KR20160040250A - Resin composition, cured film, infrared ray pass filter and method for producing same, and infrared ray sensor - Google Patents

Abstract

일반식 (A2)

The resin composition of the present invention comprises a colorant and an alkali-soluble resin, wherein the colorant includes at least a red pigment and a blue pigment represented by the following general formula (A1) and / or the following general formula (A2) The content of the pigment is 20 to 50 mass%, and the content of the blue pigment is 25 to 55 mass%.
In formula (A1)

In general formula (A2)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a cured film, an infrared ray transmitting filter, a manufacturing method thereof, and an infrared ray sensor,

The present invention relates to a resin composition, an infrared ray transmitting filter, a manufacturing method thereof, and an infrared ray sensor.

Color filters are indispensable components for solid-state image pickup devices and liquid crystal displays. Particularly, in a color filter for a solid-state image sensor, improvement in color resolution and improvement in color reproducibility are required.

Such a color filter is formed with a plurality of colored regions (colored cured films), and usually has at least red, green and blue colored regions (hereinafter also referred to as "colored patterns" or "colored pixels" . As a method of forming a coloring pattern, first, a coloring and radiation-sensitive composition having a coloring material of red, green, and blue in a first color is applied, and exposure, development, And then the same coating, exposure, development, and heating processes as necessary are repeated for the second color and the third color.

Solid-state image pickup devices are utilized as optical sensors for various applications.

For example, near-infrared rays have a longer wavelength than visible light and are therefore difficult to scatter, and can be used for distance measurement, three-dimensional measurement, and the like. In addition, since the near-infrared rays are invisible to humans, animals, and the like, they are not found by the subject even if they are illuminated with a near-infrared light source at night, and they are used for shooting nocturnal wildlife, Can also be used. The development of a color filter that can be used for a solid-state image sensing device capable of developing in various uses and sensing near-infrared rays has been desired in such an optical sensor for sensing near-infrared rays.

Patent Document 1 discloses a resin black matrix having a maximum light transmittance of 1% or less in a wavelength range of 400 nm to 700 nm and an average light transmittance of 60% or more in a wavelength range of 850 nm to 3000 nm.

Patent Document 2 discloses an aluminum phthalocyanine having a specific structure used for manufacturing a color filter.

Patent Document 3 discloses a pigment dispersant in which a quinophthalone skeleton and a triazine skeleton are bonded through an arylene group or a heteroaromatic ring and further a basic functional group is bonded to the triazine ring via a linking group.

Patent Document 1: JP-A-2009-69822 Patent Document 2: JP-A-2013-87251 Patent Document 3: JP-A-2006-291194

As a result of studying by the present inventors, it has been found that when two or more kinds of pigments are blended so as to shield light up to 800 nm or less in order to produce a resin composition that shields visible light and transmits near-infrared light, (Color irregularity) deteriorates.

In addition, recently, it is required to further improve the light shielding property of a visible light region (for example, 400 to 700 nm). Here, in order to increase the light shielding property of the visible light region, it is conceivable to increase the colorant amount. However, if the colorant amount is increased, the proportion of the curable component inevitably decreases, and the curability of the composition is inferior and the adhesion of the pattern is deteriorated.

An object of the present invention is to solve these problems, and it is an object of the present invention to provide a resin composition excellent in roughness and adhesion.

As a result of a detailed investigation by the present inventors, it has been found that a resin composition containing at least a red pigment and a specific amount of aluminum phthalocyanine as a blue pigment in a coloring material is blended in the resin composition and the content of the red pigment is 20 to 50% It has been found that the above problems can be solved by setting the content of the blue pigment to 25 to 55 mass%.

More specifically, the above-mentioned problem is solved by the following means <1>, preferably by <2> to <14>.

[1] A colorant composition, comprising: a colorant and an alkali-soluble resin, wherein the colorant comprises at least a red pigment and a blue pigment represented by the following formula (A1) and / or the following formula (A2) 20 to 50 mass%, and the content of the blue pigment is 25 to 55 mass%.

In formula (A1)

[Chemical Formula 1]

(In the general formula (A1), X ¹ to X ⁴ each independently represent a substituent, R ^0A represents a hydrogen atom or a monovalent substituent, m 1 to m 4 each independently represent an integer of 0 to 4 when m1 ~ m4 is 2 or more, X ¹ ~ X ⁴ may respectively be the same or different is.)

In general formula (A2)

(2)

(In the general formula (A2), each of X ⁵ to X ¹² independently represents a substituent, R ^0B represents a divalent substituent, m 5 to m 12 each independently represent an integer of 0 to 4. m 5 to m 12 Is 2 or more, each of X ⁵ to X ¹² may be the same or different.)

&Lt; 2 > The resin composition according to < 1 >, further comprising a pigment derivative.

&Lt; 3 > The resin composition according to < 2 >, wherein the pigment derivative has a triazine skeleton.

<4> The resin composition according to <2> or <3>, wherein the pigment derivative is represented by the following formula (I) or (II)

(3)

(Compound (I) of the, Dye is an n-valent represents an organic dye moiety, X is a single ^{bond, -CONH-Y 2 -, -SO} 2 NH-Y 2 - or ^{_{-CH 2 NHCOCH 2 NH-Y 2}} - ( Y ² represents a represents an alkylene group or arylene group), Y ¹ is is a group, a hydroxyl group, an alkoxy general formula (I-1) when represents a -NH- or -O-, Z is, n representing 1 , Or a group represented by -NH-X-Dye (X is a synonymous with X in formula (I)), and when n represents an integer of 2 to 4, it may be a hydroxyl group, an alkoxy group, R ¹ and R ² each represents an alkyl group, and R ¹ and R ² may be bonded to each other to form a heterocycle containing a nitrogen atom, and m is an integer of 1 to 6, And n represents an integer of 1 to 4. When n is 2 or more, a plurality of X, Y ¹ , R ^1, and R ² may be the same or different.)

[Chemical Formula 4]

(In formula (I-1), Y ³ represents -NH- or -O-, R ¹ and R ² each represent an alkyl group, and R ¹ and R ² are bonded to each other to form a hetero And m represents an integer of 1 to 6).

[Chemical Formula 5]

(In the formula (II), Dye represents a quinophthalone residue, and X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR'COCH ₂ NR'- , or represents a -NR'CO-, X ² is an aryl group, or represents the number of carbon atoms is 4 to 20 heteroaromatic ventilation having the carbon number of 6 to 20, these groups, -NR'-, -O-, -SO ₂ - or -CO-, X ³ represents -NR'- or -O-, R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number A represents a group represented by the following formula (II-1), a group represented by the following formula (II-2), or a group represented by the following formula -O- (CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , -Cl, -F and -X ³ -X ² -X ¹ -Dye, and R ⁸ is substituted which may also represent a nitrogen heterocycle residue, R ^9, R ^10, R ¹¹ are each a hydrogen atom, an alkyl group having a carbon number of 1 to 20, Al 2 to 20 carbon atoms And n represents an integer of 0 to 20. Either A or B is a group represented by the following formula (II-1), a group represented by the following formula (II-2) , -O- (CH ₂ ) _n -R ⁸ , -OR ^9, or -NR ¹⁰ R ¹¹ , and t represents an integer of 1 to 3. When t is 2 or more, a plurality of X ¹ , X ² , X ³ , A and B may be the same or different.)

[Chemical Formula 6]

(Wherein Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms, to 20 represents an arylene group, these _{groups, -NR'-, -O-, -SO 2 -} . or may be coupled together by a divalent linking group selected from, -CO- R 'is a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms R ¹ and R ² may be united to form a heterocyclic structure which may be further substituted with a nitrogen atom, an oxygen atom or a sulfur atom.

