KR20080070529A - Curable composition, color filter and method of producing thereof - Google Patents

Abstract

A curing composition, a color filter prepared by using the composition, and a method for preparing the color filter are provided to improve coating property, sensitivity, resolution, pattern shape and the adhesion to a substrate and to widen the latitude in case of development. A curing composition comprises a colorant; a photopolymerization initiator; an alkali-soluble resin; and a multifunctional monomer having an ethylenically unsaturated bond, wherein the photopolymerization initiator comprises a non-imidazole compound, a mercapto compound, ant at least one compound selected from an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative and a coumarin derivative; and the multifunctional monomer having an ethylenically unsaturated bond contains a hydroxyl group and has a double bond density of 09.6-11.5 mmol/g per 1 g of the multifunctional monomer.

Description

Curable composition, color filter and its manufacturing method {CURABLE COMPOSITION, COLOR FILTER AND METHOD OF PRODUCING THEREOF}

The present invention is a curable composition suitable for producing a color filter for use in a liquid crystal display (LCD) or a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS), etc.) And a color filter using the same and a method of manufacturing the same.

The color filter is an essential component of a liquid crystal display or a solid-state image sensor.

In the liquid crystal display, the display device is compact compared to a cathode ray tube (CRT), and is replaced by a CRT as a television screen, a PC screen, or other display devices in that it is more than equivalent in performance. In recent years, the trend of the development of liquid crystal displays ranges from conventional monitor applications in which screens are relatively small, to television (TV) applications in which screens are large and require high image quality.

In liquid crystal displays for TV applications, higher image quality is required as compared with conventional display applications. Moreover, the monitor size of the liquid crystal display used by the spread of a mobile telephone and a car navigation system is becoming small these days, and the display of higher resolution is calculated | required. Further, even in a color filter for a solid-state image sensor, higher definition is required.

In order to improve contrast among the above-mentioned high image quality, a smaller one is required as the particle size of a colorant (organic pigment, etc.) used in the curable composition used in the production of a color filter (for example, Japanese Patent No. 3120547 See publication number). This tends to increase the amount of dispersant added for pigment dispersion.

Moreover, as a content rate of the coloring agent (organic pigment) in solid content of a curable composition, in order to improve color purity among high image quality, the higher thing is calculated | required. Therefore, there exists a tendency for the content rate of the photoinitiator and photopolymerizable monomer to occupy in solid content in curable composition to fall. Therefore, the curable composition needed to be highly sensitive.

Higher concentration of the colorant for improving the sensitivity results in a decrease in resolution accompanied by a decrease in the content of the photopolymerization initiator and the photopolymerizable monomer, and the pattern line width becomes thicker, resulting in poor display of the display. In addition, the size of the monitor is remarkable.

In order to improve the sensitivity, a combination of a chain transfer agent such as a polyfunctional thiol and a photosensitive resin is recommended (see Japanese Patent No. 3120547), but since these materials have low alkali solubility, it is difficult to achieve high sensitivity and proper pattern formation. Do. In addition, polyfunctional thiols have high reactivity, making it difficult to secure stability over time with resist.

By the way, when resolution, such as a mobile telephone or a car navigation system, is required for the resolution and the pattern line width control, it is particularly important to reduce the thickness width of the fine line width. In order to reduce the line width, it is effective to lower the amount of the initiator, but the shape is deteriorated, so that both the line width and the shape are difficult to achieve.

In order to improve all the above-mentioned drawbacks of the prior art, the present invention is excellent in coating film properties, hardening with high sensitivity, excellent resolution, showing good pattern formability even when the coloring agent is contained at a high concentration, and has a wide latitude during development. And the curable composition excellent in adhesiveness with a support body.

Moreover, this invention provides the color filter which has the pixel excellent in the resolution which uses the curable composition of this invention, and the manufacturing method which can manufacture this color filter with high productivity.

In view of the above circumstances, the inventors of the present invention have conducted intensive studies, and have found that the use of a curable composition containing a specific photopolymerization initiator and a specific polyfunctional monomer can solve the above problems, thereby completing the present invention.

That is, this invention (1) (A) coloring agent,

(B) photoinitiator,

(C) alkali soluble resins and

(D) a polyfunctional monomer having an ethylenically unsaturated bond

As a curable composition containing

The (B) photoinitiator may be selected from (i) a biimidazole compound, (ii) a mercapto compound, and (iii) an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative, and a coumarin derivative. Containing, and

The (D) polyfunctional monomer having an ethylenically unsaturated bond has a hydroxyl group in the molecule and

The double bond density which is the number of millimoles of a double bond per 1g of polyfunctional monomers which have the said ethylenically unsaturated bond (D) contains at least 1 sort (s) of polyfunctional monomers which are 9.6 mmol / g or more and 11.5 mmol / g or less. To provide.

This invention provides the curable composition as described in said (1) characterized by the above-mentioned (D) polyfunctional monomer which has said (D) ethylenically unsaturated bond.

This invention has the pixel formed using (3) the curable composition as described in said (1) or (2), The color filter characterized by the above-mentioned.

The present invention (4) the step of applying the curable composition as described in (1) or (2) on the support to form a curable composition layer,

Exposing the curable composition layer through a mask;

It provides the manufacturing method of the color filter characterized by including the process of developing the curable composition layer after exposure, and forming a coloring pattern.

In order to improve all the above-mentioned drawbacks of the prior art, the present invention is excellent in coating film properties even when the coloring agent is contained at a high concentration, is cured with high sensitivity, shows good pattern formation properties, has a wide latitude during development, and supports Since it is excellent in adhesiveness with and the width of the line width with respect to the mask width is small, the curable composition with high resolution can be provided.

Moreover, this invention can provide the color filter which has the pixel excellent in the resolution formed using the said curable composition, and the manufacturing method which can manufacture this color filter with high productivity.

Hereinafter, the color filter which uses the curable composition of this invention, this curable composition, and its manufacturing method are demonstrated in detail.

Curable composition

The curable composition of the present invention is a radiation sensitive composition, and is particularly suitable for curing with light, and has a (A) coloring agent, (B) photopolymerization initiator, (C) alkali-soluble resin, and (D) polyfunctional unsaturated bond. A monomer, and the (B) photopolymerization initiator contains at least one compound selected from a biimidazole compound, a mercapto compound, an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative, and a coumarin derivative. (D) A polyfunctional monomer having an ethylenically unsaturated bond has a hydroxyl group in the molecule, and it contains at least one polyfunctional monomer having a double bond density of 9.6 mmol / g or more and 11.5 mmol / g or less.

The curable composition of this invention may contain a solvent and other components as needed.

