KR102146683B1 - Colored radiation-sensitive composition and color filter using the same - Google Patents

Abstract

Provision of a radiation-sensitive composition in which a solution residue is not left in an unexposed portion when a colored layer is formed, and the roughness of the surface of the colored layer is suppressed.
(a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, (c) a monomer having three or more ethylenically unsaturated double bonds, (d) a polymerization initiator and (e) a colorant, (a) A colored radiation-sensitive composition in which the content of the polymer having a polymerizable group is 1 to 14% by mass of all polymer components.

Description

Colored radiation-sensitive composition, color filter using the same TECHNICAL FIELD [COLORED RADIATION-SENSITIVE COMPOSITION AND COLOR FILTER USING THE SAME}

The present invention relates to a colored radiation-sensitive composition, a cured film using the same, a color filter, an ink jet ink, a method for producing a color filter, a solid-state imaging device, a liquid crystal display device, and an organic EL display device. In particular, it relates to a colored radiation-sensitive composition preferably used for negative development.

The color filter is an indispensable component for a display of a solid-state image sensor or a liquid crystal display device. In order to form such a color filter, a photosensitive resin composition is employed. For example, Japanese Patent Application Laid-Open No. 2009-288282 discloses a photosensitive resin composition comprising a photosensitive transparent resin, a non-photosensitive transparent resin, a polyfunctional monomer, a colorant, and the like. In addition, in Japanese Patent Laid-Open No. 2009-288282, it is described that the content of the photosensitive transparent resin in the photosensitive resin composition preferably accounts for 15 to 80% by weight based on the total weight of the photosensitive transparent resin and the non-photosensitive transparent resin. have.

However, as a result of reviewing Japanese Patent Laid-Open No. 2009-288282 by the inventor of the present application, when a colored layer was formed using the composition described in Japanese Patent Laid-Open No. 2009-288282, a solution residue remained on the unexposed portion or the surface of the colored layer was rough. I knew I was losing. It is an object of the present invention to provide a radiation-sensitive composition in which a developing residue is not left in an unexposed portion when a colored layer is formed, and the roughness of the surface of the colored layer is reduced. The purpose.

As a result of investigation by the inventor of the present application for the above problems, it was found that in Japanese Patent Laid-Open No. 2009-288282, the film cures and shrinks due to the large proportion of the photosensitive acrylic polymer contained in the photosensitive resin composition, causing the above problem. However, if the proportion of the photosensitive resin composition is reduced, Japanese Patent Laid-Open No. 2009-288282 describes that the sensitivity of the composition is inferior. In addition, it is assumed that the strength of the film of the obtained colored layer is also inferior. Under such circumstances, the inventors of the present invention further studied, and found that (a) the content of the acrylic polymer having a polymerizable group was 1 to 14% by mass of the total polymer component, and (c) 3 or more ethylenically unsaturated double bonds were It was found that the above problems could be solved by blending the possessed monomers, and the present invention was completed.

Specifically, the subject was solved by the following means <1>, preferably by the following means <2> to <18>.

<1> (a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, (c) a monomer having three or more ethylenically unsaturated double bonds, (d) a polymerization initiator and (e) a colorant. It contains, and (a) content of the acrylic polymer which has a polymerizable group is 1-14 mass% of all polymer components, The colored radiation-sensitive composition characterized by the above-mentioned.

<2> The colored radiation-sensitive composition according to <1>, wherein (a) the content of the acrylic polymer having a polymerizable group is 5 to 12% by mass of all polymer components.

<3> The colored radiation-sensitive composition according to <1> or <2>, wherein the (e) coloring agent is at least one selected from red, magenta, yellow, blue, cyan, and green.

<4> The content of the monomer (c) having three or more ethylenically unsaturated double bonds in the colored radiation-sensitive composition according to any one of <1> to <3> is 0.8 to 2.0 of all polymer components. A colored radiation-sensitive composition characterized by being twice (mass ratio).

<5> The colored radiation-sensitive composition according to any one of <1> to <4>, wherein (c) a (meth)acrylate monomer is included as a monomer having three or more ethylenically unsaturated double bonds. .

<6> The compound represented by the following general formula (i) and general formula (ii) according to any one of <1> to <4>, as (c) a monomer having three or more ethylenically unsaturated double bonds. A colored radiation-sensitive composition comprising at least one kind selected from a branching compound.

[In general formulas (i) and (ii), E represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, respectively, and y is 1~ The integer of 10 is represented, and X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.

In General Formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, m represents an integer of 0 to 10, respectively, and the total of each m is an integer of 1 to 40.

In General Formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, n each represents an integer of 0 to 10, and the total of each n is an integer of 1 to 60]

<7> The colored radiation-sensitive composition according to any one of <1> to <6>, wherein the (d) polymerization initiator is an oxime compound.

<8> The content of the monomer having three or more ethylenically unsaturated double bonds according to any one of <1> to <7> is 15 to 50% by mass of the total solid content in the colored radiation-sensitive composition. Colored radiation-sensitive composition, characterized in that.

<9> The colored radiation-sensitive composition according to any one of <1> to <8>, wherein (b) an alkali-soluble resin is contained as a polymer having no polymerizable group.

<10> The colored radiation-sensitive composition according to any one of <1> to <9>, wherein the content of all polymer components is 10 to 50% by mass of the total solid content in the colored radiation-sensitive composition.

<11> A cured film obtained by curing the colored radiation-sensitive composition according to any one of <1> to <10>.

<12> A method for producing a cured film comprising a step of applying the colored radiation-sensitive composition according to any one of <1> to <10> on a substrate, and a step of exposing the colored radiation-sensitive composition to light. .

<13> A color filter formed using the colored radiation-sensitive composition according to any one of <1> to <10>.

<14> of a color filter comprising a step of applying the colored radiation-sensitive composition according to any one of <1> to <10> on a substrate, and a step of pattern exposure of the colored radiation-sensitive composition Manufacturing method.

<15> An ink jet ink comprising the colored radiation-sensitive composition according to any one of <1> to <10>.

<16> A solid-state imaging device, a liquid crystal display device, or an organic EL display device comprising the color filter according to <13> or a color filter obtained by the method for producing a color filter according to <14>.

Moreover, the said subject was also solved by the following means.

<17> In the colored radiation-sensitive composition in any one of the above, (e) the colored radiation-sensitive composition, wherein the colorant is a pigment.

<18> The colored radiation-sensitive composition according to any one of the above, wherein the (e) colorant is a pigment, and further contains a dispersant for dispersing the (e) colorant.

<19> In the colored radiation-sensitive composition in any one of the above, (e) the colorant is a pigment, and an acrylic copolymer is included as a dispersant for dispersing the (e) colorant. Composition.

<20> The colored radiation-sensitive composition according to any one of the above, wherein (a) the acrylic polymer having a polymerizable group has an acid value of 10 to 200 mgKOH/g.

<21> As the colored radiation-sensitive composition in any one of the above, a colored radiation-sensitive composition for a negative type.

(Effects of the Invention)

According to the present invention, when a colored layer is formed, it becomes possible to provide a radiation-sensitive composition in which a solution residue is not left in an unexposed portion and roughness of the surface of the colored layer is suppressed.

Hereinafter, the content of the present invention will be described in detail. In addition, in the specification of the present application, "~" is used with a meaning including numerical values described before and after it as a lower limit value and an upper limit value.

In addition, in the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes not only having no substituent but also having a substituent. For example, the "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, in the present specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acryl" represents acrylic and methacrylic, and "(meth)acryloyl" represents acryloyl and Represents methacryloyl. In addition, in this specification, "monomer" and "monomer" are synonymous. The monomer in the present invention is classified into an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

"Radiation" in the present invention means to include visible light, ultraviolet rays, far ultraviolet rays, electron rays, X-rays, and the like. The "colored layer" used in the present invention means a layer made of a pixel and/or a black matrix used for a color filter.

Hereinafter, the colored radiation-sensitive composition of the present invention, a color filter, and a method of manufacturing the same, a solid-state imaging device, a liquid crystal display device, and an organic EL display device will be described in detail. The description of the constitutional requirements described below is made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

The colored radiation-sensitive composition of the present invention (hereinafter sometimes referred to as ``the composition of the present invention'') is (a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, and (c) 3 or more ethylene. A monomer having a sexually unsaturated double bond, (d) a polymerization initiator and (e) a colorant, and the content of (a) an acrylic polymer having a polymerizable group is 1 to 14% by mass of the total polymer component.

In the present invention, the resin component includes at least (a) an acrylic polymer having a polymerizable group and (b) a polymer having no polymerizable group.

In the present invention, the content of the acrylic polymer (a) having a polymerizable group is 1 to 14% by mass of the total polymer component, more preferably 5 to 12% by mass, and still more preferably 5 to 9% by mass. By setting it as such a range, film shrinkage is less likely to occur when forming a colored layer by curing the composition of the present invention in a layered form, and as a result, it is possible to form a colored layer having excellent pattern formation and less surface roughness.

The acid value in all the resin components used in the present invention is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g. By setting it as such a range, it becomes possible to reduce the residue of the unexposed part after development.

The total resin component in the composition of the present invention is preferably 10 to 50% by mass, and more preferably 20 to 40% by mass of the total solid content.

(a) acrylic polymer having a polymerizable group

The composition of the present invention contains an acrylic polymer having a polymerizable group. As the polymerizable group which the acrylic polymer having a polymerizable group has, an ethylenically unsaturated bonding group is illustrated, a (meth)acryloyl group and a vinyl group are preferable, and a (meth)acryloyl group is more preferable.

The acrylic polymer having a polymerizable group used in the present invention usually includes a structural unit having a polymerizable group and other structural units.

The acrylic polymer in the present invention refers to a vinyl polymer having repeating units derived from at least one of (meth)acrylic acid, (meth)acrylic acid ester, and (meth)acrylamide.

The ratio of the polymerizable group contained in the acrylic polymer having a polymerizable group is preferably 5 to 50, and more preferably 10 to 40. By setting it as such a range, coexistence of hardenability and developability is achieved more effectively. Here, the ratio of a polymerizable group means a molar copolymerization ratio.

As other structural units, structural units containing an acidic group are illustrated. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable.

Further, the acid value of the acrylic polymer having a polymerizable group used in the present invention is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g. By setting it as such a range, it becomes possible to improve the solubility of an unexposed part at the time of pattern formation. The acid value in the present invention refers to a value obtained by neutralization titration with a potassium hydroxide solution.

As an acrylic polymer having a polymerizable group, for example, glycidyl group-containing unsaturated compounds such as glycidyl (meth)acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, 2- Resins reacted with unsaturated alcohols such as hydroxymethacrylate, unsaturated compounds containing free isocyanate groups, unsaturated acid anhydrides reacted with carboxyl group-containing resins having hydroxyl groups, and polybasic acid anhydrides in addition reaction products of epoxy resins and unsaturated carboxylic acids. The reacted resin, a resin in which a polyfunctional monomer containing a hydroxyl group was reacted with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride, and a resin having a specific functional group giving an unsaturated group by causing a desorption reaction by base treatment were synthesized. As a typical resin, a resin in which an unsaturated group was generated by subjecting the resin to a base treatment is exemplified.

Among them, a resin obtained by reacting a carboxyl group-containing resin with a glycidyl group-containing unsaturated compound such as glycidyl (meth)acrylate and allyl glycidyl ether, and a resin obtained by polymerizing a hydroxyl group-containing (meth)acrylic acid ester compound (meth) A resin obtained by reacting a (meth)acrylic acid ester having a free isocyanate group such as acrylate-2-isocyanate ethyl, a resin having a structural unit represented by the general formulas (1) to (3) described below, and a base treatment to cause a desorption reaction. It is more preferable to synthesize a resin having a specific functional group to impart an unsaturated group, and to base-treat the resin to produce an unsaturated group.