In formula (II-2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-G-SO 2 -, -NR'-} G-SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO ₂ represents NR'-, G represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R 'and R "are each an alkyl group having 1 to 20 carbon atoms , An alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, Or an aryl group having 6 to 20 carbon atoms, and R ⁷ is an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms.

<5> The resin composition according to any one of <1> to <4>, wherein the red pigment contains a compound represented by the following general formula (4).

In general formula (4)

(7)

(In the general formula (4), A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, CF ₃ , or -CON (R ¹ ) R ^{2, wherein} R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group.

<6> The resin composition according to any one of <1> to <4>, wherein the red pigment comprises a red pigment having a symmetrical structure and a red pigment having an asymmetric structure.

<7> The resin composition according to any one of <1> to <6>, further comprising a polymerizable compound and a polymerization initiator.

<8> The resin composition according to any one of <1> to <7>, wherein the content of the coloring material in the total solid content in the composition is 40% by mass or more.

<9> The resin composition according to any one of <1> to <8>, which is used for forming a color filter for a solid-state imaging element.

<10> A cured film obtained by curing a resin composition according to any one of <1> to <9>.

<11> An infrared ray transmitting filter formed by the resin composition according to any one of <1> to <9>.

<12> The infrared-transmitting filter according to <11>, wherein the light transmittance at a wavelength of 400 nm, a wavelength of 520 nm, and a wavelength of 700 nm is 15% or less.

&Lt; 13 > A method for producing a transparent resin composition, comprising the steps of: forming an infrared transmitting composition layer on a substrate using the resin composition according to any one of < 1 > And a step of developing the composition layer to form a pattern.

<14> An infrared ray sensor comprising an infrared ray transmission filter according to <11> or <12> or an infrared ray transmission filter obtained by a manufacturing method of an infrared ray transmission filter according to <13>.

According to the present invention, it becomes possible to provide a resin composition excellent in roughness and adhesion.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included. The organic EL element in the present invention refers to an organic electroluminescence element.

In the present specification, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the resin composition.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation " in this specification means, for example, a line spectrum of mercury, a far ultraviolet ray, an extreme ultraviolet ray (EUV light) represented by an excimer laser, an X ray and an electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle lines such as electron beams and ion beams .

In the present specification, the term " (meth) acrylate "refers to both or either acrylate and methacrylate, and" (meth) acrylate " refers to both acrylate and methacrylate, The term "(meth) acryloyl" refers to both acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less.

The weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified. The obtained polymer was isolated by removing the solvent, and the obtained solid content was diluted with tetrahydrofuran to 0.1 mass%, and the resultant polymer was analyzed with HLC-8020GPC (manufactured by Tosoh Corporation) using TSKgel Super Multipore HZ-H Ltd., 4.6 mm ID x 15 cm) connected in series can be measured as a column. The conditions can be performed using an RI detector with a sample concentration of 0.35 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C.

In the present specification, the polymerizable compound means 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.

In the present specification, Me in the formula represents a methyl group, Et represents an ethyl group, Pr indicates a propyl group, Bu indicates a butyl group, and Ph indicates a phenyl group.

In the present specification, the roughness is a color unevenness that is generated by generation of a fine dot-shaped high-density region. Hereinafter, such color unevenness may be referred to as roughness.

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

The resin composition of the present invention comprises a colorant and an alkali-soluble resin, wherein the colorant includes at least a red pigment and a blue pigment represented by the following general formula (A1) and / or the following general formula (A2) The content of the pigment is 20 to 50 mass%, and the content of the blue pigment is 25 to 55 mass%.

By such a constitution, a resin composition excellent in roughness and adhesion can be provided.

This mechanism is presumed, but the blue pigment represented by the general formula (A1) or the general formula (A2) shown below is preferably a polar group having a high polarity (-OR ^0A in the general formula (A1) or -OR ^0B -O -), the compatibility with the alkali-soluble resin is improved to improve the compatibility, and the aggregation of the blue pigment when the resin composition is used as a film can be suppressed. As a result, the color unevenness of the blue pigment is reduced, Can be improved.

The blue pigment represented by the general formula (A1) or the general formula (A2) shown below includes a group having a high polarity, so that the curing property of the pattern is improved by interacting with the hydrophilic part of the alkali-soluble resin, .

In the resin composition of the present invention, when the content of the red pigment is less than 20% by mass, it is necessary to increase the pigment concentration in order to replenish the light-shielding region of the red pigment with another pigment, The roughness and the adhesiveness are deteriorated. Also, the light shielding property of the visible light region (for example, 400 to 700 nm) deteriorates.

When the content of the red pigment exceeds 50 mass%, the pigment concentration of the blue pigment becomes insufficient, and the shading near 600 to 800 nm becomes insufficient, so that the light shielding property of the visible light region (for example, 400 to 700 nm) It gets worse.

If the content of the blue pigment is less than 25 mass% in all the coloring materials, the influence of the curing of the entire composition due to the aluminum phthalocyanine is reduced, so that the roughness and the adhesion are deteriorated. Also, the light shielding property of the visible light region (for example, 400 to 700 nm) deteriorates.

If the content of the blue pigment exceeds 55 mass%, the proportion of the blue pigment having a low i-line transmittance increases, and the i-line transmittance of the entire composition is lowered, thereby deteriorating the roughness and adhesion.

In the resin composition of the present invention, the content of the coloring material in the total solid content in the resin composition may be 40 mass% or more, 50 mass% or more, and further 60 mass% or more. In the present invention, even when the content of the coloring material is increased as described above, the shielding property can be improved and the adhesion property can be improved. The upper limit value is not specifically defined but may be 80% by mass or less.

<Blue Pigment>

The coloring material used in the present invention includes a blue pigment represented by the following general formula (A1) or a general formula (A2) (aluminum phthalocyanine pigment) and represented by the general formula (A1) desirable. The blue pigments may be used singly or in combination of two or more.

In formula (A1)

[Chemical Formula 8]

(In the general formula (A1), X ¹ to X ⁴ each independently represent a substituent, R ^0A represents a hydrogen atom or a monovalent substituent, m 1 to m 4 each independently represent an integer of 0 to 4 when m1 ~ m4 is 2 or more, X ¹ ~ X ⁴ may respectively be the same or different is.)

In general formula (A2)

[Chemical Formula 9]

(In the general formula (A2), each of X ⁵ to X ¹² independently represents a substituent, R ^0B represents a divalent substituent, m 5 to m 12 each independently represent an integer of 0 to 4. m 5 to m 12 Is 2 or more, each of X ⁵ to X ¹² may be the same or different.)

In the general formula (A1), X ¹ to X ⁴ each independently represent a substituent. As the substituent, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio come, aryl Im come, a halogen atom, a nitro group, phthalimide methyl group _{(C 6 H 4 (CO)} 2 N-CH ₂ -) or a sulfamoyl group (H ₂ NSO ₂ -), more preferably an alkyl group or a halogen atom, and more preferably a halogen atom. When X ¹ to X ⁴ have an additional substituent, the substituents may be the same or different. Specific examples thereof include a halogen atom such as fluorine, chlorine, bromine, etc., a characteristic group such as an amino group, a hydroxyl group, , An alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and the like. A plurality of these substituents may be present.

Examples of the alkyl group include straight, branched or cyclic alkyl groups.

Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, Ethylhexyl group. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2- Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-naphthyl group, - dichlorobenzyl group and the like.

Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group and an adamantyl group. Examples of the cyclic alkyl group having a substituent include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Examples of the aryl group having a substituent include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4- dichlorophenyl group, a pentafluorophenyl group, Methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinone group, 2-aminoanthraquinone di And the like.

Examples of the heterocyclic group include pyridyl, pyrazyl, piperidino, pyranyl, morpholino and acridinyl. Examples of the heterocyclic group having a substituent include 3-methylpyridyl group, N-methylpiperidyl group and N-methylpyrrolyl group.

