JP5469471B2 - Colored photopolymerizable composition, colored pattern forming method, color filter, and liquid crystal display device, - Google Patents

Description

  The present invention relates to a colored photopolymerizable composition, a method for forming a colored pattern, a color filter, and a liquid crystal display device.

Examples of the colored photopolymerizable composition include those obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since such a colored photopolymerizable composition is polymerized and cured by irradiation with light, it is used in photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like.
In addition, as the colored photopolymerizable composition, for example, another embodiment is also known in which an acid is generated by light irradiation and the generated acid is used as a catalyst. Specifically, using a coloring reaction of a dye precursor catalyzed by the generated acid, a material for image formation, anti-counterfeiting, energy dose detection, a semiconductor utilizing a decomposition reaction catalyzed by the generated acid It is used for positive type resists for manufacturing, TFT manufacturing, color filter manufacturing, micromachine component manufacturing and the like.

  In recent years, colored photopolymerizable compositions that are particularly sensitive to light sources of short wavelengths (365 nm and 405 nm) have been desired from various applications, and compounds exhibiting excellent sensitivity to such short wavelength light sources, for example, There is an increasing demand for photopolymerization initiators. However, since a photopolymerization initiator having excellent sensitivity generally lacks stability, a photopolymerization initiator that satisfies the improvement in sensitivity and the stability over time is desired.

Thus, as photopolymerization initiators used for the colored photopolymerizable composition, the following Patent Documents 1 to 4 propose oxime ester derivatives. However, since these known oxime ester derivatives have low absorbance at a wavelength of 365 nm and a wavelength of 405 nm, they are still not satisfactory in terms of sensitivity.
In addition, as a colored photopolymerizable composition, there is a demand for a colored photopolymerizable composition that has excellent temporal stability and excellent sensitivity to light having a short wavelength such as 365 nm and 405 nm.
Furthermore, for example, Patent Document 5 discloses a colored radiation-sensitive composition for a color filter containing an oxime compound, but the stability over time and the sensitivity to light with a short wavelength are still insufficient. there were. Moreover, in the colored photopolymerizable composition for color filters, the reproducibility of the hue after pattern formation is a new problem, and improvement of the problem that the colorability changes with time has been strongly desired.

  On the other hand, a color filter for a liquid crystal display device has a strong demand for a color filter having a high coloring density in order to expand a color reproduction region. When a large amount of a colorant is added to achieve a high coloring density, the sensitivity is insufficient, and there is a tendency for pattern loss to occur frequently as a whole. In order to eliminate this loss, it is necessary to irradiate light with higher energy, so that the exposure time becomes longer and the manufacturing yield is significantly reduced. From the above, regarding a colored photopolymerizable composition for a color filter, a good pattern forming property is desired while containing a colorant at a high concentration.

  On the other hand, in order to increase the productivity of the exposure process and the development process, it has been proposed to perform pattern formation by exposing with laser light (see Patent Document 6). Unlike mercury lamps that are commonly used, lasers are expected to have features such as high straightness, high output, and ability to focus, and no need for masks for pattern formation in the exposure process. Has been. However, even with the above-described prior art, the characteristics required for the color filter are not satisfied, for example, the pixel surface is rough in the development process or the pattern is not sufficiently stable due to insufficient sensitivity. In view of reducing the total cost of the color filter, an exposure apparatus that does not use a large photomask has been proposed (see Patent Documents 7 and 8). However, there has been no presentation of specific materials, and there has been a demand for proposals for highly sensitive materials suitable for these devices.

US Pat. No. 4,255,513 US Pat. No. 4,590,145 JP 2000-80068 A JP 2001-233842 A JP 2006-195425 A JP 2003-287614 A JP 2008-76709 A JP 2008-51866 A

The first object of the present invention is to provide a colored photopolymerizable composition capable of forming a pattern having good pattern linearity and no chipping, having a wide development latitude and excellent developability. There is to do.
A second object of the present invention is to provide a method for forming a colored pattern having good pattern forming properties, a wide development latitude, and excellent productivity.
A third object of the present invention is to provide a color filter having a good pattern shape and excellent productivity, and a liquid crystal display device provided with the color filter.

As a result of intensive studies, the present inventors have solved the above problem by using an oxime compound having a specific structure. Specific means for solving the problem will be described below.
<1> (A) A colored photopolymerizable composition containing a compound represented by the following general formula (1), (B) a polymerizable compound, and (C) a colorant.

In General Formula (1), Y ¹ , Y ² , and Y ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, at least two of Y ¹ , Y ² , and Y ³ are methyl groups. R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents a monovalent substituent, and n is an integer of 0 to 5.

<2> The content of the compound represented by (A) the general formula (1) is 0.1% by mass to 30% by mass with respect to the total solid content in the colored photopolymerizable composition <1. > The colored photopolymerizable composition as described in>.
<3> The coloring according to <1> or <2>, wherein the content of the polymerizable compound (B) is 5% by mass to 80% by mass with respect to the total solid content in the colored photopolymerizable composition. Photopolymerizable composition.

<4> prior SL (C) coloring agent is a pigment, and further (D) a pigment dispersing agent <1> to colored photopolymerizable composition according to any one of <3>.