The resin having a polymerizable group is preferably a resin containing at least one type selected from structural units represented by any one of the following general formulas (1) to (3), and at least a structural unit represented by general formula (1) It is more preferable that it is a resin containing 1 type.

[In General Formulas (1) to (3), A ¹ , A ² and A ³ each represent an oxygen atom, a sulfur atom, or -N(R ²¹ )-, and R ²¹ represents an alkyl group. Each of G ¹ , G ² and G ³ represents a divalent organic group. X and Z each represent an oxygen atom, a sulfur atom, or -N(R ²² )-, and R ²² represents an alkyl group. Y represents an oxygen atom, a sulfur atom, a phenylene group, or -N(R ²³ )-, and R ²³ represents an alkyl group. R ¹ to R ²⁰ each independently represent a hydrogen atom or a monovalent organic group]

A ¹ represents an oxygen atom, a sulfur atom, or -N(R ²¹ )-, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

G ¹ represents a divalent organic group, preferably a group consisting of an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and combinations thereof, and a straight chain having 1 to 10 carbon atoms Or a branched alkylene group, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms, and a group consisting of a combination thereof, more preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms A group consisting of an alkylene group and a combination thereof is particularly preferred. These groups may further have a substituent, and a hydroxyl group is preferable as a substituent. A more preferred embodiment of G ¹ is -(CH ₂ ) _n -(cycloalkylene group which may have a substituent)-(CH ₂ ) _n -, where n is an integer of 0 to 2, and cycloalkylene group is a 5-membered ring Or a 6-membered ring (more preferably a 6-membered ring).

X represents an oxygen atom, a sulfur atom, or -N(R ²² )-, an oxygen atom or -NH- is preferable, and an oxygen atom is more preferable.

Each of R ¹ to R ³ represents a hydrogen atom or a monovalent organic group, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable. R ¹ and R ² are more preferably a hydrogen atom, and R ³ is more preferably a hydrogen atom or a methyl group.

Each of R ⁴ to R ⁶ represents a hydrogen atom or a monovalent organic group, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable. R ⁴ is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or a methyl group. R ⁵ and R ⁶ are each a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, and a hydrogen atom , An alkoxycarbonyl group, an alkyl group, and an aryl group are preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

The group may have a substituent within a range not departing from the spirit of the present invention, and examples of such a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ² each represents an oxygen atom, a sulfur atom, or -N(R ²¹ )-, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

G ² represents a divalent organic group, preferably a group consisting of an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and combinations thereof, and a linear chain having 1 to 10 carbon atoms Or a branched alkylene group, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group which may have a substituent having 6 to 12 carbon atoms, and a group consisting of a combination thereof, more preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, A group consisting of 3 to 10 cycloalkylene groups and combinations thereof is particularly preferred. A more preferred embodiment of G ² is -(CH ₂ ) _n -(cycloalkylene group)-(CH ₂ ) _n -, n is an integer of 0 to 2, respectively, and the cycloalkylene group is a 5- or 6-membered ring (more Preferably, a 6-membered ring) is preferred.

Y represents an oxygen atom, a sulfur atom, a phenylene group, or -N(R ²³ )-, and an oxygen atom, a phenylene group or -NH- is preferable, and an oxygen atom or a phenylene group is more preferable.

Each of R ⁷ to R ⁹ represents a hydrogen atom or a monovalent organic group, and a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferable. R ⁷ and R ⁸ are preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom and a methyl group.

R ¹⁰ to R ¹² each represent a hydrogen atom or a monovalent organic group, and a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, And an alkylsulfonyl group and an arylsulfonyl group, and a hydrogen atom, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable.

The group may have a substituent within a range not departing from the spirit of the present invention, and examples of such a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

A ³ represents an oxygen atom, a sulfur atom, or -N(R ²¹ )-, respectively, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

G ³ represents a divalent organic group, preferably a group consisting of an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and combinations thereof, and a linear chain having 1 to 10 carbon atoms Or a branched alkylene group, a cycloalkylene group having 3 to 10 carbon atoms, an aromatic group which may have a substituent having 6 to 12 carbon atoms, and a group consisting of a combination thereof, more preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, A group consisting of 3 to 10 cycloalkylene groups and combinations thereof is particularly preferred. A more preferred embodiment of G ³ is -(CH ₂ ) _n -(cycloalkylene group)-(CH ₂ ) _n -, n is an integer of 0 to 2, respectively, and the cycloalkylene group is a 5- or 6-membered ring (more Preferably, a 6-membered ring) is preferred.

Z represents an oxygen atom, a sulfur atom, or -N(R ²³ )-, an oxygen atom or -NH- is preferable, and an oxygen atom is more preferable.

Each of R ¹³ to R ¹⁵ represents a hydrogen atom or a monovalent organic group, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable. R ¹ and R ² are more preferably a hydrogen atom, and R ³ is more preferably a hydrogen atom or a methyl group.

R ¹⁶ to R ²⁰ each represent a hydrogen atom or a monovalent organic group, and R ¹⁶ to R ^{20 are} , for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group, an aryl Group, alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, and hydrogen atom, alkoxycarbonyl group, alkyl group, and aryl group are preferable. The group may have a substituent within a range not departing from the spirit of the present invention, and examples of such a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

The structural unit represented by the general formulas (1) to (3) is preferably a compound contained in the range of 20 to 95 mol% from the viewpoint of improving curability and reducing development residue. It is more preferably 25 to 90 mol%, and still more preferably in the range of 30 to 85 mol%.

Synthesis of a polymer compound having a structural unit represented by the general formulas (1) to (3) can be performed based on the synthesis method described in paragraphs 0027 to 0057 of JP-A-2003-262958. Among these, those by the synthesis method 1) in the same publication are preferable.

The following compounds are mentioned as a specific compound example of the high molecular compound which has a structural unit represented by General formula (1)-(3). It goes without saying that the present invention is not limited to these compounds.

The composition of the present invention contains an acrylic polymer having a polymerizable group as an essential component, but may contain a non-acrylic polymer having a polymerizable group. The blending amount of the non-acrylic polymer having a polymerizable group is preferably 5% by mass or less of the total resin component, preferably 3% by mass or less, more preferably 1% by mass or less, and substantially does not contain, for example, 0% by mass. It is particularly preferred that it is %.

(b) a polymer without a polymerizable group

In the present invention, a polymer having no polymerizable group is included. As a polymer which does not contain a polymerizable group, a dispersing agent for dispersing a pigment or the like and an additional resin are exemplified. As a polymer which does not have a polymerizable group contained in the composition of the present invention, in particular, an alkali-soluble resin used as a dispersion resin or an additional resin, a dispersant, and a dispersion resin other than an alkali-soluble resin are exemplified. Further, the acrylic polymer which is an alkali-soluble resin and has a polymerizable group corresponds to the acrylic polymer (a) having a polymerizable group. Hereinafter, the details of the polymer having no polymerizable group will be described.

In the present invention, it is preferable to include an acrylic polymer having no polymerizable group as the polymer having no polymerizable group. A preferred example of an acrylic polymer that does not have such a polymerizable group is an alkali-soluble resin.

Alkali-soluble resin

The alkali-soluble resin is a linear organic high-molecular polymer, and can be appropriately selected from among alkali-soluble resins having at least one group promoting alkali solubility in the molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). . From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic/acrylamide copolymer resin are preferable, and from the viewpoint of developing property control, acrylic resin, acrylamide resin, Acrylic/acrylamide copolymer resins are preferred.

Examples of groups that promote alkali solubility (hereinafter, also referred to as acid groups) include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. However, those soluble in a solvent and developable with a weak alkali aqueous solution are preferred. ) Acrylic acid is mentioned as a particularly preferable thing. These acid groups may be used alone or in combination of two or more.

As a monomer capable of imparting an acid group after the polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, a monomer having an epoxy group such as glycidyl (meth)acrylate, and a 2-isocyanate And monomers having an isocyanate group such as ethyl (meth)acrylate. The number of monomers for introducing these acid groups may be only one, or two or more. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter, sometimes referred to as ``a monomer for introducing an acid group'') is polymerized as a monomer component. It is good to do it.

In addition, when introducing an acid group as a monomer component from a monomer capable of imparting an acid group after polymerization, a treatment for providing an acid group as described later is required after polymerization, for example.

To manufacture the alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. When preparing an alkali-soluble resin by radical polymerization, polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. can be easily set by those skilled in the art, and conditions can be determined experimentally. .

The linear organic polymer used as an alkali-soluble resin is preferably a polymer having a carboxylic acid in the side chain, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester Alkali-soluble phenol resins, such as a maleic acid copolymer and a novolak type resin, acidic cellulose derivatives having a carboxylic acid in the side chain, and those obtained by adding an acid anhydride to a polymer having a hydroxyl group are mentioned. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is suitable as an alkali-soluble resin. Other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, and vinyl compounds. Alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, As vinyl compounds such as cyclohexyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate , Polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like, N-phenylmaleimide, N-cyclohexylmaleimide, and the like as the N-position substituted maleimide monomer described in Japanese Patent Laid-Open No. 10-300922. Moreover, only 1 type may be sufficient as these (meth)acrylic acid and another monomer copolymerizable, and 2 or more types may be sufficient as it.

The alkali-soluble resin is also preferably a resin represented by the following general formula (ED).

[In formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.] Essentially, a compound represented by (hereinafter sometimes referred to as ``ether dimer'') It is also preferable to include the polymer (a) formed by polymerizing the monomer component to be used as the polymer component (A) which is an essential component. Thereby, the curable resin composition of the present invention can form a cured coating film having excellent transparency as well as heat resistance. Although there is no particular limitation as a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² in the general formula (1) representing the ether dimer, for example, methyl group, ethyl group, n-propyl group, Linear or branched alkyl groups such as isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, and 2-ethylhexyl group; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl group, t-butyl group, cyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, and 2-methyl-2-adamantyl group; Alkyl groups substituted with alkoxy, such as 1-methoxyethyl group and 1-ethoxyethyl group; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, a substituent of a primary or secondary carbon that is difficult to desorb by acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group, is particularly preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2 -Profenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)] Bis-2-propenoate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2'-[oxybis( Methylene)]bis-2-propenoate, di(t-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-amyl)-2,2'- [Oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2 '-[Oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(1-me Toxyethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-pro Phenoate, dibenzyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diphenyl-2,2'-[oxybis(methylene)]bis-2-propenoate, dicy Chlohexyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-propeno 8, di(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2'-[oxybis(methylene) ]Bis-2-propenoate, di(isobornyl)-2,2'-[oxybis(methylene)]bis-2-propenoate,diadamantyl-2,2'-[oxybis(methylene )]Bis-2-propenoate, di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and the like. Among these, in particular, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclo Hexyl-2,2'-[oxybis(methylene)]bis-2-propenoate and dibenzyl-2,2'-[oxybis(methylene)]bis-2-propenoate are preferred. Only one type of these ether dimers may be used, and two or more types may be used. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

As the alkali-soluble resin, in particular, a benzyl (meth)acrylate/(meth)acrylic acid copolymer or a multipolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl methacrylate is suitable. Other monomers in this case include 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer and 2-hydroxy-3- described in Japanese Patent Laid-Open No. 7-140654. Phenoxypropylacrylate/polymethylmethacrylate macromonomer/benzylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/polystyrene macromonomer/methylmethacrylate/methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, etc. are mentioned.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g, and still more preferably 70 to 120 mgKOH/g. By setting it as such a range, the developed residue of an unexposed part can be effectively reduced.