Examples of the alkoxyl group include a straight chain or branched alkoxyl group. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, Dimethyl-3-pentyloxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group. Examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2- Ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like can be given.

Examples of the aryloxy group include a phenoxy group, a naphthoxy group, and an anthryloxy group. Examples of the aryloxy group having a substituent include p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, Phenoxy group and the like.

Examples of the alkylthio group include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio and octadecylthio groups. have. Examples of the alkylthio group having a substituent include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the arylthio groups include phenylthio, 1-naphthylthio, 2-naphthylthio and 9-anthrylthio groups. Examples of the arylthio group having a substituent include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, a 2-hydroxyphenylthio group, etc. have.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The substituent that the phthalimido group and the sulfamoyl group may have is synonymous with the above-mentioned substituent.

The phthalimide methyl group having a substituent means a structure in which a hydrogen atom in a phthalimide methyl group is substituted by a substituent and a sulfamoyl group having a substituent means a structure in which a hydrogen atom in a sulfamoyl group is substituted by a substituent.

m1 to m4 each independently represent an integer of 0 to 4, and 0 or 1 is preferable. When m1 m4 ~ 2 or greater, X ¹ ~ X ⁴ may respectively be the same or different is.

R ^0A represents a hydrogen atom or a monovalent substituent. -OR ^0A is preferred that, due to high polarity, and it represents a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy ^{group, -OP (= O) R 1} R 2, or -O-Si (R ^{₃₎ 3} more preferred, and an aryloxy group, ^{-OP (= O) R 1 R} 2 , or -O-Si (R ³⁾ is more preferably represents a _3, to display the ^{-OP (= O) R 1 R} 2 particularly desirable.

In particular, it is preferable that R ^0A includes a structure having a high planar structure, more preferably an aromatic ring, a heterocyclic ring, etc., and particularly preferably a benzene ring. By such a constitution, the compatibility of the blue pigment with respect to the hydrophobic portion of the alkali-soluble resin is improved, and the aggregation of the blue pigment when the resin composition is used as a film can be further suppressed. As a result, It is considered that the color unevenness becomes smaller and the roughness can be further improved. Further, it is considered that the hydrophobicity of the blue pigment is further improved and the interaction with the undercoating agent is improved, so that the adhesion is further improved.

When -OR ^0A represents an alkoxy group, the carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 15.

When -OR ^0A represents an aryloxy group, the number of carbon atoms of the aryloxy group is preferably from 1 to 30, more preferably from 1 to 15.

When -OR ^0A represents an acyloxy group, the acyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms.

When -OR ^0A represents -OP (= O) R ¹ R ² , R ¹ and R ² may be bonded to each other to form a ring. R ¹ and R ² are each independently preferably a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxyl group or an aryloxy group, more preferably an aryl group or an aryloxy group, and particularly preferably an aryloxy group.

Examples of the alkyl group for R ¹ and R ² include a linear or branched alkyl group and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert- , n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group and the like. Examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group and 2,4-dichlorobenzyl group can be given . A plurality of substituents may be present.

Examples of the aryl group in R ¹ and R ² include a phenyl group, a naphthyl group and an anthryl group. The aryl group having a substituent may be, for example, a p-tolyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4- dichlorophenyl group, a pentafluorophenyl group, Naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and the like can be used. And a phenyl group is preferable.

Examples of the alkoxyl group for R ¹ and R ² include a straight chain or branched alkoxyl group, and specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, -Butoxy group, neopentyloxy group, 2,3-dimethyl-3-pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group. The alkoxyl group having a substituent includes, for example, a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, 2-ethoxyethoxy group, 2-ethoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryloxy group in R ¹ and R ² include a phenoxy group, a naphthooxy group, and an anthryloxy group. The aryloxy group having a substituent is, for example, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, 4-chlorophenoxy group and the like.

When -OR ^0A in the general formula (A1) used in the present invention represents -OP (= O) R ¹ R ² , it is preferable that at least one of R ¹ and R ² is an aryl group or an aryloxy group , It is more preferable that both of R ¹ and R ² are an aryl group or an aryloxy group, more preferably both of R ¹ and R ² are a phenyl group or a phenoxy group, and it is particularly preferable that R ¹ and R ² are both a phenoxy group .

In the general formula (A1), when -OR ^0A represents -O-Si (R ³ ) ₃ , three R ³ may be the same or different. R ³ is preferably an alkyl group having 1 to 18 carbon atoms or an aromatic group having 4 or less rings. The alkyl group for R ³ may be linear, branched or cyclic. It is also possible to have a functional group in the range of 3 or less in total in terms of the number of heteroatoms. For example, a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec- Ethylphenyl group, ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, Methylphenacyl group, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, and a 3- (4-methylphenoxy) And a nitrophenacyl group.

As the aromatic group in R ³ , an aromatic ring may contain a hetero atom, and each aromatic ring may have a functional group in a range of 2 or less hetero atoms. Examples of the substituent include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, A zirconyl group, an o-, m-, and p-cumene group, a mesityl group, a pentalenyl group, a binaphthalene group, , An acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, an acenaphthylene group, An anthraquinolyl group, a phenanthryl group, a phenanthryl group, a triphenylene group, a pyrenyl group, a chrysenene group, a naphthacene group, a pyranthrene group, a pyrenyl group, a perylene group, a tetraphenylene group And a coronenyl group.

The blue pigment represented by the general formula (A1) is preferably represented by the following general formula (A1-1).

In general formula (A1-1)

[Chemical formula 10]

(In the general formula (A1-1), R ^0A represents a hydrogen atom or a monovalent substituent.)

In general formula (A1-1), R ^0A is synonymous with -OR ^0A in general formula (A1), and preferable range is also the same.

In the general formula (A2), each of X ⁵ to X ¹² independently represents a substituent. The substituent is synonymous with X ¹ to X ⁴ in the general formula (A1) described above, and the preferable range is also the same.

In the general formula (A2), R ^0B represents a divalent substituent. -OR ^0B -O- is preferably a group having a high polarity, and -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP (= O) R ¹⁰ -O-, and more preferably -OP (= O) R ¹⁰ -O-. R ⁶ to R ¹⁰ each independently represent preferably a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group, an alkoxyl group or an aryloxy group, more preferably an aryl group or an aryloxy group.

In particular, it is preferable that R ^0B includes a structure having a high planar structure, in the same meaning as -OR ^0A in the general formula (A1), more preferably an aromatic ring, a heterocyclic ring, etc., Is particularly preferable.

The alkyl group for R ⁶ to R ¹⁰ is the same as the alkyl group described for R ¹ and R ² in the general formula (A1).

The aryl group for R ⁶ to R ¹⁰ is the same as the aryl group for R ¹ and R ² in formula (A1).

The alkoxyl group in R ⁶ to R ¹⁰ is the same as the alkoxyl group described for R ¹ and R ² in the general formula (A1).

The aryloxy group for R ⁶ to R ¹⁰ is the same as the aryloxy group for R ¹ and R ² in formula (A1).

Is -OR ^0B -O- in the general formula ^{(A2), -O-SiR 6} R 7 when representing an -O- R ⁶ or R ^7, -OR ^0B -O- is a -O-SiR ⁶ R ⁷ -O -SiR ⁸ R ⁹ R ¹⁰ is the case where R ~ ⁶ R one or more of ^9, or -OR ^0B -O- cases indicating -O- showing an ^{-OP (= O) R 10 -O-} , aryl Or an aryloxy group, more preferably a phenyl group or a phenoxy group, and particularly preferably a phenoxy group.

Specific examples of the blue pigment represented by the above-mentioned formula (A1) or the following formula (A2) are shown below, but the present invention is not limited thereto.

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

<Red pigment>

The red pigment used in the present invention is not particularly limited and known pigments can be used. For example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: , 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 .

The red pigment may be used singly or in combination of two or more.