< 5 > a step of forming a colored photopolymerizable composition layer using the colored photopolymerizable composition according to any one of <1> to < 4 >;
Exposing and curing the colored photopolymerizable composition layer in a pattern, and
Removing the uncured colored photopolymerizable composition portion;
A method for forming a colored pattern, comprising:
< 6 > A color filter having a colored pattern formed on the support using the method described in < 5 >.
< 7 > A liquid crystal display device comprising the color filter according to < 6 >.

  According to the present invention, it is possible to provide a colored photopolymerizable composition capable of forming a pattern having good pattern linearity and having no chip, having a wide development latitude, and having excellent developability. And a color pattern having a good pattern forming property, a wide development latitude, and excellent productivity, and a color filter having a good pattern shape and excellent productivity, and the color A liquid crystal display device including a filter can be provided.

Hereinafter, the colored photopolymerizable composition of the present invention, a method for forming a colored pattern using the colored photopolymerizable composition, a color filter having the colored pattern, and a liquid crystal display device using the color filter will be described in detail. To do.
The colored photopolymerizable composition of the present invention comprises (A) a compound represented by the general formula (1) (hereinafter sometimes referred to as a specific oxime compound), (B) a polymerizable compound, and (C) coloring. It contains an agent.
First, the colored photopolymerizable composition of the present invention will be described.

<Compound represented by the general formula (1)>
The colored photopolymerizable composition of the present invention contains a compound (specific oxime compound) represented by the following general formula (1).

In General Formula (1), Y ¹ , Y ² , and Y ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, at least two of Y ¹ , Y ² , and Y ³ are methyl groups. R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents a monovalent substituent, and n is an integer of 0 to 5.

  The specific oxime compound of the present invention represented by the general formula (1) has a maximum absorption wavelength in a range of 350 nm to 480 nm in a wavelength region of 300 nm or more. The specific oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound. Therefore, when exposed with a light source of 355 nm, 365 nm, or 405 nm, excellent sensitivity is exhibited.

The specific oxime compound of the present invention preferably has a molar extinction coefficient at 365 nm of 20,000 to 200,000 from the viewpoint of sensitivity.
Here, the molar extinction coefficient of the specific oxime compound was measured at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian).

  The specific oxime compound of the present invention has a function as a photopolymerization initiator that is decomposed by light and initiates and accelerates polymerization of the polymerizable compound (B). In particular, since specific oxime compounds have excellent sensitivity to 365 nm and 405 nm light sources, they exhibit excellent effects when used as photopolymerization initiators in combination with polymerizable compounds in colored photopolymerizable compositions. To do.

  The colored photopolymerizable composition of the present invention has high sensitivity to light having a wavelength of 365 nm or 405 nm, is excellent in stability over time, and can form a cured film that can suppress coloring over time. Although the detailed mechanism is unknown, specific oxime compounds have a structure that absorbs light and suppresses recombination of radicals when cleaved, so that the amount of generated radicals increases and high sensitivity is achieved. Can do. Moreover, from the point that radical recombination is suppressed, it is considered that the reaction between the decomposition products of the specific oxime compound is suppressed during heating and coloration derived from the reaction is suppressed.

In the present invention, the color difference ΔE ^* ab may be used to evaluate the coloration of the cured film over time. Here, the color difference ΔE ^* ab can be measured with MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
As the conditions for the evaluation, first, the colored photopolymerizable composition of the present invention is subjected to an ultra-high pressure mercury lamp proximity type exposure machine or an i-line stepper exposure apparatus (365 nm) at 10 mJ / cm ^{2 to} 2500 mJ / cm. ^The film is exposed at various exposure amounts in the range of ² to form a cured film. Then, after developing as desired, the cured film is heated at 200 ° C. for 1 hour.
By measuring the color difference ΔE ^* ab before and after heating the cured film, the colored state of the cured film due to heating can be evaluated.
If the colored photopolymerizable composition of the present invention is used, the color difference ΔE ^* ab before and after heating can be made 3 or less, the color change due to heating can be greatly reduced, and a color filter with high color purity can be obtained. .

  The specific oxime compound of the present invention can be synthesized, for example, by the method described in JP-A-2007-26979 [0067] to [0069], but is not limited to this method.

Y ¹ , Y ² and Y ³ in the general formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least two of Y ¹ , Y ² and Y ³ are methyl It is a group.
R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Here, as the alkyl group having 1 to 6 carbon atoms of R ¹ and R ² , methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, iso-pentyl Group, neo-pentyl group, tert-pentyl group, hexyl group, iso-hexyl group, etc., preferably methyl group, ethyl group, and butyl group.
Particularly preferred is a compound in which when R ¹ is a methyl group or an ethyl group, R ² is an ethyl group or a butyl group.

  X in the general formula (1) represents a monovalent substituent, preferably a hydrogen atom or a methyl group. n is an integer of 0 to 5, preferably 1 or 2.

  Preferred structures of the specific oxime compound include the following compounds.

