac UPA) obtained by dispersing a dispersion obtained by dispersing a colorant or a photocurable composition as it is or diluted with a solvent. (Made by Nikkiso Co., Ltd.)) means the volume average particle diameter obtained by measurement. When the average particle diameter exceeds 150 nm, the contrast of the color filter produced using the photocurable composition is lowered.
From the viewpoint of the contrast, the average particle size of the colorant in the present invention is more preferably 100 nm or less, and particularly preferably 50 nm or less.
For this reason, it is preferable that the colorant used for dispersion is preliminarily reduced in particle size by a salt milling method or the like. A method of salt milling is described in Japanese Patent No. 3130217, Japanese Patent Publication No. 2003-504480, and the like. In addition, fine pigments formed by a build-up method can also be used.

  As the colorant in the present invention, various known inorganic pigments or organic pigments can be used, and they may be used alone or in combination.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above-mentioned metal oxides.

Examples of the organic pigment include:
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 179, 209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the photocurable composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photopolymerizable compound and the pigment has an effect.

  In the present invention, examples of the pigment that can be preferably used as the colorant include the following. However, the present invention is not limited to these.

CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CIPigment Orange 36, 71,
CIPigment Red 122, 150, 171, 175, 177, 179, 209, 224, 242, 254, 255, 264,
CIPigment Violet 19, 23, 32,
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CIPigment Green 7, 36, 37;
CIPigment Black 1, 7;

(Pigment for red (R))
The red (R) pigment as the colorant in the present invention preferably has a content ratio of 30% by mass or more in the solid content of the photocurable composition. If it is 30 mass% or more, color purity can be improved. From the viewpoint of further improving the color purity, the content ratio is more preferably 35% by mass or more, and particularly preferably 40% by mass or more.
In the present invention, the red (R) pigment means a pigment used in the red (R) photocurable composition, and a pigment other than red may be included in addition to the red pigment.
Further, in the present invention, the solid content is synonymous with the non-volatile content, and is a remaining component obtained by forming a coating film on a substrate and drying the formed coating film to remove a solvent, etc. Refers to components other than solvents.

Examples of the red (R) pigment include an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene pigment. It is preferable to use a mixed pigment with a red pigment.
For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254.
C. in terms of color reproducibility. I. Pigment Yellow 139 may be mixed. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength becomes shorter than the short wavelength, and the deviation from the NTSC target hue may increase. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

(Green (G) pigment)
Moreover, it is preferable that the content rate in the solid content of the photocurable composition of the pigment for green (G) as a coloring agent in this invention is 40 mass% or more. If it is 40 mass% or more, color purity can be improved. From the viewpoint of improving color purity, the content ratio is more preferably 45% by mass or more, and particularly preferably 50% by mass or more.
In the present invention, the green (G) pigment means a pigment used in a green (G) photocurable composition, and a pigment other than green may be included in addition to the green pigment.

As the green (G) pigment, a halogenated phthalocyanine pigment alone or a mixed pigment of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. It is preferable.
For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

Moreover, as a coloring agent in this invention, it is preferable that the pigment for blue (B) is contained and the content rate of the said coloring agent in solid content of a photocurable composition is 20 mass% or more. If it is 20 mass% or more, color purity can be improved. From the viewpoint of improving color purity, the content ratio is more preferably 25% by mass or more, and particularly preferably 30% by mass or more.
In the present invention, the blue (B) pigment means a pigment used in the blue (B) photocurable composition, and a pigment other than blue may be included in addition to the blue pigment.

  As the blue (B) pigment, a phthalocyanine pigment alone or a mixed pigment of this and a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment.
Dispersants include hydrophilic groups such as carboxyl group, OH group, sulfonic acid group, phosphoric acid group, amino group, carbonyl group, polyoxyalkylene group, phenyl group (including naphthalene ring, etc.), alicyclic ring, alkyl group, and these A compound having a lipophilic part such as a substituted group, a compound having a pigment-like structure and a hydrophilic part and / or a lipophilic part is generally used as a dispersant, but the dispersants exemplified below are used. Is possible. However, the present invention is not limited to these.
EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400.4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Ant i-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, 160, 161, 162, 163, 164, 166, 182, P- 104, P-104S, P105, 220S, 203, 204, 205, 9075, 9076, 9077 (above, manufactured by BYK), Disparlon 7301, 325, 374, 234, 1222, 2100, 2200, KS260, KS273N, 152MS (and above) Manufactured by Enomoto Kasei Co., Ltd.), Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, etc. (above, manufactured by AVECIA), Carribbon B, L-400, et al. Minol MBN-1, Sunspearl PS-2, PS-8, Ionette S-20 (above, manufactured by Sanyo Chemical Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (above Sannopco) can be used. These may be used alone or in combination of two or more.
3-30 mass parts is preferable with respect to 100 mass parts of pigments, and, as for the addition amount of a dispersing agent, More preferably, it is 5-20 mass parts.

  Moreover, a dispersion resin can be used if necessary. By using a dispersion resin, the dispersion stabilizer and storage stability are improved. As a specific example of the dispersion resin, a resin having a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or the like is preferable. Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in JP-A-53836, JP-A-59-71048, There are partially esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. These include, for example, monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) propyl acrylate, (meth) acrylate isopropyl, (meth) butyl acrylate, (meth) acrylate isobutyl, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, Allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N- Methyl acrylamide, N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, include polymers obtained by copolymerization of one or more copolymerizable component such as N- dimethylaminoethyl acrylamide. Among them, preferred is a (meth) acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ester as a constituent monomer, and a (meth) acrylic resin containing (meth) acrylic acid and styrene is also suitable. . These acrylic copolymer components are not limited to the above.

<Solvent>
The solvent contained in the photocurable composition of the present invention contains at least one solvent species having a boiling point of 200 ° C. or higher and a solvent species having a boiling point of less than 200 ° C., and the boiling point T (° C. of each solvent species). ) And the content X (mass%) of the total amount of solvent (T · X) (ΣT · X) is 120 × 10 ^{2 to} 190 × 10 ² (° C.%). When a colorant having an average particle diameter of 150 nm or less is used to improve color purity, and the content of the colorant in the solid content of the photocurable composition is increased, the photocurable composition at the slit opening When a solvent outside the above range is used, there is a risk of clogging of the slit nozzle due to drying and solidification of the photocurable composition, dry foreign matter, and slit coating unevenness. .
In the present invention, the boiling point means a boiling point under a pressure of 101.25 Pa.