Moreover, as a weight average molecular weight (Mw) of an alkali-soluble resin, 2,000-50,000 are preferable, 5,000-30,000 are more preferable, and 7,000-20,000 are especially preferable.

The content of the alkali-soluble resin in the composition of the present invention is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass with respect to the total solid content of the composition. .

Dispersant

In the composition of the present invention, from the viewpoint of further improving the dispersibility of the pigment, it is preferable to add a dispersant other than the above component.

As a dispersant (hereinafter sometimes referred to as ``pigment dispersant''), a polymer dispersant (for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified Poly(meth)acrylate, (meth)acrylic copolymer, naphthalene sulfonic acid formalin condensate) and polyoxyethylenealkyl phosphoric acid ester, polyoxyethylenealkylamine, alkanolamine, pigment derivatives, and the like.

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

The polymeric dispersant acts to prevent re-aggregation by being adsorbed on the surface of the pigment. Therefore, a terminal modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface are mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the pigment surface.

As specific examples of the pigment dispersant that can be used in the present invention, BYK Co., Ltd. ``Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) Amide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), BYK2001", "EFKA4047, 4050, 4010" manufactured by EFKA , 4165 (polyurethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester) , 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", "Azisper PB821, PB822" by Ajinomoto Fine-Techno Co., Inc., "Florene TG-710 (urethane oligomer)" by Kyoeisha Chemical Co., Ltd. )”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, Kusumoto Chemicals, Ltd. “Disperon KS-860, 873SN, 874, #2150 (aliphatic polyhydric carboxylic acid), #7004 ( Polyether ester), DA-703-50, DA-705, DA-725", Kao Corporation ``demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ", "Homogenol L-18 (polymer polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamine 86 (stearylamine acetate)", Lubrizol Corporation ``Solspurs 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft polymer) )」, Nikko C "Nikol T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by hemicals Co., Ltd. can be mentioned.

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

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

Moreover, it is preferable that it is 10-30 mass% with respect to the total solid content of a composition.

(C) a monomer having three or more ethylenically unsaturated double bonds

The composition of the present invention contains a monomer having three or more ethylenically unsaturated double bonds (hereinafter sometimes referred to as "polyfunctional monomers"). Such compounds are widely known in the above industrial field, and in the present invention, they can be used without particular limitation. The polyfunctional monomers in the present invention may be used singly or in combination of two or more. The polyfunctional monomer used in the present invention is preferably a (meth)acrylate monomer.

As these specific compounds, the compounds described in paragraphs 0095 to 0108 of Japanese Patent Laid-Open No. 2009-288705 can be suitably used also in the present invention.

In addition to the above, radical polymerizable monomers represented by the following general formulas (MO-1) to (MO-6) can also be suitably used. In addition, in the case where T is an oxyalkylene group in the formula, the terminal on the carbon atom side is bonded to R.

[In the formula, n is 0 to 14, respectively, and m is 1 to 8, respectively. R, T, and Z present in a plurality of molecules may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least 3 of R are polymerizable groups]

0-5 are preferable and, as for n, 1-3 are more preferable.

1-5 are preferable and, as for m, 1-3 are more preferable.

R is

또는

or

Is preferred,

또는

or

Is more preferable.

As a specific example of the radical polymerizable monomer represented by the general formulas (MO-1) to (MO-6), the compounds described in paragraphs 0248 to 0251 of Japanese Patent Laid-Open No. 2007-269779 are also used in the present invention. It can be used suitably.

Among them, as a polymerizable monomer, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product); Nippon Kayaku Co., Ltd.) dipentaerythritol penta (meth) acrylate (a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa (meth) acrylate (a commercial product, KAYARAD DPHA; Nippon Kayaku Co. , Ltd.) and their (meth)acryloyl groups have ethylene glycol and propylene glycol residues interposed therebetween, and diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available products are M-460; Toagosei Co., Ltd.) ., Ltd. product) is preferable. These oligomer types can also be used.

The polyfunctional monomer used in the present invention is particularly preferably at least one type selected from a compound represented by the following general formula (i) and a compound represented by the general formula (ii).

[In general formulas (i) and (ii), E represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, respectively, and y is 1~ The integer of 10 is represented, and X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.

In General Formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, m represents an integer of 0 to 10, respectively, and the total of each m is an integer of 1 to 40.

In General Formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, n each represents an integer of 0 to 10, and the total of each n is an integer of 1 to 60]

In the above formula, E represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ ) O)-, and -((CH ₂ ) _y CH ₂ O)- is desirable.

y represents the integer of 1-10, respectively, the integer of 1-5 is preferable, and 1-3 are more preferable.

X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.

In general formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, and 4 is preferable.

m represents the integer of 0-10, respectively, and 1-5 are preferable. The sum of each m is an integer of 1 to 40, and 4 to 20 are preferable.

In General Formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, with 6 being preferred.

Each n represents the integer of 0-10, and 1-5 are preferable. The sum of each n is an integer of 1 to 60, and 4 to 30 are preferable.

Since the compound represented by general formula (i) or (ii) has high reactivity, the curability of the composition of the present invention can be improved. However, when the curability was high, there was a tendency that the developability of the unexposed portion was inferior. In the present invention, such a viewpoint is solved by (a) making the content of the acrylic polymer having a polymerizable group 1 to 14% by mass of all polymer components. Accordingly, the composition of the present invention is particularly effective when a compound represented by the general formula (i) or (ii) is used as a polyfunctional monomer.

As a polyfunctional monomer, you may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, it can be used as it is, but if necessary, the acid group is reacted with a non-aromatic carboxylic anhydride to the hydroxyl group of the ethylenic compound. You may introduce it. Specific examples of the non-aromatic carboxylic anhydride used in this case include tetrahydrophthalic anhydride, tetrahydrophthalic anhydride alkyl, hexahydrophthalic anhydride, hexahydrophthalic anhydride alkyl, succinic anhydride, and maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic anhydride is reacted with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group. A functional monomer is preferred, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, the polybasic acid-modified acrylic oligomer manufactured by Toagosei Co., Ltd. includes M-305, M-510, and M-520 of the Aaronics series.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g.

For these polyfunctional monomers, the details of the structure, whether it is used alone or in combination, and the usage method such as the amount of addition can be arbitrarily set according to the final performance design of the composition. In the present invention, a method of controlling both sensitivity and strength by using in combination with other functional groups and/or other polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) is also effective. Do. In addition, it is preferable to use polyfunctional monomers having different ethylene oxide chain lengths of 3 or more and 8 functions or less in that the developability of the composition can be controlled and excellent pattern forming ability can be obtained. In addition, for compatibility and dispersibility with other components contained in the composition (e.g., polymerization initiator, colorant (pigment), resin, etc.), the method of selecting and using a polyfunctional monomer is an important factor. For example, low purity Compatibility can be improved by use of a compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving the adhesion to a hard surface such as a substrate.

The concentration (composition ratio) of the polyfunctional monomer is preferably 15% by mass or more, preferably 20% by mass or more, and more preferably 25% by mass or more with respect to the total solid content in the colored radiation-sensitive composition. Although there is no restriction|limiting in particular about an upper limit, It is preferable that it is 50 mass% or less, and it is more preferable that it is 40 mass% or less.

In the present invention, the content of the polyfunctional monomer is preferably 0.6 to 2.0 times the total resin component, more preferably 0.7 to 1.3 times.

(d) polymerization initiator

The composition of the present invention is not particularly limited as long as it has the ability to initiate polymerization of the polyfunctional monomer as a polymerization initiator containing a polymerization initiator, and can be appropriately selected from known polymerization initiators, for example, light rays (especially, It is preferable to have photosensitivity to visible light from the ultraviolet region), and may be an activator that generates an active radical by generating some action with a photo-excited sensitizer, or an initiator such as to initiate cationic polymerization depending on the type of monomer. good.

In addition, it is preferable that the polymerization initiator contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

Examples of the polymerization initiator include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

As the halogenated hydrocarbon compound having the triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. The compound described in Japan, 42, 2924 (1969), the compound described in British Patent No. 1388492, the compound described in Japanese Patent Laid-Open Publication No. 53-133428, the compound described in German Patent No. 3337024, J. Org by FC Schaefer et al. . Chem.; 29, 1527 (1964), the compound described in Japanese Patent Laid-Open Publication No. 62-58241, the compound described in Japanese Patent Laid-Open Publication No. Hei 5-281728, the compound described in Japanese Patent Laid-Open Publication No. Hei 5-34920, the United States The compounds described in the specification of Patent No. 4212976, etc. are mentioned.

As the compound described in the specification of US Patent No. 4212976, for example, a compound having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2 -Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2 -Trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromo Methyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl -5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2 -Tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.), etc. are mentioned.

In addition, as polymerization initiators other than the above, acridine derivatives (e.g., 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-phenylglycine, etc. Halogen compounds (e.g., carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (e.g., 3-(2-benzoproyl)-7-diethylaminocoumarin, 3-(2-benzoproyl)-7-(1-pyrrolidinyl)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-(2-methoxybenzoyl)-7-diethylaminocoumarin, 3 -(4-dimethylaminobenzoyl)-7-diethylaminocoumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-di Ethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3-(2-proyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamoyl)-7-diethylaminocoumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and Japanese Patent Laid-Open No. Hei 5-19475 The coumarin described in Gazette, JP 7-271028, JP 2002-363206, JP 2002-363207, JP 2002-363208, JP 2002-363209, etc. Compounds, etc.), acylphosphine oxides (e.g., bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl- Pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (e.g., bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H) -Pyrrol-1-yl)-phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1+)-hexafluorophosphate (1-), etc.), Japanese Patent Laid-Open Publication No. 53-133428 , Japanese Patent Publication No. 57-1819, 57-6096, and the compounds described in US Patent No. 3615455, and the like.

As the ketone compound, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4- Bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenones (e.g. , 4,4'-bis(dimethylamino)benzophenone, 4,4'-bisdicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(di Hydroxyethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethylthioxanthone, fluolenone, 2-benzyl -Dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydro Roxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin iso Propyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

As a polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide initiator described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Ltd.) can be used. As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Ltd.) can be used. As the aminoacetophenone initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the absorption wavelength is matched to a long-wave light source such as 365 nm or 405 nm can also be used. In addition, as an acylphosphine initiator, commercially available products IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF Ltd.) can be used.

More preferably, an oxime compound is mentioned as a polymerization initiator. As a specific example of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-80068 A, and the compound described in JP 2006-342166 can be used.

Examples of oxime compounds such as oxime derivatives suitably used as polymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutane. -2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4 -Toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

As an oxime ester compound, J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compound described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797, Japanese Patent Laid-Open No. 2006-342166, etc. Can be lifted.

In a commercial item, IRGACURE-OXE01 (manufactured by BASF Ltd.) and IRGACURE-OXE02 (manufactured by BASF Ltd.) are also suitably used.

In addition, as oxime ester compounds other than those described above, the compounds described in Japanese Patent Publication 2009-519904 in which the oxime is connected to the carbazole N position, the compounds described in US Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone moiety, The compound described in Japanese Patent Publication No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group was introduced, the ketooxime compound described in International Publication No. 2009-131189, and a US patent containing a triazine skeleton and an oxime skeleton in the same molecule The compound described in Japanese Patent Application Laid-Open No. 7556910, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, may be used.

Preferably, the cyclic oxime compounds described in JP 2007-231000 and JP 2007-322744 can be further suitably used. Among the cyclic oxime compounds, the cyclic oxime compounds condensed with carbazole dyes described in JP 2010-32985 and JP 2010-185072 are particularly preferable from the viewpoint of high sensitivity due to high light absorption. Further, the compound described in Japanese Patent Laid-Open Publication No. 2009-242469 having an unsaturated bond at a specific site of the oxime compound can also achieve high sensitivity by regenerating active radicals from polymerization inactive radicals, and thus can be suitably used.