Hereinafter, each compound contained in the curable composition of this invention is demonstrated one by one. First, the polyfunctional monomer which has the said (D) ethylenically unsaturated bond is demonstrated.

(D) a polyfunctional monomer having an ethylenically unsaturated bond

The curable composition of this invention contains the (D) polyfunctional monomer which has an ethylenically unsaturated bond (henceforth "the polyfunctional monomer in this invention").

The polyfunctional monomer having an (D) ethylenically unsaturated bond, which is an addition polymerizable compound having at least one ethylenically unsaturated double bond, which can be used in the present invention has one hydroxyl group in the molecule, and the double bond density is 9.6. mmol / g or more and 11.5 mmol / g or less.

When exposing and developing the curable composition layer formed by using the curable composition which has the said polyfunctional monomer, the thickness and pattern shape of the line width conventionally observed are not observed, and both line width and pattern shape are attained. Moreover, the speed (break time) which an unexposed part lacks by image development also becomes quick.

The binding position in the molecule | numerator of the said hydroxyl group which the polyfunctional monomer in this invention has is not specifically limited.

Although the said double bond density in this invention needs to be in the said range in order to show the effect of this invention, in view of a sensitivity, a pattern shape, fine adjustment of a line width, and the improvement of a resolution, the unsaturated group content per molecule is a specific value. It is preferably 10.0 mmol / g or more and 11.5 mmol / g or less, More preferably, it is 10.2 mmol / g or more and 11.5 mmol / g or less, Especially preferably, it is 10.5 mmol / g or more and 11.5 mmol / g It is as follows.

Here, "double bond density (mmol / g)" in this invention means the number of millimoles of a double bond per polyfunctional monomer (1g) (mmol). For example, with respect to exemplary compound A-1, the double bond density is 10.1 (3000 (mmol) /298.29 (g)) in that the molecular weight is 298.29 and the double bond is 3000 mmol.

Although the polyfunctional monomer in this invention should have the said hydroxyl group, and should have a double bond density of the said specific range, it is preferable that it is trifunctional or more from a viewpoint of a pattern shape, a line width, and a resolution, and trifunctional or more than 8 functional is more preferable. And trifunctional or more than 6 functional is more preferable, and trifunctional and tetrafunctional are especially preferable.

By setting the polyfunctional monomer in this invention to trifunctional or more, it becomes excellent in pattern formation property, and it becomes the tendency for a crack and peeling of a pattern to be less likely to occur, and it is preferable.

Although the polyfunctional monomer in this invention may be used individually by 1 type, and may use plurality together, in order to raise the intensity | strength of an image part, ie, a cured film, it is necessary to use together the group which has a different functional number and / or another polymerizable group, It is effective in controlling both of the strengths.

As a monomer which has the said other functional number and / or another polymerizable group, the polyfunctional monomer which has ethylenically unsaturated bond other than the polyfunctional monomer in this invention mentioned later is mentioned.

Although the specific example of the polyfunctional monomer in this invention is listed below, it is not limited to this.

A commercial item may be used for the polyfunctional monomer in this invention, and what synthesize | combined suitably may be used.

It is preferable that content of the polyfunctional monomer in this invention is 1 mass% or more and 90 mass% or less in solid content of the curable composition of this invention, It is more preferable that they are 5 mass% or more and 80 mass% or less, 10 mass% or more and 70 mass% It is more preferable that it is% or less.

In particular, when using the curable composition of this invention for formation of the coloring pattern of a color filter, it is preferable that they are 5 mass% or more and 50 mass% or less in the range of the said content, It is more preferable that they are 7 mass% or more and 40 mass% or less. It is more preferable that they are 10 mass% or more and 35 mass% or less.

In this invention, it is also a preferable aspect to add the polyfunctional monomer which has ethylenically unsaturated bond other than the polyfunctional monomer in this invention.

Compounds containing ethylenically unsaturated double bonds usable in the present invention are addition polymerizable compounds having at least one ethylenically unsaturated double bond, and compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Is selected from. Such a compound group is widely known in the said industrial field, and can use these without limitation in this invention. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, and amides are mentioned. Preferably, ester of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and amides of unsaturated carboxylic acid and aliphatic polyamine compound are used. Moreover, the dehydration condensation of the addition reaction product of monofunctional or polyfunctional isocyanate or epoxy, and unsaturated carboxylic acid ester or amide which have nucleophilic substituents, such as an amino group and a mercapto group, with monofunctional or polyfunctional carboxylic acid Reaction products etc. are also used preferably. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, and desorption substituents such as halogen groups and tosyloxy groups Substituted reactants of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

Specific examples of the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol di as acrylic acid esters. Acrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimetholethane triacrylate, hexanediol diacryl Rate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate , Polyester acrylate oligomer, isocyanate And the like acid EO modified triacrylate.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimetholpropane trimethacrylate, trimethol ethane trimethacrylate, ethylene glycol di Methacrylate, 1,3-butanedioldimethacrylate, hexanedioldimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, bis- [p- (methacryloxyethoxy) phenyl] Dimethylmethane and the like.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and the like. Examples of crotonic acid esters include ethylene glycol dicrotonate and tetramethylene glycol dicrotonate. Isocrotonic acid ester includes ethylene glycol diisocrotonate and the like. Examples of maleic acid esters include ethylene glycol dimaleate and triethylene glycol dimaleate.

As examples of other esters, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 51-47334, Japanese Patent Publication No. 57-196231, Japanese Patent Publication No. 59-5240, Japanese Patent Publication No. 59-5241, and Japanese Patent The thing which has an aromatic skeleton of Unexamined-Japanese-Patent 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are also used preferably. In addition, the ester monomer mentioned above can also be used as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and an unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such an example, it has two or more isocyanate groups in 1 molecule described in Unexamined-Japanese-Patent No. 48-41708, for example. The vinylurethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (V) to a polyisocyanate compound are mentioned.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (V)

(Wherein R ⁴ and R ⁵ represent H or CH ₃ ).

Further, urethane acrylates and Japanese Patent Publications No. 58-49860 and Japanese Patent Publications as described in Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-open No. Hei 2-16765. Also preferred are urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 The photopolymerizable composition excellent in the photosensitive speed can be obtained.

Other examples include polyester acrylates, epoxy resins and (meth) as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Polyfunctional acrylates and methacrylates, such as epoxy acrylate which made acrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, and the vinyl phosphonic acid type-compound of Unexamined-Japanese-Patent No. 2-25493 are mentioned. And the like. In certain cases, a structure containing a perfluoroalkyl group described in Japanese Patent Application Laid-open No. 61-22048 is preferably used. Moreover, what was introduced as a photocurable monomer and oligomer can also be used by Japanese adhesion association vol.20, No. 7, page 300-308 (1984).