From the viewpoint of further suppression of clogging of the slit nozzle, dry foreign matter, and slit coating unevenness, the total (ΣT · X) is more preferably 140 × 10 ^{2 to} 185 × 10 ² (° C. ·%), and 150 × 10 ^2. ˜185 × 10 ² (° C./%) is particularly preferable.
The ratio of the solvent species having a boiling point of 200 ° C. or higher and the solvent species having a boiling point of less than 200 ° C. is such that the sum (ΣT · X) falls within the above range. When the ratio is within this range, it is possible to avoid the occurrence of coating unevenness and the like that are presumed to be caused by dry foreign matter, solidified foreign matter, or foreign matter due to agglomeration of pigment in the coating process.

(Solvent type with boiling point of 200 ° C or higher)
Examples of the solvent species having a boiling point of 200 ° C. or higher include diethylene glycol monoethyl ether (202 ° C.), γ-butyl lactone (204 ° C.), dipropylene glycol monomethyl ether acetate (209 ° C.), propylene glycol n-butyl ether acetate (211 ° C. ), 3,5,5-trimethyl-2-cyclohexen-1-one (213 ° C.), terpioneel (about 220 ° C.), diethylene glycol monoethyl ether acetate (217 ° C.), dipropylene glycol mono n-butyl ether (229 ° C.) ), Tripropylene glycol methyl ether acetate (263 ° C.), diethylene glycol monobutyl ether (231 ° C.), 1,3-butylene glycol diacetate (232 ° C.), dipropylene glycol n-propylene Ether acetate (232 ° C), propylene carbonate (242 ° C), propylene glycol monophenyl ether (243 ° C), diethylene glycol monobutyl ether acetate (217 ° C), dipropylene glycol n-butyl ether acetate (251 ° C), propylene glycol Examples include phenyl ether acetate (258 ° C.), triacetin (260 ° C.), tripropylene glycol n-butyl ether acetate (294 ° C.), and tripropylene glycol mono n-butyl ether (274 ° C.).
Among the above, preferred solvent types are dipropylene glycol monomethyl ether acetate, propylene glycol n-butyl ether acetate, 1,3-butylene glycol diacetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate. is there.
Among these, the most preferable solvent species are dipropylene glycol monomethyl ether acetate, 1,3-butylene glycol diacetate, and propylene glycol n-butyl ether acetate.
These solvent species may be used alone or in combination.

(Solvent species with boiling point less than 200 ° C)
Examples of the solvent species having a boiling point of less than 200 ° C. include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-oxypropionic acid Me , 2-oxypropionic acid alkyl esters such as ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- Ethyl 2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetra Drofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as toluene and xylene.
Among these solvent types, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, n-butyl acetate , Isobutyl acetate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, 3-heptanone and the like are preferable, and among them, propylene glycol monomethyl ether acetate and cyclohexanone are most preferable.
These solvent species may be used alone or in combination.

(Preferred combinations of solvent types)
As a preferable combination of the solvent species contained in the photocurable composition of the present invention, a solvent species having a boiling point of 200 ° C. or higher is dipropylene glycol monomethyl ether acetate, propylene glycol n-butyl ether acetate, 1,3-butylene. It is at least one of glycol diacetate, dipropylene glycol n-propyl ether acetate and dipropylene glycol n-butyl ether acetate, and the solvent type having a boiling point of less than 200 ° C. is ethyl lactate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, n-butyl acetate, isobutyl acetate, 2-heptanone, cyclohexane A combination of at least one of sanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and 3-heptanone is preferred, and the solvent species having a boiling point of 200 ° C. or higher is 1,3-butylene glycol diacetate. And a combination in which the solvent species having a boiling point of less than 200 ° C. is any one of propylene glycol monomethyl ether acetate and cyclohexanone.

<Alkali-soluble resin>
The photocurable composition of the present invention contains at least one alkali-soluble resin. When a colorant having an average particle size of 150 nm or less is used for improving the contrast, the photocurable composition is easily dried and solidified at the slit opening. Therefore, a resin having an alkylene oxide chain in the molecular side chain is used. By selecting, fluidity suitable for slit coating can be maintained, and slit coating unevenness can be suppressed.
Moreover, the alkali-soluble resin in the present invention has a high concentration of the colorant in the photocurable composition by having a group having the alkylene oxide chain in the side chain and further having an alkali-soluble group or a hydrophobic group in the side chain. When it is contained, pattern exposure can be performed with high sensitivity, and the development speed is optimized by controlling the penetration of the developer into the film at the time of development, so that a wide development latitude is obtained and the tact time of the process is shortened It is effective.

The alkylene oxide chain is a group represented by Formulas 1 to 3.
_{- (C m H 2m O)} n - ··· Formula 1
_{- (C l H 2l-1} CH 3 O) k - ··· Equation 2
_{- (C m H 2m O)} n - (C l H 2l-1 CH 3 O) k - ··· Equation 3
In the present invention, l and m are each preferably preferably 1 to 5, and more preferably 1 to 3. Further, k and n are each independently preferably 1 to 15, and more preferably 2 to 10.
Specific examples of the alkylene oxide chain include a polymethyleneoxy group, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polybutyleneoxy group (polytetramethyleneoxy group), and a polypentamethyleneoxy group. It is done. These polyalkyleneoxy groups are directly or indirectly bonded to the main chain skeleton. The end of the side chain may be an OH group, but is preferably blocked with an alkyl group such as a methyl group, an ethyl group or an isopropyl group, or a phenyl group.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of the alkali-soluble resin having an alkylene oxide chain in the molecular side chain is preferably 3000 to 50000, more preferably 3000 to 20000.

The alkali-soluble resin having an alkylene oxide chain in the molecular side chain can be easily synthesized by copolymerizing an acrylic monomer as described below, but is not limited thereto.
Specific examples of the acrylic monomer include compounds having a polyalkylene oxide group such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, and polyethylene glycol. Polytetramethylene glycol mono (meth) acrylate, and these terminal OH groups are substituted with methoxy, ethoxy, isopropoxy, octoxy. These compounds include, for example, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-500, PP-800, PP-1000, AP-150, AP-400. AP-550, AP-800, 50PEP-300, 70PEP-350B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 10PPB-500B, PME-100, PME-200, PME -350, PME-400, PME-550, PME-1000, AME-400, AEE-100, 50POEP-800B, 50AOEP-800B (manufactured by NOF Corporation), NK ester M-20G, M-40G, M -90G, AMP-10G, AMP-20G, AMP- 0G, AMP-90G, E-30G, E-60G (Shin-Nakamura Chemical Co., Ltd.), and the like.
Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and among them, a carboxyl group is preferable. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and partially esterified maleic acid. Among them, acrylic acid and methacrylic acid are preferable.