In particular, preferably, an oxime compound having a specific substituent shown in JP 2007-269779 or an oxime compound having a thioaryl group shown in JP 2009-191061 is mentioned.

Specifically, as the oxime polymerization initiator, a compound represented by the following formula (1) is preferable. Further, the N-O bond of the oxime may be an oxime compound of the (E) body, an oxime compound of the (Z) body, or a mixture of the (E) body and (Z) body.

[In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group]

The monovalent substituent represented by R is preferably a monovalent non-metal group.

Examples of the monovalent non-metal group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. In addition, the above-described substituent may be further substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2- Naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluoro A phenacyl group, a 3-trifluoromethylphenacyl group, and a 3-nitrophenacyl group can be illustrated.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specifically, a phenyl group, a biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1- Pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quaterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, ternaphtanyl group, quaternaphthalenyl group, heptarenyl group, biphenyrenyl group, indacenyl group, fluoranthenyl group, acenaphthyl Nyl group, aseantrirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group , Chrysenyl group, naphthacenyl group, pleiadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexaenyl group, rubixenyl group, coronenyl group, trinaph A thilenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an ovarenyl group can be illustrated.

The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, and specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, and a 1-naphthoyl group , 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4 -Cyanobenzoyl group and 4-methoxybenzoyl group can be illustrated.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, An octadecyloxycarbonyl group and a trifluoromethyloxycarbonyl group can be illustrated.

Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, and 4- Dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group , 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group and 4-methoxyphenyloxycarbonyl group can do.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocycle containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specifically, thienyl group, benzo[b]thienyl group, naphtho[2,3-b]thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, clomenyl group, xanthenyl group, phenoxa Thiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolidinyl group, isoindolyl group, 3H-indolyl group, Indolyl group, 1H-indazolyl group, furinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthaladinyl group, naphthylidinyl group, quinoxaniryl group, quinazolinyl group, cynnolinyl group, p Teridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenantholinyl group, phenadinyl group, phenalsadinyl group, isothiazolyl Group, phenothiadinyl group, isoxazolyl group, prazanyl group, phenoxadinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidi Illustrative examples include a nil group, a pyrazolinyl group, a piperidyl group, a piperadinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, and a thioquisanthryl group.

Examples of the alkylthiocarbonyl group which may have a substituent include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, and trifluoromethylthiocarbonyl group. I can.

As an arylthiocarbonyl group which may have a substituent, specifically, 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthio Carbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-tri Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, and 4-methoxyphenylthiocarbonyl group.

The monovalent substituent represented by B above represents an aryl group, heterocyclic group, arylcarbonyl group, or heterocyclic carbonyl group. Moreover, these groups may have one or more substituents. As a substituent, the substituent mentioned above can be illustrated. In addition, the above-described substituent may be further substituted with another substituent.

Especially, it is a structure shown below especially preferably.

In the following structures, Y, X, and n have the same meaning as Y, X, and n in Formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. Moreover, these groups may have one or more substituents. As a substituent, the substituent mentioned above can be illustrated. In addition, the above-described substituent may be further substituted with another substituent.

Among them, A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (e.g., methyl group, ethyl group, tert-butyl group, dodecyl group) and alkenyl group from the viewpoint of enhancing sensitivity and suppressing coloration due to heating over time. (E.g., vinyl group, allyl group) substituted alkylene group, aryl group (e.g., phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, sty Aryl group) substituted alkylene group is preferable.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may further have a substituent. Examples of the substituent include the same substituents introduced in the substituted aryl groups listed above as specific examples of the aryl groups which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing the sensitivity and suppressing coloration due to elapse of heating.

In formula (1), it is preferable from the viewpoint of sensitivity that the structure of "SAr" formed with S adjacent to Ar is a structure shown below. In addition, Me represents a methyl group, and Et represents an ethyl group.

It is preferable that the oxime compound is a compound represented by the following formula (2).

[In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is an integer of 0-5]

R, A, and Ar in formula (2) have the same meaning as R, A, and Ar in formula (1), and preferred examples are also the same.

Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. Moreover, these groups may have one or more substituents. As a substituent, the substituent mentioned above can be illustrated. In addition, the above-described substituent may be further substituted with another substituent.

Among these, X is preferably an alkyl group from the viewpoint of solvent solubility and improvement of absorption efficiency in a long wavelength region.

In addition, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

The structure shown below is mentioned as the divalent organic group represented by the said Y. In addition, in the group shown below, "" represents a bonding position of a carbon atom adjacent to Y in the formula (2).

Among them, the structure shown below is preferable from the viewpoint of high sensitivity.

In addition, it is preferable that the oxime compound is a compound represented by the following formula (3).

[In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0-5]

R, X, A, Ar, and n in formula (3) have the same meaning as R, X, A, Ar, and n in formula (2), respectively, and preferred examples are also the same.

Specific examples (C-4) to (C-13) of the oxime compound suitably used below are shown below, but the present invention is not limited thereto.

The oxime compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably a high absorbance of 365 nm and 455 nm.

As for the oxime compound, the molar extinction coefficient at 365 nm or 405 nm is preferably 1,000 to 300,000 from the viewpoint of sensitivity, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000.

The molar extinction coefficient of the compound can be determined using a known method, but specifically, a concentration of 0.01 g/L using ethyl acetate solvent in an ultraviolet visible spectrophotometer (Varian Medical Systems, Inc., Carry-5 spectrophotometer). It is preferable to measure as.

The polymerization initiator used in the present invention may be used in combination of two or more as necessary.

The content of the polymerization initiator in the colored radiation-sensitive composition (total content in the case of two or more types) is preferably in the range of 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the total solid content of the radiation-sensitive composition. %, particularly preferably 1 to 8 mass%. If it is within this range, good sensitivity and pattern formation are obtained.

In the present invention, a sensitizer may be contained for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the wavelength of the photosensitive wavelength. As a sensitizer that can be used in the present invention, it is preferable to increase or decrease the polymerization initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer include compounds described in paragraphs 0101 to 0154 of JP 2008-32803 A.

The content of the sensitizer in the composition of the present invention is preferably 0.1% by mass to 20% by mass in terms of solid content from the viewpoint of the light absorption efficiency to the core and the starting decomposition efficiency when blended, and 0.5% by mass to 15% by mass Is more preferable.

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

(e) colorant

The colorant used in the present invention is not particularly limited, and conventionally known various dyes or pigments may be used alone or in combination of two or more, and these are appropriately selected according to the use of the composition of the present invention. When the composition of the present invention is used in the manufacture of a color filter, it is generally used for chromatic colorants (chromic colorants) such as red, magenta, yellow, blue, cyan and green that form color pixels of a color filter and for forming a black matrix. Any one of the black colorants (black colorants) used as can be used. In the present invention, it is preferable that the colorant is at least one selected from red, magenta, yellow, blue, cyan and green.

Hereinafter, a colorant suitable for use in color filters will be described in detail with respect to the colorant.

As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. In addition, considering that whether it is an inorganic or organic pigment having a high transmittance, it is preferable to use a thin one. Considering handling properties, the average primary particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm to 0.05m is more preferable.

Examples of inorganic pigments include metal compounds represented by metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and silver And composite oxides of the above metals. As the nitride of titanium, a tin compound, a silver compound, or the like can also be used.

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

C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37 :1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 , 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.,

C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 71, 73, etc.,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48: 4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279

C. I. Pigment Green 7, 10, 36, 37, 58

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80

C. I. Pigment Black 1

These organic pigments can be used alone or in various combinations to increase color purity.

When the colorant is a dye, it is possible to obtain a colored composition uniformly dissolved in the composition.

The dye that can be used as the colorant contained in the colored radiation-sensitive composition is not particularly limited, and conventionally known dyes for color filters can be used. For example, pyrazole azo system, anilino azo system, triphenylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazol azo system, pyridone azo system, cyanine system, phenothiazine system, blood Dyes such as rolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dye can be used. Moreover, you may use a multimer of these dyes.

In addition, when developing with water or alkali, from the viewpoint of completely removing the binder and/or the dye of the unirradiated portion by development, the acidic dye and/or its derivative may be suitably used in some cases.

Other direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes, and/or derivatives thereof can also be usefully used.

Although specific examples of the acidic dye are given below, it is not limited to these. For example,

acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40~45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324:1; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; 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, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; And derivatives of these dyes.

Further, azo-based, xanthene-based, and phthalocyanine-based acid dyes other than the above are also preferable, and C. I. Solvent Blue 44, 38; C. I. Solvent orange 45; Acid dyes such as Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, triarylmethane-based, anthraquinone-based, azomethine-based, benzylidene-based, oxonol-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo It is preferable that it is a coloring agent selected from a pyrazole azo system, an anilino azo system, a pyrazolo triazol azo system, a pyridone azo system, and an anthrapyridone pyromethene system.

Moreover, you may use it combining a pigment and a dye.

In the present invention, C. I. Pigment Red 122 and C. I. Pigment Yellow 185 are particularly preferred.

It is preferable that the colorant which can be used in the colored radiation-sensitive composition is a dye or a pigment. Particularly, a pigment having an average particle diameter (r) of 20 nm≦r≦300 nm, preferably 125 nm≦r≦250 nm, and particularly preferably 30 nm≦r≦200 nm is preferable. By using a pigment having such an average particle diameter, a pixel having a high contrast ratio and a high light transmittance can be obtained. The "average particle diameter" as used herein refers to the average particle diameter of the secondary particles in which primary particles (single microcrystals) of the pigment are collected. The average primary particle diameter can be determined by observing by SEM or TEM, measuring 100 particle sizes at a portion where particles do not aggregate, and calculating an average value.

In addition, the particle diameter distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter simply referred to as ``particle diameter distribution'') is (average particle diameter ± 100) that the secondary particles entering the nm are not less than 70% by mass of the total. , Preferably it is preferably 80 mass% or more. In addition, in this invention, the particle diameter distribution was measured using the scattering intensity distribution.

The pigment having the average particle diameter and particle diameter distribution is a pigment mixture obtained by mixing a commercially available pigment with other pigments (average particle diameter usually exceeds 300 nm), preferably with a dispersant and a solvent, For example, it can be prepared by mixing and dispersing while pulverizing using a grinder such as a bead mill or a roll mill. The pigment thus obtained usually takes the form of a pigment dispersion.

-Miniaturization of pigments-

In the present invention, a fine and sized organic pigment can be used as necessary. Refinement of the pigment is achieved by preparing a liquid composition having a high viscosity together with the pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and subjecting it to a step of grinding by applying stress using a wet grinding device or the like.

Water-soluble organic solvents used in the pigment refining process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoethyl ether. Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, etc. are mentioned.

In addition, other solvents that have low or no water solubility, such as benzene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, as long as they are adsorbed to the pigment and are not lost in wastewater by using a small amount. Quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methylethylketone , Methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, or the like may be used.

Only one solvent may be used in the pigment refining step, or two or more solvents may be mixed and used as necessary.

In the present invention, examples of the water-soluble inorganic salt used in the pigment refining step include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate, and the like.

The amount of the water-soluble inorganic salt used in the micronization step is 1 to 50 mass times that of the pigment, and a larger one has a grinding effect, but a more preferable amount is 1 to 10 mass times from the viewpoint of productivity. In addition, it is preferable to use inorganic salts having a moisture content of 1% or less.

The amount of the water-soluble organic solvent used in the refining step is in the range of 50 parts by mass to 300 parts by mass, and preferably in the range of 100 parts by mass to 200 parts by mass per 100 parts by mass of the pigment.