Content of the specific oxime compound in the colored photopolymerizable composition of this invention is 0.1-30 mass% in the total solid of a colored photopolymerizable composition, 1-25 mass% is more preferable, 2 -20% by weight is particularly preferred.
A specific oxime compound may be used individually by 1 type, and may use 2 or more types together.

In the colored photopolymerizable composition of the present invention, a known photopolymerization initiator other than the specific oxime compound may be used in combination as long as the effects of the present invention are not impaired.
The photopolymerization initiator that can be used in combination is a compound that is decomposed by light and starts and accelerates polymerization of a polymerizable compound described later, and preferably has absorption in a wavelength region of 300 to 500 nm. Specifically, for example, organic halogenated compounds, oxadiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, biimidazole compounds, organic boron Examples thereof include acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds. More specifically, for example, polymerization initiators described in paragraph numbers [0081] to [0139] of JP-A-2006-78749 can be mentioned.

<(B) Polymerizable compound>
The polymerizable compound (B) that can be used in the colored photopolymerizable composition is an addition polymerizable compound having at least one ethylenically unsaturated double bond, preferably at least one terminal ethylenically unsaturated bond. Is selected from compounds having two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Examples of these polymerizable compounds include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethyl After adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as Ruetan (meth) those acrylated, such as those of poly (meth) acrylate of pentaerythritol or dipentaerythritol.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, in general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a colored photopolymerizable composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

For these polymerizable compounds, details on how to use them, such as what type of structure is used, whether they are used alone or in combination, and how much is added, are optional depending on the performance design of the final photosensitive material. Can be set. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using the compound) is also effective. From the viewpoint of development speed and precipitation in a developer, a compound having a preferable molecular weight and hydrophobicity can be selected.
Further, the selection and use method of the polymerizable compound is also an important factor with respect to the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.).

From these viewpoints, the content of the polymerizable compound is preferably 5 to 80% by mass, more preferably 25 to 75% by mass, based on the total solid content of the colored photopolymerizable composition.
These polymerizable compounds may be used alone or in combination of two or more. In addition, the use method of the polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fog resistance, refractive index change, surface adhesiveness, and the like. .

<(C) Colorant>
The colored photopolymerizable composition of the present invention contains (C) a colorant. By containing a colorant, a colored photopolymerizable composition having a desired color can be obtained. The colored photopolymerizable composition of the present invention contains (A) a specific oxime compound having excellent sensitivity to a 365 nm or 406 nm light source that is a short wavelength light source, and therefore contains a colorant at a high concentration. In addition, it can be cured with high sensitivity.

  The colorant used in the colored photopolymerizable composition is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination, and these can be used as a colored photopolymerizable composition. It is appropriately selected according to the use of the product. If the colored photopolymerizable composition of the present invention is used for color filter production, it is generally used for forming chromatic colorants such as R, G, and B that form color pixels of color filters, and black matrix formation. Any of the black colorants used can be used.

Hereinafter, the colorant of the colored photopolymerizable composition will be described in detail using a colorant suitable for color filter applications as an example.
As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible.

  Examples of inorganic pigments 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, etc. And metal oxides of the above metals.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment violet 19, 23, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66, 79, 80;
C. I. Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene pigment A mixture with a red pigment can be used. 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, and C.I. I. Mixing with CI Pigment Yellow 139 is preferred. The mass ratio of the yellow pigment to the red pigment (yellow pigment / red pigment) is preferably 5/100 to 50/100 from the viewpoint of color purity and hue shift. In particular, the mass ratio is optimally in the range of 10/100 to 30/100. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. 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. Mixture with CI Pigment Yellow 185 is preferred. The mass ratio of yellow pigment to green pigment (yellow pigment / green pigment) is preferably in the range of 5/100 to 150/100 from the viewpoints of color purity and hue shift. On the other hand, if it exceeds 150/100, the dominant wavelength becomes longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 30/100 to 120/100.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with 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 purple pigment to blue pigment (purple pigment / blue pigment) is preferably in the range of 0/100 to 60/100, more preferably 40/100 or less.

Moreover, when using a colored photopolymerizable composition when forming black films, such as a black matrix, a black thing (black coloring agent) is used as a coloring agent.
In the present invention, as the black colorant, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density in a small amount, carbon black, titanium black, titanium oxide, iron oxide, Manganese oxide, graphite and the like are preferable, and among them, it is preferable to include at least one of carbon black and titanium black.
These black colorants may be used alone or in combination of two or more.

  The volume resistance value of carbon black is such that propylene glycol monomethyl ether is used so that carbon black has a molar ratio of benzyl methacrylate to methacrylic acid of 70:30 (mass average molecular weight 30,000) and 20:80 mass ratio. A coating solution is prepared by dispersing in, and coating on a chromium substrate having a thickness of 1.1 mm, 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm. The coating film is further heated at 220 ° C. in a hot plate, After heat treatment for about 5 minutes, a high resistivity meter manufactured by Mitsubishi Chemical Corporation conforming to JIS K 6911, Hirestar UP (MCP-HT450) was applied, and the volume resistance value was 23 ° C. and relative humidity 65%. Measure under the environment of Carbon black having a volume resistance value of 105 Ω · cm or more, more preferably 106 Ω · cm or more, and particularly preferably 107 Ω · cm or more is preferable.

