TWI438568B - Curable composition, color filter and production thereof - Google Patents

Description

Curable composition, color filter and preparation method thereof

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

The color filter is an indispensable component for a liquid crystal display device or a solid-state image sensor.

When compared with a CRT (Cathode Ray Tube) with a display device, the liquid crystal display device is used as a TV screen, a personal computer screen, or the like because it is small and exquisite in terms of performance and equivalent in performance. The display device is being replaced by a CRT. In addition, in recent years, the development trend of liquid crystal display devices has evolved from the use of monitors having a relatively small screen size to TV (television) applications in which the screen size is large and high image quality is required.

For color filter applications for liquid crystal display devices (LCDs), substrates have been enlarged in size for producing large TVs, and it is required to be hardened at low energy in order to improve productivity when using large substrates. Further, for a liquid crystal display device for TV use, it is required to have a higher image quality than those of the monitors used so far. That is, it is required to improve contrast and color purity. In order to improve the contrast, the particle size of the coloring agent (organic pigment or the like) used for the curable composition used for the production of the color filter is required to be smaller (see, for example, Japanese Patent Laid-Open No. 2006-30541). Bulletin). Along with this, the amount of the dispersant used for dispersing the pigment tends to increase. Further, in order to increase the color purity, the content of the color former (organic pigment) in the solid content of the curable composition is required to be higher. Therefore, the content of the polymerization initiator and the photopolymerizable monomer contained in the solid component in the curable composition tends to decrease.

On the other hand, for color filter applications for solid-state image sensors, it is also required to be hardened at low energy. In addition, the thin film formation of the pattern has progressed, and as a result, the pigment concentration in the composition has been improved. Further, in the case of the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment is refined. In addition, in order to cope with problems such as color unevenness caused by relatively coarse particles, it has been proposed to disclose a technique in which an organic solvent-soluble dye is used in place of a pigment (see, for example, Japanese Patent Laid-Open No. 2-127602 Bulletin). However, in the case of a dye-based color filter, the problem of suppressing the polymerization effect derived from the dye with the increase in the dye concentration also becomes very remarkable. As a result of the above-mentioned factors, the photopolymerization initiator and the photopolymerizable monomer are required for curing the curable composition in any case for a liquid crystal display device or a solid-state image sensor. It will be limited, for example, because the concentration of the colorant becomes high, so that the sensitivity is low, the hardening cannot be obtained sufficiently, the adhesion to the substrate is insufficient, and the formation of the desired pattern is significantly difficult. problem. In response to the problem, there has been a proposal to introduce a decane coupling agent for improving the adhesion of the substrate (see, for example, Japanese Laid-Open Patent Publication No. H11-38226, No. 2,874,091).

The present invention has been made in view of the problems as described above, and provides a film which can be cured with high sensitivity, has good pattern formability, and is excellent in pattern formation even in the case of containing a high concentration of coloring agent. A hardenable composition with excellent adhesion to a hard surface.

Further, another object of the present invention is to provide a color filter comprising a coloring pattern having excellent resolution and adhesion to a support using the curable composition of the present invention, and can be manufactured with high productivity. A method of manufacturing the color filter.

As a result of intensive studies, the inventors of the present invention have found that the present invention can be solved by solving the technical problems as described above by using a specific polymerizable compound. That is, the method for solving the technical problems as described above is as follows.

(1) A curable composition comprising: (A) a radically polymerizable compound having an ethylenically unsaturated double bond in a molecule and an adhesive group for a hard material, and (B) ) Photopolymerization initiator.

(2) The curable composition according to the item (1), wherein the (A) is a radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material. The adhesive group for the hard material is selected from the group consisting of an acid group, an acid ester group, an acid sulfonium salt, an acidic metal salt, a substituent of a silanol group which is hydrolyzed, a mercapto group, a phenolic hydroxyl group, and a bisexual group. One or more of the group consisting of an ionic group and a chelating group.

(3) The hardenable composition according to Item (1), wherein the hard material is a glass substrate or a ruthenium substrate, and the (A) has an ethylenically unsaturated double bond in the molecule and is a hard material. In the radically polymerizable compound of the adhesive group, the substituent of the hard material is hydrolyzed to generate a substituent of a stanol group.

(4) The curable composition according to Item (1), wherein the (A) radical polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material is There are a plurality of ethylenically unsaturated double bonds in the molecule.

(5) The curable composition according to Item (2), wherein the (A) radical polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material is There are a plurality of ethylenically unsaturated double bonds in the molecule.

(6) The curable composition according to Item (3), wherein the (A) radical polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material is There are a plurality of ethylenically unsaturated double bonds in the molecule.

(7) The curable composition according to Item (4), wherein the (A) radical polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material is It has an acrylonitrile group in the molecule.

(8) The curable composition according to any one of (1) to (4), further comprising (C) a coloring agent having a maximum absorption in a visible wavelength range of from 400 nm to 700 nm.

(9) A color filter comprising a colored pattern comprising the curable composition according to item (8) on a support.

(10) A method of producing a color filter, comprising: a step of applying a curable composition as described in item (8) to a support to form a colored curable composition layer, and hardening the layer The step of exposing the layer of the composition layer through the hood and developing the exposed layer of the curable composition to form a colored pattern.

With regard to the preferred embodiment of the curable composition of the present invention as described in the item (1), the curable composition of the present invention can be used for producing a colored pattern of a color filter, from which it can be used as a support. The hard material is preferably selected from the group consisting of inorganic materials represented by glass and ruthenium substrates, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, and nitrocellulose. a group of resin materials such as polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and used as a sealant The adhesive foundation of the support formed by such a hard material can be formed from a surface selected from the surface of the hard material by a covalent bond, an ionic bond, a hydrogen bond, a polar interaction, van der Waal's The functional group of the interaction in the ethnic group formed by the interaction.

And an adhesive group on the surface of the versatile glass or resin material which can serve as a color filter support, preferably an acid group selected from the group consisting of a sulfonic acid group, a phosphonic acid group, a carboxyl group, and the like; an ester group of the acid; a metal salt of such an acid; a mercapto group such as an ammonium group or a pyridinium group; a substituent such as an alkoxyalkyl group which is hydrolyzed to produce a stanol group; a zwitterionic group such as a phenolic hydroxyl group or an N-oxide group; a base; and a base of a chelating group such as an imidodiacetic acid.

According to the present invention, in the case where the coloring agent is contained in a high concentration, it is also possible to provide a hardening which can be cured with high sensitivity, has good pattern formability, and is excellent in adhesion to a hard surface of a substrate. Sexual composition.

Further, according to the present invention, by using the curable composition of the present invention as described above, it is possible to provide a color filter having a coloring pattern having excellent resolution and adhesion to a support. And a manufacturing method capable of producing the color filter with high productivity.

[Best Practice]

Hereinafter, the curable composition of the present invention will be described in detail using a color filter comprising the curable composition and a method for producing the same.

[sclerosing composition]

The curable composition of the present invention is characterized by comprising: (A) a radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material (hereinafter referred to as appropriately (A) a specific polymerizable compound) and (B) a photopolymerization initiator.

First, the components (A) and (B) which are essential components of the curable composition of the present invention will be described.

<(A) A radically polymerizable compound having an ethylenically unsaturated double bond in the molecule and an adhesive group for a hard material>

The (A) specific polymerizable compound which can be used in the present invention is a compound having an addition polymerizable compound having at least one ethylenically unsaturated double bond and having an adhesive group for a hard material in the molecule.

The "ethylenically unsaturated bond" includes a vinyl group, an unsaturated carboxylic acid (for example, (meth)acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or an unsaturated phosphonic acid. An ester or a guanamine, styrene, vinyl ether or the like, of which (meth)acrylic acid is preferred.

The (A) specific polymerizable compound of the present invention contains at least one, preferably two or more, more preferably three or more, still more preferably four or more, and most preferably five or more of the ethylenic groups. A compound which saturates a bond and which contains at least one of the following compounds for the hard material of the hard material.

That is, the (A) specific polymerizable compound has an ethylenically unsaturated double bond group, and an adhesion group capable of improving the adhesion to the surface of the hard material which can be applied to the curable composition of the present invention. It is characterized by it.

The "hard material" can be applied to the material of the support substrate of the curable composition of the present invention, and for example, "inorganic material" such as glass or ruthenium substrate; or cellulose diacetate or cellulose triacetate can be used. Cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal Such as "organic resin materials" and the like. When the curable composition of the present invention is used to form a colored pattern of a color filter, a transparent hard material or a tantalum substrate selected from the above is used, and among them, a glass or tantalum substrate is preferable.

(A) The specific polymerizable compound is appropriately selected according to the properties of the hard material applied to the curable composition.

The adhesive groups are capable of forming a functional group on the surface of the hard material selected from the group consisting of a covalent bond, an ionic bond, a hydrogen bond, a polar interaction, and a van der Waals interaction, specifically In other words, it includes a substituent selected from the group consisting of an acid group, an acid ester group, an acidic phosphonium salt, an acidic metal salt, a stanol group derived from hydrolysis, a mercapto group, a phenolic hydroxyl group, a zwitterionic group, and a chelate group. The basis of more than one part of the constituents of the group.

Examples of preferred "adhesive groups" include, for example, those selected from the group consisting of sulfonic acid groups, phosphonic acid groups, and the like, or esters thereof, carboxyl groups and salts thereof, ammonium groups, pyridinium groups, acetamidine acetone. a functional group in a group consisting of a substituent derived from a stanol group derived by hydrolysis. Among them, an ammonium group, a substituent of a stanol group which is hydrolyzed, a phosphonic acid group and an ester group thereof are preferred.

Among them, from the viewpoint of the strength of the interaction, a substituent capable of forming an ionic bond, a multi-point hydrogen bond, or a covalent bond is preferable. In addition, from the viewpoint of the substrate adhesion from the strength of the interaction with the substrate, the viewpoint of the developability of the unexposed portion and the film strength of the exposed portion is more preferably selected from the group consisting of ammonium groups. a functional group in a group consisting of a phosphonic acid group, an ester group thereof, and an alkoxyalkyl group.

The (A) specific polymerizable compound of the present invention which has a polymerizable compound having an ethylenically unsaturated double bond and an adhesive group for a hard material, which is represented by the following formula (A).

In the above formula (A), M represents a moiety having an ethylenically unsaturated double bond, L represents an n+1 valent organic linking group, and X represents an adhesive group for a hard material. The n series represents an integer from 1 to 5, and the m system represents an integer from 1 to 3.