There is no particular limitation on the operating conditions of the wet grinding device in the pigment refining process, but in order to effectively proceed grinding by the grinding media, the operating conditions when the device is a kneader is the rotation speed of the blade in the device of 10 to 200 rpm. It is preferable, and a relatively large rotational ratio of the two axes is preferable because the grinding effect is large. The operating time is preferably 1 to 8 hours in addition to the dry grinding time, and the internal temperature of the device is preferably 50 to 150°C. Further, the water-soluble inorganic salt, which is a pulverizing medium, has a pulverized particle size of 5 to 50 µm, a sharp particle diameter distribution, and a spherical shape is preferable.

-Pigment combination (color combination)-

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of the combination are shown below. For example, as a red pigment, anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, disazo yellow pigment, isoindolin yellow pigment, quinophthalone yellow pigment, or Mixing of a perylene-based red pigment, an anthraquinone-based red pigment, and a diketopyrrolopyrrole-based red pigment can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, and CI pigment red 224 is mentioned as a diketopyrrolopyrrole pigment Pigment red 254 is mentioned, and a mixture of CI pigment yellow 83, CI pigment yellow 139, or CI pigment red 177 is preferable from the viewpoint of color reproducibility. Further, the mass ratio of the red pigment and other pigments is preferably 100:5 to 100:80. In this range, the light transmittance of 400 nm to 500 nm is suppressed to improve color purity, and sufficient color development power is achieved. In particular, as the mass ratio, the range of 100:10 to 100:65 is optimal. Moreover, in the case of a combination of red pigments, it can be adjusted according to the chromaticity.

In addition, as the green pigment, a halogenated phthalocyanine-based pigment may be used alone or a mixture of this and a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment, or an isoindolin-based yellow pigment. For example, as such examples, CI pigment green 7, 36, 37, 58 and CI pigment yellow 83, CI pigment yellow 138, CI pigment yellow 139, CI pigment yellow 150, CI pigment Mixture of pigment yellow 180 or CI pigment yellow 185 is preferable. The mass ratio of the green pigment and the yellow pigment is preferably 100:5 to 100:200. Mass ratio In the above range, the light transmittance of 400 to 450 nm can be suppressed, so that the color purity is improved, and the dominant wavelength does not become close to a long wavelength, and a color near the NTSC target color at the sub-position can be obtained. have. The mass ratio is particularly preferably in the range of 100:20 to 100:150.

As the blue pigment, it is possible to use a phthalocyanine-based pigment alone or a mixture of this and a dioxadine-based purple pigment. Particularly preferred examples include a mixture of a phthalocyanine metal complex (e.g., aluminum phthalocyanine) and CI pigment blue 15:6 or CI pigment violet 23, aluminum phthalocyanine and CI pigment blue 15: The combination of 6 is more preferable.

The mass ratio of the blue pigment and the purple pigment is preferably 100:0 to 100:100, more preferably 100:70 or less.

The pigment used as the colorant of the present invention is preferably a green pigment.

As the pigment, an inorganic pigment may be used, and examples of the inorganic pigment include a metal pigment, a metal-containing inorganic pigment composed of a metal compound or a metal oxide, and carbon black.

In addition, the composition of the present invention may be used not only to form a colored region (pixel) of a color filter, but also to form a black matrix. As a black pigment used in the composition for forming a black matrix, carbon, titanium black, iron oxide, titanium oxide, silver In addition to tin, silver, etc., a pigment made of a metal mixture containing a metal oxide such as titanium oxide may be used.

Hereinafter, the titanium black dispersion will be described in detail.

The titanium black dispersion is a dispersion containing titanium black as a coloring material.

The dispersibility and dispersion stability of titanium black are improved by including titanium black as a pre-prepared titanium black dispersion in the composition of the present invention.

Hereinafter, titanium black will be described.

-Titanium black-

Titanium black is a black particle having titanium atoms. Preferably, they are low-order titanium oxide or titanium oxynitride. The titanium black particles can be modified on the surface as necessary for the purpose of improving dispersibility and suppressing cohesion. It is possible to coat with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, and zirconium oxide, and treatment with a water-repellent material as shown in Japanese Patent Laid-Open No. 2007-302836 is also possible.

The particle diameter of the particles of titanium black is not particularly limited, but from the viewpoint of dispersibility and colorability, it is preferably 3 to 2000 nm, more preferably 10 to 500 nm, and still more preferably 20 to 200 nm.

The specific surface area of titanium black is not particularly limited, but in order to obtain a predetermined performance after surface treatment of such titanium black with a water repellent, the value measured by the BET method is usually about 5 to 150 m 2 /g, especially 20 to 100 It is preferably about m2/g.

As an example of a commercially available product of titanium black, for example, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N manufactured by Mitsubishi Materials Corporation, Ako Kasei Co., Ltd. Tilack D and the like may be mentioned, but the present invention is not limited thereto.

As the content (concentration) of the colorant contained in the colored radiation-sensitive composition, it is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass, based on the total solid content of the colored radiation-sensitive composition. Although there is no restriction|limiting in particular about an upper limit, Preferably it is 45 mass% or less.

By setting the content of the colorant in the above range, when a color filter is produced from the colored radiation-sensitive composition, an appropriate chromaticity is obtained. In addition, since photocuring proceeds sufficiently to maintain the strength as a film, it is possible to prevent the development latitude at the time of alkali development from narrowing.

The colored radiation-sensitive composition of the present invention may contain other components. Examples of other components include solvents, surfactants, UV absorbers, polymerization inhibitors, and adhesion enhancers.

<solvent>

The colored radiation-sensitive composition of the present invention can be generally constituted using a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored radiation-sensitive composition, but it is particularly preferably selected in consideration of the solubility, coatability and safety of the ultraviolet absorber and the binder resin. Moreover, when preparing the colored radiation-sensitive composition in this invention, it is preferable to contain at least two types of solvent.

Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and lactic acid. Ethyl, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) ), 3-oxypropionate alkyl esters (eg, 3-oxypropionate methyl, 3-oxypropionate ethyl, etc. (eg, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, etc.), 2-oxypropionic acid alkyl esters (e.g. 2-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionate propyl, etc.) (e.g., 2-methoxypropionate methyl, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-oxy-2-methylpropionate methyl and 2-oxy-2-methylpropionate ethyl ( For example, 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid As methyl, ethyl 2-oxobutanoate, etc. and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, methyl cellosolve Acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene As glycol monopropyl ether acetate and the like and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. and aromatic hydrocarbons , For example, xylene etc. are mentioned suitably.

It is also preferable to mix two or more types of these solvents from a viewpoint of solubility of an ultraviolet absorber and an alkali-soluble resin, improvement on a coating surface, etc. In this case, particularly preferably, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone , Cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the solvent in the colored radiation-sensitive composition is preferably an amount such that the total solid content concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, and 10 to 50% by mass from the viewpoint of applicability. % Is particularly preferred.

<Surfactant>

Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, since the composition of the present invention further improves the liquid properties (especially fluidity) when prepared as a coating liquid by containing a fluorine-based surfactant, uniformity of the coating thickness and liquid saving properties can be further improved.

That is, in the case of forming a film using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the liquid to be coated, thereby improving the coating property to the surface to be coated. . For this reason, even when a thin film of about several µm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness irregularities.

The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving property, and has good solubility in the composition.

As a fluorine-based surfactant, for example, Megapack F171, Copper F172, Copper F173, Copper F176, Copper F177, Copper F141, Copper F142, Copper F143, Copper F144, Copper R30, Copper F437, Copper F475, Copper F479, and F482 , F554, F780, F781 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumimoto 3M Ltd.), Suflon S-382, SC-101, SC- 103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 , PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether. , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF Ltd.) Of Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Pionine D-6112-W (manufactured by Takemoto Oil & Fat Co., Ltd.), Solspurs 20000 (made by Lubrizol Corporation Japan), etc. are mentioned.

Specifically as a cationic surfactant, a phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid (co-operated) )Polymer polyflow No. 75, N. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

As a silicone surfactant, for example, Dow Corning Toray Co., Ltd. "Toray Silicon DC3PA", "Toray Silicon SH7PA", "Toray Silicon DC11PA", "Toray Silicon SH21PA", "Toray Silicon SH28PA", "Toray Silicon SH29PA" '', ``Toray Silicon SH30PA'', ``Toray Silicon SH8400'', Momentive Performance Materials Inc. ``TSF-4440'', ``TSF-4300'', ``TSF-4445'', ``TSF-4460'', ``TSF-4452'', Shin-Etsu Chemical Co., Ltd. "KP341", "KF6001", "KF6002", BYK Co., Ltd. "BYK307", "BYK323", "BYK330", etc. are mentioned.

Only one type of surfactant may be used, or two or more types may be combined.

When blending, the amount of surfactant added is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the composition.

<Polymerization inhibitor>

In the composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor to prevent unnecessary thermal polymerization of the polyfunctional monomer during preparation or storage of the composition.

As a polymerization inhibitor that can be used in the present invention, hydroquinone, p-methoxyphenol, o-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4 '-Thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, etc. Can be mentioned.

Further, the radiation-sensitive composition may contain a synergistic sensitizer for the purpose of further improving the sensitivity of the sensitizing dye or the initiator to active radiation, or inhibiting polymerization of the polyfunctional monomer by oxygen. Further, in order to improve the physical properties of the cured film, known additives such as a diluent, a plasticizer, and a sensing agent may be added as necessary.

When using the polymerization inhibitor, it is preferably in the range of 0.001% by mass to 0.015% by mass, more preferably 0.03% by mass to 0.09% by mass, based on the total solids in the colored photosensitive resin composition used in the present invention.

<Adhesion improver>

An adhesion improving agent may be added to the composition of the present invention in order to improve adhesion to a hard surface such as a substrate.

Examples of the adhesion improving agent include a silane coupling agent and a titanium coupling agent.

It is preferable that the silane coupling agent has an alkoxysilyl group as a hydrolyzable group capable of chemical bonding with an inorganic material. In addition, it is preferable to have a group exhibiting affinity by interacting or forming a bond with an organic resin, and as such a group, one having a (meth)acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group It is preferable, and among them, it is preferable to have a (meth)acryloyl group or a glycidyl group.

That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group, a (meth)acryloyl group or an epoxy group, and specifically, a (meth)acryloyl-trimethoxysilane compound having the following structure, And glycidyl-trimethoxysilane compounds.

Further, the silane coupling agent in the present invention is also preferably a silane compound having at least two functional groups having different reactivity per molecule, and particularly preferably having an amino group and an alkoxy group as the functional group. Examples of such silane coupling agents include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), and N-β-aminoethyl-γ -Aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trier Toxisilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl- Triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

When using a silane coupling agent, it is preferable that it is in the range of 0.1 mass%-5.0 mass% with respect to the total solid content in the colored photosensitive resin composition used for this invention, and 0.2 mass%-3.0 mass% is more preferable.

<Ultraviolet absorber>

The composition of the present invention may contain an ultraviolet absorber.

As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.

Examples of salicylate ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like, and examples of benzophenone ultraviolet absorbers include 2,2'-dihydroxy- 4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-me Oxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like. Further, examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' -tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2 -(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5 -Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-1,1,3,3-tetramethyl)phenyl]benzotriazole, and the like.

Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. In addition, as an example of the triazine-based ultraviolet absorber, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl Mono, such as phenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (Hydroxyphenyl) triazine compound; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3 -Methyl-4-propyloxyphenyl)-6- (4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6 Bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxyl Roxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1 And tris(hydroxyphenyl)triazine compounds such as ,3,5-triazine, and the like.