The acrylic copolymer which is an alkali-soluble resin in the present invention can introduce a hydrophobic group by copolymerizing at least one of the following acrylic monomers containing a hydrophobic group. By having these hydrophobic groups in the side chain, when a film is formed, it is possible to appropriately control the development speed by controlling the penetration of the developer into the film during development. Furthermore, even when chromatic colors such as red, green, and blue are employed as the colorant without chemical coloring over time, deterioration of color characteristics over time can be reduced.
Examples of acrylic monomers containing a hydrophobic group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Examples of other monomers include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.

Further, in the acrylic copolymer according to the present invention, the ratio of the alkali-soluble group is preferably 10 to 60%, more preferably 10 to 40% in terms of a molar ratio with respect to one molecule of the acrylic copolymer. It is particularly preferably 10 to 30%, and the acid value of the acrylic copolymer is preferably in the range of 30 to 200 mgKOH / g. The ratio of the group having an alkylene oxide chain in the side chain is preferably from 2 to 30%, more preferably from 3 to 20% in terms of molar ratio to one molecule of the acrylic copolymer, and the ratio of the hydrophobic group is acrylic. The molar ratio is preferably 5 to 80%, more preferably 30 to 70%, relative to one molecule of the system copolymer.
The presence of an alkali-soluble group, a group having an alkylene oxide chain in the side chain, and a hydrophobic group can be confirmed by, for example, acid value measurement, infrared absorption spectrum analysis, or mass spectrometry.

If necessary, a compound having a hydroxyl group can be copolymerized. Hydroxyl groups have high hydrophilicity and are effective in adjusting the development speed in alkali development by being contained in the resin. Specific examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylate and hydroxyaryl (meth) acrylate.
The alkyl group of the hydroxyalkyl (meth) acrylate preferably has 2 to 12 carbon atoms. The alkyl group may be linear, branched or cyclic. In the alkyl group, the hydrogen atom may be substituted with a substituent. Examples of the substituent include an aryl group, a halogen group, a phenyl group, and an alkoxyl group. Specific examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a cyclohexyl group, and a benzyl group. Particularly preferred hydroxyalkyl (meth) acrylates are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
The aryl group of hydroxyaryl (meth) acrylate preferably has 6 to 12 carbon atoms. In the aryl group, the hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen group, a phenyl group, and an alkoxyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group, and a benzyl group. A preferred hydroxyaryl (meth) acrylate is hydroxyphenyl (meth) acrylate.
The said hydroxy group containing (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.

These resins can also have an ethylenic double bond added to the side chain. By imparting a double bond to the side chain, photocurability is increased, and resolution and adhesion can be further improved.
Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444. Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained. In particular, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

  As content in the photocurable composition of the acrylic copolymer which concerns on this invention, 5-40 mass% is preferable with respect to the total mass of a photocurable composition, and 5-30 mass% is more preferable. . When the content is within the above range, high sensitivity can be maintained even when the concentration of the colorant increases, and the development speed is optimized to obtain good development performance, thereby shortening the tact time of the process. be able to.

The acrylic copolymer according to the present invention can be used in combination with an acrylic copolymer having no alkylene oxide chain in the side chain. As an example of an acrylic copolymer having no alkylene oxide chain in the side chain, an acrylic monomer having an alkylene oxide chain in the side chain from the structure of the acrylic copolymer having the alkylene oxide chain in the side chain. And a copolymer structure having at least a hydrophobic group and an alkali-soluble group, more preferably an ethylenic double bond in the side chain.
Specific examples of these compounds include, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyethane, acrylic collimator Diamond Shamock), Biscoat R-264, KS resist 106 (all of which are Osaka Organic Chemical Industries, Ltd.) Product), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB), and the like.

<Polymerizable compound>
The photocurable composition of the present invention contains at least one polymerizable compound. The polymerizable compound is polymerized and cured under the action of an active species from a photopolymerization initiator described later to form an image. As the polymerizable compound, a compound having at least three ethylenically unsaturated groups having a boiling point of 100 ° C. or higher under normal pressure, or at least three ethylenically unsaturated groups having a boiling point of 100 ° C. or higher under normal pressure A compound having an alkylene oxide group is preferred.

As a compound having at least three ethylenically unsaturated groups having a boiling point of 100 ° C. or higher under normal pressure, and a compound having at least three ethylenically unsaturated groups having an boiling point of 100 ° C. or higher and an alkylene oxide group under normal pressure Are, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, sorbitol triacrylate, sorbitol tetraacrylate, tri ((meth) acryloyloxyethyl) isocyanurate can also be used, and glycerin, trimethylolethane After adding an alkylene oxide group such as ethylene oxide or propylene oxide to a trifunctional or higher alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, triisocyanurate triethanol or the like, (meth) acrylate is converted to (meta) A compound having 3 or more acryloyl groups in the molecule is a preferred compound. Examples of these compounds are described in JP-A No. 10-62986 as general formulas (1) and (2) together with specific examples thereof, “Alkylene oxides such as ethylene oxide and propylene oxide in trifunctional or higher alcohols”. (Meth) acrylated compound after addition of "can be used.
Among them, acryloyl groups such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (acryloyloxyethyl) isocyanurate, glycerin triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. A structure in which ethylene oxide, propylene oxide, or the like is interposed between the alcohol residue and the alcohol residue is preferable. The addition number per molecule of ethylene oxide or propylene oxide is preferably 3 to 20, and more preferably 6 to 12. These oligomer types are also used.
Commercially available products include NK ester A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-11E, A-GLY-18E, A-GLY-20E, AT. -20E, A-TMPT-6EO, A-TMPT-6PO, ATM-4E, ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate TMP-3EO-A, TMP-6EO-A (Made by Kyoeisha Chemical Co., Ltd.), LumiCure ETA-300 (made by Dainippon Ink & Chemicals), New Frontier TMP-3, TMP-15, TMP-2P, TMP-3P (above, first Manufactured by Kogyo Seiyaku Co., Ltd.) Aronix M-310, M-315, M-320, M-350, M-360, TO-924, TO-1231 (above, manufactured by Toagosei Co., Ltd.), DP- 1040 Manufactured by Nippon Kayaku Co., Ltd.) and the like, these are trifunctional or more acrylate compounds containing an alkylene oxide group, either can be used.

A polymeric compound can be used individually by 1 type or in combination of 2 or more types. Further, a trifunctional or higher functional acrylic monomer containing an alkylene oxide group and a monomer having no alkylene oxide group can be used in combination.
The content of the polymerizable compound in the photocurable composition is preferably 10 to 50% by mass and more preferably 15 to 40% by mass with respect to the photocurable composition (total solid content). . When the content is within the above range, sufficient curing is possible, pigment dispersion is good, and quality is improved.