  Examples of carbon black include, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, and JP-A-11-80584. Resin-coated carbon black described in Kaihei 9-124969 and JP-A-9-95625 can also be used.

  Examples of the titanium black suitable for the present invention include 12S, 13M, 13M-C, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Chemical Corporation.

The colorant that can be used in the colored photopolymerizable composition is a pigment satisfying an average particle size r (unit: nm) of 20 ≦ r ≦ 300, preferably 25 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. desirable. By using a pigment having such an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. Here, the “average particle size” means the average particle size of secondary particles in which primary particles (single crystallites) of the pigment are aggregated.
The particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of secondary particles having an average particle size of ± 100 nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments to be used (the average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is preferably preliminarily made into a pigment dispersion and used for the preparation of the colored photopolymerizable composition.

  The content of the colorant contained in the colored photopolymerizable composition is preferably 10 to 70% by mass in the total solid content of the colored photopolymerizable composition from the viewpoint of chromaticity and development latitude. 10-65 mass% is more preferable, and 10-60 mass% is still more preferable.

<(D) Pigment dispersant>
When the colored photopolymerizable composition contains a pigment as (C) a colorant, it is preferable to add (D) a pigment dispersant from the viewpoint of improving the dispersibility of the pigment.

Examples of the (D) pigment dispersant that can be used in the colored photopolymerizable composition of the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, and modified polyurethanes. , Modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, etc. Can be mentioned.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the colored photopolymerizable composition of the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group) manufactured by BYK Chemie. Polymer)), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), manufactured by EFKA “EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 ( Fatty acid polyester), 6745 (derivatized phthalocyanine) ), 6750 (Azo Pigment Derivatives) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. Polymer) ”, manufactured by Enomoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA- 725 ", Kao's" Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymer polycarboxylic acid) Acid) "," Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearylamine acetate) ”, Lubrizol Corporation“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (functional part at the terminal part) 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. Can be mentioned.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the pigment dispersant in a colored photopolymerizable composition, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, and 10-60 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment.
In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  The content of the pigment dispersant is preferably 3% by mass or more and 40% by mass or less based on the total solid content in the colored photopolymerizable composition from the viewpoint of dispersibility of the pigment as the colorant. More preferably, the content is from 35% by mass to 35% by mass, and further preferably from 7% by mass to 30% by mass.

The colored photopolymerizable composition may further contain optional components described in detail below, if necessary.
Hereinafter, optional components that the colored photopolymerizable composition may contain will be described.

<(E) Sensitizer>
The colored photopolymerizable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes the above-mentioned (A) specific oxime compound by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm. Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums ( For example, squarylium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 20% by mass with respect to the total solid content of the colored photosensitive composition from the viewpoints of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

<(F) Co-sensitizer>
The colored photopolymerizable composition preferably further contains (F) a co-sensitizer.
In the present invention, the co-sensitizer further improves the sensitivity of (A) the specific oxime compound and (E) the sensitizer to active radiation, or suppresses the inhibition of polymerization of the polymerizable compound (B) by oxygen. Has an effect.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1 to 30% by mass with respect to the total solid content of the colored photopolymerizable composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. The range is preferable, the range of 1 to 25% by mass is more preferable, and the range of 1.5 to 20% by mass is further preferable.

  The colored photopolymerizable composition preferably contains a thiol compound as a co-sensitizer. A thiol compound may be used individually by 1 type, or may use 2 or more types together. When a thiol compound is used in combination, only two or more compounds represented by any of the general formulas described above may be used in combination, or compounds represented by different general formulas may be used in combination.

  When the colored photopolymerizable composition contains a thiol compound, the content thereof is the total solid content of the colored photopolymerizable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. On the other hand, the range of 0.5-30 mass% is preferable, the range of 1-25 mass% is more preferable, and the range of 3-20 mass% is still more preferable.

<(G) Binder polymer>
In the colored photopolymerizable composition, a binder polymer can be further used as necessary for the purpose of improving the film properties. It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. No. 271741, JP 2002-107918, etc., urethane-based binder polymer containing acid groups, and JP-A 2002-107918, urethane-based binders having an acid group and a double bond in the side chain The polymer is very excellent in strength and advantageous in terms of suitability for low exposure.
Further, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patents 993966, European Patents 1204000, JP-A-2001-318463, etc. is excellent in the balance of film strength and developability, and is suitable. It is. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomers as required] copolymers, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition-polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity and developability.

The weight average molecular weight of the binder polymer that can be used in the colored photopolymerizable composition is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1, It is 000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the colored photopolymerizable composition include known compounds such as an azo initiator and a peroxide initiator.

<(H) Polymerization inhibitor>
In the colored photopolymerizable composition, a small amount of a thermal polymerization inhibitor may be added to prevent unnecessary thermal polymerization of the polymerizable compound (B) during the production or storage of the colored photopolymerizable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the colored photopolymerizable composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

<(I) Adhesion improver>
In the colored photopolymerizable composition, an adhesion improver can be added in order to improve adhesion with a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

  Silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  The addition amount of the adhesion improver is preferably 0.5 to 30% by mass, more preferably 0.7 to 20% by mass in the total solid content of the colored photopolymerizable composition.