In the present invention, the various ultraviolet absorbers may be used singly or in combination of two or more.

The composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.1% by mass based on the total solids mass of the composition of the present invention. It is more preferable that it is mass% or less.

<Preparation of colored radiation-sensitive composition>

Although it does not specifically limit about the preparation form of the colored radiation-sensitive composition of this invention, For example, it can prepare by mixing the essential component of this invention and various additives used in combination as desired.

The colored radiation-sensitive composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matters or reducing defects. It can be used without any particular limitation as long as it has been conventionally used for filtration purposes.

The "method of adjusting the turbidity to be 30 ppm or less by filter filtration" is, in other words, a method of producing a polymerization solution having a turbidity of 30 ppm or less by filtering a polymerization solution containing a dye. In this method, aggregates of the dye are removed from the polymerization solution so that the turbidity of the polymerization solution becomes 30 ppm or less.

This method has the advantage that the choice of solvent for the pigment is wide.

The filter used for filter filtration can be used without any particular limitation as long as it is a filter conventionally used for filtration applications and the like.

Examples of the material of the filter include fluororesins such as PTFE (polytetrafluoroethylene); Polyamide resins such as nylon-6 and nylon-6,6; Polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra-high molecular weight); And the like. Among these materials, polypropylene (including high-density polypropylene) is preferable.

There is no particular limitation on the pore diameter of the filter, but is, for example, about 0.01 to 20.0 µm, preferably about 0.01 to 5 µm, and more preferably about 0.01 to 2.0 µm.

By setting the pore diameter of the filter within the above range, fine particles can be removed more effectively, and turbidity can be further reduced.

Here, the pore diameter of the filter can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, Pall Corporation, Toyo Roshi Kaisha, Ltd., Entegris Japan Co., Ltd. (formerly Nippon Microless Co., Ltd.) or Kitz Micro Filter Corporation can select from various filters provided by, for example. .

In the filter filtration, two or more types of filters may be used in combination.

For example, first, filtration can be performed using a first filter, and then filtration can be performed using a second filter having a different pore diameter from that of the first filter.

In that case, filtering by the first filter and filtering by the second filter may be performed only once, or may be performed twice or more.

The second filter may be formed of the same material as the first filter.

The composition of the present invention is preferably for application by ink jet, and preferably has physical properties suitable for application to an ink jet recording apparatus.

That is, when the composition of the present invention is used in an inkjet recording method, the ink viscosity at the temperature at the time of discharge is preferably 100 MPa·s or less, more preferably 50 MPa·s or less, taking into account discharge properties (discharge properties). , It is preferable to determine by appropriately adjusting the composition ratio so as to be within the above range.

In addition, the viscosity of the colored radiation-sensitive composition at 25°C (room temperature) is 0.5 MPa·s or more and 200 MPa·s or less, preferably 1 MPa·s or more and 100 MPa·s or less, and more preferably 2 MPa·s. It is not less than s and not more than 50 MPa·s. By setting the viscosity at room temperature to be high, liquid spillage of the radiation-sensitive composition is prevented even when applied to a substrate with irregularities, and as a result, a uniform light-shielding film can be formed. When the viscosity at 25° C. is greater than 200 MPa·s, a problem may occur in conveyance of the radiation-sensitive composition (transporting state of the liquid in the apparatus).

The surface tension of the composition of the present invention is preferably 20 mN/m to 40 mN/m, more preferably 23 mN/m to 35 mN/m. When applied to a silicon substrate or a metal wiring surface, 20 mN/m or more is preferable from the viewpoint of suppressing liquid spillage, and 35 mN/m or less is preferable from the viewpoint of adhesion and affinity to a substrate or the like.

The colored radiation-sensitive composition of the present invention can be applied to various applications such as cured films, color filters for solid-state imaging devices, color filters for liquid crystal displays, color filters for organic EL displays, printing inks, inkjet inks, etc. I can.

Cured film and its manufacturing method:

The cured film obtained by curing the composition of the present invention has high color purity, a high absorption coefficient is obtained in a thin layer, and has good fastness (in particular, heat resistance and light resistance). In addition, even when a white LED is used as a backlight, the effect is remarkable when applied to a liquid crystal display device including a white LED because it is possible to form colored pixels of good color, and the effect is remarkable in a color filter for a liquid crystal display device. Used for formation of colored pixels.

The method for producing a cured film includes a step of applying a colored radiation-sensitive composition on a substrate, and a step of exposing the colored radiation-sensitive composition to light. Specifically, when forming a cured film on an arbitrary substrate or substrate, a colored radiation-sensitive composition may be applied, or a substrate or the like may be immersed in a colored radiation-sensitive composition to form a colored radiation-sensitive composition layer and cured. In addition, when forming a pattern-shaped cured film, it may be applied on the substrate by an inkjet recording method, or a known printing method such as printing or offset printing may be applied, but from the viewpoint of forming a high-precision pattern, the substrate described later A method of forming a colored radiation-sensitive composition layer on the top and developing after exposing in a pattern shape to remove the unexposed portion of the colored radiation-sensitive composition layer is preferred.

The film thickness of the cured film in the present invention can be, for example, 0.5 to 1.5 µm.

Color filter and its manufacturing method:

The manufacturing method of the color filter of this invention includes a process of applying a colored radiation-sensitive composition on a substrate, and a process of pattern exposure of the said colored radiation-sensitive composition. Specifically, a step of forming a colored radiation-sensitive composition layer by applying the above-described colored radiation-sensitive composition of the present invention on a support (hereinafter also referred to as ``a colored radiation-sensitive composition layer forming step''), and the colored radiation-sensitive A step of exposing the composition layer to a pattern through a mask (hereinafter, also referred to as ``exposure step''), and a step of developing a colored radiation-sensitive composition layer after exposure to form a colored pattern (hereinafter also referred to as ``colored pixel'') ( Hereinafter, also referred to as "development process") is included.

In addition, it is exemplified that the color filter of the present invention is manufactured by the method of manufacturing the color filter of the present invention.

<Colored radiation-sensitive composition layer formation process>

In the process of forming a colored radiation-sensitive composition layer, a colored radiation-sensitive composition layer is formed by applying the colored radiation-sensitive composition of the present invention on a support.

As a support that can be used in this process, for example, a solid-state imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is installed on a substrate (for example, a silicon substrate). An element substrate can be used.

The colored pattern in the present invention may be formed on the imaging device formation surface side (surface) of the solid-state imaging device substrate, or may be formed on the imaging device non-formation surface side (rear surface).

A light-shielding film may be provided between the respective imaging elements in the solid-state imaging element substrate or on the back surface of the solid-state imaging element substrate.

In addition, an undercoat layer may be formed on the support as necessary to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate.

As a method of applying the colored radiation-sensitive composition of the present invention onto a support, various coating methods such as slit coating, ink jet method, rotation coating, casting coating, roll coating, and screen printing method can be applied.

The film thickness of the colored radiation-sensitive composition layer is preferably 0.1 µm to 10 µm, more preferably 0.2 µm to 5 µm, and still more preferably 0.2 µm to 3 µm.

Drying (pre-baking) of the colored radiation-sensitive composition layer applied on the support may be performed in a hot plate, oven, or the like at a temperature of 50° C. to 140° C. for 10 seconds to 300 seconds.

<Exposure process>

In the exposure process, the colored radiation-sensitive composition layer formed in the colored radiation-sensitive composition layer forming process is pattern-exposed through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper.

As the radiation (light) that can be used at the time of exposure, ultraviolet rays such as g-rays and i-rays are particularly preferably used (especially, preferably i-rays). The irradiation amount (exposure amount) is preferably 30 to 1500 mJ/cm 2, more preferably 50 to 1000 mJ/cm 2, and most preferably 80 to 500 mJ/cm 2.

<Development process>

Subsequently, by performing development such as an alkali development treatment, the colored radiation-sensitive composition layer of the unirradiated portion in the exposure step is eluted in an aqueous alkali solution, and only the photocured portion remains.

As the developer, an organic alkali developer that does not cause damage to the underlying imaging element or circuit is preferable. The developing temperature is usually 20°C to 30°C, and the developing time is, for example, 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it may be performed for 120 seconds to 180 seconds. In addition, in order to further improve the residue removal property, the step of further supplying the developer by shaking the developer every 60 seconds may be repeated several times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dia And organic alkaline compounds such as zabicyclo-[5,4,0]-7-undecene, and these alkali agents are diluted in pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution is preferably used as a developer.

In addition, an inorganic alkali may be used for the developer, and examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, and the like.

In addition, when a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Next, it is preferable to perform heat treatment (post-baking) after drying. If it is to form a multicolored colored pattern, a cured film can be produced by sequentially repeating the above process for each color. Thereby, a color filter is obtained.

Post-baking is a heat treatment after development for complete curing, and a heat curing treatment of usually 100°C to 240°C, preferably 200°C to 240°C is performed.

This post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the coating film after development becomes the above conditions.

In addition, the manufacturing method of the present invention may have a known process as a manufacturing method of a color filter as a process other than the above, if necessary. For example, after performing the said colored radiation-sensitive composition layer formation process, an exposure process, and a developing process, you may include a curing process of hardening the colored pattern formed as needed by heating and/or exposure.

In addition, when the colored radiation-sensitive composition according to the present invention is used, for example, clogging of the nozzle or pipe portion of the discharging portion of the coating device, or contamination due to adhesion, sedimentation, and drying of the colored radiation-sensitive composition or pigment into the applicator It may occur. Therefore, you may wash the contamination caused by the colored radiation-sensitive composition of the present invention.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 µm or less, and more preferably 1.0 µm or less.

In addition, as the size (pattern width) of the colored pattern (colored pixel), 2.5 µm or less is preferable, 2.0 µm or less is more preferable, and 1.7 µm or less is particularly preferable.

The color filter of the present invention can be used for a liquid crystal display device, a solid-state imaging device, or an organic EL device, and is particularly suitable for solid-state imaging applications. When used in a liquid crystal display device, a metal complex dye having excellent spectral characteristics and heat resistance is contained as a colorant, but there is little misalignment of the liquid crystal molecules accompanying a decrease in specific resistance, and the color tone of a display image is good, so that display characteristics are excellent.

<Liquid crystal display device>

The color filter of the present invention is particularly suitable as a color filter for a liquid crystal display device because it has a color pixel excellent in hue and excellent light resistance. A liquid crystal display device equipped with such a color filter can display a high-quality image excellent in display characteristics because the color tone of the displayed image is good.

For the definition of the display device and the details of each display device, for example, "Electronic Display Device (Teruo Sasaki, Kogyo Chosakai Publishing Co., Ltd. published in 1990)" and "Display Device (Sumiaki Ibuki, Sangyo)", for example Tosho Publishing Co., Ltd. published in 1989). In addition, about a liquid crystal display device, it describes in "next-generation liquid crystal display technology (edited by Tatsuo Uchida, published in Kogyo Chosakai Publishing Co., Ltd. 1994)", for example. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above "next-generation liquid crystal display technology".

The color filter of the present invention is particularly effective for a liquid crystal display device of a color TFT system. About the color TFT type liquid crystal display device, it is described in "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD. published in 1996)", for example. In addition, the present invention can be applied to a liquid crystal display device with an enlarged viewing angle, such as a transverse electric field driving method such as IPS and a pixel division method such as MVA, or to STN, TN, VA, OCS, FFS and R-OCB.