<Photopolymerization initiator>
Next, the photopolymerization initiator contained in the photocurable composition of the present invention will be described.
Examples of the photopolymerization initiator include halomethyloxadiazole described in JP-A-57-6096; halomethyl-s-- described in JP-B-59-1281 and JP-A-53-133428. Active halogen compounds such as triazines; aromatic carbonyl compounds such as ketals, acetals or benzoin alkyl ethers described in US Pat. No. US Pat. No. 4,318791 and European Patent Publication EP-88050A; aromatics such as benzophenones described in US Pat. No. 4,1994,420 Group ketone compounds; (thio) xanthones or acridine compounds described in Fr-2456541; compounds such as coumarins or lophine dimers described in JP-A-10-62986; sulfoniums described in JP-A-8-015521 Use organic boron complex, etc. Rukoto can.

  In the present invention, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimer It is preferable to use a photopolymerization initiator such as a series or biimidazole.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferable examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl bezoate.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (p Preferred examples include -N, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferable examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

Other examples of the photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2, Examples include 4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt, and the like.
Also, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. (above, manufactured by Asahi Denka Co., Ltd.), OXE-01, OXE-02, CGI-113, IR -369, IR-379, IR-907, IR-184, IR-819 (manufactured by Ciba Specialty Chemicals Co., Ltd.) can also be used as the photopolymerization initiator.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds are exemplified.
Moreover, these photoinitiators can also be used together.

  The usage-amount of the said photoinitiator is 0.1-10.0 mass% of the total solid of a photocurable composition, Preferably it is 0.5-5.0 mass%. When the amount of the photopolymerization initiator used is less than 0.1% by mass, the polymerization may not proceed easily, and when it exceeds 10.0% by mass, the film strength may be weakened.

<Surfactant>
When the pigment concentration is increased due to high color purity, the thixotropy of the coating solution generally increases, which prevents uneven coating thickness that tends to occur. It is important to form a uniform thickness coating by leveling. Therefore, it is preferable that the photocurable composition of the present invention contains an appropriate surfactant.

Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Examples of the surfactant for improving the coating property include nonionic surfactants, fluorosurfactants, and silicone surfactants.
Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters and the like are preferable. Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene Polyoxyalkylene dialkyl esters such as dilaurate and polyoxyethylene distearate, sorbidan fatty acid Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters. Specific examples of these are: Adeka Pluronic series, Adecanol series, Tetronic series (above, manufactured by ADEKA), Emulgen series, Rheodor series (above, made by Kao Corporation), Elenomol series, Nonipole series, Octopole Series, Dodecapol Series, New Pole Series (Sanyo Kasei Co., Ltd.), Pionein Series (Takemoto Yushi Co., Ltd.), Nissan Nonion Series (Nippon Yushi Co., Ltd.), etc. . These commercially available products can be used as appropriate. The HLB value is preferably 8 to 20, and more preferably 10 to 17.

  Preferred examples of the fluorosurfactant include compounds having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain. Specifically, as a commercial product, for example, MegaFuck F142D, F172, F173, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Chemical Co., Ltd.) ), Fluorad FC-135, FC-170C, FC-430, FC-431 (Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351 352, 801, 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF- 8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (or more, GE Toshiba Silicone Co., Ltd.).

  The above surfactant can be used in an amount of preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the photocurable composition. When the amount of the surfactant is within this range, roughening of the coating film surface in the coating and drying process is suppressed, and a smoother dried coating film is obtained.

<Other ingredients>
In the photocurable composition of the present invention, various additives such as a filler, a polymer compound other than the alkali-soluble resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like are included as necessary. Can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group An alkali-soluble resin such as a polymer having an acid anhydride added thereto, an alcohol-soluble nylon, a phenoxy resin formed from bisphenol A and epichlorohydrin;

UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

  Further, when promoting the alkali solubility of the light non-irradiated portion and further improving the developability of the photocurable composition of the present invention, the photocurable composition of the present invention is preferably an organic carboxylic acid, preferably Addition of a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be performed. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

<Method for producing photocurable composition>
The photocurable composition of the present invention is a mixture of a colorant, an acrylic copolymer (alkali-soluble resin) according to the present invention, a polymerizable compound, a solvent, a photopolymerization initiator, and other components as necessary. It can be prepared by mixing and dispersing using various mixers and dispersers.

The mixing and dispersing step (mixing and dispersing step) is preferably composed of a kneading and dispersing step followed by a fine dispersion treatment step, but kneading and dispersing can be omitted. In addition, it is preferable that the pigment type used for kneading and dispersing is previously refined in particle size by a salt milling method or the like. The method of salt milling is described in Japanese Patent No. 3130217, Japanese translations of PCT publication No. 2003-504480, and the like. In addition, fine pigments formed by a build-up method can also be used.
In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to be wetted with the constituent components mainly composed of the resin component of the vehicle, and the colorant particles and the solids of the vehicle solution / Convert to solution interface. In the fine dispersion treatment step, the colorant particles are dispersed to a fine state close to primary particles by mixing and stirring together with a dispersion medium for fine particles of glass, zirconia or ceramic. Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the colorant particle surface from air to a solution. Therefore, a strong shearing force and a compressive force are required. Desirably, on the other hand, in the fine dispersion treatment step, it is necessary to distribute the particles uniformly and stably to a fine state, and a dispersing machine that applies impact force and shear force to the aggregated colorant particles, Desirably, the dispersion has a relatively low viscosity.

In the photocurable composition of the present invention, for example, the kneading and dispersing step for producing a color filter is performed by first using a colorant such as an organic pigment or carbon black, and the acrylic copolymer (alkali-soluble resin) according to the present invention. A part and, if necessary, a dispersant or a surface treatment agent are kneaded together with a part of the solvent. Examples of the machine used for kneading include two rolls, three rolls, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder, and the like. Next, the remaining solvent and the acrylic copolymer according to the present invention (alkali-soluble resin; the remainder not used for the kneading) are added, and mainly a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. And dispersed with beads having a particle diameter of 0.01 to 1 mm, zirconia, ceramics or the like. When the kneading step is omitted, beads such as a colorant such as a pigment, the acrylic copolymer (alkali-soluble resin) according to the present invention, and a dispersant or a surface treatment agent as necessary are dispersed. In this case, it is preferable to add the acrylic copolymer (alkali-soluble resin) according to the present invention for use in kneading during the dispersion.
For details on kneading and dispersing, see T.W. C. Also described in “Paint Flow and Pigment Disslon” by Patton (1964, published by John Wiley and Sons).

  The photocurable composition of the present invention is suitable for production of a color filter used in a liquid crystal display that requires high image quality, and is particularly excellent in application suitability on a large substrate. Suitable for display. For example, it is suitable for color filters used in display units for notebook personal computers, mobile phones, and thin TVs.