<(J) Diluent>
The colored photopolymerizable composition may use various organic solvents as a diluent.
Examples of the organic solvent used here include methyl ethyl ketone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, γ-butyrolactone, methyl lactate, and ethyl lactate.
These solvents can be used alone or in combination. The amount of the organic solvent in the colored photopolymerizable composition is preferably used so that the solid content concentration of the colored photopolymerizable composition is 2 to 60% by mass.

<(K) Other additives>
Furthermore, a known additive such as a plasticizer may be added to the colored photopolymerizable composition in order to improve the physical properties of the cured film.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added to the total mass of the polymerizable compound and the binder polymer.

  Moreover, by containing a fluorine-type organic compound and surfactant, the liquid characteristic (especially fluidity | liquidity) when it is set as a coating liquid can be improved, and the uniformity of coating thickness and liquid-saving property can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. 3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

As the surfactant, various nonionic, cationic and anionic surfactants can be used. Among these, nonionic surfactants are preferable.
Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred.

  It is also effective to contain a thermal polymerization component in the colored photopolymerizable composition of the present invention. By adding a thermal polymerization component such as an epoxy compound, the strength of the coating film can be increased and the solvent resistance is improved. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. The cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type As alicyclic epoxy compounds, such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, Examples include GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Other examples include diglycidyl esters, amine-type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl esters obtained by modifying the skeleton of bisphenol A-type epoxy resin with dimer acid.

<Coloring pattern forming method and color filter having the same>
Next, the color pattern forming method of the present invention and the color filter having the color pattern will be described. The color filter of the present invention has a colored pattern formed on the support using the colored photopolymerizable composition of the present invention.
Hereinafter, the colored pattern forming method of the present invention and the color filter having the same will be described in detail.

  The colored pattern forming method of the present invention comprises a step of forming a colored photopolymerizable composition layer on a support using the colored photopolymerizable composition of the present invention (hereinafter referred to as “colored photopolymerizable composition layer as appropriate”). Abbreviated as “formation step”), a step of exposing and curing the colored photopolymerizable composition layer in a pattern (hereinafter abbreviated as “exposure step” where appropriate), development, and uncured. And a step of removing the colored photopolymerizable composition layer (hereinafter abbreviated as “development step” as appropriate).

Specifically, the colored photopolymerizable composition of the present invention is applied directly or via another layer onto a support (substrate) to form a colored photopolymerizable composition layer (colored photopolymerizable). Composition layer forming step), exposing in a pattern through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), developing with a developer (development step), and these steps Is repeated to form a colored pattern having pixels of each color (three colors or four colors) to manufacture a color filter.
Hereinafter, each process in the formation method of the coloring pattern of this invention is demonstrated.

[Colored photopolymerizable composition layer forming step]
In the colored photopolymerizable composition layer forming step, the colored photopolymerizable composition layer of the present invention is coated on the support to form a colored photopolymerizable composition layer.

Examples of the support that can be used in this step include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and image sensors. For example, a photoelectric conversion element substrate such as a silicon substrate or a complementary metal oxide semiconductor (CMOS) is used. These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the colored photopolymerizable composition on the support, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

The coating film thickness of the colored photopolymerizable composition is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, and still more preferably 0.2 μm to 3 μm in terms of the film thickness after drying.
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness of a coloring photopolymerizable composition, 0.35 micrometer-1.5 micrometers are preferable from a viewpoint of resolution and developability, and 0.40 micrometer. -1.0 micrometer is more preferable.

  The colored photopolymerizable composition coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a colored photopolymerizable composition layer.

[Exposure process]
In the exposure step, the colored photopolymerizable composition layer formed in the colored photopolymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

  Other exposure light sources include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

<Exposure process using laser light source>
In an exposure method using a laser light source, an ultraviolet laser is used as the light source. Laser is an acronym for English Light Amplification by Stimulated Emission of Radiation. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The wavelength that can be used in the present invention is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. It is preferable in that it does.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  An exposure apparatus using a laser light source that can be used in the present invention is not particularly limited, but commercially available devices include Callisto (buoy technology), EGIS (buoy technology), and DF2200G (large). Nippon Screen Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.

  Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

  Since the parallelism of the ultraviolet laser is good, pattern exposure can be performed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene at a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution diluted with pure water so as to be 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the colored pattern forming method of the present invention, after the above-described colored photopolymerizable composition layer forming step, exposing step, and developing step, the formed colored pattern is heated and / or if necessary. A curing step of curing by exposure may be included.

  By repeating the above-described colored photopolymerizable composition layer forming step, exposing step, and developing step (and, if necessary, the curing step) for the desired number of hues, a colored pattern having a desired hue is obtained, and color A filter is produced.

Here, as a method for forming the colored pattern of the present invention, the embodiment using the colored photopolymerizable composition of the present invention when forming the colored pattern of the color filter has been mainly described, but the present invention is limited to this embodiment. It is not something. For example, the colored photopolymerizable composition of the present invention can also be applied to the formation of a black matrix that isolates the colored patterns (pixels) constituting the color filter.
Specifically, using the colored photopolymerizable composition of the present invention containing a black colorant such as carbon black or titanium black, as described above, a colored photopolymerizable composition layer forming step, an exposure step, and development. A black matrix (black pattern) can be formed on the substrate by performing a process (and a curing process if necessary).