About these addition polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of the final sensor. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure containing a large amount of unsaturated groups per molecule is preferable, and in most cases, bifunctional or more is preferable. In addition, in order to increase the intensity | strength of an image part, ie, a cured film, it is good that it is trifunctional or more, and has another functional number and / or another polymerizable group (for example, acrylic acid ester, methacrylic acid ester, a styrene-type compound, vinyl ether) The method of adjusting both sensitivity and intensity | strength by using together the thing of system compound) is also effective. It is preferable to use the compound containing 2 or more of (meth) acrylic acid ester structures from a viewpoint of hardening sensitivity, It is more preferable to use the compound containing 3 or more, It is most preferable to use the compound containing 4 or more desirable. Moreover, it is preferable to contain an EO modified body from a hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part strength.

The addition and / or use of the addition polymeric compound is also an important factor in terms of compatibility and dispersibility with other components (eg, binder polymers, initiators, colorants (pigments, dyes, etc.)) in the polymerizable layer. Compatibility may be improved by using a purity compound or using 2 or more types. Moreover, a specific structure can also be selected for the purpose of improving adhesiveness, such as a board | substrate and an overcoat layer mentioned later.

From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified body, a trimethol propane triacrylate, a trimethol propane tri (acryloyloxypropyl) ether, a trimethol ethane triacrylate, and tetraethylene Glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified Sieve, dipentaerythritol hexaacrylate EO modified body, etc. are mentioned as a preferable thing, Moreover, as a commercial item, urethane oligomer UAS-10 and UAB-140 (made by Sanyo-Kokusaku Pulp Co., Ltd.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha Chemical Co., Ltd. make) is preferable.

Among these, bisphenol A diacrylate EO modified product, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexa Commercially available products such as acrylate EO modified product include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI -600 (made by Kyoeisha Chemical Co., Ltd.) is more preferable.

It is preferable to contain content of the compound which has the said ethylenic double bond other than the polyfunctional monomer in this invention within the range of content of the polyfunctional monomer in this invention.

(B) photoinitiator

The (B) photoinitiator contained in the curable composition of the present invention is a biimidazole compound, a mercapto compound, at least one compound selected from aminobenzene derivatives, alkoxy benzene derivatives, thioxanthone derivatives and coumarin derivatives It refers to the photoinitiator further containing "specific sensitizing dye."

The photoinitiator in this invention is a compound which decomposes | disassembles by light, and initiates and accelerates superposition | polymerization of the polyfunctional monomer which has the said (D) ethylenically unsaturated bond, It is preferable to have absorption in the region of wavelength 300-500 nm. Do.

The photoinitiator in this invention becomes highly sensitive by combining with a biimidazole compound, a mercapto compound, and a specific sensitizing dye.

In this invention, a hexaaryl biimidazole compound is preferable as a biimidazole compound. For example, various compounds described in each specification, such as Japanese Patent Publication No. Hei 6-29285, US Patent No. 3,479,185, US Pat. No. 4,311,783, US Pat. No. 4,622,286, specifically 2,2'-bis (o- Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl))-4,4', 5,5'-tetraphenylbiimidazole , 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2 , 2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5 ' -Tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, etc. are mentioned.

Among these, 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole is preferable. These can be used individually or in combination of 2 or more types.

The mercapto compound used for the photopolymerization initiator further improves the sensitivity of the sensitizing dye or the biimidazole compound to the active radiation, or inhibits the polymerization inhibition of the polymerizable compound (polyfunctional monomer) by oxygen. It is a donor sensitizer.

Specific examples of the mercapto compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimetholpropane tristyoplopionate (TMTP), pentaerythritol tetrakistioplopionate ( Mercaptopropionic acid derivatives such as PETP) and THEIC-BMPA; Mercapto ethers such as di (mercaptoethyl) ether; Hexanedithiol, decandithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthioglycolate, trimetholol propane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristyopiopioneate, etc. Aromatic mercapto compounds such as aliphatic polyfunctional mercapto compounds, mercaptobenzthiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazolin, β Mercaptonaphthalene can be illustrated. These can be used individually or in combination of 2 or more types.

Moreover, the compound which has a structure below is illustrated.

As a photoinitiator other than the biimidazole type compound and mercapto compound in this invention, the said aminobenzene derivative (For example, Michler's ketone, N-aryl oxazolidinones, ((4-N, N-diethylaminophenyl) buta-1,3-dienyl) benzene and 7-diethylamino-4-methyl-chromen-2-one; Michler's ketone and compound B are preferable), Alkoxybenzene derivatives (e.g., 9,10-dialkoxyanthracene, 3- (4-alkoxyphenyl) -chromen-2-one, ((4-alkoxyphenyl) buta-1,3-dienyl) benzene, ((3,4-alkoxyphenyl) buta-1,3-dienyl) benzene, ((3,4,5-alkoxyphenyl) buta-1,3-dienyl) benzene, and ((4- Methoxyphenyl) buta-1,3-dienyl) benzene), thioxanthone derivatives (e.g., thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro Thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned. High, 2-ethyl thioxanthone, 2-isopropyl thioxanthone are preferred) and coumarin derivatives (for example, 3-methyl-5-amino-((s-triazin-2-yl) amino)- 3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazine- 2-yl) amino) -3-phenylcoumarin and the like, and are selected from 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin is preferred). At least one compound.

Among these, Michler's Ketone, Compound B, and those described in Japanese Patent Laid-Open No. 2006-171689, paragraphs [0022] to [0042] are preferable, and the following compound B is particularly preferable.

The said specific sensitizing dye in the said invention can be used individually or in combination of multiple.

Among the above, as a preferable combination of a biimidazole type compound, a mercapto compound, and a sensitizing dye, the combination of each preferable compound is more preferable.

The specific example of the said preferable combination is shown below.

For example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole can be mentioned as a biimidazole type compound, Examples of the capto compound include N-phenyl mercaptobenzimidazole, and examples of the sensitizing dye include Michler's ketone and compound B.

The said biimidazole type compound, a mercapto compound, and a specific sensitizing dye each may be used individually by 1 type, or the combination which used multiple types together may be sufficient.

The ratio which combines a biimidazole type compound, a mercapto compound, and a sensitizing dye is a biimidazole type compound (especially 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5 with respect to a sensitizing dye). '-Tetraphenylbiimidazole) is preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents.

In addition, a mercapto compound is 0.5-10 equivalent with respect to a biimidazole type compound (especially 2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole). It is preferable and 1-3 equivalents are more preferable.

It is preferable that content of (B) photoinitiator in the curable composition of this invention is 3 mass% or more and 20 mass% or less with respect to the total solid of a curable composition, More preferably, it is 5 mass% or more and 10 mass% or less Range.