In the present invention, it is preferable to include a red pigment having a symmetrical structure and a red pigment having an asymmetric structure. By such a constitution, the crystallization of the pigment can be suppressed, and generation of foreign objects in the form of a needle can be effectively suppressed.

When the red pigment contains a compound having a symmetrical structure and a compound having an asymmetric structure, the mass ratio of the compound having a symmetrical structure to the compound having an asymmetric structure is preferably from 99: 1 to 80:20, more preferably from 99: 1 to 85:15 More preferably from 98: 2 to 90: 10.

In particular, it is more preferable to include C.I. Pigment Red 254 and a compound which is not C.I. Pigment Red 254 as a compound represented by the following general formula (4). By employing such a constitution, the crystallization of the pigment can be further suppressed, and generation of needle-like foreign matter can be suppressed more effectively.

In general formula (4)

[Chemical Formula 19]

(In the general formula (4), A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, CF ₃ , or -CON (R ¹ ) R ^{2, wherein} R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group.

In the general formula (4), in the groups A and B, the alkyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl group, and tert-butyl group.

The alkoxyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec- - buttock period.

In R ¹ and R ² , the alkyl group having 1 to 20 carbon atoms may be linear or branched, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- a heptyl group, an octadecyl group, an icosyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a heptyl group, a heptyl group, a heptyl group, a heptyl group, an octyl group, Butyl group, a 2-ethylhexyl group and the like.

Examples of the phenyl group include a phenyl group having a substituent such as a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a nitro group, a carbamoyl group, , A halogen atom is preferable, and a bromine atom is more preferable.

Particularly, it is preferable that A and B represent a hydrogen atom on one side and a halogen atom (preferably a bromine atom) on the other.

Specific examples of the red pigment used in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

In addition, for compounds represented by the general formula (4), see paragraphs 0025 to 0047 of the publication No. 2012-181378, the contents of which are incorporated herein by reference.

<Other color materials>

The coloring material used in the present invention may contain a coloring material other than the red and blue pigments described above. Examples of the coloring material include pigments and dyes. A pigment and a dye may be used in combination.

The pigment is preferably an organic pigment, and the following may be mentioned.

CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12,13,14,15,16,17,18,20,24,31,32,34,35,35,136 , 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,

CI 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 (Above, orange pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, violet pigment)

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

C. I. Pigment Black 1, 7, etc. (above, black pigment)

These organic pigments may be used singly or in various combinations.

In the present invention, in addition to the above-mentioned red pigment and blue pigment, it is preferable to further include yellow and purple coloring materials.

CI Pigment Yellow 139, CI Pigment Yellow 150 and CI Pigment Yellow 185 are preferable, and CI Pigment Yellow 139 is more preferable as the yellow coloring material.

As the violet coloring material, CI Pigment Violet 23 and CI Pigment Violet 37 are preferable, and CI Pigment Violet 23 is more preferable.

The dye is not particularly limited, and known dyes for color filters can be used. The dyes may be used alone, or two or more dyes may be used in combination.

In addition, other pigments and / or dyes may be contained in the range not departing from the gist of the present invention. These other pigments and dyes are preferably not more than 1% by mass of the total colorant.

For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, Patent Document 4808501, US Patent Publication No. 5667920, US Patent Publication No. 505950, US Patent Publication No. 5667920, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid- 51115, JP-A-6-194828, and the like can be used. Examples of the chemical structure include a pyrazole azo group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazoazo group, a pyridazo group, a sacynide, a phenothiazine group, And a pyrazole azo methane-based dye.

As the dye, a dye multimer may be used. Examples of the colorant multimer include compounds described in JP-A-2011-213925, JP-A-2013-041097, and the like.

The total content of the coloring materials other than the above-mentioned red pigment and blue pigment among the total coloring materials of the resin composition of the present invention is preferably 5 to 45 mass%, more preferably 15 to 35 mass%.

<< Dispersant >>

The composition of the present invention may further comprise a dispersant. In particular, it preferably contains a dispersant containing a structural unit represented by any one of the following general formulas (1) and (2).

(25)

(1) and (2), R ¹ to R ⁶ each represent a hydrogen atom or a monovalent organic group, X ¹ and X ² each represent -CO-, -C (= O) L ¹ and L ² each represent a single bond or a divalent organic linking group; A ¹ and A ² each represent a single bond or a divalent organic linking group; M and n each represent an integer of 2 to 8, and p and q represent an integer of 1 to 100, respectively.

In the general formulas (1) and (2), R ¹ to R ⁶ each represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group has a substituent, examples of the substituent include a hydroxyl group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Time and so on.

Specific examples of the preferable alkyl group include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, -Hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group.

In the general formulas (1) and (2), R ¹ , R ² , R ⁴ and R ⁵ are preferably hydrogen atoms and R ³ and R ⁶ are each a hydrogen atom or a methyl group, .

In the general formulas (1) and (2), X ¹ and X ² each represent -CO-, -C (= O) O-, -CONH-, -OC (= O) - or a phenylene group . Among them, -C (= O) O-, -CONH- and phenylene groups are preferable from the viewpoint of adsorption to pigments, and -C (= O) O- is most preferable.

In the general formulas (1) and (2), L ¹ and L ² each represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group having a partial structure including an alkylene group and a hetero atom or a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. The hetero atom in the partial structure containing a hetero atom includes, for example, an oxygen atom, a nitrogen atom and a sulfur atom, and among them, an oxygen atom and a nitrogen atom are preferable.

Specific examples of the preferable alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group and a tetramethylene group.

When the alkylene group has a substituent, examples of the substituent include a hydroxyl group and the like.

Examples of the divalent organic linking group include a partial structure containing a hetero atom or a hetero atom selected from -C (═O) -, -OC (═O) -, -NHC (═O) - at the terminal of the aforementioned alkylene group And is bonded to adjacent oxygen atoms via a partial structure containing the hetero atom or the hetero atom is preferable in view of the adsorption property to the pigment. Here, the adjacent oxygen atom means an oxygen atom bonded to the side chain terminal side with respect to L ¹ in the general formula (1) and L ² in the general formula (2).

In the general formulas (1) and (2), A ¹ and A ² each represent a monovalent organic group. As the monovalent organic group, a hydroxyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group is preferable.

Examples of preferred alkyl groups include linear, branched and cyclic alkyl groups of 1 to 20 carbon atoms.

As the substituent of the substituted alkyl group, a group of a monovalent non-metallic atom group other than hydrogen is used. Preferred examples include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, A carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-alkylcarbamoyloxy group, an N, N-dialkylamino group, An N, N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxide group, an arylsulfoxide group, an acyloxy group, An acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an acyl group, Alkyl group, an aryl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, Lt; RTI ID = 0.0 &gt;N'-N'-dialkyl-N-alkylureido groups, N'-dialkyl-N-alkylureido groups, N'- N'-diaryl-N-alkylureido group, N'-N'-diaryl-N-arylureido group, N'- Alkyl-N'-aryl-N-alkylureido groups, N'-alkyl-N'-aryl-N-arylureido groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, An N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group , An aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an N, N-diarylcarbamoyl group, aryl carbamoyl group, alkyl seolpin group, aryl seolpin group, alkylsulfonyloxy group, an arylsulfonyloxy group, a sulfo group (-SO ₃ H) and its conjugated salts device, Al An N, N-dialysulfanamoyl group, an N, N-diarylsulfinamoyl group, an N, N-dialysulfanamoyl group, an N- Alkylsulfamoyl groups, N-alkylsulfamoyl groups, N-alkylsulfamoyl groups, N-alkylsulfamoyl groups, N, N-dialkylsulfamoyl groups, N-arylsulfamoyl groups, (-PO ₃ (alkyl) ₂ ) group, a phosphonic group (-PO ₃ H ₂ ) and a conjugated salt thereof (hereinafter referred to as a phosphonato group), a dialkylphosphono group (-PO ₃ (aryl) ₂ ), an alkylarylphosphono group (-PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (-PO ₃ H (-OPO ₃ H ₂ ) and its conjugate salt apparatus, a monoarylphosphono group (hereinafter referred to as an alkylphosphonato group), a monoarylphosphono group (-PO ₃ H (aryl)) and a conjugate salt thereof, alkyl phosphono oxy group _{(-OPO 3 (alkyl) 2)} , diaryl phosphono oxy group _{(-OPO 3 (aryl) 2)} , Al Aryl phosphono oxy group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphono oxy group (-OPO ₃ H (alkyl)) and its conjugated salts device, monoaryl phosphono oxy group (-OPO ₃ H ( (hereinafter referred to as arylphosphonate tooxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group and a silyl group.