  Since the color filter thus obtained uses the colored photopolymerizable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is resistant to development. Therefore, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

Compound 1 which is a specific oxime compound was synthesized by the following method.
(Synthesis Example 1: Synthesis of Compound 1 which is a specific oxime compound)
First, Compound A was synthesized according to the following scheme.
Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C., aluminum chloride (70.3 g, 0.527 mol) was added. Subsequently, o-tolyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. Next, after cooling to 0 ° C., aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. A mixed solution of 156 ml of 35 mass% hydrochloric acid aqueous solution and 392 ml of distilled water was cooled to 0 ° C., and the reaction solution was added dropwise. The precipitated solid was filtered with suction, washed with distilled water and methanol, and recrystallized with acetonitrile to obtain Compound A (yield 164.4 g, yield 77%) having the following structure.

Next, Compound B is synthesized using Compound A according to the following scheme.
Compound A (86.5 g, 209 mmol) was dissolved in 277 ml of THF, 2,6-dimethylbenzenethiol (30 g, 217 mmol) and sodium iodide (3.0 g, 20.0 mmol) were added, and the mixture was stirred at 40 degrees. Subsequently, sodium hydroxide (8.66 g, 216 mmol) was added to the reaction solution, and the mixture was refluxed at 40 ° C. for 2 hours. Next, after cooling to 0 ° C., a methanol solution of sodium methoxide (concentration 28 wt%, 48 g, 249 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 2 hours. Next, after cooling to 0 ° C., isopentyl nitrite (29.3 g, 250 mmol) was added dropwise over 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted with 105 ml of acetone and washed with a 0.1N hydrochloric acid aqueous solution cooled to 0 ° C. After extracting the organic phase with ethyl acetate, methanol was added and the precipitated solid was filtered with suction. Subsequently, recrystallization was performed with acetonitrile to obtain Compound B having the following structure (yield: 76.6 g, yield: 67%).

Subsequently, compound 1 is synthesized by the following scheme using compound B.
Compound B (46.4 g, 85 mmol) was dissolved in 230 ml of ethyl acetate and triethylamine (10.3 g, 101 mmol) was added. Next, after cooling to 0 ° C., acetyl chloride (8.0 g, 102 mmol) was added dropwise over 20 minutes, and then the mixture was warmed to room temperature and stirred for 1 hour. The reaction solution was washed with 1000 ml of distilled water cooled to 0 ° C. and extracted with ethyl acetate. After concentration under reduced pressure, the solution was added dropwise to 100 ml of distilled water, and the precipitated solid was subjected to suction filtration, washed with 150 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound 1 having the following structure (yield 49.7 g, yield 99%). )

The structure of the obtained compound 1 was identified by NMR.
( ¹ H-NMR 400 MHz CDCl ₃ ): 8.84 (s, 1H), 8.57 (s, 1H), 8.31 (d, 1H, J = 8.0 Hz), 8.08 (d, 1H , J = 8.0 Hz), 7.446-7.24 (m, 4H), 7.48 (q, 2H, 7.4 Hz), 7.09 (d, 3H), 3.10-2.90. (M, 4H), 2.50 (s, 6H), 2.35 (s, 3H), 2.17 (s, 3H), 1.48 (t, 3H, 7.4 Hz)

  The structures of Comparative Compound 1 to Comparative Compound 3 are as follows.

[Example 1-1]
[1. Preparation of colored photopolymerizable composition A-1]
As the colored photopolymerizable composition, a negative colored photopolymerizable composition A-1 containing a colorant (pigment) was prepared, and a color filter was produced using the negative colored photopolymerizable composition A-1.

(Synthesis Example 2) Synthesis of Resin (i-1) 6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature. A polyester resin (i-1) was obtained.
A synthesis scheme is shown below.

(Synthesis Example 3) Synthesis of Resin (J-1) Polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) 10 g and polyester resin (i-1) 100 g were mixed, and 120 ° C. for 3 hours. The intermediate (J-1B) was obtained by heating. Thereafter, the mixture was allowed to cool to 65 ° C., 200 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Then, PGMEA was added and the 10% PGMEA solution of resin (J-1) was obtained. Resin (J-1) has a side chain derived from polyester (i-1) and a carboxy group derived from succinic anhydride.
A synthesis scheme is shown below.

1-1. Preparation of pigment dispersion -Preparation of dispersion of yellow pigment PY150-
As a pigment, C.I. I. 40 parts (average particle diameter 60 nm) of Pigment Yellow 150 (PY150), 223 parts of PGMEA 10% solution of the resin (J-1) (22.3 parts in terms of solid content) was mixed with a bead mill (zirconia beads 0. 3 mm) to mix and disperse for 3 hours to prepare a pigment dispersion.