≪Color filter and manufacturing method≫
The color filter of the present invention is prepared by applying the photocurable composition onto a substrate by slit coating and drying to form a coating film, pattern exposure is performed on the coating film, and then alkali development is performed. Can do. Since the fluidity of the photocurable composition is good, the present invention is particularly suitable for a slit coating device having a rotary roller type preliminary discharge device, but the slit nozzle is wiped and cleaned immediately before coating in single wafer coating. The coating method and the spin coating method can also be used.

  The pattern exposure is a step of irradiating the coating film with radiation through a predetermined mask pattern. As the radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used. As an exposure system, a proximity system exposure machine, a mirror projection system, or a stepper system can be used, but a proximity system in which the exposure area expands by diffraction is particularly preferable.

The alkali development is a process in which the light-irradiated portion in the pattern exposure is eluted in an alkaline aqueous solution, leaving only the photocured portion. As the developer, any developer can be used as long as it dissolves the coating film of the composition on the light non-irradiated portion and does not dissolve the light irradiated portion. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, ammonium water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, An alkaline aqueous solution in which an alkaline compound such as pyrrole or piperidine is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is suitable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is preferably in the range of 20 to 90 seconds.
Next, after the excess developer is washed away and dried, heat treatment (post-bake) is usually performed at a temperature of 200 ° C. to 240 ° C.

  By repeating the above process for each color of R (red), G (green), and B (blue), colored pixels of each color can be formed. Thereby, a color filter is obtained. The application order of R, G, and B may be any. A black matrix is preferably provided in advance between each pixel.

  As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements, etc., and those having a transparent conductive film attached thereto, photoelectric conversion used for solid-state imaging elements, etc. An element substrate, such as a silicon substrate, can be used. Furthermore, a plastic substrate is also possible.

  The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  Drying (prebaking) of the coating film of the composition of the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds with a hot plate, an oven, etc., combined with vacuum drying. It is preferable to use it.

  The coating thickness (after drying) of the coating film of the composition of the present invention is generally 0.3 to 5.0 μm, desirably 0.5 to 3.5 μm, and most desirably 1.0 to 2.5 μm. .

  As the use of the photocurable composition of the present invention, the use mainly for the color pixels of the color filter has been mainly described, but it is of course applicable to the black matrix provided between the pixels of the color filter. The black matrix can be formed by pattern exposure and alkali development of a composition to which a black colorant such as carbon black or titanium black is added, and then post-baking to promote film hardening.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. Unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.

[Example 1]
≪Preparation of red (R) photocurable composition≫
<Kneading and dispersion treatment>
Each component of the following RED composition A was kneaded in a kneader for 30 minutes. After kneading, a high viscosity dispersion treatment was further performed with two rolls to obtain a dispersion.

-RED composition A-
Pigment Red 254 ... 29 parts Pigment Yellow 139 ... 6 parts Benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin) Polypropylene glycol repeating unit: 4, propylene glycol monomethyl ether acetate solution with a weight average molecular weight Mw of 10,000 (solid content: 50%) ... 22 parts Dispersant (trade name: Disperbyk-161, manufactured by Big Chemie) ... 2 parts (30% solution of mixed solvent of propylene glycol methyl ether acetate and butyl acetate)

<Fine dispersion processing>
Each component of the following RED composition B was added to the dispersion obtained by the kneading dispersion treatment, and the mixture was stirred for 3 hours using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

-RED composition B-
Propylene of benzyl methacrylate / methacrylic acid / methoxy terminal polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ... 22 parts ・ Propylene glycol monomethyl ether acetate (solvent type with boiling point less than 200 ° C; solvent type 1) ... 200 parts

<High pressure dispersion treatment>
Using the high-pressure disperser with a pressure reducing mechanism (trade name: NANO-3000-10, manufactured by Nippon BEE Co., Ltd.), the mixed solution obtained by the fine dispersion treatment was flowed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ^3. Then, the dispersion treatment was performed. The high-pressure dispersion treatment was repeated 10 times to obtain a dispersion.

<Preparation of photocurable composition>
Each component of the following RED composition C was added to a dispersion obtained by repeating the high-pressure dispersion treatment 10 times, and the mixture was stirred and mixed to prepare a red (R) photocurable composition.

-RED composition C-
・ Dipentaerythritol hexaacrylate (polymerizable compound)
... 23 parts. 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl)-
2,6-di (trichloromethyl) -s-triazine (photopolymerization initiator)
... 4 parts, 1,3-butylene glycol diacetate (solvent type with a boiling point of 200 ° C or higher; solvent type 2)
... 150 parts

[Comparative Example 1]
In Example 1, a red (R) photocurable composition was prepared in the same manner as in Example 1 except that the kneading dispersion treatment was not performed.

[Comparative Example 2]
The alkali-soluble resin having the RED composition A and the RED composition B used in Example 1 is a propylene glycol monomethyl ether of a benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight Mw: 10,000). A red (R) photocurable composition was prepared in the same manner as in Example 1 except that the acetate solution (solid content: 50%) was changed.

[Comparative Example 3]
A red (R) photocurable composition was prepared in the same manner as in Example 1 except that the solvent type 2 of the RED composition C used in Example 1 was changed to methyl ethyl ketone (boiling point 80 ° C.).

[Example 2]
<< Preparation of green (G) photocurable composition >>
In Example 1, a green (G) photocurable resin composition was prepared in the same manner as in Example 1 except that the RED compositions A, B, and C were changed to the following GREEN compositions A, B, and C, respectively. .

-GREEN composition A-
Pigment Green 36 ... 28 parts Pigment Yellow 150 ... 14 parts Benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin) Polypropylene glycol repeating unit: 4, propylene glycol monomethyl ether acetate solution having a weight average molecular weight Mw of 10,000 (solid content: 50%) ... 20 parts, dispersant (trade name: Disperbyk-161, manufactured by Big Chemie) ... 4 parts

-GREEN composition B-
Propylene of benzyl methacrylate / methacrylic acid / methoxy terminal polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ... 10 parts ・ Propylene glycol monomethyl ether acetate (solvent type with boiling point less than 200 ° C; solvent type 1) ... 200 parts

-GREEN composition C-
・ Dipentaerythritol hexaacrylate (polymerizable compound)
... 18 parts · 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl)-
2,6-di (trichloromethyl) -s-triazine (photopolymerization initiator)
... 4 parts, 1,3-butylene glycol diacetate (solvent type with a boiling point of 200 ° C or higher; solvent type 2)
... 150 parts

[Comparative Example 4]
In Example 2, a green (G) photocurable composition was prepared in the same manner as in Example 2 except that the kneading and dispersing treatment was not performed.