Preferred examples of the structure represented by M include esters of unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), guanamines. . Further, it includes an addition reaction of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, a substitution reaction of an unsaturated carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol is included. The structure formed. Further, in other examples, a compound group of the unsaturated phosphonic acid, styrene, vinyl ether or the like may be substituted instead of the unsaturated carboxylic acid as described above. Among them, a (meth) acrylonitrile group, a styrene, and a vinyl ether structure are preferable, and a structure having a (meth) acryl fluorenyl group is more preferable.

In the above formula (A), the L system represents an n+1 valent organic linking group depending on the number (n) of the partial structures having an ethylenically unsaturated double bond, but it has in its structure: a hydrocarbon ring structure composed of an oxygen atom, a nitrogen atom, a sulfur atom or 3 to 10 carbon atoms, selected from an aromatic ring, a heterocyclic ring, a urethane bond, a thiocarbamate bond, an ester bond And a part of the structure of the group consisting of a guanamine bond, a urea bond, and a thiourea bond, and the n+1 valence linkage group consisting of a plurality of species alone or in combination.

The linking group as described above may further have a substituent, and the substituent which may be introduced into the linking group of L includes, for example, an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a thiol group. , cyano, nitro, aliphatic hydroxy, aromatic hydroxy, heterocyclic hydroxy, aliphatic thio, aromatic thio, heterocyclic thio, aliphatic sulfonylamino, aromatic sulfonylamino, heterocyclic Sulfonyl, fluorenyl, decyloxy, decylamino, aliphatic hydroxycarbonyl, aromatic hydroxycarbonyl, heterocyclic hydroxycarbonyl, aliphatic hydroxycarbonylamino, aromatic hydroxycarbonylamino, heterocyclic hydroxycarbonylamine Base, aliphatic thiocarbonylamino group, aromatic thiocarbonylamino group, heterocyclic thiocarbonylamino group, aliphatic amine carbonyl amine group, aromatic amine carbonyl amine group, heterocyclic amine carbonyl amine group, amine mercapto group, amine Methoxycarbonyl, amine carbamide, aliphatic sulfonyl, aromatic sulfonyl, heterocyclosulfonyl, aliphatic hydroxylamine, aromatic hydroxylamine, heterocyclic hydroxylamine, decyl, aliphatic hydroxy a decyl group, a decyloxy group, an aliphatic hydroxycarbonyloxy group, an aromatic hydroxycarbonyloxy group, a heterocyclic hydroxycarbonyloxy group, Aminesulfonyloxy, aliphatic sulfonyloxy, aromatic sulfonyloxy, anilino, aliphatic azo, aromatic azo, heterocyclic azo, aliphatic sulfinyl, aromatic A sulfinyl group, a heterocyclic sulfinyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, an amine sulfonyl group, a sulfo group, a phosphonium group, a phosphonium group.

[(A) Specific Example of Specific Polymerizable Compound]

In the structure represented by M, specific examples in which an ethylenic double bond group is selected as an acrylonitrile group [(M-1) to (M-11)] are listed below, but are not limited thereto. This is the case. Further, the propylene fluorenyl group may be substituted with a substituent other than the acryl fluorenyl group as described above. Further, two or more ethylenic double bond groups different from each other may be contained in the structure represented by M.

X in the above formula (A), when m is 1, is preferably selected from the group consisting of monovalent functional groups represented by the formula shown below.

In the above formula, R ¹¹ to R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group, and the M ¹ and M ² systems independently represent a hydrogen atom, a metal atom, or The thiol group, the X ^- line represents a counter anion.

X in the above formula (A), when m is 2, is preferably selected from the group consisting of divalent functional groups represented by the formula shown below.

In the above formula, R ¹² to R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkynyl group or an alkenyl group, and the M ² group represents a hydrogen atom, a metal atom, or an ammonium group, and an X ^- line system. Represents a counter anion.

X in the above formula (A), when m is 3, is preferably selected from the group consisting of trivalent functional groups represented by the formula shown below.

In the above formula, R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an alkynyl group or an alkenyl group, respectively, and the X ^- system represents a counter anion.

X as in the above formula (A), if it has a counter anion as a partial structure, the counter anion X ^- includes hydrogen such as a fluoride anion, a chloride anion, a bromine anion, an iodine anion or the like. Anion; acetate anion, trifluoroacetate anion, sulfate anion, hydrogen sulfate anion, methanesulfonate anion, trifluoromethanesulfonate anion, perchlorate anion, tetrafluoroborate anion, hexafluorophosphate anion, hexachloroguanidine Acid anion, hexafluoroantimonate anion, and the like. Among these, from the viewpoint of solubility and stability of the compound, a halogen anion, an trifluoromethanesulfonate anion, a methanesulfonate anion, a sulfate anion, a hydrosulfate anion, and a tetrafluoroborate anion are preferable. And hexafluorophosphate anion and the like. The counter anion X ^- can be exemplified even in the case where m is from 1 to 3.

[(A) Synthesis method of specific polymerizable compound]

Next, an example of the synthesis method of the (A) specific polymerizable compound represented by the general formula (A) will be described, but the synthesis method is not limited thereto.

The method for synthesizing the specific polymerizable compound represented by the general formula (A) includes an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group and having a dense Addition reaction of monofunctional or polyfunctional alcohols, amines, and thiols, and also includes unsaturated carboxylic acid esters having a destructive substituent such as a halogen group or a tosyloxy group or The guanamines are substituted with a monofunctional or polyfunctional alcohol having an adhesive group, an amine, or a thiol. Further, it includes a compound having an electrophilic substituent such as an isocyanate group or an epoxy group and having an adhesive group, and a compound having a hydroxyl group, an amine group or a hydrogenthio group and having at least one ethylenic double bond. Addition reaction. Further, the (A) specific polymerizable compound represented by the formula (A) may be an amine or a thiol having an adhesive group, and Michael (Michael) having a compound having two or more ethylenic double bonds. The addition reaction is carried out to synthesize.

The structure of M in the above formula (A) is exemplified as the above-described structure (M-6), and an example in which the adhesion group X for the hard material is introduced in the structure is exemplified. The compound (1) to (20)] is an example of the (A) polymerizable compound of the present invention, but the structure of M in the formula (A) can be appropriately changed to the above (M-1) to (M). -11), etc., and any of them can be synthesized by a conventional synthesis method. In addition, the invention is not limited to the above.

The examples in which the structure of M in the general formula (A) as described above is changed to (M-1) to (M-11) other than the above-exemplified structure (M-6) are listed (exemplified compounds (21) And (30)], which is an example of the (A) polymerizable compound of the present invention, but is not limited thereto.

The (A) specific polymerizable compound, the method of use, whether it can be used alone or in combination, and the amount of addition, can be arbitrarily set in consideration of the final performance design target or use of the curable composition. For example, it can be selected from the following points of view.

From the viewpoint of sensitivity, it is preferred that the content of the unsaturated group per molecule is large, and most of them are preferably two or more functional groups. Further, when it is desired to increase the strength of the cured film, it is preferably a trifunctional or higher functional group, and by using a different functional number. It is also effective to adjust the sensitivity and strength by using a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound).

For the adhesive base of the hard material, for example, in the case where the support system uses a glass plate, since a plurality of stanol groups or hydroxyl groups are present on the surface of the glass, it is preferred to introduce them to form a covalent bond interaction with the groups. a dialkylalkoxyalkylene group, an alkyl alkoxyalkylene group, a trialkoxyalkylene group, an ammonium group capable of forming an ion dipole interaction or the like, and a phosphonic acid capable of forming a multi-point hydrogen bond or an ester group thereof .

Further, when a cellulose-based material such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate or nitrocellulose is used, it is preferred to select an ammonium group. A synthetic resin such as a polyphosphonate, a polyethylene, a polystyrene, a polypropylene, a polycarbonate, or a polyvinyl acetal is used as a binding group such as a phosphonic acid or an ester group thereof. In the case of a hard material, it is preferred to select a dense group such as a phosphonic acid or an ester group thereof.

In addition, the choice of addition polymerization compound for compatibility and dispersibility with other components (for example, initiator, colorant (pigment, dye), etc., binder polymer, etc.) contained in the curable composition . It is also possible to increase the compatibility by using a low-purity compound or a combination of two or more, which is an important factor in the use of the method. In addition, there is a case where a specific structure other than the above-described adhesive foundation is selected for the purpose of improving adhesion to a substrate or the like.

Further, in the present invention, the (A) specific polymerizable compound can be used in combination with the general radical polymerizable property which does not have the above-mentioned adhesive group in the molecule, without mitigating the effect of the present invention. Compound (E). The general radical polymerizable compound which does not have an adhesive group includes those which do not have an adhesive base in a molecule in the specific polymerizable compound (A) mentioned above. Further, it may be used alone or in combination of two or more. Next, a general radical polymerizable compound (E) having no adhesive group will be described.

<General Free Radical Polymerizable Compound (E) Without Adhesive Group>

The general radical polymerizable compound (E) which can be used in the present invention without an adhesive group can be used as a compound having an ethylenically unsaturated double bond in the industrial field without particular limitation. A well-known compound. These have chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and the like, and the like. Examples of the monomer and its copolymer include: an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or an ester thereof or a guanamine. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound is used. Further, an unsaturated carboxylic acid ester having a core-requiring substituent such as a hydroxyl group, an amine group or a sulfhydryl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy group, and a monofunctional group Or a dehydration condensation reaction product of a polyfunctional carboxylic acid or the like is also suitably used. Further, an addition reaction of an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and A substituted carboxylic acid ester or decyl amine having a detachable substituent such as a halogen group or a tosyloxy group, and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable for use. . Further, other examples may be substituted with a compound group of unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid as described above.

Specific examples of the monomer of the aliphatic polyol compound and the ester of the unsaturated carboxylic acid, "acrylate" include ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol diacrylate. Tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, triacrylic acid Trimethylolethane ethane, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, di pentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, sorbitol hexaacrylate, Tris(propylene oxy)ethyl isocyanate, polyester acrylate oligomer, and the like. In addition, EO (ethylene oxide) modified products of these compounds or PO (propylene oxide) modified materials are also included.