-Preparation of dispersion of green pigment PG36-
As a pigment, C.I. I. A mixed liquid consisting of 40 parts of pigment green 36 (PG36) (average particle diameter 60 nm) and 200 parts of resin (i-1) (20 parts in terms of solid content) was mixed for 3 hours using a bead mill (zirconia beads 0.3 mm). Dispersed to prepare a pigment dispersion. With respect to the pigment dispersion, the average primary particle diameter of the pigment was measured using a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.

1-2. Preparation of colored photopolymerizable composition A-1 (coating liquid) The components of the following composition A-1 were mixed and dissolved to prepare a colored photopolymerizable composition A-1.

<Composition A-1>
-Green pigment PG36 dispersion 26.1 parts-Yellow pigment PY150 dispersion 14.3 parts-Binder resin (benzyl methacrylate-methacrylic acid copolymer (= copolymerization molar ratio 7: 3), weight average molecular weight 5000)
2.8 parts / polymerizable monomer having 5 to 6 polymerizable groups in one molecule (Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA, 7: 3 of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Mass ratio) mixture
3.54 parts-photopolymerization initiator (compound 1) 1.02 parts-compound having an epoxy ring (1,2-epoxy-4- (2-oxolanyl of 2,2-bis (hydroxymethyl) -1-butanol) ) Cyclohexane adduct, manufactured by Daicel Chemical Industries, Ltd. EHPE-3150) 0.480 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0018 parts ・ Surfactant (fluorine-based surfactant, manufactured by DIC, Inc., trade name: Megafuck F781) -F)
0.0334 parts ・ Silane coupling agent (3-methacryloyloxy-trimethoxysilylpropane)
0.320 parts Solvent (PGMEA) 51.42 parts

In addition, the conditions of the gel permeation chromatography method (GPC) measurement which calculates | requires a weight average molecular weight and a number average molecular weight are as follows.
Column used: TSKgel Multipore HXL-M
(Porous polydisperse type linear column) manufactured by Tosoh Eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Tosoh HLC-8220)

[2. (Production of color filter)
2-1. Formation of Colored Photopolymerizable Composition Layer Using a colored photopolymerizable composition A-1 containing the pigment obtained as described above as a resist solution, slit coating was performed on a glass substrate provided with a black matrix of 550 mm × 650 mm under the following conditions. Thereafter, vacuum drying (66 Pa) and prebaking (80 ° C., 160 seconds) were performed to form a colored photopolymerizable composition coating film (colored photopolymerizable composition layer).

(Slit application conditions)
Opening gap at the tip of the coating head: 100 μm
Coating speed: 150 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure, Development Then, the colored photopolymerizable composition layer was exposed in a pattern at 60 mJ / cm ² using a proximity exposure machine (manufactured by Hitachi High-Technology Corporation, LE5565A). The entire surface of the colored photopolymerizable composition layer after exposure is showered with a 1.0% aqueous solution (25 ° C.) of an inorganic developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.). It was set to 0.2 MPa, developed for 60 seconds, and washed with pure water.

2-3. Heat treatment Thereafter, pure water was sprayed onto the colored photopolymerizable composition layer in a shower to wash away the developer, and then heated in an oven at 220 ° C. for 1 hour (post-bake).

2-4.
Thereafter, a colored pattern is formed with a blue colored photopolymerizable composition (CB-9500L; manufactured by Fuji Film Electronics Materials Co., Ltd.), and further a red colored photopolymerizable composition (CR-9500L; Fuji Film Electronics). A colored pattern is formed with Materials Co., Ltd., ITO is deposited, a spacer is formed using a photopolymerizable composition (CSP-3210L; manufactured by FUJIFILM Electronics Materials Co., Ltd.), and the substrate is formed on the substrate. Color filters having green, red, and blue coloring patterns were obtained.

[3. (Performance evaluation)

-Colored layer development process, colored layer baking (post-baking) process-
The same operations as those up to the above step 2-1 are performed, and then using a developing device (manufactured by Hitachi High-Technologies Corporation), a potassium hydroxide developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) The shower pressure was set to 0.2 MPa with a 1.0% developer (CDK-1 1 part by weight, pure water 99 parts by weight diluted solution, 25 ° C.), and the development time was 10 to 110 seconds. And developed in increments of 10 seconds and washed with pure water (Example 3-1). In addition, Example 3-2 to Example 3-8 and Comparative Example 103-1 to Comparative Example 103-3 were carried out by changing the initiator as shown in Table 1.

  Sensitizers A1 to A3 and cosensitizers F1 to F3 shown in Table 1 are the compounds shown below.

-Evaluation of development time-
The substrate with a development time of every 10 seconds was observed with an optical microscope, and the development status was evaluated. In Table 2, the lower limit of the development time is the lower limit number of seconds of usable development time, and the non-pixel portion cannot be removed in a time shorter than this time. The upper limit of the development time is the upper limit of the usable development time in seconds. If the time is longer than this time, the pixel is missing or dropped out. Moreover, 80 seconds or less are preferable from the restriction of the process (tact time). The development latitude indicates a difference in the number of seconds between the upper limit of the development time and the lower limit of the development time.