As mentioned above as a photoinitiator in this invention, high sensitivity can be achieved by combining with a biimidazole type compound, a mercapto compound, and a specific sensitizing dye, and also it is curable with the polyfunctional monomer in the said invention. By using for a composition, it can harden with high sensitivity, it is excellent in resolution, shows favorable pattern formation property, the latitude at the time of image development, and can be set as the composition excellent in adhesiveness with a support body.

In the present invention, the mass ratio (photopolymerization initiator / polyfunctional monomer) of the photopolymerization initiator in the present invention and the polyfunctional monomer in the present invention is preferably 0.25 or more from the viewpoint of controllability of the line width and pattern formation, and is preferably 0.25 or more and 0.4. The following are more preferable, and 0.25 or more and 0.3 or less are especially preferable.

When the said mass ratio is less than 0.25, it is unpreferable in the point that pattern formation property worsens and there exists a tendency for cracking and peeling to occur.

(A) Colorant

The curable composition of this invention contains the (A) coloring agent. By using a coloring agent, the colored hardening body which consists of curable compositions can be formed, and it can apply to the coloring pattern formation of an image forming material and a color filter.

There is no restriction | limiting in particular in the coloring agent added to the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. It is preferable that it is a pigment from a viewpoint of durability, such as heat resistance and light resistance, as said coloring agent.

As a pigment which can be used for the curable composition of this invention, various conventionally well-known inorganic pigments or organic pigments can be used. In addition, considering that the inorganic pigment or the organic pigment is preferably a high transmittance, the use of the finest one is preferable, and considering the handling property, the average primary particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm to 0.06 micrometer is more preferable.

Here, in this invention, the average primary particle diameter is the value measured as follows.

In this invention, an average particle diameter is a volume average particle obtained by measuring using a light scattering method particle size distribution analyzer (brand name: Microtrac UPA (made by Nikkiso Co., Ltd.)). Means diameter.

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

As said organic pigment, for example,

CI Pigment yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199 ,;

C. I. Pigment orange 36, 38, 43, 71;

C.I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment violet 19, 23, 32, 39;

C.I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

C. I. Pigment brown 25, 28;

C.I. Pigment black 1, 7;

Carbon black, and the like.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the dispersibility mechanism is not fully elucidated, it is presumed that the excellent affinity of the photosensitive polymerization component containing the polyfunctional monomer in this invention, and a pigment is having an influence.

The following can be mentioned as a pigment which can be used preferably in this invention. However, the present invention is not limited to these.

Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

Pigment Orange 36, 71,

Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. pigment violet 19, 23, 32,

Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment Black 1

These organic pigments can be used individually or in combination in order to raise color purity. The specific example of the said combination is shown below. For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrol pigment alone or at least one thereof as a red pigment, and a disazo yellow pigment and isophosphate. A mixture of an isolindoline-based yellow pigment, a quinophthalone-based yellow pigment, or a perylene-based red pigment can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red as a diketopyrrolopyrrole pigment. 254, and mixing with CI pigment yellow 139 is preferable at the point of color reproducibility. Moreover, as for mass ratio (red pigment: yellow pigment) of a red pigment and a yellow pigment, 100: 5-100: 50 are preferable. If it is 100: 4 or less, it may be difficult to suppress the light transmittance of 400 nm-500 nm, and color purity may not be improved. Further, at 100: 51 or more, the dominant wavelength may be shorter, and the deviation from the NTSC target color may increase. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. In addition, when it is a combination of red pigments, it can adjust to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow Mixing of 185 is preferred. As for the mass ratio (green pigment: yellow pigment) of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. As said mass ratio, the range of 100: 30-100: 120 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually or the mixture of this and a dioxazine type purple pigment can be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferred. As for mass ratio (blue pigment: purple pigment) of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

As the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon and titanium carbon (carbon: titanium carbon) is preferably in the range of 100: 0 to 100: 60.

When using the composition of this invention for color filters, 10-100 nm of the above-mentioned range is preferable, as for the primary particle diameter of a pigment from a viewpoint of a color stain and contrast, 10-70 nm is more preferable, 10-60 Nm is more preferable, 10-50 nm is especially preferable, and 10-40 nm is the most preferable.

In addition, when using the composition of this invention for a color filter, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of a color stain and contrast.

There is no restriction | limiting in particular as dye which can be used as a coloring agent contained in the curable composition of this invention, A well-known dye can be used as a conventional color filter use. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent No. 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 Japanese Patent Application Laid-Open No. Hei 6-194828, Japanese Patent Application Laid-Open No. Hei 8-211599, Japanese Patent Application Laid-Open No. Hei 4-249549, Japanese Patent Application Laid-Open No. Hei 10-123316, Japanese Patent Application Laid-Open No. 11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215 JP-A-11-343437, JP-A-8-62416, Japan Patent Publication Publication 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Application Laid-Open No. 8-302224, Japanese Patent Application Laid-Open No. 8- The pigment | dye disclosed in Unexamined-Japanese-Patent No. 73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. can be used.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pyrrolo. Dyestuffs, such as a pyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, can be used.

In addition, after exposing the pattern of the curable composition and curing of the exposed portion, the unexposed portion is removed by water or alkali development to form a pattern, for example, when forming a colored pattern of a resist or a color filter. An acid dye and / or its derivative can be used preferably from a viewpoint of completely removing the binder, dye, etc. of a tailings irradiation part.

In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil dyes, food dyes and / or derivatives thereof, and the like may also be usefully used.

The acid dye is not particularly limited as long as it has an acid group such as sulfonic acid or carboxylic acid, but is not particularly limited, solubility in an organic solvent or developer, salt formation with a basic compound, absorbance, interaction with other components in the composition, light resistance, and heat resistance. And so on, taking into account all of the required performance.

Hereinafter, although the specific example of acid dye is listed, it is not limited to these in this invention. For example,

acid alizarin violet N;

acid black 1, 2, 24, 48;

acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

acid chrome violet K;

acid Fuchsin;

acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;

acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

acid violet 6B, 7, 9, 17, 19;

acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

Mordant Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Mordant Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;

Food Yellow 3;

And derivatives of these dyes.

Among the acid dyes, acid black 24;

acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;

acid orange 8, 51, 56, 74, 63;

acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249;

acid violet 7;

acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;

Dyes such as Acid Green 25 and derivatives of these dyes are preferred.

Moreover, the azo-type, xanthene type, and phthalocyanine-type acid dye of that excepting the above is also preferable, C.I. Solvent Blue 44, 38; C.I. Solvent orange 45; Acid dyes such as Rhodamine B and Rhodamine 110 and derivatives of these dyes are also preferably used.