Specific examples of the alkyl group in these substituents include the above-mentioned alkyl groups, and they may further have a substituent.

Examples of the substituent include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N, N-dialkylamino group, an N, N-diarylamino group, A heteroaryl group, an alkenyl group, an alkynyl group and a silyl group are preferable in terms of dispersion stability.

Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesyl group, a cumene group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, A phenoxyphenyl group, a methylthiophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxyphenylcarbonyl group, a phenoxycarbonyl group, a phenoxyphenyl group, a phenoxyphenyl group, A naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group, a naphthylphenyl group,

As A ¹ and A ² , a straight-chain, branched-chain alkyl group of 3 to 20 carbon atoms and a cyclic alkyl group of 5 to 20 carbon atoms are preferable in terms of dispersion stability and developability , More preferably a linear chain of from 4 to 15 carbon atoms, a branched chain of from 4 to 15 carbon atoms and a cyclic alkyl group of from 6 to 10 carbon atoms, more preferably a linear chain of from 6 to 10 carbon atoms , And branched alkyl groups having 6 to 12 carbon atoms are more preferable.

In the general formulas (1) and (2), m and n each represent an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

In the general formulas (1) and (2), p and q each represent an integer of 1 to 100. p may be different, and q may be different or two or more may be mixed. p and q are preferably from 5 to 60, more preferably from 5 to 40, and still more preferably from 5 to 20, from the viewpoints of dispersion stability and developability.

The copolymer comprising the structural unit represented by any one of the general formulas (1) and (2) preferably contains the repeating unit represented by the general formula (1) from the viewpoint of dispersion stability.

The repeating unit represented by the general formula (1) is more preferably a repeating unit represented by the following general formula (1) -2.

(1) -2

(26)

In the general formula (1) -2, R ¹ to R ³ each represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, Lb represents -C (= O ) -, or NHC (= O) -, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100.

The repeating units represented by the general formula (1), (2), or (1) -2 may be obtained by polymerizing or copolymerizing the monomers represented by the following general formula (i), (ii) , As a repeating unit of a polymer compound.

(27)

Each of R ¹ to R ⁶ represents a hydrogen atom or a monovalent organic group; and X ¹ and X ² each represent -CO-, -O-, L ¹ and L ² each independently represent a single bond or a divalent organic linking group; La represents a single bond or a divalent organic linking group; (= O) - or NHC (= O) -, A ¹ and A ² each represent a monovalent organic group, and m and n are each an integer of 1 to 10, Each represent an integer of 2 to 8, and p and q represent an integer of 1 to 100, respectively.

Specific preferred examples of the monomer represented by the general formula (i), (ii), or (i) -2 are the monomers (XA-1) to (XA-1) described in paragraphs 0081 to 0084 of Japanese Patent Application Laid- XA-23) are exemplified, but the present invention is not limited thereto.

The copolymer comprising the structural unit represented by any one of the general formulas (1) and (2) is obtained by copolymerizing at least one repeating unit selected from the repeating units represented by any one of formulas (1) and (2) And may include only one species or two or more species.

In the copolymer containing the structural unit represented by any one of the general formulas (1) and (2), the content of the repeating unit represented by any one of formulas (1) and (2) However, when the total amount of the repeating units contained in the polymer is 100% by weight, the amount of the repeating units represented by any one of formulas (1) and (2) is preferably 5% by weight or more, more preferably 50% , More preferably from 50% by mass to 80% by mass.

The copolymer comprising the structural unit represented by any one of the general formulas (1) and (2) is preferably a copolymer comprising a monomer having a functional group capable of adsorbing to the pigment and a monomer having a functional group capable of adsorbing to the pigment, (i), (ii) and (i) -2.

Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an acidic group, a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and a monomer having an ionic group. Among them, monomers having an acidic group, monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of adsorption ability to a pigment.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.

The copolymer comprising a structural unit represented by any one of the general formulas (1) and (2) preferably contains a repeating unit derived from a monomer having an acidic group as described above.

The copolymer comprising the structural unit represented by any one of the general formulas (1) and (2) may contain only one type of repeating unit derived from a monomer having an acidic group, do.

A preferred embodiment of the copolymer comprising the structural unit represented by any one of the general formulas (1) and (2) is a copolymer comprising a monomer represented by at least the general formula (i), (ii) A monomer having an acidic group or a monomer having an organic dye structure or a heterocyclic structure, more preferably a monomer copolymerized with at least a monomer represented by the general formula (i) -2 and an acid group.

As other dispersant, it is also preferable to use a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer. In addition, a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate and a copolymer of 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / Acrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

In the present invention, as the dispersant, those shown below are particularly preferable.

(28)

[Chemical Formula 29]

(30)

(31)

(32)

The acid value of the dispersant is preferably 10 to 400 mgKOH / g, more preferably 20 to 200 mgKOH / g, and even more preferably 30 to 150 mgKOH / g. The acid value of the dispersant can be calculated from the average content of acid groups in the dispersant, for example.

The weight average molecular weight (Mw) of the dispersant used in the present invention is preferably 2,000 to 50,000, more preferably 5,000 to 40,000.

The content of the dispersant is preferably 10 to 80 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the total pigment.

The dispersant may be contained in only one kind of the composition of the present invention, or may contain two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

<< Pigment Derivatives >>

The composition of the present invention preferably has a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the pigment is substituted with a basic group. Examples of the pigment for constituting the pigment derivative include quinoline pigments, benzimidazolone pigments, isoindolin pigments, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, Based pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, etc. .

As the pigment derivative, a quinoline-based, benzimidazolone-based, or isoindoline-based pigment derivative is preferable, and a benzimidazolone-based pigment derivative is more preferable.

The basic group of the pigment derivative is preferably an amino group. As such a compound, for example, the following compounds may be mentioned.

(33)

The pigment derivative used in the present invention preferably has a structure having a high planar structure. Examples of structures having a high planar structure include a structure containing an aromatic hydrocarbon group, a structure containing an aromatic heterocyclic group, and the like, and it is particularly preferable to have a triazine skeleton. Since the pigment derivative has a triazine skeleton, the planar structure becomes higher, so that the interaction in the resin composition of the present invention is further improved and the curability is further improved, so that the adhesion can be further improved. In addition, since the pigment derivative has a triazine skeleton, the interaction with the undercoating agent is improved, so that the adhesion can be further improved.

In particular, at least one of the pigment derivatives represented by the following general formulas (I) to (IV) is preferable. Hereinafter, the pigment derivatives represented by the following general formulas (I) to (IV) will be described.

- a pigment derivative represented by the general formula (I)

(34)

(Compound (I) of the, Dye is an n-valent represents an organic dye moiety, X is a single ^{bond, -CONH-Y 2 -, -SO} 2 NH-Y 2 - or ^{_{-CH 2 NHCOCH 2 NH-Y 2}} - ( Y ² represents an alkylene group or an arylene group which may have a substituent, Y ¹ represents -NH- or -O-, and Z represents a hydroxyl group, an alkoxy group, a group represented by the following formula Or a group represented by the formula (I-1) or -NH-X-Dye (X is a synonymous with X in the formula (I)). When n represents an integer of 2 to 4, Or a group represented by the following general formula (I-1), R ¹ and R ² each represent an alkyl group which may have a substituent, and even when R ¹ and R ² are bonded to each other to form a heterocycle containing a nitrogen atom M represents an integer of 1 to 6 and n represents an integer of 1 to 4. When n is 2 or more, a plurality of X, Y ¹ , R ¹ and R ² may be the same or different .)