"Methacrylate" includes: tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate , trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl dimethacrylate Tetraol ester, neopentyl glycol trimethacrylate, neopentyl glycol tetramethacrylate, dineopentyl glycol dimethacrylate, dineopentaerythritol hexamethacrylate, trimethacrylic acid Sorbitol ester, sorbitan tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(meth)醯 ethoxy ethoxy) phenyl] dimethyl methane and the like, and these EO (ethylene oxide) modified materials, PO (propylene oxide) modified material.

"Iconic acid esters" include: diethylene glycol iconate, propylene glycol diconiate, 1,3-butylene glycol diconiate, 1,4-butanediol diaconate , Icylene tetramethylene glycol ester, diconcanic acid pentaerythritol ester, tetraconcanic acid sorbitol ester, and the like. The "crotonate" includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, neopentyl glycol dicrotonate, and sorbitol tetracrotonate. The "isocrotonate" includes ethylene glycol diisocrotonate, neopentyl glycol diisocrotonate, and sorbitol tetraisocrotonate. "maleate" includes: ethylene dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, tetrabutylene Sorbitol ester and the like.

As an example of the other ester, an aliphatic alcohol-based ester disclosed in, for example, Japanese Patent Publication No. 51-47334, Japanese Patent Laid-Open No. 57-196231, or Japanese Patent Laid-Open No. 59-5240 Japanese Patent Laid-Open No. 59-5241, Japanese Patent Application Laid-Open No. Hei No. 2-226149, and an amine-based group disclosed in Japanese Laid-Open Patent Publication No. Hei No. 1-156613. Further, the ester monosystem as described above can also be used as a mixture.

Further, specific examples of the "monomeric compound of an aliphatic polyamine compound and a decylamine of an unsaturated carboxylic acid" include methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6- Hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, di-ethyltriamine propylene amide, hydrazine bis acrylamide, hydrazine Acrylamide and the like. Other examples of preferred amide-based monomers include those having a cyclohexylene structure disclosed in Japanese Patent Publication No. 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitably used, and specific examples thereof include, for example, disclosed in Japanese Patent Publication No. 48-41708. A polyisocyanate compound having two or more isocyanate groups in one molecule, and a vinyl monomer having a hydroxyl group represented by the following formula (E) is added to prepare a polymer having two or more polymerizable ethylene in one molecule. a vinyl urethane compound or the like.

CH ₂ =C(R ¹ )COOCH ₂ CH(R ² )OH (E) (however, R ¹ and R ² represent H or CH ₃ ).

In addition, the urethane acrylates disclosed in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765 are disclosed in Japanese Patent Publication No. Sho. A urethane compound having an ethylene oxide-based skeleton, which is also used, is also suitable for use in the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In addition, an amine-based structure or sulfide is contained in the molecule by using the Japanese Patent Laid-Open Publication No. SHO-63-277653, JP-A-63-260909, and JP-A No. 1-105238. A structure-addition polymerizable compound can produce a hardenable composition having a very excellent photosensitive rate.

Other examples include polyester acrylates and epoxy resins disclosed in Japanese Laid-Open Patent Publication No. 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490, and each publication. A polyfunctional acrylate or methacrylate such as an epoxy acrylate which is reacted with (meth)acrylic acid. In addition, it also includes a specific unsaturated compound disclosed in Japanese Patent Publication No. 46-43946, Japanese Special Fair No. 1-40337, Japanese Special Fair No. 1-40336, or disclosed in Japanese Patent Laid-Open No. 2-25493 A vinyl phosphonic acid compound or the like. Further, in some cases, a structure containing a perfluoroalkyl group disclosed in Japanese Laid-Open Patent Publication No. 61-22048 is suitably used. Further, it can also be used as a photocurable monomer and oligomer in the Japanese Association of the Association, No. 20, No. 7, and pages 300 to 308 (1984).

In the present invention, when a general radical polymerizable compound (E) having no adhesive group is added, from the viewpoint of curing sensitivity, it is preferred to contain two or more ethylenically unsaturated bonds, and Jiawei contains more than three. Among them, it is preferable to contain two or more (meth) acrylate structures, and it is more preferable to contain three or more, and it is preferable to contain four or more. Further, from the viewpoint of the hardening sensitivity and the developability of the unexposed portion, it is preferable to contain an EO (ethylene oxide) modified product. From the viewpoint of the hardening sensitivity and the strength of the exposed portion, it is preferred to contain a urethane bond.

From the above viewpoints, preferred are bisphenol A diacrylate, EO (ethylene oxide) modified product of bisphenol A diacrylate, trimethylolpropane triacrylate, and trimethylolpropane tri (Propylene methoxypropyl)ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol triacrylate, neopentyl glycol tetraacrylate Ester, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, sorbitol hexaacrylate Alcohol ester, tris(propylene oxy)ethyl isocyanate, EO (ethylene oxide) modification of tetrapentyl tetraacrylate, EO (cyclohexane) Ethylene oxide), etc., and commercially available products are preferably urethane oligomers UAS-10, UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei Corporation).

Among them, EO (ethylene oxide) modified product of bisphenol A diacrylate, neopentyl glycol triacrylate, neopentyl glycol tetraacrylate, di pentaerythritol pentaacrylate, and hexaacrylic acid are preferred. Neopentyl alcohol ester, tris(propylene oxy)ethyl isocyanate, EO (ethylene oxide) modification of neopentyl tetraacrylate, EO of dipentaerythritol hexaacrylate (Ethylene oxide) modified product, etc.; more preferably commercially available grades are DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Gongrong Company).

In addition, the curable composition of the present invention is preferably (A) a specific polymerizable compound plus a ratio as described below, from the viewpoints of the curing sensitivity, the developability of the unexposed portion, and the strength of the exposed portion. A general radical polymerizable compound (E) which does not have an adhesive group. The weight ratio of (A) specific polymerizable compound relative to (E) the total weight of the other polymerizable compound having an ethylenic double bond and (A) the specific polymerizable compound [(A)/(A)+(E) It is preferably 0.01 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, still more preferably 0.01 or more and 0.3 or less, and most preferably 0.01 or more and 0.15 or less. If [(A)/(A)+(E)] is less than 0.01, sufficient substrate adhesion cannot be obtained.

Further, the total weight of the (E) other polymerizable compound having an ethylenic double bond and (A) the specific polymerizable compound is preferably from 1 to 90%, more preferably 1% by weight based on the solid content of the composition of the present invention. Up to 80%, preferably 1 to 70%.

In particular, in the case where the curable composition of the present invention is used in the formation of a colored pattern of a color filter, it is preferably from 5 to 50%, more preferably from 7 to 40%, further preferably in the above content range. It is 10 to 35%.

Further, it is preferable that the weight ratio of the (B) photopolymerization initiator to the total weight of the (A) polymerizable compound having an ethylenic double bond and (A) the specific polymerizable compound is [(B)/( A) + (E)] is 0.1 or more and 0.8 or less, more preferably 0.2 or more and 0.7 or less, and most preferably 0.3 or more and 0.6 or less.

The (A) component and the (E) other radically polymerizable compound can be arbitrarily selected from the viewpoints of the size, resolution, coverage, refractive index change, surface adhesion, and the like of the oxidative polymerization of oxygen and oxygen, Mix and add amount.

<(B) Photopolymerization initiator>

The curable composition of the present invention contains (B) a photopolymerization initiator.

The photopolymerization initiator in the present invention is decomposed by light to initiate a compound which promotes polymerization of the (A) specific radical polymerizable compound as described above, and is preferably in the range of 300 to 500 nm. The wavelength domain has an absorber. Further, the photopolymerization initiator may be used singly or in combination of two or more.

"Photopolymerization initiator" includes, for example, an organic halogenated compound, Diazole compound, carbonyl compound, ketal compound, benzoin compound, acridine compound, organic peroxidation compound, azo compound, coumarin compound, azide compound, metallocene A compound, a hexaarylbiimidazole compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, a mercaptophosphine (oxide) compound.

The organic halogenated compound, specifically, is disclosed in "Bull Chem. Soc Japan" 42 and 2924 (1969), and the US Patent No. 3,905,815, and Japanese Patent Publication No. 46-4605 , JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, Japan, JP-A-61-169835, and JP-A-61-169837 No. 62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, MP Hutt, "Journal of Heterocyclic Chemistry" , Book 1 (No. 3) (1970), the compounds in the book, in particular, substituted by trihalomethyl Azole compound, s-triazo (triazine) compound.

"s-trinitrogen The compound" preferably has at least one mono-, di- or tri-halogen-substituted methyl group bonded to the s-triazo S-trinitrogen Derivatives, in particular, include, for example, 2,4,6-cis (monochloromethyl)-s-triazole , 2,4,6-gin(dichloromethyl)-s-trinitrogen , 2,4,6-parade (trichloromethyl)-s-trinitrogen 2-methyl-4,6-bis(trichloromethyl)-s-triazole 2-n-propyl-4,6-bis(trichloromethyl)-s-triazole , 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazole 2-phenyl-4,6-bis(trichloromethyl)-s-triazole , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazole ,2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazole , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazole 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl 2-[1-(p-methoxyphenyl)) -2,4-butadienyl]-4,6-bis(trichloromethyl)-s-triazole 2-styryl-4,6-bis(trichloromethyl)-s-triazole , 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazole , 2-(p-iso-propoxystyryl)-4,6-bis(trichloromethyl)-s-triazole , 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazole ,2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazole 2-phenylthio-4,6-bis(trichloromethyl)-s-triazole 2-Benzylthio-4,6-bis(trichloromethyl)-s-triazole , 2,4,6-parade (dibromomethyl)-s-trinitrogen , 2,4,6-parade (tribromomethyl)-s-trinitrogen 2-methyl-4,6-bis(tribromomethyl)-s-triazole 2-methoxy-4,6-bis(tribromomethyl)-s-triazole Wait.

" The oxadiazole compound includes, for example, 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(naphthalen-1-yl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4- Diazole and the like.

"Carbonyl compounds" include, for example, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone. "benzophenone derivative" such as ketone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p- Isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2-methyl-(4'-(methylthio)phenyl)-2-morpholinyl-1 - "Benzene, 1,1,1-trichloromethyl-(p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholinyl butyl benzene, etc. Ethyl ketone derivative (thioxanthone), 2-ethyloxysulfide 2-isopropyloxysulfur 2-chlorooxosulfur 2,4-dimethyloxosulfur 2,4-diethyloxysulfide 2,4-diisopropyloxysulfide Oxygen sulfur "Derivative";"benzoatederivative" such as p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester.