-Evaluation of pattern linearity-
An edge portion of the colored pattern was photographed and evaluated using an optical microscope (200 times in reflection mode). Observe the pixel edge in a 5cm x 5cm photo, and "good" if the pixel edge looks straight, part of the pixel edge (within 1/3 of the total length) "Slightly good" if it is not linear but not jagged, or if the pixel edge part is not linear with more than 1/3 of the total length, or part (1 of the total length / 4 or less) is “slightly bad”, and the pixel edge portion is more than ¼ of the entire length and is “bad”.
The edge portion of the pixel pattern is preferably linear. If the edge portion of the pixel pattern becomes jagged due to the remaining film, undercut, or the like, it is necessary to increase the overlap with the black matrix, which widens the width of the black matrix and lowers the aperture ratio. Further, when the overlap with the black matrix is not increased, there is a possibility that a white portion without a colored layer is formed near the edge of the black matrix. Furthermore, when the edge portion of the pixel pattern is jagged, there is a problem that the transparent electrode formed thereon is disconnected and the resistance value is increased.

−Evaluation of bites−
The edge portion of the pixel pattern was photographed and evaluated using an optical microscope (200 times in reflection mode). The edge of the pixel is observed in a 5cm x 5cm photo, and it becomes a chipped shape (usually a half-moon-shaped edge part. Depending on the case, it may be even longer, but the line width from the periphery. Was discontinuously thinned and was recognized as being missing), it was evaluated as “B” with the presence of chipping. The case where no chip was seen was designated as “A”.
When chipping occurs, the portion is white and light is lost, which is not preferable.

  From Table 2, Examples 3-1 to 3-8 using the specific oxime compound of the present invention have high development latitude in pattern formation, good linearity of the pattern, and good developability without occurrence of chipping. Indicated. In contrast, Comparative Examples 103-1 to 103-3, which do not use a specific oxime compound, have a small development latitude and poor pattern linearity. In Comparative Example 103-3, chipping occurs and the developability is poor. I understand.

Furthermore, instead of Compound 1, Example 3 was used using Compound 2 and Compound 3 exemplified in the text (synthesized in the same manner as in Synthesis Example 1 except that benzenethiol was changed to the corresponding compound). When the colored photopolymerizable composition was prepared in the same manner as in Example -1 and evaluated in the same manner as in Example 3-1, the same result as in Example 3-1 was obtained. Further, in the pixel obtained in Example 3-1, when processing at 230 ° C. for 30 minutes was performed in an oven, ΔE ^* ab was 3 or less.

(Example 4-1)
In the composition of Example 3-1, the dispersion of the green pigment PG36 is the same as that of the blue pigment PB15: 6 (except that the pigment type is PB15: 6 and the dispersant is Disperbyk-161, Big Chemie). The composition was prepared in the same manner as the PG36 dispersion.) In 28.9 parts, the dispersion of yellow pigment PY150 was a dispersion of purple pigment PV23 (the pigment type was PV23, and the dispersant was Disperbyk- The composition was the same as that of the PG36 dispersion except that it was changed to 161.) In 11.5 parts, a polymerizable compound having 5 to 6 polymerizable groups in one molecule was added to NK ester A-TMMT. Using the same as that of Shin-Nakamura Chemical Co., Ltd., and using the same procedure as in Example 3-1, except that the exposure process was changed to the following, A compatible composition was prepared, and developability (development latitude, pattern linearity, chipping) was evaluated in the same manner as in Example 3-1. Good developability results similar to those of Example 3-1 were obtained.

From this result, it can be seen that even with pattern exposure using a laser exposure machine, the excellent effects of the present invention can be obtained as with exposure using a high-pressure mercury lamp.
(Exposure process)
Using EGIS (buoy technology Co., Ltd., YAG laser third harmonic wavelength 355 nm, pulse width 6 nsec) as the laser exposure apparatus, the colored photopolymerizable composition layer surface was irradiated with a pulse of about 1 mJ / cm ^2. It was done through a photomask.

Claims (7)

(A) A colored photopolymerizable composition containing a compound represented by the following general formula (1), (B) a polymerizable compound, and (C) a colorant.


In General Formula (1), Y ¹ , Y ² , and Y ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, at least two of Y ¹ , Y ² , and Y ³ are methyl groups. R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents a monovalent substituent, and n is an integer of 0 to 5.   The content of the compound represented by (A) the general formula (1) is 0.1% by mass to 30% by mass with respect to the total solid content in the colored photopolymerizable composition. Colored photopolymerizable composition.   The colored photopolymerizable composition according to claim 1 or 2, wherein the content of the polymerizable compound (B) is 5% by mass to 80% by mass with respect to the total solid content in the colored photopolymerizable composition. Composition. The colored photopolymerizable composition according to any one of claims 1 to 3 , wherein the (C) colorant is a pigment and further contains (D) a pigment dispersant. Forming a colored photopolymerizable composition layer using the colored photopolymerizable composition according to any one of claims 1 to 4 , and
Exposing and curing the colored photopolymerizable composition layer in a pattern, and
Removing the uncured colored photopolymerizable composition portion;
A method for forming a colored pattern, comprising: A color filter having a colored pattern formed on the support using the method according to claim 5 . A liquid crystal display device comprising the color filter according to claim 6 .