(35)

(In the general formula (I-1), Y ³ represents -NH- or -O-, R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² are bonded to each other to form a nitrogen And m represents an integer of 1 to 6).

Dye represents an organic dye residue of n. Examples of the organic dye residue include a coloring atom in a pigment, a similar structure thereof, or a partial structure thereof as described above. Specifically, a skeleton having an azo group, a skeleton having a urea structure, a skeleton having an amide structure, Structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring, and Dye is a structure containing at least one of these organic dye moieties Lt; / RTI &gt;

The dye preferably has a pigment precursor structure or a pigment precursor structure and an aromatic ring, or a nitrogen-containing aromatic ring, or an oxygen-containing aromatic ring or a sulfur-containing aromatic ring, and the amino group may be a pigment precursor structure, an aromatic ring, , The oxygen-containing aromatic ring, and the sulfur-containing aromatic ring, either directly or via a linking group. Specific examples include quinolinone residue, benzimidazolone residue, isoindolin residue, diketopyrrolopyrrole residue, azo residue, phthalocyanine residue, anthraquinone residue, quinacridone residue, Based residue, a dioxazine residue, a perylene residue, a perylene residue, a perylene residue, a thioindigo residue, an isoindolin residue, an isoindolin residue, a quinophthalone residue, a tral residue or a metal complex residue.

Specific examples of the organic dye residue represented by Dye include a copper phthalocyanine residue, the following organic dye residue, and the like. In the formulas, * represents a bonding site with X in formula (I).

(36)

(37)

(38)

[Chemical Formula 39]

Among them, a monoazo dye having a benzimidazolone skeleton is preferable.

X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² -, with a single bond being preferred.

Y ² represents an alkylene group or an arylene group which may have a substituent. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. The alkylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples thereof include a phenylene group, a naphthylene group, and an anthraceneylene group.

The alkylene group and the arylene group may have a substituent, and examples of the substituent include the groups described in the above substituent.

Y ¹ represents -NH- or -O-, and -NH- is preferable.

R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a heterocycle containing a nitrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl. The alkyl group may have a substituent, and examples of the substituent include the groups described in the section of the substituent.

It is preferable that R ¹ and R ² represent an alkyl group which may have the same substituent.

m represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 3.

n represents an integer of 1 to 4, preferably 1 to 3, more preferably 1 or 2.

Z represents a hydroxyl group, an alkoxy group, a group represented by the following general formula (I-1) or -NH-X-Dye (X is a synonym of X in the general formula (I)) when n represents 1, , and when n represents an integer of 2 to 4, each represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (I-1).

When n represents 1, Z is preferably a group represented by the following formula (I-1) or -NH-X-Q, more preferably a group represented by the following formula (I-1).

When n represents an integer of 2 to 4, it is preferable that Z is a group represented by the following general formula (I-1).

In general formula (I-1)

(40)

(In the general formula (I-1), Y ³ represents -NH- or -O-, R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² are bonded to each other to form a nitrogen And m represents an integer of 1 to 6).

Y ³ represents -NH- or -O-, and -NH- is preferable. Y ³ preferably represents the same group as Y ¹ in the general formula (I).

Each of R ¹ and R ² in the general formula (I-1) represents an alkyl group which may have a substituent and is synonymous with R ¹ and R ² in the general formula (I), and the preferable range is also the same. It is preferable that R ¹ and R ² in the general formula (I-1) represent an alkyl group which may have the same substituent. Further, in the formula ^(I-1) R 1 and R ² it is, preferably represents an alkyl group which may have the same substituent as R ¹ and R ² in the formula (I).

m represents an integer of 1 to 6, preferably 1 to 4, and more preferably 1 to 3. m is preferably the same integer as m in the general formula (I).

Specific examples of the pigment derivative used in the present invention are shown below, but the present invention is not limited thereto.

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

- a pigment derivative represented by the general formula (II)

In general formula (II)

(58)

(In the general formula (II), Dye represents a quinophthalone residue which may have a substituent and X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR ' COCH ₂ NR'-, or -NR'CO-, X ² represents an arylene group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent these _{groups, -NR'-, -O-, -SO 2 -} .. or may be cross-coupled to the or a divalent connecting group selected from -CO- X ³ shows a -NR'- or -O- R 'Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent. and B are, respectively, a group represented by the general formula (II-1) below, the group represented by the general formula (II-2), -O- ( CH 2) n -R 8, -OR 9, -NR 10 R ^11, -Cl, -F and -X ³ -X ² -X ¹ -Dye robu Represents a group selected, R ⁸ is also optionally substituted represents a nitrogen heterocyclic residue, R ^9, R ^10, R ¹¹ are each, a hydrogen atom, an alkyl group having a carbon number of 1 to 20 which may have a substituent, the substituent An optionally substituted alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent and n is an integer of 0 to 20. Either A or B is preferably an alkenyl group having 2 to 20 carbon atoms, -1), a group represented by the following formula (II-2), -O- (CH ₂ ) nR ⁸ , -OR ⁹ or -NR ¹⁰ R ¹¹ , and t represents an integer of 1 to 3. When t is 2 or more, a plurality of X ¹ , X ² , X ³ , A and B may be the same or different.)

[Chemical Formula 59]

(In the general formula (II-1), Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, Or an arylene group having 6 to 20 carbon atoms, which may have a substituent, and these groups are a divalent linking group selected from -NR'-, -O-, -SO ₂ -, and -CO- R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms, which may have a substituent, R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent and R ¹ and R ² are And is optionally substituted by a substituent including an additional nitrogen atom, an oxygen atom or a sulfur atom It is to form a heterocyclic structure which may.

In formula (II-2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-G-SO 2 -, -NR'-} G-SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO ₂ represents NR'-, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R ' R "each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, Having 6 to 20 carbon atoms R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent.

In the general formula (II), Dye represents a quinophthalone residue which may have a substituent. The quinophthalone residue is specifically represented by the following general formula (II-3).

(II-3)

(60)

(In the general formula (II-3), D and E are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded with D and E, A hydroxyl group, an alkoxyl group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester having 1 to 20 carbon atoms or an amide having 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, -NR'R " , And a nitro group. In the formulas, R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkene having 2 to 20 carbon atoms which may have a substituent P represents an integer of 0 to 4, and q represents an integer calculated by 4-p. * Represents an integer of from 0 to 4 in the formula (II) ¹ &lt; / RTI &gt;

D and E are each a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring bonded with D and E, an aromatic ring or heterocyclic group which may have a substituent, A carboxyl group or a salt thereof, an ester of 1 to 20 carbon atoms, an amide of 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, a sulfamoyl group, or an alkoxyl group of 1 to 20 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group) R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 2 to 20 carbon atoms which may have a substituent Or an aryl group having 6 to 20 carbon atoms which may have a substituent.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

Examples of the aromatic ring or heterocyclic ring include a phenyl group, a naphthyl group, a thiophene ring group, a pyridine ring group and a pyrrole ring group.

The aromatic ring or heterocyclic group represented by D and E, the alkyl group having 1 to 20 carbon atoms represented by R 'and R ", the alkenyl group having 2 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms may have a substituent, Include the groups described in the section of the above substituents.

Among them, D and E are preferably a hydrogen atom or a halogen atom.

p represents an integer of 0 to 4, more preferably an integer of 1 to 4, and further preferably 4. q represents an integer calculated by 4-p, specifically, an integer of 0 to 3 is preferable, an integer of 2 to 3 is more preferable, and a value of 4 is more preferable.