The "ketal compound" includes, for example, benzylmethylketal, benzyl-β-methoxyethylethylacetal, and the like.

The "benzoin compound" includes, for example, m benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, o-benzyl benzoic acid methyl ester, and the like.

The "acridine compound" includes, for example, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, and the like.

"Organic peroxidic compound" includes, for example, trimethylcyclohexanone peroxide, etidylacetone peroxide, 1,1-bis(tertiary-butylperoxy)-3,3,5-trimethyl Cyclohexane, 1,1-bis(tertiary-butylperoxy)cyclohexane, 2,2-bis(tertiary-butylperoxy)butane, tertiary butyl hydroperoxide , cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetra Butyl butyl hydroperoxide, tertiary butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tertiary-butyl Oxy)hexane, 2,5-calyx peroxide, succinic acid peroxide, benzhydryl peroxide, 2,4-dichlorobenzhydryl peroxide, peroxydicarbonate Isopropyl ester, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, peroxydicarbonate Bis(3-methyl-3-methoxybutyl) ester, tertiary butyl peroxyacetate, tertiary butyl butyl trimethylacetate, Tert-butyl oxy neodecanoate, tertiary butyl peroxyoctanoate, tertiary butyl laurate, 3,3',4,4'-tetra-(tertiary-butyl Peroxycarbonyl)benzophenone, 3,3',4,4'-tetra-(tertiary-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-( P-isopropylcumyl phenyloxycarbonyl)benzophenone, carbonyl bis(peroxy-dihydrodiphthalate tert-butyl ester), carbonyl bis(peroxydihydrodiphthalate) Tertiary-hexyl ester) and the like.

The azo compound includes, for example, an azo compound disclosed in Japanese Laid-Open Patent Publication No. 8-108621.

"Kaempferol compound" includes, for example, 3-methyl-5-amino-((s-trinitrogen) -2-yl)amino)-3-phenylinoclavin, 3-chloro-5-diethylamino-((s-triazo) -2-yl)amino)-3-phenylinoclavin, 3-butyl-5-dimethylamino-((s-trinitrogen) -2-yl)amino)-3-phenylinoclavin, and the like.

"Azide compound" includes, for example, an organic azide compound, 2,6-bis (4-azide) disclosed in the specification of U.S. Patent No. 2,848,328, U.S. Patent No. 2,852,379, and U.S. Patent No. 2,940,853. Benzomethylene)-4-ethylcyclohexanone (BAC-E) and the like.

The "metallocene compound" is disclosed in, for example, Japanese Laid-Open Patent Publication No. 59-152396, Japanese Laid-Open Publication No. 61-151197, Japanese Laid-Open Patent Publication No. 63-41484, and Japan. Various titanocene compounds such as di-cyclopentadienyl-Ti-bis-benzene, which are disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. , bis-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl , di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorobenzene -1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis- 2,6-Difluorophenyl-1-yl, bis-methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, bis-methylcyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, bis-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorobenzene-1- , Disclosed in Japanese Laid-Open Patent Publication No. 1-304453, Publication of Japanese Patent Laid-Open No. 1-152109 iron - allene complexes and the like.

The hexaarylbiimidazole compound includes, for example, various compounds disclosed in the specification of Japanese Patent Application Laid-Open No. Hei 6-29285, U.S. Patent No. 3,479,185, the same as No. 4,311,783, and No. 4,622,286. Specifically, it includes: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-bromobenzene) Base)) 4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenyl Bis-imidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-double (ortho) , o-'-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (o- Trifluorophenyl)-4,4',5,5'-tetraphenyldiimidazole and the like.

Specific examples of the "organic borate compound" are as follows. For example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. Hei 9-188685, Japanese Patent Laid-Open No. Hei 9-188686, and Japanese Patent Laid-Open No. 9-188710 Japanese Laid-Open Patent Publication No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, No. 2764769, and Japanese Patent Application No. 2000-310808, and published in Kunz, Martin "Rad Tech '98. Proceeding April 19-22, Organic borate such as "Chicago" in 1998, and an organic boron lanthanum complex or organic compound disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The organoboron iodine complex which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Boron yttrium complexes, which are disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping No. 7-292014, etc. Organic boron transition metal coordination complexes and the like.

The "disulfonic acid compound" includes a compound disclosed in Japanese Laid-Open Patent Publication No. 61-166544, Japanese Patent Laid-Open Publication No. 2002-328465, and the like.

"Oxime ester compounds" include: JCS Perkin II (1979) 1653-1660), JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and Japanese Special Open 2000 A compound of the Japanese Patent Publication No. Hei. No. 2000-80068, and a compound disclosed in Japanese Laid-Open Patent Publication No. 2004-534797.

"Onium salt compound" includes, for example, diazonium salt disclosed in SISchlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et., Polymer, 21, 423 (1980), Ammonium salts disclosed in U.S. Patent No. 4,069,055, U.S. Patent No. 4,365,049, et al., U.S. Patent No. 4,069,055, the entire disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosure of Japanese Patent Publication No. 339,049, the entire disclosure of which is incorporated herein by reference.

It can be suitably used in the iodonium salt-based diaryliodonium salt of the present invention, and from the viewpoint of stability, it is preferably an electron-donating group such as an alkyl group, an alkoxy group or an aryloxy group. Replace two or more. Further, in another preferred form of the onium salt, one of the substituents of the triarylsulfonium salt has a kaempferin and an anthracene structure, and has an absorbed iodonium salt at 300 nm or more.

Suitable salts for use in the present invention include those disclosed in European Patent Nos. 370,693, 390,214, 233, 567, 297, 443, 297, 442, U.S. Patent No. 4,933,377, and 161,811. No. 410,201, the same as No. 4, 760, 013, the same as the 4th, 734, 444, the same as the 2, 833, 827, the German invention patent No. 2, 904, 626, the same as the 3, 604, 580, the same as the description of the 3,604, 581, and From the standpoint of the sensitivity of stability, it is preferably replaced by an electron attracting group. The electron attracting group is preferably a Hammett's value which is larger than 0. Preferred electron attracting groups include halogen atoms, carboxylic acids and the like.

In addition, other preferred onium salts include those in which one of the substituents of the triarylsulfonium salt has a oxazin, an anthracene structure, and an absorption of an anthracene salt above 300 nm. Other preferred onium salts include those having a triarylsulfonium salt substituent having an aryloxy group and an arylthio group having an absorption of more than 300 nm.

In addition, sulfonium salt compounds include: disclosed in JVCrivello et. al, Macromolecules, 10 (6), 1307 (1977), JVCrivello et. al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979) Selenium salt, disclosed in CSWen et. al, Teh. Proc. Conf. Rad. Curing ASIA, page 478 Tokyo, September (1988), arsenic salts and the like.

The "nonylphosphine oxide compound" includes Irgacure 819, Darocure 4265, Darocure TPO, and the like manufactured by Ciba Specialty Chemicals Co., Ltd.

The "(B) photopolymerization initiator" used in the present invention is preferably selected from the group consisting of trihalomethyltrinitrogen from the viewpoint of exposure sensitivity. Compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, mercaptophosphine compound, phosphine oxide compound, metallocene compound, lanthanide compound, triallyl group A carbazole dimer, an oxime compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, and a halogenated group base A compound of the group consisting of an oxadiazole compound and a 3-aryl substituted oxacin compound.

Trihalomethyltrinitrogen Compound, α-amino ketone compound, mercaptophosphine compound, phosphine oxide compound, oxime compound, triallyl carbazole dimer, oxime compound, benzophenone compound, acetophenone system a compound selected from trihalomethyltrinitrogen At least one compound selected from the group consisting of a compound, an α-amino ketone compound, an anthraquinone compound, a triallyl carbazole dimer, and a benzophenone compound.

The content of the (B) photopolymerization initiator contained in the curable composition of the present invention is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight, based on the total solid content of the curable composition, particularly preferably 1 to 20% by weight. Good sensitivity and pattern formation can be achieved in this range.

<(C) Colorant>

By using a coloring agent for the curable composition of the present invention, a colored cured product composed of a curable composition can be formed, and it can be applied to a coloring pattern formation of an image forming material or a color filter.

The coloring agent to be added to the curable composition of the present invention is not particularly limited, and one or a mixture of two or more kinds of conventional dyes or pigments may be used in combination. The coloring agent is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

As the pigment which can be used for the curable composition of the present invention, various conventional inorganic pigments or organic pigments can be used. Further, in consideration of whether the inorganic pigment or the organic pigment is preferably a high transmittance, it is preferred to use a finer one as much as possible, and if the usability is also considered, the average particle diameter of the pigment is higher. It is preferably from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm. Further, the inorganic pigment includes a metal compound represented by a metal oxide, a metal salt or the like, and specifically, a metal including iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, bismuth or the like. An oxide and a composite oxide of the above metals.

The organic pigments as described above include, 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; CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255 , 264, 270; CI Pigment Violet 19, 23, 32, 39; CI Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37; CI pigment brown 25, 28; CI pigment black 1, 7; carbon black and the like.

In the present invention, it is particularly suitable to use a basic N atom in the structural formula of the pigment. These pigments having a basic N atom can exhibit good dispersibility in the composition of the present invention. Although the reason for this has not been clarified, it can be presumed to be affected by the affinity of a good photosensitive polymerization component and a pigment.

Pigments suitable for use in the invention of the present application include the following. However, the invention is not limited to these.

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

These organic pigments can be used alone or in combination to improve color purity. Specific examples of the combination are as follows. For example, a red pigment may be used: an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment alone or at least one of them, and a disazo yellow pigment, an isoporphyrin yellow pigment. , quinacridone yellow pigment or lanthanum red pigment, quinophthalone (quinophthalone) yellow pigment or lanthanide red pigment mixture. For example, bismuth pigments can be used with CI Pigment Red 177, lanthanide pigments can be used: CI Pigment Red 155, CI Pigment Red 224, Diketopyrrolopyrrole pigments can be used: CI Pigment Red 254, and reproducible from color From the viewpoint, it is preferably mixed with CI Pigment Yellow 139 (CI Pigment Yellow 139). Further, the weight ratio of the red pigment to the yellow pigment is preferably from 100:5 to 100:50. When it is 100:4 or less, there is a possibility that it is difficult to suppress the light transmittance of 400 nm to 500 nm and the color purity cannot be improved. On the other hand, if it is 100:51 or more, the main wavelength will be biased to a short wavelength, which may cause a deviation from the target hue of the NTSC (National Television System Committee). In particular, the weight ratio is most suitably in the range of 100:10 to 100:30. Further, when the color pigments are combined with each other, they can be adjusted in accordance with the chromaticity.