[Comparative Example 5]
The alkali-soluble resin used in Example 2 is a propylene glycol monomethyl ether acetate solution (solid content: benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight Mw: 10,000). A green (G) photocurable composition was prepared in the same manner as in Example 2 except that it was changed to (50%).

[Comparative Example 6]
A green (G) photocurable composition was prepared in the same manner as in Example 2 except that the solvent type 2 used in Example 2 was changed to methyl ethyl ketone.

[Example 3]
<< Preparation of blue (B) photocurable composition >>
In Example 1, a blue (B) photocurable resin composition was prepared in the same manner as in Example 1 except that the RED compositions A, B, and C were changed to the following BLUE compositions A, B, and C, respectively. .

-BLUE composition A-
Pigment Blue 15: 6 16 parts Pigment Violet 23 3 parts Benzyl methacrylate / methacrylic acid / methoxy terminal polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali Soluble resin, propylene glycol monomethyl ether acetate solution of polyethylene glycol repeating unit: 4, weight average molecular weight Mw: 10000) (solid content: 50%) ... 20 parts, dispersant (trade name: Disperbyk-161, Big Chemie) Made) 4 parts

-BLUE composition B-
Propylene of benzyl methacrylate / methacrylic acid / methoxy terminal polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ... 10 parts ・ Propylene glycol monomethyl ether acetate (solvent type with boiling point less than 200 ° C; solvent type 1) ... 200 parts

-BLUE composition C-
・ Dipentaerythritol hexaacrylate (polymerizable compound)
... 18 parts · 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl)-
2,6-di (chloromethyl) -s-triazine (photopolymerization initiator) 4 parts 1,3 butylene glycol diacetate (solvent type with a boiling point of 200 ° C. or higher; solvent type 2)
... 150 parts

[Comparative Example 7]
In Example 3, a blue (B) photocurable composition was prepared in the same manner as in Example 3 except that the kneading and dispersing treatment was not performed.

[Comparative Example 8]
The alkali-soluble resin used in Example 3 is a propylene glycol monomethyl ether acetate solution (solid content: benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight Mw: 10,000). A blue (B) photocurable composition was prepared in the same manner as in Example 3 except that it was changed to 50%).

[Comparative Example 9]
A blue (B) photocurable composition was prepared in the same manner as in Example 3 except that the solvent type 2 used in Example 3 was changed to methyl ethyl ketone.

[Example 4]
The following RED composition D was stirred for 3 hours using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser using 0.3 mm zirconia beads. The obtained mixed solution was subjected to a high-pressure dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser with a decompression mechanism. This high-pressure dispersion treatment was repeated 10 times to obtain a dispersion. Each component of the following RED composition E was added to the obtained dispersion and mixed by stirring to prepare a red (R) photocurable composition. That is, as compared with Example 1, kneading with a kneader and high viscosity dispersion treatment with two rolls were not performed.

-RED composition D-
Pigment Red 254 29 parts Pigment Yellow 139 6 parts Benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin) Polypropylene glycol repeating unit: 4, propylene glycol monomethyl ether acetate solution having a weight average molecular weight Mw of 10,000 (solid content: 50%) ... 22 parts Dispersant (trade name: Disperbyk-161, manufactured by Big Chemie) ... 2 parts (30% solution of mixed solvent of propylene glycol methyl ether acetate and butyl acetate)
Propylene glycol monomethyl ether acetate (solvent type with a boiling point of less than 200 ° C .: solvent type 1) 200 parts

-RED composition E-
Propylene of benzyl methacrylate / methacrylic acid / methoxy terminal polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ・ ・ ・ 19 parts ・ Epoxy resin ・ ・ ・ 0.5 part (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.)
Polymerizable resin (trade name: Cyclomer P ACA-200, manufactured by Daicel Chemical Industries, Ltd .; 50% solution of dipropylene glycol monomethyl ether, solid content acid value: 118 KOH mg / g, double bond equivalent: 450 g / mol -Acrylic) 2 parts dipentaerythritol hexaacrylate (polymerizable compound) 23 parts 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine (photoinitiator) 2 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1・ 1 part (trade name: IR369, manufactured by Ciba Specialty Chemicals Co., Ltd .; photopolymerization initiator)
・ 2,4-diethylthioxanthone (photopolymerization initiator) ・ ・ ・ 0.5 part ・ p-methoxyphenol (polymerization inhibitor) ・ ・ ・ 0.01 part ・ Fluorine-based surfactant (trade name: Megafac R08, Dainippon Ink & Chemicals, Inc.) ... 0.001 part, nonionic surfactant ... 0.5 part (trade name: Emulgen A-60, manufactured by Kao Corporation)
・ 1,3-butylene glycol diacetate (solvent species having a boiling point of 200 ° C. or higher; solvent species 2) 150 parts

[Example 5]
In Example 4, a green (G) photocurable resin composition was prepared in the same manner as in Example 4 except that the RED compositions D and E were changed to the following GREEN compositions D and E, respectively.

-GREEN composition D-
Pigment Green 36 ... 28 parts Pigment Yellow 150 ... 14 parts Benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin) Polyethylene glycol is a propylene glycol monomethyl ether acetate solution having a repeating unit of 4 and a weight average molecular weight Mw of 10,000 (solid content: 50%) ... 20 parts / dispersant (trade name: Disperbyk-161, manufactured by Big Chemie)・ ・ ・ 4 parts ・ Propylene glycol monomethyl ether acetate (solvent type with boiling point less than 200 ° C .; solvent type 1) ・ ・ ・ 200 parts

-GREEN composition E-
Propylene of benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol is repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ... 6 parts, epoxy resin ... 1 part (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.)
Polymerizable resin (trade name: Cyclomer P ACA-200, manufactured by Daicel Chemical Industries, Ltd .; 50% solution of dipropylene glycol monomethyl ether, solid content acid value: 118 KOH mg / g, double bond equivalent: 450 g / mol -Acrylic) ... 2 parts, dipentaerythritol hexaacrylate (polymerizable compound) ... 18 parts, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl-2,6 -Di (trichloromethyl) -s-triazine (photoinitiator) 2 parts 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 part ( Product name: IR369, manufactured by Ciba Specialty Chemicals, Inc .; photopolymerization initiator)
2,4-diethylthioxanthone (photopolymerization initiator) 0.8 parts p-methoxyphenol (polymerization inhibitor) 0.01 parts fluorinated surfactant 0.001 part (Product name: Megafac R08, manufactured by Dainippon Ink)
-Nonionic surfactant: 0.2 part (trade name: Emulgen A-60, manufactured by Kao Corporation)
・ 1,3-butylene glycol diacetate: 150 parts (solvent species having a boiling point of 200 ° C. or higher; solvent species 2)

[Example 6]
In Example 4, a blue (B) photocurable resin composition was prepared in the same manner as in Example 4 except that the RED compositions D and E were changed to the following BLUE compositions D and E, respectively.