The binding site with X ¹ in the general formula (II) is not particularly limited, but it is preferable that the 5th or 8th position of the quinolin skeleton in the quinophthalone residue is a binding site, and the 8th position is a binding site desirable.

In the general formula (II), X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR'COCH ₂ NR'-, or -NR'CO-, -NR'SO ₂ - is preferred. When t is 2 or more, a plurality of X ¹ may be the same or different.

R 'in X ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms An aryl group, and a hydrogen atom are preferable.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group.

These may have a substituent, and examples of the substituent include the groups described in the above substituent.

X ² in the general formula (II) represents an arylene group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent, , -O-, -SO ₂ - or -CO- (R 'is the same as R' in X ¹ above, and the preferred range is also the same). When t is 2 or more, a plurality of X ² may be the same or different.

The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 10 carbon atoms, and specific examples thereof include a phenylene group, a naphthylene group and an anthraceneylene group.

The complex aromatic ring having 4 to 20 carbon atoms is preferably a heterocyclic aromatic ring having 4 to 10 carbon atoms, and specific examples thereof include a thiophene ring group, a pyridine ring group and a pyrrole ring group.

These may have a substituent, and examples of the substituent include the groups described in the above substituent.

X ³ represents -NR'- or -O-, and -NR'- is preferable. When t is 2 or more, a plurality of X ³ may be the same or different. R 'is synonymous with R' above, and the preferred range is also the same.

A and B each represent a group represented by the following formula (II-1) or the following formula (II-2), -O- (CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , represents a group selected from -Cl, -F, or -X ³ -X ² -X ¹ -Dye, either one of A and B is a group represented by the general formula (II-1) or (II-2), - O- (CH ₂ ) n R ⁸ , -OR ⁹ , or -NR ¹⁰ R ¹¹ . A and B are preferably groups represented by the following general formula (II-1) or the following general formula (II-2) -2), and more preferably A and B are the same group.

R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and specific examples thereof include a pyrrole ring residue and a pyridine ring residue.

R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An aryl group having 6 to 20 carbon atoms. R ⁹ , R ¹⁰ and R ¹¹ are the same as the above R ', and preferable ranges are also the same.

In general formula (II-1)

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(Wherein Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, an alkylene group having 2 to 20 carbon atoms which may have a substituent, Or an arylene group having 6 to 20 carbon atoms, which may have a substituent, and these groups are a divalent linking group selected from -NR'-, -O-, -SO ₂ -, and -CO- R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms, which may have a substituent, represents a 20 aryl. R ^1, R ² are each an alkyl group having the carbon number of which may have a substituent of 1 to 20, or the number of carbon atoms which may have a substituent 2-20 is shown an alkenyl group (R ¹ and R ² is And is substituted with an additional nitrogen atom, an oxygen atom or a sulfur atom Or may form a heterocyclic structure which may exist).

Y ¹ represents -NR'- or -O-, and -NR'- is preferable. R 'is synonymous with R' above, and the preferred range is also the same.

Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms, which may have a substituent, _{groups, -NR'-, -O-, -SO 2 -} , or may be coupled together by a divalent connecting group selected from -CO- (R a 'is the R' and consent, the same is also the preferred range).

The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. The alkylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

The alkenylene group having 2 to 20 carbon atoms is preferably an alkenylene group having 1 to 10 carbon atoms, more preferably an alkenylene group having 1 to 6 carbon atoms, and still more preferably an alkenylene group having 1 to 3 carbon atoms. Specific examples include a vinylene group, a propyleneylene group, a butyleneylene group, a pentyleneylene group and a hexyleneylene group. The alkenylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples thereof include a phenylene group, a naphthylene group, and an anthraceneylene group. The arylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent (R ¹ and R ² are combined to form an additional nitrogen And may form a heterocyclic structure which may be substituted including an atom, an oxygen atom or a sulfur atom).

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

These groups may have a substituent, and examples of the substituent include the groups described in the above section of the substituent. It is preferable that R ¹ and R ² represent the same group.

(II-2)

(62)

(In the general formula (II-2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " -G-SO ₂ -, -NR'-G-SO ₂ NR "-, -OG-CO-, -OG-CONR'-, -OG-SO ₂ - or -OG-SO ₂ NR'- , G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms and may have a substituent, and R ' And R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, The number of carbon atoms which may be present is 6 to 20 Aryl group, R ⁷ is the number of carbon atoms that the number of carbon atoms which may have a substituent may have 1 to 20 in the alkyl group, or an optionally substituted 2-20 which represents the alkenyl group.)

Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR "-, -NR'-G-SO ₂ -, -NR -G-SO ₂ NR "-, -OG-CO-, -OG-CONR'-, -OG-SO ₂ - or -OG-SO ₂ NR'-, with single bonds being preferred.

R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms R 'and R "are the same as R' in formula (II-1), and the preferred ranges are also the same.

G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms, which may have a substituent. G agrees with Y ² in the general formula (II-1), and the preferable range thereof is also the same.

R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, And an aryl group having 6 to 20 carbon atoms. R ³ , R ⁴ , R ⁵ , and R ⁶ are synonymous with R 'in formula (II-1), and the preferred ranges are also the same.

R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. R ⁷ is synonymous with R ¹ in formula (II-1), and the preferable range thereof is also the same.

In the general formula (II), t represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Specific examples of the pigment derivative represented by the general formula (II) used in the present invention are shown below, but the present invention is not limited thereto.

(63)

&Lt; EMI ID =

(65)

(66)

(67)

(68)

(69)

In addition, specific examples of the pigment derivative used in the present invention are shown below, but the present invention is not limited thereto.

(70)

The content of the pigment derivative in the present invention is preferably 0 to 30 parts by mass, more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total pigment.

The pigment derivative may be contained in only one kind or two or more kinds in the composition of the present invention. When two or more kinds are included, the total amount is preferably in the above range.

<Alkali-soluble resin>

The resin composition of the present invention further contains an alkali-soluble resin. By such a constitution, it can interact with the blue pigment represented by the above-mentioned general formula (A1) or (A2) to improve the roughness and adhesion.

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, which are soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution And a (meth) acrylic acid group is particularly preferable. These acid groups may be only one kind, or two or more kinds.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, monomers having an epoxy group such as glycidyl (meth) acrylate, And monomers having isocyanate groups such as isocyanate ethyl (meth) acrylate. The monomers for introducing these acid groups may be one kind or two or more kinds. When an acid group is introduced into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization (hereinafter sometimes referred to as "monomer for introducing an acid group & To be polymerized.

Further, in the case of introducing an acid group into a monomer component capable of imparting an acid group after polymerization, a treatment for imparting an acid group as described later, for example, is required after polymerization.

For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, have.

As the linear organic polymer used as an alkali-soluble resin, a polymer having a carboxylic acid in its side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, Maleic anhydride copolymers, maleic acid copolymers and novolac resins, and acidic cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to the polymer having a hydroxyl group. Particularly, a copolymer of (meth) acrylic acid and other monomers copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Examples of the 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 , And cyclohexyl (meth) acrylate. Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like as the N-substituted maleimide monomer described in JP-A No. 10-300922 , N-phenylmaleimide, N-cyclohexylmaleimide and the like. In addition, these monomers copolymerizable with (meth) acrylic acid may be either one type alone or two or more types.

As the alkali-soluble resin, it is also preferable that the alkali-soluble resin includes a polymer (a) obtained by polymerizing a monomer component essentially containing a compound represented by the following formula (ED) (hereinafter may be referred to as "ether dimer"

(71)

In the general 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.