Further, the green pigment may be a phthalocyanine pigment alone or a diazo yellow pigment, a quinophthalone (quinoline yellow) yellow pigment, an azomethine yellow pigment or The isoporphyrin yellow pigment is used in combination. For example, such examples are preferably a mixture of C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185. The weight of the green pigment and the yellow pigment is preferably from 100:5 to 100:150. The weight ratio is particularly preferably in the range of 100:30 to 100:120.

Blue pigment can be used alone or in combination with anthraquinone pigments A dioxane is a mixture of purple pigments. Preferably, for example, a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 is used. The weight of the blue pigment and the purple pigment is preferably from 100:0 to 100:30, more preferably 100:10 or less.

Further, the pigment for the black matrix may be used alone or in combination of carbon, titanium carbon, iron oxide or titanium oxide, but a combination of carbon and titanium carbon is preferred. Further, the weight of carbon and titanium carbon is preferably in the range of 100:0 to 100:60.

When the composition of the present invention is used as a color filter, the primary particle diameter of the pigment is preferably from 10 to 100 nm, more preferably from 10 to 70 nm, from the viewpoint of color unevenness or contrast. Further preferably, it is 10 to 50 nm, and most preferably 10 to 40 nm.

Further, when the composition of the present invention is used as a color filter, it is preferred to use a dye which can be uniformly dissolved in the composition from the viewpoint of unevenness or contrast color.

The dye which can be used as the coloring agent contained in the curable composition of the present invention is not particularly limited, and a dye which has hitherto been known as a color filter can be used. For example, it is disclosed in Japanese Laid-Open Patent Publication No. SHO-64-90403, the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. U.S. Patent No. 2, 592, 207, U.S. Patent No. 4, 808, 501, U.S. Patent No. 5,667, 920, U.S. Patent No. 5,059,500, Japanese Patent Application Laid-Open No. Hei No. 5-333207, and Japanese Patent Laid-Open No. Hei 6-35183 Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Tongtekai No. 2002-14222 Japanese Patent Publication No. 2002-124223, Japanese Patent Application Publication No. 8-302224, and Japanese Patent Application Publication No. Hei No. 8-- No. Hei. Wait for the pigment.

The chemical structure can be used: pyrazo azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, OXONOL, pyrazole triazole azo Department, pyridone azo, cyanine, thiophene Pyrrolopyrazole-imine, A dye such as (xanthene), anthracycline, benzopyran, indigo or the like.

Further, in the case of performing a water or alkali development resist, it is possible to use an acid dye and/or from the viewpoint of completely removing the binder and/or dye which does not irradiate the light portion by development. Or the case of its derivatives.

Other, direct dyes, basic dyes, mordant dyes, acid mordant dyes, insoluble azo dyes, disperse dyes, oil-soluble dyes, food dyes, and/or such derivatives may also be used.

When the acid dye has an acidic group such as a sulfonic acid or a carboxylic acid, there is no particular limitation, and all solubility in an organic solvent or a developing solution, salt formation with a basic compound, absorbance, and The necessary properties of the interaction of other components in the composition, light resistance, heat resistance, and the like are selected.

Specific examples of the acid dye will be listed below, but the present invention is not limited by the above. For example, acid arizarin 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 fuchsine 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, 95107, 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, 261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349,382,383 422, 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, 2, 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 purple (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; morden green 1, 3, 4 , 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53; food yellow 3; and derivatives of such dyes.

Among the acid dyes shown above, 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 purple 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; acid green 25 and the like A derivative of a dye.

In addition, the azo system other than the above, Is also an acid dye of the cordierin system, CI Solvent Blue 44, 38; CI Solvent Orange 45; Rhodamine (Rhodamine) B, Rhodamine 110 and other acid dyes and derivatives of such dyes Also suitable for use.

Among them, the "(C) colorant" is preferably selected from the group consisting of: triallyl methane, fluorene, carbamide, benzylidene, OXONOL (Fuji exclusive dye), 赛恩宁, Thiophene Department, pyrrolopyrazole-imine, (xanthene), cordierin, benzene A coloring agent of a meperane type, an indigo type, a pyridine azo type, an anilino azo type, a pyrazole triazole azo type, a pyridone azo type, and an anthrapyridone type.

The content of the colorant used in the curable composition of the present invention is preferably from 5 to 80% by weight, more preferably from 10 to 70% by weight, still more preferably from 20 to 70% by weight, based on the total solid content of the curable composition. 70% by weight.

In particular, when the curable composition of the present invention is used in the formation of a colored pattern of a color filter, the content of the colorant is preferably 20% by weight or more, and more preferably 30% by weight or more in the above content range.

When the coloring agent is too small, when a color filter is produced by the curable composition of the present invention, there is a possibility that an appropriate chromaticity cannot be obtained. On the other hand, if it is too much, the photohardening does not proceed sufficiently, and the strength which the film should have may fall, and the latitude of the development at the time of alkali development may become narrow.

The curable composition of the present invention, if necessary, the components (A) and (B) described above, plus the component (C) which is added as desired, may simultaneously contain any of the details detailed below. Ingredients. Hereinafter, any component which can be contained in the curable composition of the present invention will be described.

<(D) Dispersant>

When the curable composition of the present invention contains a pigment as the coloring agent (C), it is preferred to add a dispersing agent (D) to improve the dispersibility of the pigment.

The dispersant (pigment dispersant) which can be used in the present invention includes: a polymer dispersant [for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, and a modified polyamine. Carbamate, modified polyester, modified poly(meth)acrylate, (meth)acrylic copolymer, formalin condensate naphthalenesulfonate, and polyoxyethylene alkyl phosphate, polyoxyethylene oxide Alkylamine, alkanolamine, pigment derivative, and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

The polymer dispersant has an effect of adsorbing on the surface of the pigment to prevent re-agglomeration. Therefore, a preferred structure is a terminal modified polymer, a graft polymer, or a block polymer having a fixed portion on the surface of the pigment. Further, the pigment derivative is modified to the surface of the pigment, that is, it has an effect of promoting adsorption of the polymer dispersant.

Specific examples of the pigment dispersant which can be used in the present invention include: Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer) manufactured by BYK Chemie Co., Ltd., 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymeric copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid); EFKA" 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 ( High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (anthraquinone derivative), 6750 (azo pigment derivative)"; Ajinomoto "Ajisper PB821, manufactured by Fine-Techno" PB822", "Flowlen TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Kyoei Chemical Co., Ltd.; Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; manufactured by Kao Corporation Demol RN, N (formalin polycondensate), MS, C, SN-B (aromatic polysulfonate polycondensate), "Homogenol L-18 (polymeric polycarboxylic acid)", "Emalgen 920" , 930, 935, 985 (polyoxyethylene nonylphenyl ether), "Acetamin 86 (stearylamine acetate)"; "Solspers 5000 (anthraquinone derivative), 22000 (azo) manufactured by Lubrizol Pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional portion at the terminal portion), 24000, 28000, 32000, 38500 (graft-type polymer)"; manufactured by Nikko Chemical Co., Ltd. "Nikkol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)".

These dispersing agents may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a combination of a pigment derivative and a polymer dispersant.

The dispersant content in the present invention is preferably from 1 to 100% by weight, more preferably from 3 to 100% by weight, still more preferably from 5 to 80% by weight, based on the pigment.

Specifically, when a polymer dispersant is used, the amount thereof is preferably from 5 to 100% by weight, more preferably from 10 to 80% by weight, based on the pigment. Further, when a pigment derivative is used, it is preferably used in an amount of from 1 to 30% by weight, more preferably from 3 to 20% by weight, particularly preferably from 5 to 15% by weight based on the pigment. The range of %.

In the present invention, when a pigment and a dispersing agent as a coloring agent are used, the sum of the content of the coloring agent and the dispersing agent is preferably from the viewpoint of the hardening sensitivity and the coloring concentration with respect to the entire composition constituting the hardening composition. The solid content is 30% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 85% by weight or less, still more preferably 50% by weight or more and 80% by weight or less.

<(F) sensitizer>

The curable composition of the present invention contains (F) a sensitizer for the purpose of improving the production efficiency of the radical initiator and the long wavelength of the photosensitive wavelength. The sensitizer which can be used in the present invention is preferably one which is sensitized to the photopolymerization initiator as described above by an electron moving mechanism or an energy moving mechanism.

The sensitizer which can be used in the present invention includes those belonging to the following compounds and having an absorption wavelength in a wavelength range of from 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the 330 nm to 450 nm domain.

The system includes, for example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, a terphenyl, 9,10-dialkoxyfluorene); Classes (eg, fluorescent yellow, blush, red algae, rhodamine (rose red) B, bengal rose); oxysulfide Isopropyl oxysulfide Diethyl oxysulfide Chlorooxysulfide ); Cyanine (eg thiaquinoline blue, Quinoline blue); merocyanoids (eg, anthocyanins, carbon anthocyanins); anthracyclines; thiazide Classes (such as thiazide, methylene blue, toluidine blue); acridines (such as acridine orange, chloroflavin, acriflavine); terpenoids (such as guanidine); horned sharks (such as horn shark mites) ); acridine orange, oxacillin (eg 7-diethylamino-4-methyl oxacin), ketoin; thiophene Class, brown Class, vinyl benzene, azo compound, diphenylmethane, triphenylmethane, distyrylbenzene; carbazole; porphyrin, spiro compound, quinophthalone, indigo, styryl, pyr A ruthenium compound, a pyrrole compound, a pyrazole triazole compound, a benzothiazole compound, a barbituric acid derivative, a thiobarbituric acid derivative, an acetophenone, a benzophenone, an oxysulfide , an aromatic ketone compound such as michelitone; N-aryl a heterocyclic compound such as oxadione or the like. Further, it includes compounds disclosed in the European Patent No. 568,993, the specification of the U.S. Patent No. 4,508,811, the specification of the same Japanese Patent No. 5,227,227, the Japanese Patent Laid-Open No. 2001-125255, and the Japanese Patent Laid-Open No. 11-271969. Wait.

Examples of more preferred sensitizers include the compounds represented by the general formulae (I) to (V) shown below:

(In the formula (I), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus which forms a pigment together with adjacent A ² and adjacent carbon atoms. The non-metal atomic group, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metal atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic core of the dye. W represents an oxygen atom or a sulfur atom. .)