Especially, as (A) coloring agent, triallyl methane type, anthraquinone type, azomethine type, benzylidene type, oxonol type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, benzopyran It is preferable that it is a coloring agent chosen from a system, an indigo system, a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, and an anthrapyridone system.

As content in the case of using a coloring agent for the curable composition of this invention, it is preferable that it is 5-80 mass% in the total solid of a curable composition, 10-70 mass% is more preferable, 20-70 mass% is more preferable. 40-70 mass% is more preferable.

In particular, when using the curable composition of this invention for formation of the coloring pattern of a color filter, content of a coloring agent is preferable that it is 20 mass% or more in the range of the said content, More preferably, it is 30 mass% or more, 40 mass More than%

By setting it as said range, the color purity and contrast at the time of producing a color filter using the curable composition of this invention are preferable at the point which becomes excellent.

(C) alkali-soluble resin

In the curable composition of this invention, alkali-soluble resin is used as a binder polymer for the purpose of the improvement of a film characteristic, etc.

As alkali-soluble resin, it is preferable to use a linear organic polymer. As such a "linear organic polymer", a well-known thing can be used arbitrarily. Preferably, a linear organic polymer is selected that is soluble or swellable in water or weakly alkaline water in order to enable water development or weakly alkaline water development. The linear organic polymer is selected and used depending on its use as a film-forming agent as well as water, weakly alkaline water or an organic solvent developer. For example, the use of a water-soluble organic polymer enables water development. As such linear organic polymers, radical polymers having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication No. 54 -25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Laid-Open No. 59-71048, that is, a resin obtained by singly or copolymerizing a monomer having a carboxyl group, an acid Resins obtained by hydrolyzing or half-esterifying or half-amidating an monomer having anhydride alone or copolymerizing, an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, and the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride and the like.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group is useful.

When using alkali-soluble resin as a copolymer, you may use other monomers other than the monomer mentioned above as a compound to copolymerize. As an example of another monomer, the compound of following (1)-(12) is mentioned.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl meth Acrylic esters and methacrylic acid esters which have aliphatic hydroxyl groups, such as a acrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, Alkyl acryl, such as 3, 4- epoxycyclohexyl methyl acrylate, vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-aryloxy ethyl acrylate, and propargyl acrylate. Rate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic Acid cyclohexyl, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, Alkyl methacrylates, such as 1-propenyl methacrylate, allyl methacrylate, 2-aryloxyethyl methacrylate, and propargyl methacrylate.

(4) Acrylamide, methacrylamide, N-methyrolacrylamide, N-ethylacrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide , N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N- diallyl acrylamide, N, N- diallyl methacrylamide, allyl acrylamide, Acrylamide or methacrylamide, such as allyl methacrylamide.

(5) Vinyl ethers, such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(6) Vinyl esters, such as vinyl acetate, vinyl chloro acetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

(8) Vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins, such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.

(11) Unsaturated imides, such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(12) Methacrylic acid monomers in which a hetero atom is bonded at the α position. For example, the compound described in JP 2001-115595 specification, JP 2001-115598 specification, etc. are mentioned.

Of these, (meth) acrylic resins having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and alkali-soluble resins having double bonds in the side chains described in JP-A-2000-187322 and JP-A-2002-62698; Alkali-soluble resin which has an amide group in the side chain described in Unexamined-Japanese-Patent No. 2001-242612 is preferable because it is excellent in the balance of film strength, a sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication A urethane-based binder polymer containing an acid group described in JP-A No. 63-287947, Japanese Patent Application Laid-Open No. Hei 1-271741, Japanese Patent Application Hei. The urethane-based binder polymer having a very excellent strength is advantageous in terms of resistance to breaking and / or low exposure.

In addition, an acetal modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open No. 2001-318463 and the like is preferred because of its excellent balance between film strength and developability.

In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as water-soluble linear organic polymer. Alcohol soluble nylon, polyethers of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful for increasing the strength of the cured coating.

As weight average molecular weight of alkali-soluble resin which can be used by this invention, Preferably it is 5,000 or more, More preferably, it is the range of 10,000-300,000, About a number average molecular weight, Preferably it is 1,000 or more, More preferably, 2,000 It is in the range of ~ 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably one or more, more preferably in the range of 1.1 to 10.

These polymers may be any of random polymers, block polymers, and graft polymers.

As addition amount of alkali-soluble resin, it is preferable that it is the range of 5-20 mass% in the total solid of the curable composition of this invention, and 5-12 mass% is more preferable.

Hereinafter, other preferable additives etc. are demonstrated.

Notary sensitizer

It is also preferable that the curable composition of this invention contains a sensitizer as desired. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the actinic radiation, or inhibiting the inhibition of polymerization of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MRSander et al., Journal of Polymer Society, Vol. 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japan Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, Research The compound of Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethyl aniline, p-methylthio dimethylaniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides, for example, the thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, Japan The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto- 4 (3H) -quinazolin, (beta) -mercaptonaphthalene, etc. are mentioned.

Other examples of the sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965, Japanese Patent Publication The hydrogen donor of Unexamined-Japanese-Patent No. 55-34414, the sulfur compound (for example, trithiane, etc.) of Unexamined-Japanese-Patent No. 6-308727, etc. are mentioned.

As for content of these co-sensitizers, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the hardening rate by the balance of a polymerization growth rate and a chain transfer, and the range of 1-25 mass% Is more preferable, and the range of 0.5-20 mass% is still more preferable.

solvent

The curable composition of this invention can contain at least 1 type of solvent.

Specifically, the solvent is preferably selected from a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, and a chlorine-containing solvent.

Examples of the glycol ether solvent include ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), and methyl methoxybutanol. (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Methyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, etc. are preferable.

As said alcohol solvent, methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, etc. are preferable.

Examples of the ester solvents include ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), and 3-methyl-3-methoxybutyl Preference is given to acetates, 3-ethoxypropionate (EEP), lactic acid esters (e.g., methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and the like).

As the ketone solvent, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, acetone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), Isophorone (3,5,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like are preferable.

As the amide solvent, dimethylformamide (DMF), N-methylpyrrolidone (4-methylaminolactam or NMP) and the like are preferable.

As the chlorine-containing solvent, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, methylene chloride, carbon tetrachloride, chloroform, dichloroethane, dichlorobenzene and the like are preferable.

As content in the curable composition of the solvent in this invention, 15-60 mass% is preferable with respect to the said curable composition, 20-50 mass% is more preferable, 30-40 mass% is especially preferable. If the said content is in the said range, the solubility of the coloring agent in a composition, and stability with time at the time of storage after melt | dissolution can be improved effectively.