In addition, the color filter of the present invention can be provided to a bright and high-definition color-filter on array (COA) method. In the liquid crystal display of the COA system, in addition to the general required characteristics as described above, the required characteristics for the interlayer insulating film, that is, the low dielectric constant and resistance to the stripping solution are sometimes required. In the color filter of the present invention, it is obtained by curing by containing and curing the complex-forming compound of the (B) present invention together with the (A) metal complex dye in the above ratio, and a decrease in the specific resistance of the liquid crystal material is drastically prevented. Therefore, it is considered that the inhibition of the alignment of the liquid crystal molecules, that is, the deterioration of display characteristics, is eliminated. As a result, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability because good color tone such as color purity is excellent. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be formed on the color filter layer.

In addition, in the colored layer formed by the COA method, in order to conduct the ITO electrode disposed on the colored layer and the terminal of the driving substrate under the colored layer, a rectangular through hole having a side length of about 1 to 15 μm or a co It is necessary to form a conductive path such as a shaped pit, and it is particularly preferable that the dimension (ie, the length of one side) be 5 μm or less, but by using the present invention, a conductive path of 5 μm or less is formed. It is also possible. These image notation methods are described, for example, on page 43 of "EL, PDP, LCD Display-Latest Trends in Technology and Market-(Toray Research Center, Inc. Research and Research Section 2001)".

In addition to the color filter of the present invention, the liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these members, for example, "The market for materials and chemicals around the '94 liquid crystal display (Kentaro Shima CMC Publishing Co., Ltd. published in 1994)" and "The current state and future prospects of the 2003 liquid crystal-related market (second volume)" (Ryokichi Omote Fuji Chimera Research Institute, Inc., published in 2003).

The backlight is described in SID Meeting Digest 1380 (2005) (A. Konno et. al), pages 18 to 24 (Yasuhiro Shima) and pages 25 to 30 (Takaaki Yagi) of the December 2005 issue of Monthly Display.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventionally known three-wavelength tube of a cold cathode tube, but more luminance by using red, green, and blue LED light sources (RGB-LEDs) as backlights. It is possible to provide a liquid crystal display device having high color purity and excellent color reproducibility.

<Solid image sensor>

The solid-state image pickup device of the present invention includes the color filter for solid-state image pickup devices of the present invention described above. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for a solid-state imaging device of the present invention, and there is no particular limitation as long as it functions as a solid-state imaging device, but examples include the following configurations.

A plurality of photodiodes constituting a light-receiving region of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a support and a transfer electrode made of polysilicon, etc., and a light receiving unit of the photodiode on the photodiode and the transfer electrode It has a light-shielding film made of tungsten or the like that is only open, and has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion on the light-shielding film, and a color filter for a solid-state image pickup device of the present invention on the device protective film. Configuration.

Further, it may be a configuration having a condensing means (for example, a microlens, etc. hereinafter) on the device protective layer and below the color filter (the side close to the support), a configuration having condensing means on the color filter, or the like. good.

Example

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to the following examples unless it goes beyond the gist. In addition, unless otherwise specified, "parts" and "%" are based on mass.

[Preparation of pigment dispersion (Y)]

The mixture of the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.)) using 0.3 mm diameter zirconium oxide beads. ) Was prepared.

·C. I. Pigment Yellow 185 18.0 copies

Dispersant ((b) polymer without polymerizable group): 1.8 parts of BYK-2001 manufactured by BYK Co., Ltd.

Resin 1 ((b) polymer having no polymerizable group): 9.9 parts of benzyl methacrylate/methacrylic acid copolymer (=70/30 molar ratio, Mw: 30000, acid value: 110 mgKOH/g)

Solvent: 70.3 parts of propylene glycol methyl ether acetate

[Preparation of pigment dispersion (M)]

The mixture of the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.)) using 0.3 mm diameter zirconium oxide beads. ) Prepared.

·C. I. Pigment Red 122 (magenta) 18.0 parts

Dispersant ((b) polymer without polymerizable group): 1.8 parts of BYK-2001 manufactured by BYK Co., Ltd.

Resin 1 ((b) polymer having no polymerizable group): 9.9 parts of benzyl methacrylate/methacrylic acid copolymer (=70/30 molar ratio, Mw: 30000)

Solvent: 70.3 parts of propylene glycol methyl ether acetate

[Preparation of pigment dispersion (Cy)]

The mixture of the following composition was mixed and dispersed for 3 hours in a bead mill (high-pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon Biei Co., Ltd.)) using 0.3 mm diameter zirconium oxide beads. ) Prepared.

·C. I. Pigment Blue 15: 67.4 parts

・10.6 parts of aluminum phthalocyanine

Dispersant ((b) polymer without polymerizable group): BYK-2001 manufactured by BYK Co., Ltd.

Part 1.8

Resin 1 ((b) polymer having no polymerizable group): 9.9 parts of benzyl methacrylate/methacrylic acid copolymer (=70/30 molar ratio, Mw: 30000)

Solvent: 70.3 parts of propylene glycol methyl ether acetate

(Example 1)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Y-1).

Pigment dispersion (Y) 36.1 parts

(A) 0.6 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

4.5 parts of alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group))

-Polymerizable compound 1: dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. product name Kayarad DPHA) 2.0 parts

Polymerizable compound 2: pentaerythritol ethylene oxide-modified tetraacrylate (product name RP-1040 manufactured by Nippon Kayaku Co., Ltd.) 6.0 parts

Polymerization initiator 1: 1.2 parts of the following structure (manufactured by BASF Ltd., IRGACURE-OXE01)

Solvent: 49.6 parts of propylene glycol methyl ether acetate

(Example 2)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Y-2).

Pigment dispersion (Y) 36.1 parts

(A) 1.05 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

-Alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group)) 4.05 parts

-2.0 parts of polymerizable compound 1

-Polymerizable compound 2 6.0 parts

·Polymerization initiator 11.2 parts

Solvent: 49.6 parts of propylene glycol methyl ether acetate

(Example 3)

[Preparation of colored radiation-sensitive composition]

The following components were mixed and colored radiation-sensitive composition Y-3 was prepared.

Pigment dispersion Y 36.1 parts

(A) 1.2 parts of an acrylic polymer having a polymerizable group (Cychromer P, manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group)) 3.9 parts

-2.0 parts of polymerizable compound 1

-Polymerizable compound 2 6.0 parts

·Polymerization initiator 1 1.2 parts

Solvent: 49.6 parts of propylene glycol methyl ether acetate

(Example 4)

[Preparation of colored radiation-sensitive composition]

Except having changed the polymerizable compounds 1 and 2 of Example 1 to M-510 manufactured by Toagosei Co., Ltd., they were mixed in the same composition ratio as in Example 1 to prepare a colored radiation-sensitive composition (Y-4).

[Synthesis Example of Binder]

(Synthesis of Binder 1)

A solution having the following composition was prepared in a container for dropping a monomer.

-Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate (hereinafter referred to as "DM") 20 parts

-Benzyl methacrylate (BzMA) 70 parts

10 parts of methyl methacrylate (MMA)

30 parts of methacrylic acid (MAA)

2 parts of t-butylperoxy-2-ethylhexanoate

25 parts of diethylene glycol dimethyl ether

A solution having the following composition was prepared in a container for dropping a chain transfer agent.

6 parts of n-dodecanethiol

20 parts of diethylene glycol dimethyl ether

157 parts of diethylene glycol dimethyl ether was added to the reaction vessel (separable flask with a cooling tube), replaced with N ₂ gas, and heated to raise the temperature of the reaction vessel to 90°C.

After confirming temperature stability, dropping was started from the monomer dropping container and the chain transfer agent dropping container, respectively, and dropping of the monomer and chain transfer agent was completed in 140 minutes while maintaining the temperature at 90°C. After completion of the dropwise addition, the temperature was further increased 60 minutes, the temperature of the reaction vessel was raised to 110°C, and maintained at 110°C for 180 minutes. After that, the inside of the reaction vessel was replaced with air.

Then, the composition of the following composition was put into the reaction container, and it was made to react at the temperature of 110 degreeC for 9 hours.

GMA (glycidyl methacrylate) 35 parts

0.2 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol)

・0.4 parts of triethylamine

After completion of the reaction, it was cooled to room temperature.

In this way, a solution of binder 1 (solid content concentration 40%) was obtained.

The component derived from each monomer of the obtained binder 1 was analyzed using ¹ H-NMR. In addition, about the weight molecular weight, it measured by GPC (weight average molecular weight: 11000).

(Example 5)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Y-5).

Pigment dispersion (Y) 36.1 parts

(A) 1.5 parts of acrylic polymer having a polymerizable group (solution of the synthetic binder 1)

4.5 parts of alkali-soluble resin (the above resin 1 ((b) polymer not having a polymerizable group))

-2.0 parts of polymerizable compound 1

-Polymerizable compound 2 6.0 parts

·Polymerization initiator 1 1.2 parts

Solvent: 48.7 parts of propylene glycol methyl ether acetate

(Example 6)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (M-1).

Pigment dispersion (M) 43.06 parts

(A) 0.6 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer not having a polymerizable group)) 2.6 parts

·Polymerizable compound 1 2.1 parts

-Polymerizable compound 2 6.3 parts

-Polymerization initiator 1 0.6 parts

Solvent: 44.7 parts of propylene glycol methyl ether acetate

(Example 7)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (M-2).

Pigment dispersion (M) 43.06 parts

(A) 0.9 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group)) 2.3 parts

·Polymerizable compound 1 2.1 parts

-Polymerizable compound 2 6.3 parts

-Polymerization initiator 1 0.6 parts

Solvent: 44.7 parts of propylene glycol methyl ether acetate

(Example 8)

[Preparation of colored radiation-sensitive composition]

The following components were mixed and the colored radiation-sensitive composition (M-3) was prepared.

Pigment dispersion (M) 43.06 parts

(A) 1.0 part of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

2.2 parts of alkali-soluble resin (the resin 1 ((b) polymer without polymerizable group))

·Polymerizable compound 1 2.1 parts

-Polymerizable compound 2 6.3 parts

-Polymerization initiator 1 0.6 parts

Solvent: 44.7 parts of propylene glycol methyl ether acetate

(Example 9)

[Preparation of colored radiation-sensitive composition]

Except having changed the polymerizable compounds 1 and 2 of Example 6 to M-510 manufactured by Toagosei Co., Ltd., they were mixed in the same composition ratio as in Example 6 to prepare a colored radiation-sensitive composition (M-4).

(Example 10)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (M-5).

Pigment dispersion (M) 43.06 parts

(A) 1.5 parts of acrylic polymer having a polymerizable group (solution of the synthetic binder 1)

Alkali-soluble resin (Resin 1 ((b) polymer not having a polymerizable group)) 2.6 parts

·Polymerizable compound 1 2.1 parts

-Polymerizable compound 2 6.3 parts

-Polymerization initiator 1 0.6 parts

Solvent: 43.8 parts of propylene glycol methyl ether acetate

(Example 11)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Cy-1).

Pigment dispersion (Cy) 27.8 parts

(A) 0.6 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group)) 6.8 parts

-Polymerizable compound 1 6.3 parts

-Polymerizable compound 2 2.1 parts

·Polymerization initiator 1 1.0 part

Solvent: 55.4 parts of propylene glycol methyl ether acetate

(Example 12)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Cy-2).

Pigment dispersion (Cy) 27.8 parts

(A) 1.15 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer not having a polymerizable group)) 6.25 parts

-Polymerizable compound 1 6.3 parts

-Polymerizable compound 2 2.1 parts

·Polymerization initiator 1 1.0 part

Solvent: 55.4 parts of propylene glycol methyl ether acetate

(Example 13)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Cy-3).