(In the formula (II), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond via -L ³ -. The L ^{3 group} represents -O- or -S-. In addition, the W system It is synonymous with the one shown in the general formula (XIV).)

(In the formula (III), A ² represents a sulfur atom or NR ⁵⁹ , and L ⁴ represents a non-metal atomic group which forms a basic nucleus of a dye together with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ and R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a group of a monovalent non-metal atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

(In the formula (IV), A ³ and A ⁴ each independently represent -S- or -NR ⁶² - or -NR ⁶³ -, and R ⁶³ and R ⁶⁴ each independently represent a substituted or unsubstituted alkyl group. a substituted or unsubstituted aryl group, wherein the L ⁵ and L ⁶ groups independently represent a non-metal atomic group of a basic nucleus which forms a dye together with adjacent carbon atoms adjacent to A ³ and A ⁴ , and R ⁶⁰ and R ^6l are They are independently monovalent non-metal radicals or may be bonded to each other to form an aliphatic or aromatic ring.)

(In the formula (V), R ⁶⁶ represents an aromatic ring or a heterocyclic ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or -NR ^{67 -} . The R ⁶⁴ , R ⁶⁵ and R ⁶⁷ systems are each independently The ground represents a hydrogen atom or a monovalent non-metal atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each may be bonded to each other to form an aliphatic or aromatic ring.)

Preferred specific examples of the compounds represented by the general formulae (I) to (V) include those shown below.

The sensitizer may be used alone or in combination of two or more.

The content of the sensitizer in the curable composition of the present invention is preferably from 0.1 to 20% by weight, more preferably from 0.5% by weight in terms of solid content, from the viewpoint of light absorption efficiency in the deep portion and initial decomposition efficiency. Up to 15% by weight.

<(G) binder polymer>

In the curable composition of the present invention, for the purpose of improving film properties and the like, a binder polymer may be further used as necessary. The binder is preferably a linear organic polymer. These "linear organic polymers" can be used as they are known. It is preferred to select a linear organic polymer which is soluble or swellable to water or weakly alkaline water for achieving water development or weak alkaline water development. The linear organic polymer is used not only as a film forming agent but also as a developer for water, weak alkaline water or an organic solvent. For example, if a water-soluble organic polymer is used, water development can be achieved. Such a linear organic polymer includes a radical polymer having a carboxylic acid group in a side chain, and is disclosed, for example, in Japanese Laid-Open Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, and Japanese Special Public Showa. 58-12577, Japanese Invention Patent No. 54-25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, and Japanese Laid-Open No. 59-71048, that is, a resin having a carboxyl group alone or copolymerized, a resin obtained by separately or copolymerizing a monomer having an acid anhydride, or a resin which is hydrolyzed or semi-esterified or semi-aminated, or unsaturated. An epoxy acrylate or the like which is modified with a monocarboxylic acid and an acid anhydride. A single system having a "carboxy group" includes acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid fumaric acid, 4-carboxystyrene, etc., and a single system having an "anhydride" includes Maleic anhydride or the like.

And likewise, there is an acidic cellulose derivative having a carboxylic acid group in a side chain. Others may be those obtained by adding a cyclic anhydride to a polymer having a hydroxyl group.

When the alkali-soluble resin is used as a copolymer, the compound used for the copolymerization may be a monomer other than the monomers listed above. Examples of the other monomer include the compounds of (1) to (12) shown below.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, A "Amino acid-containing acrylates and methacrylates" such as 3-hydroxypropyl acrylate or 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, acrylic acid -2-chloroethyl ester, glycidyl acrylate, 3,4-epoxycyclohexyl methacrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, acrylic acid 2 - "alkyl acrylate" such as allyloxyethyl acrylate or propargyl acrylate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate , vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate Such as "alkyl methacrylate".

(4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, "Acrylamide or methyl" such as N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide Acrylamide.

(5) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. "Vinyl ether" category.

(6) "vinyl esters" such as vinyl acetate, vinyl chloroacetate, vinyl butyrate or vinyl benzoate.

(7) "Styrene" such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene.

(8) "Vinyl ketone" such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone or phenyl vinyl ketone.

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

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

(11) maleimide, N-propylene decyl acrylamide, N-ethyl methacryl decylamine, N-propenyl methacrylamide, N-(p-chlorophenyl "Alkyl" is an "unsaturated quinone imine" such as methacrylamide.

(12) A methacrylic monomer in which a hetero atom is bonded to the α-position. The compounds include, for example, the compounds disclosed in Japanese Patent Application No. 2001-115595, and the specification of Japanese Patent Application No. 2001-115598.

In the above, the (meth) acrylate resin having an allyl group or a vinyl ester group and a carboxyl group in the side chain is disclosed on the side of JP-A No. 2000-187322 and JP-A-2002-62698. An alkali-soluble resin having a double bond in the chain, or an alkali-soluble resin having a guanamine group in a side chain disclosed in Japanese Laid-Open Patent Publication No. 2001-242612, which has excellent film strength, sensitivity, and developability in balance, and thus is suitable use.

In addition, it is disclosed in Japanese Special Fair No. 7-12004, Japanese Special Fair No. 7-120041, Japanese Special Fair No. 7-120042, Japanese Special Fair No. 8-12424, and Japanese Special Open No. 63-287944. An acid group-containing urethane-based binder polymer such as Japanese Laid-Open Patent Publication No. SHO-63-287947, No. 1-271741, or a side chain disclosed in Japanese Laid-Open Patent Publication No. 2002-107918 Aminoester-based binder polymer with acid group and double bond, because of its superior strength, for brush resistance. The low exposure suitability aspect is advantageous.

In addition, the polyvinyl alcohol-based binder polymer having an acid group-like acetal modification, such as the European invention patent No. 993966, the European invention patent No. 1204000, and the Japanese Patent Laid-Open No. 2001-318463, has a balance. Excellent film strength and developability, so it is suitable for use.

Further, as the other "water-soluble linear organic polymer", polyvinylpyrrolidone or polyethylene oxide can be used. Further, in order to improve the strength of the hardened film, an alcohol-soluble nylon (nylon) or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

The weight average molecular weight of the binder polymer which can be used in the present invention is preferably 5,000 or more, more preferably from 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably from 2,000 to 250,000. range. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more and 1.1 to 10 range.

The binder polymer may be any of a random copolymer, a block copolymer, a graft polymer, and the like.

The binder polymer which can be used in the present invention can be synthesized by a conventionally known method. The solvent used in the synthesis includes, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetic acid 2 - methoxyethyl ester, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N , N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, water, and the like. These solvents are used singly or in combination of two or more. In the synthesis of the binder polymer which can be used in the present invention, the radical polymerization initiator to be used is a well-known compound such as an azo initiator or a peroxide initiator.

<(H) Co-sensitizer>

The curable composition of the present invention preferably further contains a co-sensitizer. The co-sensitizer in the present invention has an effect of further increasing the sensitivity of the sensitizing dye or the initiator to actinic radiation, or suppressing the polymerization of the polymerizable compound due to oxygen.

Examples of such co-sensitizers include amines, which are disclosed, for example, by MRSander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972), Japanese Knot, Sho. 44-20189, Japan. Japanese Laid-Open Patent Publication No. 51-82102, Japanese Laid-Open Patent Publication No. SHO-52-134692, Japanese Laid-Open Patent Publication No. 59-138205, Japanese Patent Laid-Open No. 60-84305, and Japanese Patent Laid-Open No. 62- No. 18537, Japanese Patent Laid-Open No. 64-33104, and Research Disclosure No. 33825, and the like, specifically, include: triethanolamine, p-dimethylaminobenzoic acid ethyl ester, and p-A. Mercaptodimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the co-sensitizer include: mercaptans and sulfides, and are disclosed in, for example, Japanese Laid-Open Patent Publication No. 53-702, Japanese Patent Publication No. Sho 55-500806, and Japanese Patent Laid-Open No. 5-142772 a thiol compound, a disulfide compound of JP-A-56-75643, and the like, specifically, 2-hydroxythiobenzothiazole, 2-hydrothiobenzophenone Oxazole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, and the like.

Further, other examples of the co-sensitizer include an amino acid compound (for example, N-phenylglycine), and an organometallic compound disclosed in Japanese Patent Publication No. 48-42965 (for example, tributyl zinc acetate). A hydrogen donor which is disclosed in Japanese Patent Publication No. 55-34414, and a sulfur compound (for example, trithiane or the like) disclosed in JP-A-6-308727.

<(I) Polymerization inhibitor>

In the present invention, in order to suppress unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during production or storage of the curable composition, it is preferred to add a small amount of a thermal polymerization inhibitor.

The "thermal polymerization inhibitor" which can be used in the present invention includes: hydroquinone, p-methoxyphenol, di-tertiary-butyl-p-cresol, gallic phenol, tert-butyl catechol, Phenylhydrazine, 4,4'-thiobis(3-methyl-6-tertiary-butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol) N-nitrosophenylhydroxylamine first sulfonium salt and the like.

The amount of the thermal polymerization inhibitor added is preferably from about 0.01% by weight to about 5% by weight based on the total weight of the total composition. Further, if necessary, a higher fatty acid derivative such as rosin or decylamine may be added to prevent the polymerization of oxygen, and the drying process after coating may be unevenly applied to the surface of the photosensitive layer. The higher fatty acid derivative is preferably added in an amount of from about 0.5% by weight to about 10% by weight based on the total composition.

<Other Additives>

Further, in the present invention, an additive such as an inorganic filler or a plasticizer or a lipid-sensitizing agent capable of improving the ink adhesion on the surface of the photosensitive layer may be added to improve the physical properties of the cured film.

"Plasticizer" includes, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresyl phosphate, adipic acid When a binder is used, the total weight of the compound having an ethylenically unsaturated double bond and the binder may be preferably 10% by weight or less based on the total weight of the octyl ester, dibutyl sebacate or triethyl decyl glycerin. .

The above-mentioned curable composition of the present invention can be hardened under high sensitivity, and storage stability is also good. Further, it is possible to exhibit high adhesion to the surface of a hard material such as a substrate suitable for a curable composition. Therefore, the curable composition of the present invention is suitably used in the fields of, for example, three-dimensional light shaping or holography, image forming materials for color filters or inks, paints, adhesives, coating agents and the like.

[Color filter and method of manufacturing the same]

Next, the color filter of the present invention and a method of manufacturing the same will be described.