Among the above solvents, ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylmethoxybutanol (3-methyl-3- Methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy -2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate,

Ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 3-e Ethyl oxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate,

2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5, 5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone),

N-methylpyrrolidone (4-methylaminolactam or NMP),

Methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol and the like are preferable.

Moreover, in the curable composition of this invention, the said solvent can be used individually or in combination of 2 or more types.

In addition, when preparing the curable composition of this invention, you may use together solvents other than the solvent enumerated above. The solvent other than the above is not particularly limited as long as it satisfies the solubility of each component and the applicability of the curable composition, but is preferably selected in consideration of the solubility, coatability, and safety of the colorant and the alkali-soluble resin (binder).

Examples of the solvents other than the above are esters other than those exemplified above, for example amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl oxyacetate and oxyacetic acid. Ethyl, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate and the like;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.); 2-oxypropionic acid alkyl esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionic acid (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and 2-methoxypropionic acid) Propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-e Ethyl oxy-2-methylpropionate and the like); Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers other than those exemplified above, for example, diethylene glycol dimethyl ether, tetrahydrofuran, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol propyl ether acetate and the like;

Ketones other than those exemplified above, for example, methyl ethyl ketone, 2-heptanone, 3-heptanone, and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Among these, methyl 3-ethoxypropionate, ethyl cellosolve acetate, diethylene glycol colldimethyl ether, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, and the like are preferable.

Dispersant

When the curable composition of this invention contains a pigment as a (c) coloring agent, it is preferable to add a dispersing agent from a viewpoint of improving the dispersibility of the said pigment.

As a dispersant (pigment dispersant) which can be used in the present invention, a polymer dispersant [for example, a polyamideamine and its salt, a polycarboxylic acid and its salt, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly ( Meta) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate] and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, the terminal modified | denatured type | mold polymer | macromolecule, graft type polymer, and block type polymer which have anchor site | part to a pigment surface are mentioned as a preferable structure. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

Specific examples of the pigment dispersant usable in the present invention include "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group), 130 (polyamide), 161 manufactured by BYK Chemie. , 162, 163, 164, 165, 166, 170 (polymer copolymer), `` BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), `` EFKA4047, 4050, 4010, 4165 (polyurethane), '' EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative), "Ajipa PB821, PB822" made by Ajinomoto Pantech Co., Ltd., "FLOWLEN TG-710 (urethane oligomer)" by Kyoeisha Chemical Co., Ltd., " POLYFLOW No. 50E, No. 300 (acrylic copolymer), Kusumoto Chemical Co., Ltd. (Kusumoto Chemicals, Ltd.) "DISPERON KS-860, 873SN, 874, # 2150 (aliphatic polyhydric carboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725" , "DEMOL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)" by Kao Corporation, "HOMOGENOL L-18 ( Polymer polycarboxylic acid) "," EMERGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (stearylamine acetate) ", Lubrizol Corporation (The Lubrizol Corporation) `` SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 ( Graft-type polymer) ", Nikko Chemicals Co., Ltd." NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene mono) Stearate) ”and the like.

These dispersing agents may be used independently and may be used in combination of 2 or more type. In this invention, it is especially preferable to use combining a pigment derivative and a polymer dispersing agent.

As content of the dispersing agent in this invention, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, 10-60 mass% is more preferable.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass, based on the pigment. Moreover, when using a pigment derivative, as the usage-amount, it is preferable to exist in the range of 1-30 mass% with respect to a pigment, It is more preferable to exist in the range of 3-20 mass%, and to the range of 5-15 mass% It is particularly desirable to have.

When using the pigment and dispersing agent as a coloring agent in this invention, it is preferable that the sum total of content of a coloring agent and a dispersing agent is 25 mass% or more and 95 mass% or less with respect to the total solid which comprises a curable composition from a hardening sensitivity and a color concentration. It is more preferable that they are 25 mass% or more and 80 mass% or less, and it is still more preferable that they are 30 mass% or more and 70 mass% or less.

Polymerization inhibitor

In this invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound which has a polymerizable ethylenically unsaturated double bond in manufacture or storage of a curable composition.

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 amine cerium salt, etc. are mentioned.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of the whole composition. Furthermore, in order to prevent the inhibition of polymerization by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added, and may be localized on the surface of the photosensitive layer in the drying process after coating. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

Adhesion enhancer

In this invention, in order to improve adhesiveness with the hard surface (substrate) which is a base material, an adhesion promoter can also be added. As an adhesion promoter, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy Silane, methyltrimethoxysilane, methyltriethoxysilane, Vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxy Ethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryl Oxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane, etc. are mentioned. Can be.

Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane and γ-mercaptopropyltri Methoxysilane, (gamma) -aminopropyl triethoxysilane, and phenyl trimethoxysilane are preferable, and (gamma) -methacryloxypropyl trimethoxysilane is the most preferable.

0.1-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of an adhesion improving agent, 0.5-10 mass% is more preferable.

Other additives

Moreover, in this invention, in order to improve the physical property of a hardened film, well-known additives, such as an inorganic filler, a plasticizer, and a sensing agent which can improve the ink buildability of the photosensitive layer surface, are used. You may add.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and the like. 10 mass% or less can be added with respect to the total mass of the compound which has an ethylenically unsaturated double bond, and a binder.

The curable composition of the present invention is cured with high sensitivity, and storage stability is also good. Moreover, high adhesiveness to the surface of hard materials, such as a board | substrate which applies a curable composition, is shown. Therefore, the curable composition of this invention can be used suitably in the field of image forming materials, such as a three-dimensional light shaping | molding, holography, and a color filter, an ink, a coating material, an adhesive agent, and a coating agent.

Color filter and its manufacturing method

Next, the color filter of this invention and its manufacturing method are demonstrated.

The color filter of this invention has a pixel (coloring pattern) formed on the support body using the curable composition of this invention, It is characterized by the above-mentioned.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method (manufacturing method of the color filter of this invention).

Process of apply | coating curable composition of this invention on support body, forming curable composition layer (henceforth abbreviated suitably "curable composition layer formation process"), and exposing the said curable composition layer through a mask. (Hereinafter abbreviated as "exposure process" suitably) and the process of developing the said curable composition layer after exposure, and forming a coloring pattern, (it abbreviates as "development process" suitably hereafter), It is characterized by the above-mentioned. .

Hereinafter, each process in the manufacturing method of this invention is demonstrated.

Curable Composition Layer Forming Process

In the curable composition layer forming step, the curable composition of the present invention is applied onto a support to form a curable composition layer.