Pigment dispersion (Cy) 27.8 parts

(A) 1.4 parts of acrylic polymer having a polymerizable group (trade name Cychromer P manufactured by Daicel Corporation)

Alkali-soluble resin (Resin 1 ((b) polymer not having a polymerizable group)) 6.0 parts

-Polymerizable compound 1 6.3 parts

-Polymerizable compound 2 2.1 parts

·Polymerization initiator 1 1.0 part

Solvent: 55.4 parts of propylene glycol methyl ether acetate

(Example 14)

[Preparation of colored radiation-sensitive composition]

Except having changed the polymerizable compounds 1 and 2 of Example 6 to M-510 manufactured by Toagosei Co., Ltd., they were mixed in the same composition ratio as in Example 11 to prepare a colored radiation-sensitive composition (Cy-4).

(Example 15)

[Preparation of colored radiation-sensitive composition]

The following components were mixed to prepare a colored radiation-sensitive composition (Cy-5).

Pigment dispersion (Cy) 27.8 parts

(A) 1.5 parts of acrylic polymer (solution of binder 1) having a polymerizable group

Alkali-soluble resin (Resin 1 ((b) polymer without polymerizable group)) 6.8 parts

-Polymerizable compound 1 6.3 parts

-Polymerizable compound 2 2.1 parts

·Polymerization initiator 1 1.0 part

Solvent: 54.5 parts of propylene glycol methyl ether acetate

Spectroscopic properties were evaluated using each of the obtained colored radiation-sensitive compositions. The results are shown in the table below.

[Spectral characteristics]

Each colored radiation-sensitive composition was spin-coated on a glass substrate, applied so that the film thickness after post-baking became (1.0) µm, dried on a hot plate at 100°C for 120 seconds, dried, and then 300°C using a hot plate at 200°C. Secondary heat treatment (post-baking) was further performed.

[Production of color filter]

On an 8-inch silicon wafer, a photosensitive transparent composition, CT-2010 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) is uniformly coated by spin coating to form a coating film, and the formed coating film is heated in an oven at 220°C for 60 minutes. did. Further, the number of rotations of the spin coating application was adjusted so that the film thickness of the coating film after the heat treatment was about 1.0 µm.

In the manner described above, a silicon wafer with an undercoat layer was obtained.

The colored radiation-sensitive composition of Example 1 was applied on the silicon wafer with the undercoat layer obtained above with a spin coater so that the thickness after drying became 1.0 µm, and heated for 120 seconds using a hot plate at 100°C. Processing (pre-baking) was performed.

Next, the i-line stepper exposure apparatus FPA-3000 i5+ (manufactured by Canon Inc.) was used, and the pattern exposure was performed on a total of 399 locations of patterns arranged in a matrix of 21 rows x 19 columns. At this time, the 21 rows of the matrix have a minimum exposure amount of 500J/m2, and the exposure amount is increased for each row at intervals of 500J/m2 to 500J/m2. 0.0 µm) as the center, and changing the focal length at 0.1 µm intervals. In other words, using a photomask that is imaged so that a square pixel pattern of 3.0 µm × 3.0 µm is arranged within a range of 4 ㎜ × 3 ㎜ under the condition that the focal length is changed for each column with one center column as the optimal focal length value. did.

After that, the silicon wafer on which the exposed coating film was formed is placed on a horizontal rotating table of a spin shower developing device (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2060 (FUJIFILM Electronic Materials Co., Ltd.) Agent), paddle development was performed at 23° C. for 60 seconds to form a colored pattern on a silicon wafer.

The silicon wafer on which the colored pattern was formed was rinsed with pure water, and then spray dried.

Further, heat treatment (post-baking) was performed for 300 seconds using a 200°C hot plate to obtain a silicon wafer having colored pixels corresponding to the colorant.

<Evaluation>

(Pattern formation)

The colored pattern formed on the wafer obtained above was measured using a measuring SEM (S-9260 scanning electron microscope manufactured by Hitachi Ltd.), and the dimensions of the colored pattern of the exposed portion and the degree of the developed residue of the unexposed portion were evaluated on the SEM image. did. It is preferable that the solubility of the developer between the exposed portion and the unexposed portion is different, so that the exposed portion is imaged with the dimensions of the mask design, and the unexposed portion has no dissolved residue. The results are shown in the table below. Although the evaluation criteria are shown below, A and B are practical use levels.

<Evaluation criteria>

A: The exposed portion had an image of 1:1 with respect to the mask size, and the unexposed portion had no dissolution residue, and the pattern shape was a good rectangle.

B: An image of the exposed portion was formed at 1:1 with respect to the mask size, and no dissolved residue was seen in the unexposed portion.

C: Although the pattern was formed in the exposed part, it was not formed at 1:1 with respect to the mask size, or development defect was seen in the unexposed part.

D: The unexposed part was hardly dissolved, and the exposed part was not formed 1:1 with respect to the mask size.

(Surface roughness)

The colored pattern formed on the wafer was observed using a measuring SEM (S-9260 scanning electron microscope manufactured by Hitachi Ltd.), and the surface roughness of the colored pattern of the exposed portion was evaluated on the SEM. It is preferable that the exposed portion does not have surface roughness due to heat shrinkage after post-baking. The results are shown in the table below. Although the evaluation criteria are shown below, A, B, and C are practical use levels.

<Evaluation criteria>

A: Surface roughness is not seen at all.

B: The surface roughness is very slight.

C: The surface roughness is slightly seen.

D: Surface roughness is seen seriously.

As evident from the above results, (a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, (c) a monomer having three or more ethylenically unsaturated double bonds, (d) a polymerization initiator and (e) ) It was found that the colored radiation-sensitive composition containing a colorant and having a content of (a) an acrylic polymer having a polymerizable group of 1 to 14% by mass of the total polymer component has excellent pattern formation and less surface roughness (each Example). On the other hand, it was found that (a) when a colored radiation-sensitive composition in which the content of the acrylic polymer having a polymerizable group was out of the range of 1 to 14% by mass of the total polymer component was used, pattern formation was poor, and surface roughness was large.

In particular, the effect of the present invention was found to be effective in a colored radiation-sensitive composition in which (a) the content of the acrylic polymer having a polymerizable group is 5 to 12% by mass of the total polymer component.

[Example 100]

Fabrication of solid-state imaging device

<Production of a silicon substrate with an undercoat layer attached>

A 6-inch silicon wafer was heated in an oven at 200°C for 30 minutes. Subsequently, CT-2010 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on the silicon wafer to a dry film thickness of 1.0 µm, followed by heating and drying in an oven at 220°C for 1 hour to form an undercoat layer. A silicon wafer substrate with a coating layer was obtained.

<Pattern formation>

The colored radiation-sensitive composition of Example 1 was applied onto the undercoat layer of a silicon wafer with an undercoat layer attached thereto to form a colored curable composition layer (coating film). Then, heat treatment (prebaking) was performed for 120 seconds using a 100°C hot plate so that the dry film thickness of this coating film was 1.0 µm.

Next, the i-line stepper exposure apparatus FPA-3000i 5+ (manufactured by Canon Inc.) was used to expose the pattern at a wavelength of 365 nm through a Bayer pattern mask having 3.0 µm in all directions.

After that, the silicon wafer substrate on which the irradiated coating film has been formed is mounted on a horizontal rotating table of a spin-shower developing device (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2060 (FUJIFILM Electronic Materials Co., Ltd.) Ltd.) was used for paddle development at 23°C for 60 seconds to form a 3.0 µm×3.0 µm yellow colored pattern on a silicon wafer substrate.

The silicon wafer substrate on which the colored pattern was formed was rinsed with pure water, and further heat-treated (post-baked) for 300 seconds using a 200°C hot plate to obtain a silicon wafer substrate having colored pixels.

Next, a 3.0 µm x 3.0 µm magenta colored pattern was formed using the colored radiation-sensitive composition of Example 6.

Further, a cyan colored pattern of 3.0 µm x 3.0 µm was formed using the colored radiation-sensitive composition of Example 11 to prepare a color filter for a solid-state image sensor.

<Evaluation>

As a result of incorporating a full color color filter into a solid-state imaging device, it was confirmed that the solid-state imaging device has high resolution and excellent color separation.

Claims (27)

(a) an acrylic polymer having a polymerizable group, (b) a polymer having no polymerizable group, (c) a monomer having three or more ethylenically unsaturated double bonds, (d) a polymerization initiator and (e) a colorant, (a) The content of the acrylic polymer having a polymerizable group is a colored radiation-sensitive composition that is 1 to 14% by mass of all polymer components,
(C) the content of the monomer having three or more ethylenically unsaturated double bonds in the colored radiation-sensitive composition is 0.8 to 2.0 times (mass ratio) of all polymer components,
(c) a monomer having three or more ethylenically unsaturated double bonds, characterized in that it contains at least one selected from a compound represented by the following general formula (i) and a compound represented by the general formula (ii) Radiation-sensitive composition.

[In general formulas (i) and (ii), E represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, respectively, and y is 1~ The integer of 10 is represented, and X represents a hydrogen atom, an acryloyl group, a methacryloyl group, or a carboxyl group, respectively.
In General Formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, m represents an integer of 0 to 10, respectively, and the total of each m is an integer of 1 to 40.
In General Formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, n each represents an integer of 0 to 10, and the total of each n is an integer of 1 to 60] The method of claim 1,
(a) A colored radiation-sensitive composition, wherein the content of the acrylic polymer having a polymerizable group is 5 to 12% by mass of all polymer components. The method of claim 1,
(e) The coloring radiation-sensitive composition, characterized in that the coloring agent is at least one selected from red, magenta, yellow, blue, cyan and green. delete delete delete The method according to claim 1 or 2,
(d) The polymerization initiator is an oxime-based compound, characterized in that the colored radiation-sensitive composition. The method according to claim 1 or 2,
(c) A colored radiation-sensitive composition, wherein the content of the monomer having three or more ethylenically unsaturated double bonds is 15 to 50% by mass of the total solid content in the colored radiation-sensitive composition. The method according to claim 1 or 2,
(b) A colored radiation-sensitive composition comprising an alkali-soluble resin as a polymer having no polymerizable group. The method according to claim 1 or 2,
The colored radiation-sensitive composition, wherein the content of all polymer components is 10 to 50% by mass of the total solid content in the colored radiation-sensitive composition. The method of claim 2,
(e) The coloring radiation-sensitive composition, characterized in that the coloring agent is at least one selected from red, magenta, yellow, blue, cyan and green. delete delete A cured film obtained by curing the colored radiation-sensitive composition according to claim 1. A method for producing a cured film comprising a step of applying the colored radiation-sensitive composition according to claim 1 on a substrate, and a step of exposing the colored radiation-sensitive composition to light. A color filter formed using the colored radiation-sensitive composition according to claim 1. A method for producing a color filter, comprising a step of applying the colored radiation-sensitive composition according to claim 1 on a substrate, and a step of pattern-exposing the colored radiation-sensitive composition. An ink jet ink comprising the colored radiation-sensitive composition according to claim 1. A solid-state imaging device comprising the color filter according to claim 16. A solid-state imaging device comprising a color filter obtained by the method for manufacturing a color filter according to claim 17. A liquid crystal display device comprising the color filter according to claim 16. An organic EL display device comprising the color filter according to claim 16. A liquid crystal display device comprising a color filter obtained by the method for producing a color filter according to claim 17. An organic EL display device comprising a color filter obtained by the method for manufacturing a color filter according to claim 17. The method of claim 1,
(a) The colored radiation-sensitive composition, wherein the content of the acrylic polymer having a polymerizable group is 5 to 9% by mass of all polymer components. The method of claim 1,
(e) The colored radiation-sensitive composition, characterized in that the colorant is a chromatic colorant. The method of claim 26,
The colored radiation-sensitive composition, wherein the content of the chromatic colorant is 10% by mass or more with respect to the total solid content of the colored radiation-sensitive composition.