-BLUE composition D-
Pigment Blue 15: 6 16 parts Pigment Violet 23 3 parts benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali Soluble resin, polyethylene glycol is propylene glycol monomethyl ether acetate solution (solid content: 50%) with repeating unit: 4 and weight average molecular weight Mw: 10000 20 parts Dispersant (trade name: Disperbyk-161, Big Chemie) 4 parts) Propylene glycol monomethyl ether acetate (solvent type with boiling point less than 200 ° C; solvent type 1) ... 200 parts

-BLUE composition E-
Propylene of benzyl methacrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 75/15/10 [mass ratio]) copolymer (alkali-soluble resin, polyethylene glycol is repeating unit: 4, weight average molecular weight Mw: 10,000) Glycol monomethyl ether acetate solution (solid content: 50%) ... 6 parts, epoxy resin ... 1 part (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.)
Polymerizable resin: (trade name Cyclomer P ACA-200, manufactured by Daicel Chemical Industries, Ltd .; 50% solution of dibromopyrene glycol monomethyl ether, solid content acid value: 118 KOH mg / g, double bond equivalent: 450 g / mol -Acrylic) 2 parts dipentaerythritol hexaacrylate (polymerizable compound) 18 parts 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2, 6-di (trichloromethyl) -s-triazine (photoinitiator) 2 parts 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 3 parts (trade name: IR369, manufactured by Ciba Specialty Chemicals, Inc .; photopolymerization initiator)
・ 2,4-diethylthioxanthone (photopolymerization initiator) ・ ・ ・ 0.5 part ・ p-methoxyphenol (polymerization inhibitor) ・ ・ ・ 0.01 part ・ Fluorine-based surfactant (trade name: Megafac R08, Dainippon Ink & Chemicals, Inc.) ... 0.001 part, nonionic surfactant ... 0.2 part (trade name: Emulgen A-60, manufactured by Kao)
・ 1,3 Butylene glycol diacetate ... 150 parts (solvent type with a boiling point of 200 ° C or higher; solvent type 2)

[Examples 7 to 9]
In each of Examples 4, 5, and 6, the polymerizable compound was replaced with an ethylene oxide 4-adduct of tetramethylolmethane tetraacrylate (Aronix TO-924, manufactured by Shigeo Gosei Co., Ltd.), and further used for composition E of each color. R, G, and B photocurable resin compositions in the same manner as in Examples 4, 5, and 6 except that solvent type 2 was replaced with dipropylene glycol monomethyl ether acetate (boiling point: 209 ° C). Was prepared.

[Examples 10 to 12]
In each of Examples 4, 5, and 6, each of the alkali-soluble resins was a benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight Mw: 10,000) propylene glycol monomethyl ether acetate solution. In place of (solid content 50%), the polymerizable compound was replaced with ethylene oxide 6 adduct of trimethylolpropane triacrylate (TMP-6EO-3A, manufactured by Kyoeisha Chemical Co., Ltd.), and further used for composition E of each color. Except that 150 parts of 1,3-butylene glycol diacetate was replaced with 100 parts of propylene glycol methyl ether acetate and 50 parts of 1,3-butylene glycol diacetate, the same as in each of Examples 4, 5, and 6, R, G, and B color curable resin compositions were prepared.

[Examples 13 to 15]
In each of Examples 4, 5, and 6, each of the alkali-soluble resins was a benzyl methacrylate / methacrylic acid (= 70/30 [mass ratio]) copolymer (weight average molecular weight Mw: 10,000) propylene glycol monomethyl ether acetate solution. Instead of (solid content 50%), the polymerizable compound was replaced with 18 ethoxylated glycerin triacrylate (NK ester A-GLY-18E, manufactured by Shin-Nakamura Chemical Co., Ltd.). -R, G in the same manner as in Examples 4, 5 and 6, except that 150 parts of butylene glycol diacetate was replaced with 100 parts of propylene glycol methyl ether acetate and 50 parts of 1,3-butylene glycol diacetate. , B photocurable resin compositions of each color were prepared.

[Examples 16 to 18]
In each of Examples 4, 5, and 6, the alkali-soluble resin was converted into a benzyl methacrylate / butyl acrylate / methacrylic acid / methoxy-terminated polyethylene glycol acrylate (= 40/35/20/5 [mass ratio]) copolymer, respectively. 1,3-butyleneglycol diethylene glycol used in the composition E of each color in place of a propylene glycol monomethyl ether acetate solution (solid content 50%) having an alkali-soluble resin, polyethylene glycol repeating unit: 12, weight average molecular weight Mw: 8000) Except for replacing 150 parts of acetate with 100 parts of propylene glycol methyl ether acetate and 50 parts of 1,3-butylene glycol diacetate, each of R, G, and B colors was obtained in the same manner as in Examples 4, 5, and 6. A photocurable resin composition was prepared.

[Examples 19 to 21]
In each of Examples 4, 5, and 6, 150 parts of 1,3-butylene glycol diacetate used for composition E of each color was replaced with 135 parts of propylene glycol methyl ether acetate and 15 parts of 1,3-butylene glycol diacetate. Except for the above, in the same manner as in Examples 4, 5, and 6, photocurable resin compositions of R, G, and B colors were prepared.

[Comparative Examples 10-12]
In each of Examples 4, 5 and 6, each of Examples 4, 5, and 6 except that the solvent (solvent type 2) of each color composition E was replaced with propylene glycol phenyl ether acetate (boiling point 258 ° C.) Similarly, photocurable resin compositions of R, G, and B colors were prepared.

[Comparative Examples 13 to 15]
In each of Examples 4, 5, and 6, the same as each of Examples 4, 5, and 6 except that the solvent (solvent type 2) of each color composition E was replaced with dipropylene glycol dimethyl ether (boiling point 175 ° C.). Thus, R, G, B color photocurable resin compositions were prepared.