As a support body which can be used for this process, it is used, for example, soda glass, Pyrex (trademark) glass, quartz glass used for a liquid crystal display element, etc., and a transparent conductive film adhered to these, an imaging element, etc. Examples thereof include a photoelectric conversion element substrate, for example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), and the like. These substrates may be provided with black stripes separating each pixel.

Moreover, you may form a primer layer on these support bodies in order to improve the adhesion with an upper layer, to prevent the diffusion of a substance, or to planarize the surface of a board | substrate as needed.

As a coating method of the curable composition of this invention on a support body, various methods, such as a slit coating, an ink jet method, rotational coating, casting | coating, roll coating, screen printing, etc. The application method can be applied.

As coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is more preferable.

Drying (pre-bake) of the curable composition layer applied on the substrate can be performed in a hot plate, oven, or the like at 10 to 300 seconds at a temperature of 50 ° C to 140 ° C.

Exposure process

In an exposure process, the curable composition layer formed in the said curable composition layer formation process is exposed through the mask which has a predetermined mask pattern.

In the exposure in this step, the pattern exposure of the coating film is exposed through a predetermined mask pattern, and only a portion of the coating film irradiated with light is cured and developed with a developer, and the pixels of each color (three or four colors) are exposed. This can be done by forming a patterned film made of a film. Especially as radiation which can be used at the time of exposure, ultraviolet rays, such as g line | wire and i line | wire, are used preferably. 5-1500mJ / cm <2> is preferable, 10-1000mJ / cm <2> of irradiation amount is more preferable, and 10-500mJ / cm <2> is the most preferable.

When the color filter of this invention is for liquid crystal display elements, 5-200 mJ / cm <2> is preferable in the said range, 10-150 mJ / cm <2> is more preferable, 10-100 mJ / cm <2> is the most preferable. Moreover, when the color filter of this invention is for a solid-state image sensor, 30-1500mJ / cm <2> is preferable in the said range, 50-1000mJ / cm <2> is more preferable, 80-500mJ / cm <2> is the most preferable.

Developing process

Subsequently, by performing the alkali development treatment, the tailings irradiated portion is eluted in the aqueous alkali solution by the exposure, leaving only the photocured portion. As a developing solution, the organic alkali developing solution which does not cause damage to a circuit of an underlayer etc. is preferable. As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkaline agent used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabi Organic alkaline compounds, such as cyclo- [5,4,0] -7-undecene, are mentioned, Alkali which diluted these alkaline agents with pure water so that concentration might be 0.001-10 mass%, Preferably it is 0.01-1 mass%. An aqueous solution is used suitably as a developing solution. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it is generally wash | cleaned (rinse) with pure water after image development.

Subsequently, the excess developer is washed and removed and dried, followed by heat treatment (post-bake). Thus, a cured film can be manufactured by repeating the said process for each color one by one.

As a result, a color filter is obtained.

Post-baking is the post-development heat processing for making hardening perfect, and a thermosetting process of 100 degreeC-240 degreeC is normally performed. When a board | substrate is a glass substrate or a silicon substrate, 200 degreeC-240 degreeC is preferable also in the said temperature range.

This post-baking process can be performed continuously or batch type using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the coating film after image development may be in said condition.

Moreover, in the manufacturing method of this invention, after performing the above-mentioned curable composition layer forming process, exposure process, and image development process, you may include the hardening process which hardens the coloring pattern formed by heating and / or exposure as needed.

The color filter which consists of a desired color is produced by repeating the curable composition layer forming process, exposure process, and image development process (in addition, the hardening process as needed) by the number of desired colors demonstrated above.

Although the use mainly of the color filter to the pixel was mainly demonstrated as a use of the curable composition of this invention, it goes without saying that it is applicable also to the black matrix formed between the pixel of a color filter. The black matrix was subjected to pattern exposure, alkali development, and then post-baked by the same method as the pixel production method except that a black colorant such as carbon black or titanium black was added to the curable composition of the present invention. It can be formed by promoting curing.

Since the color filter of this invention uses the curable composition of the said invention, the formed coloring pattern shows high adhesiveness with a support substrate, and since the hardened composition is excellent in developability, it is excellent in exposure sensitivity and the board | substrate of an exposure part. Adhesiveness with is favorable, and the high resolution pattern which gives a desired cross-sectional shape can be formed. Therefore, it can use suitably for solid-state image sensors, such as a liquid crystal display element and CCD, and is especially preferable for a CCD element, CMOS, etc. of high resolution exceeding 1 million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises CCD, and the microlens for condensing.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but is not limited thereto. In addition, "%" "part" is a mass reference | standard unless there is particular notice.

Comparative Example 1

Preparation of Green Curable Composition

-GREEN Composition A- Dispersion

11 parts of Pigment Green 36 (average particle diameter 19 nm in scanning electron microscope (SEM) observation)

7 parts of Pigment Yellow 150 (average particle diameter 22 nm by SEM observation)

6 parts of a dispersant (trade name: Disperbyk-161, manufactured by BYK Corporation, 30% solution)

4 parts of the propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) of alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000).

Solvent B (3-ethoxypropionate methyl ether acetate) 70 parts

-GREEN Composition B- Coating Liquid

GREEN Composition A- 100 parts of dispersion

Epoxy resin (trade name EHPE 3150, manufactured by Daicel Chemical Industries, Ltd.) 2 parts

8 parts of a polymeric compound (Dipentaerythritol hexaacrylate)

2.2 parts of polymerization initiators 1 (2,2'-bis (O-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (biimidazole compound))

0.8 part of polymerization initiator 2 (the following compound D: specific sensitizing dye)

0.5 part of polymerization initiator 3 (the following compound M: mercapto compound)

0.001 part of polymerization inhibitor (p-methoxyphenol)

0.02 parts of a fluorine-based surfactant (trade name: Megafac R08, manufactured by Dainippon Ink and Chemicals, Inc.)

0.5 part of nonionic surfactant (trade name: Emulgen A-60, manufactured by KAO Co., Ltd.)

Solvent A (1,3-butylene glycol diacetate) 50 parts

Solvent B (3-ethoxypropionate methyl ether acetate) 100 parts

The GREEN composition B-coating solution was mixed and stirred to obtain a colored curable composition.

Example 1

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that 4 parts of dipentaerythritol hexaacrylate and 4 parts of compound A-1 were used instead of 8 parts of dipentaerythritol hexaacrylate.

Example 2

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that 4 parts of dipentaerythritol hexaacrylate and 4 parts of Compound A-4 were used instead of 8 parts of dipentaerythritol hexaacrylate.

Example 3

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that 4 parts of dipentaerythritol hexaacrylate and 4 parts of Compound A-5 were used instead of 8 parts of dipentaerythritol hexaacrylate.