The color filter of the present invention is characterized in that it has a colored pattern formed by using the curable composition of the present invention on a support.

The color filter of the present invention, and a method for producing the same (manufacturing method of the color filter of the present invention) will be collectively described below.

It is characterized in that it comprises a step of applying a curable composition of the present invention on a support to form a curable composition layer (hereinafter, simply referred to as "curable composition layer forming step"); a step of exposing the layer of the material through the hood (hereinafter referred to as "exposure step" as appropriate); and developing the layer of the curable composition after exposure to form a colored pattern (hereinafter referred to as "Development step").

Hereinafter, each step in the production method of the present invention will be described.

<Step of forming a hardenable composition layer>

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

The support which can be used in this step includes, for example, soda lime glass for a liquid crystal display element, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, or a photoelectric element for an image pickup element or the like. The conversion element substrate, for example, a germanium substrate or the like, or a complementary metal oxide film semiconductor (CMOS) or the like. These substrates also have a black stripe that is formed to isolate each pixel.

Further, on the support, if necessary, the undercoat layer may be provided to improve adhesion to the upper layer, prevent diffusion of the substance, or planarize the surface of the substrate.

The coating method of the curable composition of the present invention on the support can be applied to a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, a screen printing method, or the like. Various coating methods.

The coating film thickness of the curable composition is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, still more preferably from 0.2 to 3 μm.

The drying (prebaking) of the photocurable composition layer coated on the substrate can be carried out by hot plate, oven or the like at a temperature of 50 ° C to 140 ° C for 10 to 300 seconds.

<Exposure step>

In the exposure step, the curable composition layer formed in the step of forming the curable composition layer is exposed through a mask having a specific hood pattern.

In the exposure of this step, the pattern exposure of the coating film is partially exposed by the specific hood pattern, and only the portion of the coating film subjected to light irradiation is hardened, and then developed with a developing solution to form The pattern-like film composed of pixels of three colors or four colors is used. The radiation that can be used during exposure is suitable for ultraviolet rays such as g-line or i-line. The irradiation amount is preferably from 5 to 1,500 mJ/cm ² , more preferably from 10 to 1,000 mJ/cm ² , most preferably from 10 to 500 mJ/cm ² .

When the color filter of the present invention is used for a liquid crystal display element, it is preferably 5 to 200 mJ/cm ² , more preferably 10 to 150 mJ/cm ² , most preferably 10 to 10 in the above range. 100 mJ/cm ² . Further, when the color filter of the present invention is used in a solid-state image pickup element, it is preferably from 30 to 1,500 mJ/cm ² , more preferably from 50 to 1,000 mJ/cm ² in the above range, and most preferably 80 to 500 mJ/cm ² .

<Development Step>

Next, by performing an alkali development treatment, the unexposed portion of the light can be eluted in the aqueous alkali solution by the above-described exposure to leave only the photohardened portion. The developer is preferably an organic alkali developer which does not cause damage to the underlying circuit or the like. The development temperature is usually from 20 ° C to 30 ° C and the development time is from 20 to 90 seconds.

The alkali agent for the developer includes, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dioxinbicyclo[5 An organic basic compound such as 4,0]-7-undecene, which is diluted with pure water to a concentration of 0.001 to 10% by weight, preferably 0.01 to 1% by weight, in an aqueous alkaline solution. Used as a developer. Further, when such a developing solution composed of an alkaline aqueous solution is used, it is usually washed with pure water after development.

Next, the remaining developer is removed by washing, and after drying, heat treatment (post-baking) is performed. Thus, the hardened film can be produced by repeating the above steps in order of the respective colors. Thereby, a color filter can be obtained.

Post-baking is a heat-hardening treatment usually applied at 100 ° C to 240 ° C in order to achieve a heat treatment after development which is applied to the improvement. When the substrate is a glass substrate or a tantalum substrate, it is preferably in the range of 200 ° C to 240 ° C in this temperature range.

In the post-baking treatment, the developed coating film is heated in a continuous manner using a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heater in accordance with the above conditions. Or it can be implemented in batch mode.

Further, in the manufacturing method of the present invention, after the hardening composition layer forming step, the exposing step, and the developing step as described above are carried out, if necessary, the formed coloring pattern may be included by heating and/or exposure. The step of hardening is carried out.

By repeating the above-described curable composition layer forming step, exposure step, and development step (and, if necessary, adding a hardening step), the desired color phase number can be obtained. A color filter composed of the desired hue.

The use of the curable composition of the present invention has been described above for the use of pixels of a color filter, but it is of course also applicable to a light-shielding layer such as a black matrix provided between color filter pixels. The black matrix may be subjected to pattern exposure or alkali development in the same manner as the above-described pixel production method, except that a black colorant such as carbon black or titanium black is added as a colorant in the curable composition of the present invention. Thereafter, post-baking is applied to promote hardening of the film to form.

In the color filter of the present invention, since the curable composition of the present invention as described above is used, the formed coloring pattern exhibits high adhesion to the support substrate, and the cured composition has excellent development resistance. With excellent exposure sensitivity, the adhesion of the substrate of the exposed portion is good, and a high resolution pattern conforming to the cross-sectional shape of the desired one can be formed. Therefore, it is suitably used for a solid-state image pickup element such as a liquid crystal display element or a CCD, and is particularly suitable for use in, for example, a high-resolution CCD element, CMOS, or the like exceeding 1 million pixels. The color filter of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting the CCD and a microlens for collecting light.

"Embodiment"

Hereinafter, the present invention will be specifically described by way of examples, but is not limited to the following examples. In addition, unless otherwise noted, "%" and "parts" are weight basis.

The specific synthesis method of the above-exemplified compound (1) will be described below. The other (A) specific polymerizable compound used in the present invention can also be synthesized in the same scheme. In addition, the synthesis method is not limited to the method described below.

[Synthesis Example 1]: Synthesis of exemplified compound (1)

After adding 12 ml of acetonitrile to 12 g (0.023 mol) of pentaerythritol pentaacrylate and dissolving it, 0.16 g (0.25 mmol) of ginseng (2-ethylhexanoate) was added. And 5.9 g (0.23 mol) of triethoxy(3-isocyanatepropyl)decane, and stirred at 55 ° C to 65 ° C for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and then 50 ml of n-hexane was added and washed three times, and the lower layer was taken. Then, the solvent was distilled off to obtain 17 g (0.022 mol (yield: 95%)) of Compound (1).

For the compound (1) obtained by the method described above, the structure was confirmed by NMR (nuclear magnetic resonance), and the result was 1H-NMR (400 MHz, solvent: chloroform-d; standard material: four Base decane) δ 6.40 (5H, dd), 6.10 ppm (5H, dd), 5.85 ppm (5H, dd), 5.10 ppm (1H, brt), 4.25 ppm (6H, s), 4.20 ppm (4H, s) 4.16 ppm (2H, s), 3.81 ppm (6H, q), 3.48 ppm (2H, s), 3.45 ppm (2H, s), 3.15 ppm (2H, m), 1.62 ppm (2H, m), 1.23 Ppm (9H, t), 0.63 ppm (2H, m).

The hardenable composition of the present invention will be more specifically described by way of examples, but the present invention is not limited to the embodiments without departing from the spirit and scope of the invention.

[Example 1] (1. Modulation of hardenable composition)

Here, a curable composition containing a colorant (pigment) is prepared as a color filter for use as a liquid crystal display element, and will be described as an example.

1-1. Mixing and Dispersing Treatment of Pigments First, the components shown below were mixed and dispersed by a two-roll type roll mill.

Further, the components shown below were added to the dispersion prepared as described above and subjected to a sand mill for a day and night microdispersion treatment.

1-2. Preparation of Curable Composition (Coating Liquid) The above-described dispersion-treated pigment was further added with the components shown below, and stirred and mixed to prepare a curable composition solution.

(2. Manufacture of color filters)

2-1. Formation of a hardenable composition layer A curable composition containing the above pigment is used as a photoresist solution, and after being subjected to slit coating on a 550 mm × 650 mm glass substrate under the following conditions, it is still in its state. After standing for 10 minutes, vacuum drying and prebaking (100 ° C, 80 seconds) were applied to form a curable composition coating film (curable composition layer).

(Slit coating condition) Gap of the opening end of the coating head: 50 μm Coating speed: 100 mm/sec Clearance between the substrate and the coating head: 150 μm Coating thickness (dry thickness): 2 μm coating temperature :23°C

2-2. After exposure and development, the photocurable coating film was exposed to a pattern using a 2.5 kw ultrahigh pressure mercury lamp and a test reticle having a line width of 20 μm, and after exposure, an organic developer solution was used ( Trade name: CD, Fuji Film Arti Co., Ltd.) 10% aqueous solution covers the entire coating film and makes it stand still for 60 seconds.

2-3. After the heat treatment is at rest, the pure water is sprayed into a spray to spray the developer, and then the coating film to which the photohardening treatment and the development treatment are applied is heated in an oven at 220 ° C for 1 hour (post-baking) grilled). Thereby, a colored resin film (color filter) was formed on the glass substrate.

(3. Performance evaluation)

The storage stability of the colored curable composition coating liquid prepared as described above and the curable composition coating film formed on the glass substrate using the colored curable composition were evaluated by the method described below. Exposure sensitivity (substrate adhesion), substrate adhesion, developability, and pattern cross-sectional shape. The results are shown in Table 1.

3-1. Storage solution storage stability After the coating liquid as described above was stored for one month at room temperature, the degree of foreign matter precipitation was evaluated visually and on the following criteria.

<Judgment criterion> ○: No precipitation was observed.

△: The precipitation was slightly observed.

X: I saw the precipitation.

3-2. Exposure sensitivity of the coating film (colored layer), exposure amount is changed to 10 to 100 mJ/cm ² of each exposure amount, and the line width of the pattern after post-baking is 20 μm. The exposure is evaluated as exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity.

3-3. Development property, pattern cross-sectional shape, and substrate adhesion The surface and cross-sectional shape of the substrate after post-baking were observed by an optical microscope and a SEM (scanning electron microscope) photograph, and confirmed by a usual method.

The presence or absence of the residue of the region (unexposed portion) which was not irradiated with light in the exposure step was observed to evaluate the developability.

<Developability> ○: No residue was completely confirmed in the unexposed portion.

△: The residue was slightly confirmed in the unexposed portion, but it was a practically problem-free level.