The volume average particle diameters of the pigments used in the above Examples and Comparative Examples were as follows as a result of observing 50 powders before kneading and dispersing with SEM.
[Examples 1 to 3 and Comparative Examples 1 to 9]
Pigment Red 254 40nm
Pigment Yellow 139 45nm
Pigment Green 36 25nm
Pigment Yellow 150 35nm
Pigment Blue 15: 6 25 nm
Pigment Violet 23 40nm
[Examples 4 to 21 and Comparative Examples 10 to 15]
Pigment Red 254 20nm
Pigment Yellow 139 18nm
Pigment Green 36 19nm
Pigment Yellow 150 22nm
Pigment Blue 15: 6 15 nm
Pigment Violet 23 23nm

≪Measurement and evaluation≫
Using the photocurable compositions obtained in the above examples and comparative examples, the following measurements and evaluations were performed. The measurement and evaluation results are shown in Table 1.
<Measurement of average particle diameter of pigment>
The photocurable compositions obtained in the above examples and comparative examples were diluted 500 times with propylene glycol monomethyl ether acetate, and a light scattering particle size distribution analyzer (trade name: Microtrac UPA, manufactured by Nikkiso Co., Ltd.) The volume average particle size of the pigment in the photocurable composition was measured by a light scattering method.

<Evaluation of slit coating unevenness>
The slit coating unevenness was evaluated by the following method using a slit coating device having a slit head having a slit interval of 50 μm and a coating effective width of 20 mm and having a rotary roller type preliminary ejection device.
First, after 10 sheets were intermittently applied on a glass substrate, the slit head was kept in the air for 5 minutes. Subsequently, on a rectangular glass substrate having a width of 230 mm, a length of 300 mm, and a thickness of 0.7 mm, the distance between the slit and the substrate is adjusted so that the thickness of the coating film after drying is 2 μm. Ten sheets of the photocurable composition were intermittently applied again at a speed to obtain 10 coated substrates having a coated surface with a coating width of 210 mm and a length of 260 mm. After the application, it was pre-baked at 90 ° C. for 60 seconds with a hot plate, and then the number of stripe-like unevenness on the 10th application surface was visually counted under a sodium beam.
Evaluation was made with “◯” indicating no streak-like unevenness on the coated surface, “Δ” indicating 1-5, and “x” indicating 6 or more.

<Contrast evaluation>
Contrast was evaluated by measuring the contrast of the coated substrate obtained as described above with a contrast measuring device (trade name: BM-7, manufactured by Topcon Corporation). Here, an F10 three-wavelength tube is used as a backlight light source, the coated substrate is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, NPF-G1220DUN), and the polarizing plate shows the luminance when the polarizing plates are parallel. The value divided by the luminance when orthogonal was taken as the contrast value.

(Lattice pattern formation)
The obtained photocurable composition was applied on a 100 mm × 100 mm glass substrate (trade name: 1737, manufactured by Corning) so as to have a film thickness of 2.0 μm and dried in an oven at 90 ° C. for 120 seconds ( Pre-baked) to form a photocurable coating film. Then, using a HITACHI exposure machine LE4000A (all wavelengths), exposure was performed at 100 mJ / cm ² with a proximity gap of 300 μm using a mask having a line width of 15 μm (illuminance: 20 mW / cm ² ). Then, it developed with the 1.0% developing solution (25 degreeC) of alkali developing solution CDK-1 (Fuji Film Electronics Materials Co., Ltd.), and formed the grid pattern (colored resin film) for color filters.
At this time, the change of the line width with respect to the development time of the lattice pattern was measured with an optical microscope (200 times) and shown in Table 2 below. Further, the development latitude is compared based on the change in the line width with respect to the development time (see Table 2 and FIGS. 1 to 6 below). “○” indicates a relatively good and manufacturable aptitude, and “×” indicates a poorly manufacturable aptitude. The production suitability is not maintained as it is, but those requiring adjustment of the process conditions are shown as “Δ” and summarized in Table 1 below.

The symbols in Table 1 are as follows.
• BzMA: benzyl methacrylate • MAA: methacrylic acid • BA: butyl acrylate • Acr (EO) _n R: polyethylene glycol acrylate with alkoxy terminal • 1,3BGDA: 1,3-butylene glycol diacetate • DPMA: dipropylene glycol monomethyl ether Acetate, PPA: Propylene glycol phenyl ether acetate, DPDM: Dipropylene glycol dimethyl ether, PGMEA: Propylene glycol monomethyl ether acetate, MEK: Methyl ethyl ketone

As seen in Table 1, it was found that the photocurable composition of the present invention did not cause uneven coating of slits, had a high contrast value, had a wide development latitude, and a good color filter was obtained.
On the other hand, the contrast of the color filters (Comparative Examples 1, 4, and 7) having an average particle diameter of greater than 150 nm was significantly inferior to the contrast of the color filters of Examples 1 to 3.
In addition, a photocurable composition that does not have an alkylene oxide chain in the molecule of the alkali-soluble resin or polymerizable compound (Comparative Examples 2, 5, and 8), and a photocurable composition that does not contain a solvent having a boiling point of 200 ° C. or higher (Comparison) In Examples 3, 6, and 9), slit coating unevenness occurred.

It is a graph which shows the line | wire width change with respect to the development time in an Example. 6 is a graph comparing line width changes with development time in Example 1 and Comparative Example. It is a graph which shows the line | wire width change with respect to the development time in an Example. 7 is a graph comparing line width changes with development time in Example 2 and Comparative Example. It is a graph which shows the line | wire width change with respect to the development time in an Example. 7 is a graph comparing line width changes with development time in Example 3 and Comparative Example.

Claims (7)

In a photocurable composition containing a colorant, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the colorant has an average particle size of 150 nm or less, and the alkali-soluble resin has a molecular side chain. It has an alkylene oxide chain, and the solvent contains at least one kind of solvent having a boiling point of 200 ° C. or more and a kind of solvent having a boiling point of less than 200 ° C. A photocurable composition characterized in that a sum (ΣT · X) of a product (T · X) with a content X (% by mass) is 120 × 10 ^{2 to} 190 × 10 ² (° C. ·%). In a photocurable composition containing a colorant, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, the colorant has an average particle size of 150 nm or less, and the polymerizable compound has an alkylene oxide group. The solvent contains at least one kind of solvent having a boiling point of 200 ° C. or more and a kind of solvent having a boiling point of less than 200 ° C., and the content ratio X ( A photocurable composition characterized in that a sum (ΣT · X) of a product (T · X) with a mass%) is 120 × 10 ^{2 to} 190 × 10 ² (° C. ·%).   The photocurable composition according to claim 1 or 2, wherein the colorant is a pigment for red (R), and the content ratio in the solid content is 30% by mass or more.   The photocurable composition according to claim 1 or 2, wherein the colorant is a pigment for green (G), and the content ratio in the solid content is 40% by mass or more.   The photocurable composition according to claim 1 or 2, wherein the colorant is a blue (B) pigment, and the content ratio in the solid content is 20% by mass or more.   The color filter produced using the photocurable composition of any one of Claims 1-5.   The photocurable composition according to any one of claims 1 to 5 is applied onto a substrate by slit coating and dried to form a coating film, and pattern exposure is performed on the coating film, followed by alkali development. A method for producing a color filter characterized by the above.

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