Example 4

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that 4 parts of dipentaerythritol hexaacrylate and 4 parts of compound A-9 were used instead of 8 parts of dipentaerythritol hexaacrylate.

Comparative Example 2

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that Compound A-12, shown below, was used instead of dipentaerythritol hexaacrylate.

Comparative Example 3

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that Compound A-13, shown below, was used instead of dipentaerythritol hexaacrylate.

Comparative Example 4

A colored curable composition was obtained in the same manner as in Comparative Example 1 except that Compound A-14, shown below, was used instead of dipentaerythritol hexaacrylate.

Production of color filter

1-1. Formation of Curable Composition Layer

Each curable composition obtained as described above was subjected to a slit coating on a glass substrate of 550 mm x 650 mm under the following conditions as a resist solution, and then allowed to stand in that state for 10 minutes, followed by vacuum drying and prebaking (100 ° C. for 80 seconds). ) Was formed to form a curable composition coating film (curable composition layer).

Slit application condition

Gap between the openings of the dispensing head tip: 50 μm

Dispense rate: 100 mm / sec

Clearance of substrate and coating head: 150 μm

Coating thickness (dry thickness): 2 μm

Application temperature: 23 ℃

1-2. Exposure, development

Subsequently, the photocurable coating film (curable composition coating film) was exposed in a pattern form using a test mask having a line width of 20 µm using an ultra-high pressure mercury lamp of 2.5 kw, and after the exposure, the entire coating film surface was organic-based. It was covered with a 10% aqueous solution of a developing solution (trade name: CDK-1, manufactured by Fuji Film Electronic Materials Co., Ltd.), and stopped for 90 seconds.

1-3. Heat treatment

After stopping, the pure water was sprayed in the shower phase, the developer was wash | cleaned, and the coating film which performed this photocuring process and image development process was heated in the oven of 220 degreeC for 1 hour (postbaking). This formed the colored resin film (color filter) on the glass substrate.

2. Evaluation of Curable Compositions and Color Filter Performance

The storage stability of the curable composition adjusted above and the line width of the curable composition coating film (colored layer) formed on the glass substrate using the curable composition, substrate adhesion, developability, and pattern cross-sectional shape are as follows. Evaluated. The results are shown in Table 1.

2-1. Storage Stability of Curable Compositions

After storing the curable composition which is the said coating liquid for 1 month at room temperature, the precipitation degree of the foreign material was evaluated by visual observation according to the following evaluation criteria.

Evaluation standard

(Circle): Precipitation was not confirmed.

(Triangle | delta): Precipitation was confirmed slightly.

X: Precipitation was confirmed.

2-2. Line width thickness

The dimension of the formed pattern was measured by the size measuring device (ICRON, Olympus make), and the thickness width with respect to 20 micrometers of masks was shown in the table | surface. The smaller the value, the better.

2-3. Exposure sensitivity of coating film (color layer)

The exposure amount was changed into the various exposure amounts of 10-200mJ / cm <2> shown in Table 1, and it exposed, and the exposure amount which the pattern line width after postbaking becomes 20 micrometers was evaluated as exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity.

2-4. Developability, Pattern Cross-sectional Shape, Substrate Adhesion

The board | substrate surface and cross-sectional shape after postbaking were confirmed by the conventional method by optical microscope and SEM photograph observation.

Developability

In the exposure process, the presence or absence of the residue of the area | region (unexposed part) which was not irradiated with light was observed, and the developability was evaluated by the following reference | standard.

Evaluation standard

(Circle): The residue was not confirmed at all in an unexposed part.

(Triangle | delta): Although the residue was confirmed in the unexposed part a little, it was a degree which is satisfactory practically.

X: The residue was remarkably confirmed by the unexposed part.

Pattern cross section shape

The cross-sectional shape of the formed pattern was observed.

Evaluation standard

(Double-circle): The taper angle is 30 or more and less than 70 degrees (pure taper)

○: range of taper angle of 70 or more and less than 90 degrees (pure taper)

△: taper angle of 90 degrees (rectangular)

X: taper angle exceeds 90 degrees (reverse taper)

Substrate Adhesion

It was observed whether the pattern defect was generated as evaluation of board | substrate adhesiveness. These evaluation items were evaluated based on the following criteria.

Evaluation standard

○: No pattern defect was observed at all.

(Triangle | delta): A pattern defect was hardly observed but a partial defect was observed.

X: Pattern defect was remarkably observed.

As is clear from Table 1, the color filter in which the colored pixel is formed using the curable composition of the present invention can be patterned with high sensitivity, has excellent developability and pattern formability, and the substrate adhesiveness is equivalent to that of the comparative example. The width | variety of the line | wire width | variety was improved by being 1-3 micrometers fine with respect to a comparative example, and it was preferable as a color filter.

Claims (11)

(A) a colorant, (B) photoinitiator, (C) alkali soluble resins and (D) Curable composition containing the polyfunctional monomer which has an ethylenically unsaturated bond: The (B) photoinitiator may be selected from (i) a biimidazole compound, (ii) a mercapto compound, and (iii) an aminobenzene derivative, an alkoxybenzene derivative, a thioxanthone derivative and a coumarin derivative. Containing; The (D) polyfunctional monomer having an ethylenically unsaturated bond has a hydroxyl group in a molecule; And The double bond density which is the number of millimoles of a double bond per 1g of polyfunctional monomers which have the said (D) ethylenically unsaturated bond is 9.6 mmol / g or more and 11.5 mmol / g or less. The curable composition according to claim 1, wherein the double bond density is 10.0 mmol / g or more and 11.5 mmol / g or less. The curable composition of claim 1, wherein the double bond density is 10.1 mmol / g or more and 10.7 mmol / g or less. The curable composition according to claim 1, wherein the (D) polyfunctional monomer having an ethylenically unsaturated bond is at least trifunctional. The curable composition according to claim 1, wherein the (D) polyfunctional monomer having an ethylenically unsaturated bond is 3 to 8 functional. The curable composition according to claim 1, wherein the compound (VII) is an aminobenzene derivative. The curable composition according to claim 1, wherein the compound (VII) is an alkoxybenzene derivative. The curable composition according to claim 1, wherein the compound (VII) is a thioxanthone derivative. The curable composition according to claim 1, wherein the compound (VII) is a coumarin derivative. It has a pixel formed using the curable composition in any one of Claims 1-9, The color filter characterized by the above-mentioned. Process of apply | coating the curable composition of any one of Claims 1-9 on a support body, and forming a curable composition layer; Exposing the curable composition layer through a mask; And The manufacturing method of the color filter characterized by including the process of developing the curable composition layer after exposure, and forming a coloring pattern.