X: Residue was remarkably confirmed in the unexposed portion.

The cross-sectional shape of the formed pattern was observed. The shape of the cross-section of the pattern is preferably the shape of the trapezoidal shape, and the shape of the rectangle is second. The inverted cone shape is not good.

The evaluation of the adhesion of the substrate is to observe whether or not a pattern defect is generated. These assessments are evaluated against the following benchmarks.

<Substrate Adhesion> ○: Pattern defects were not observed at all.

△: There is almost no pattern defect, but a part of the defect is seen.

X: A significant pattern defect was seen.

[Examples 2 to 9]

In the curable composition of the first embodiment, the coloring was carried out in the same manner as in Example 1 except that the exemplified compound (1) which is a specific polymerizable compound (A) was substituted with the exemplified compound shown in Table 1 below. The pattern was evaluated and the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

[Example 10]

In the curable composition of the first embodiment, the exemplary compound (1) which is substituted for the (A) specific polymerizable compound is an exemplary compound shown in the following Table 1, and the glass substrate of the substrate is changed to the same size of polyparaphenylene. The ethylene glycol formate substrate (described as "PET substrate" in the table) and the post-baking step were changed to the irradiation step of 10,000 mJ/cm ² under a high pressure mercury lamp, and the rest were all the same as in the first embodiment. The manner of implementation was carried out to obtain a colored pattern, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

[Comparative Example 1]

In the curable composition of Example 1, except that the exemplified compound (1) which is a specific polymerizable compound of (A) is a comparative polymerizable compound shown in Table 1 below, all of them are in the same manner as in Example 1. Implementation. The results are shown in Table 1.

[Comparative Example 2]

In the curable composition of the first embodiment, the exemplified compound (1) which is substituted for the specific polymerizable compound (A) is substituted with the exemplified compound shown in the following Table 1, and the glass substrate of the substrate is changed to the same size of polyparaphenylene. The ethylene glycol formate substrate was changed to a 10,000 mJ/cm ² irradiation step under a high pressure mercury lamp, and the rest was carried out in the same manner as in Example 1 to obtain a colored pattern, and the same was carried out. The same evaluation as in Example 1. The results are shown in Table 1.

As is apparent from the results of Table 1, the colored curable composition of the embodiment using the curable composition of the present invention has excellent storage stability in the form of a solution, and when an image is formed on the support, A comparative example of a polyfunctional acrylate-based comparative polymerizable compound which is outside the scope of the present invention has any of excellent developability, substrate adhesion, and pattern cross-sectional shape. Further, it has been found that the increase in the double bond density in the vicinity of the substrate and the adhesion of the substrate can suppress the etching caused by the developer, and as a result, the exposure sensitivity is improved.

In the following, a curable composition containing a coloring agent (dye) is prepared as a color filter for use as a solid-state image sensor, and will be described as an example.

[Example 11] (1. Modulation of photoresist)

The components of the following composition are mixed and dissolved to prepare a photoresist.

<composition>

(2. Manufacture of tantalum substrate with base coating)

A 6 inch wafer was heat treated in an oven at 200 ° C for 30 minutes. Next, the photoresist solution as described above is applied to the tantalum wafer to have a dry film thickness of 2 μm, and then heated in an oven at 220 ° C for 1 hour to dry to form a base coat layer. A tantalum wafer substrate with a base coating.

(3. Modulation of a colorant-containing hardening composition (dye system))

The compound of the following composition A-1 was mixed and dissolved to prepare a colored photosensitive resin composition A-1.

(composition A-1)

(5. Fabrication and evaluation of color filters using a coloring photosensitive resin composition)

- Evaluation of pattern formation and sensitivity - application of the colorant-containing hardenable composition A-1 prepared in the above item 3 to the base layer coated with the base material obtained in the above item 2 A base coat layer of the wafer substrate is formed to form a hardenable composition layer (coating film). Further, heat treatment (prebaking) was performed for 120 seconds using a 100 ° C hot plate so that the dried film thickness of the coating film was 0.9 μm.

Next, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used to transmit an Island (Island) pattern mask having a pattern of 2 μm square at a wavelength of 365 nm and at 100 to 1600 mJ. Various exposures of /cm ² were exposed.

Thereafter, the wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotary table of a spin-on-jet (DW-30 type, manufactured by Chemitronics Co., Ltd.) using CD- 2000 (manufactured by Fuji Photo Film Electronic Materials Co., Ltd.) was subjected to paddle development at 23 ° C for 60 seconds to form a colored pattern on the tantalum wafer substrate.

The germanium wafer substrate on which the colored pattern has been formed is fixed to the horizontal rotating table by a vacuum chuck, and the germanium wafer substrate is rotated by a rotation number of 50 rpm by a rotating device, and the nozzle is Pure water is supplied in a spray form to carry out a washing treatment, followed by spray drying. Then, the size of the colored pattern was measured using a length measuring SEM (scanning electron microscope) "S-9260A" (manufactured by Hitachi Hi-Technology Co., Ltd.). The exposure amount of 2 μm with the base coat layer to which the pattern line width can be attached with the base coat layer was evaluated as exposure sensitivity. The smaller the value of the exposure sensitivity, the higher the sensitivity. The results of the measurement evaluation are shown in Table 2 of the following table.

The presence or absence of the residue of the region (unexposed portion) which was not irradiated with light in the exposure step was observed to evaluate the developability.

<Developability> ○: No residue was completely confirmed in the unexposed portion.

△: The residue was slightly confirmed in the unexposed portion, but it was a practically problem-free level.

X: Residue was remarkably confirmed in the unexposed portion.

The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is preferably rectangular, and the inverted cone shape is not preferable.

The evaluation of the adhesion of the substrate is to observe whether or not a pattern defect is generated. These assessments are evaluated against the following benchmarks.

<Substrate Adhesion> ○: Pattern defects were not observed at all.

△: There is almost no pattern defect, but a part of the defect is seen.

X: A significant pattern defect was seen.

[Examples 12 to 15]

The exemplified compound (1) used in the following section (3. Preparation of the colorant containing the curable composition) is the same as the compound shown in the following Table 2 except for the compound shown in Table 2 below. The manner was carried out to obtain a colored pattern, and the same evaluation as in Example 11 was carried out. The results are shown in Table 2.

[Comparative Example 3]

The exemplified compound (1) used in the following section (3. Preparation of the colorant containing the curable composition) is the comparative polymerizable compound shown in the following Table 2, and the rest are all in the same manner as in the examples. 11 was carried out in the same manner to obtain a colored pattern, and the same evaluation as in Example 11 was carried out. The results are summarized in Table 2.

[Example 16]

Modulation of a curable composition (pigment system) for color filters used for solid-state imaging devices

1-1. Mixing and Dispersing of Pigments

First, the following components were mixed and dispersed by a two-roll type roll mill.

Further, the following ingredients were added to the above-obtained dispersion and subjected to a sand mill for a day and night microdispersion treatment.

1-2. Preparation of a curable composition (coating liquid) Further, a pigment which has been subjected to the above-described dispersion treatment is further added with the following components, and stirred and mixed to prepare a curable composition solution.

The coating liquid was used to carry out the coating as described in Example 11 of the curable composition of the above-mentioned "Preparation of a curable composition for a color filter for use in a solid-state image sensor (dye system)". exposure. Development and performance evaluation. The results are summarized in Table 2.

[Comparative Example 4]

The exemplified compound (1) used in the above [1-2. Preparation of the curable composition (coating liquid)] in the above-mentioned Example 16 is changed to the following Table 2, and the rest are in the same manner as in the examples. 16 is implemented in the same way. The results are summarized in Table 2.

As a result of the results of Table 2, the coloring-curable composition of the embodiment using the curable composition of the present invention is the same as the case of using a pigment as a coloring agent, even when a dye is used as a coloring agent. It also has superior storage stability in the form of a solution.

Further, when an image is formed on the support, the comparative example of the polyfunctional acrylate-based polymerizable compound which is used only in the range of the present invention has excellent developability, substrate adhesion, and pattern cross-sectional shape. Any one. Further, from these results, it is known that the double bond density in the vicinity of the substrate and the substrate adhesion can be suppressed, and the etching caused by the developer can be suppressed. As a result, the exposure sensitivity is improved.

Claims (10)

A curable composition comprising (A) a substituent having four or more ethylenically unsaturated double bonds in a molecule and a stanol group derived by hydrolysis as an adhesion group to a hard material a radically polymerizable compound, (B) a photopolymerization initiator, and (E) a radically polymerizable compound having no (3) or more (meth) acrylate structure without a binding group, wherein E) a radically polymerizable compound having no (3) or more (meth) acrylate structure and having (A) having more than 4 ethylenically unsaturated double bonds in the molecule and hydrolyzing The weight ratio of the (A) radically polymerizable compound which gives the substituent of the decyl alcohol group as the total weight of the radically polymerizable compound of the hard material to the hard material [(A)/(A)+(E )] is 0.01 or more and 0.3 or less. The hardenable composition according to claim 1, wherein the hard material is a glass substrate or a tantalum substrate. The sclerosing composition according to claim 1, wherein the (A) has four or more ethylenically unsaturated double bonds in the molecule and a substituent which generates a stanol group by hydrolysis as a hard The radically polymerizable compound of the adhesive group of the material has an acrylonitrile group in the molecule. The sclerosing composition according to claim 1, wherein the (A) has four or more ethylenically unsaturated double bonds in the molecule and a substituent which generates a stanol group by hydrolysis as a hard a radically polymerizable compound having a close-knit group of materials, having 5 in the molecule The ethylenically unsaturated double bond. The sclerosing composition according to claim 1 or 2, further comprising (C) a coloring agent having a maximum absorption in a visible wavelength range of from 400 nm to 700 nm. The curable composition according to claim 1, further comprising a colorant, wherein the concentration of the colorant is from 30 to 70% by weight based on the solid content of the curable composition. The sclerosing composition according to claim 1, wherein the photopolymerization initiator is an oxime ester compound. The curable composition according to claim 1, wherein the ratio of [(A)/(A)+(E)] is 0.01 or more and 0.15 or less. A color filter characterized in that a coloring pattern comprising a curable composition as described in claim 5 of the patent application is provided on a support. A method for producing a color filter, comprising: coating a curable composition according to claim 5 of the patent application to form a color hardening composition layer on the support, and forming the hardenability composition a step of exposing the layer of matter through the hood, and developing the exposed layer of the curable composition to form a colored pattern.