As a result, the resin composition of the present invention can form a cured coating film having excellent heat resistance as well as excellent transparency. Of the above-mentioned ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ₁ and R ₂ is not particularly limited and includes, for example, methyl, ethyl, n- Straight or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl and 2-ethylhexyl; An aryl group such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like; An alkyl group substituted by alkoxy such as 1-methoxyethyl or 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Of these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a substituent of a primary or secondary carbon which is difficult to desorb by heat are preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include dimethyl-2,2 '- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2' - [oxybis (Isopropyl) -2,2 '- [oxybis (methylene)] -2-propenoate, di (n-propyl) )] Bis-2-propenoate, di (n-butyl) -2,2 '- [oxybis (methylene)] bis- Di (tert-butyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (tert- Di (stearyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di (lauryl) -2 Bis (2-ethylhexyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di - methoxyethyl) -2,2 '- [oxy Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, dibenzyl- Bis (2-propenyl) bis [2-propenyl] biphenyl-2, 2 '- [oxybis (methylene)] bis-2-propenoate, dicyclohexyl- (Methylene)] bis-2-propenoate, di (tert-butylcyclohexyl) -2,2 '- [oxybis Di (tricyclodecanyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate, di Bis (2-propenyl) -2,2'- [oxybis (methylene)] bis-2-propenoate, diadamanthyl- Di (2-methyl-2-adamantyl) -2,2 '- [oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2'- [oxybis (methylene)] bis-2-propenoate, diethyl-2,2 '- [oxybis (methylene)] bis- Propylene glycol dicyclohexyl-2,2 '- [oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2' - [oxybis (methylene)] bis-2-propenoate. These ether dimers may be either one kind or two or more kinds. The structure derived from the compound represented by the formula (ED) may be copolymerized with another monomer.

In addition to the above, it is preferable to include the ethylenically unsaturated monomer (a) represented by the following formula (X) as a monomer copolymerized with an alkali-soluble resin.

The formula (X)

(72)

(In the formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring, Alkyl group, and n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group of R ² is preferably 2 to 3. The alkyl group of R ³ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (isopropyl) group.

Examples of the ethylenically unsaturated monomer (a) include ethylene oxide (EO) modified (meth) acrylate of phenol, EO or propylene oxide (PO) modified (meth) acrylate of paracylphenol, EO- (Meth) acrylate of nonylphenol, and the like.

In order to improve the crosslinking efficiency of the resin composition of the present invention, an alkali-soluble resin having a polymerizable group may be used. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include DYNAL NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), Viscot R-264, 106 (all manufactured by Osaka Yuki Kagaku Kogyo K.K.), Cyclomer P series, Flackcell CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel Chemical Industries, Ltd.) . As the alkali-soluble resin containing these polymerizable groups, it is preferable that an isocyanate group and an OH group are previously reacted to leave an unreacted isocyanate group, and a compound containing a (meth) acryloyl group and a Acrylic resin containing an unsaturated group obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in a molecule, Acid pendant epoxy acrylate resin, a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond, an acrylic resin containing an OH group, an isocyanate and a polymerizable group , A resin obtained by reacting a compound having an epoxy group-containing compound 207 and JP-A No. 2003-335814, a resin obtained by basic treatment of a resin having on its side chain an ester group having a leaving group such as a halogen atom or a sulfonate group on?

As the alkali-soluble resin, a multi-component copolymer composed of a (meth) acrylic acid benzyl / (meth) acrylic acid copolymer and a (meth) benzyl acrylate / (meth) acrylic acid / other monomer is suitable. (Meth) acrylic acid benzylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate copolymer disclosed in Japanese Patent Application Laid-open No. 7-140654 (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / Methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / meta Acrylic acid copolymers, and particularly preferable examples thereof include copolymers of benzyl methacrylate / methacrylic acid and the like.

As the alkali-soluble resin, reference may be made to Japanese Patent Laid-Open Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of US Patent Application Publication No. 2012/0235099) Which is incorporated herein by reference.

In addition, the copolymer (B) described in paragraphs Nos. 0029 to 0063 described in JP-A-2012-32767 and the alkali-soluble resin used in the examples, and the copolymer described in paragraphs 0088 to 0098 of JP-A- The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and the binder resin used in the examples of Japanese Laid-Open Patent Publication No. 2013-024934 To 0143 and binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, and Japanese Laid-Open Patent Publication No. 2012-032770, paragraph No. 0030 It is preferable to use the binder resin described in [0072]. The contents of which are incorporated herein by reference. More specifically, the following resins are preferable. The ratio in the following repeating units is a molar ratio.

(73)

&Lt; EMI ID =

(75)

[Formula 76]

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g, and particularly preferably 50 to 150 mgKOH / g.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 5,000 to 25,000.

The content of the alkali-soluble resin in the resin composition is preferably 5 to 35 mass%, more preferably 5 to 25 mass%, and particularly preferably 5 to 15 mass%, based on the total solid content of the resin composition .

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

<Polymerizable compound>

The resin composition of the present invention may contain a polymerizable compound. As the polymerizable compound, a known polymerizable compound capable of crosslinking by radicals, acids and heat can be used. For example, a polymerizable compound containing an ethylenic unsaturated bond, a cyclic ether (epoxy, oxetane) . The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity. Of these, polyfunctional polymerizable compounds having four or more functionalities are preferable, and polyfunctional polymerizable compounds having five or more functionalities are more preferable.

Such a group of compounds is well known in the art, and the present invention can be used without any particular limitation. These may be, for example, monomers, prepolymers, i.e., chemical forms such as dimers, trimer and oligomers or mixtures thereof and their oligomers. The polymerizable compounds in the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like), esters thereof, amides, And esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, Unsaturated carboxylic acid esters or amides having a clearing substituent such as alcohols, amines and thiols are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As specific compounds of these compounds, compounds described in paragraphs [0095] to [0108] of JP-A No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propol paint (acryloyloxypropyl) ether (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane, and (meth) acrylate, Japanese Examined Patent Publication 48 (Meth) acrylates described in JP-A-41708, JP-A-50-6034, JP-A-51-37193, Polyester acrylates described in JP-B-48-64183, JP-A-49-43191, JP-A-52-30490, epoxies which are reaction products of epoxy resins and (meth) acrylic acid And polyfunctional acrylates and methacrylates such as acrylates, and mixtures thereof.

(Meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether such as glycidyl (meth) acrylate and a compound having an ethylenic unsaturated group.

As other preferable polymerizable compounds, those having a fluorene ring and having an ethylenic unsaturated group as a bifunctional group, such as those described in JP-A-2010-160418, JP-A-2010-129825 and JP-B-4364216, Or more, and a carboxy resin can also be used.

As the compound having a boiling point of 100 占 폚 or more at normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization, compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

In addition to the above, radically polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Formula 77]

(78)

In the above general formula, n is 0 to 14, and m is 1 to 8. R and T present in plural in one molecule may be the same or different.

At least one of the plural Rs present in each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) is -OC (= O) CH = CH ₂ or -OC ) C (CH ₃₎ represents a group represented by = CH _2.

Specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A No. 2007-269779 Can be used.

Further, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol represented by the general formulas (1) and (2) together with the specific examples thereof and then (meth) acrylated The compound may also be used as a polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (commercially available products such as KAYARAD D-320; Nippon Kayaku Co., (KAYARAD D-310 manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) Ltd.), and a structure in which these (meth) acryloyl groups are interposed between ethylene glycol and propylene glycol moieties. These oligomer types can also be used.

As the polymerizable compound, a polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, the ethylenic compound can be used as it is. If necessary, the hydroxyl group of the above-mentioned ethylenic compound is reacted with a nonaromatic carboxylic acid anhydride, . In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group . Especially preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd., M-510 and M-520.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are degraded. If the acid value is too high, the production and handling become difficult and the photopolymerization performance deteriorates, resulting in poor curability such as surface smoothness of the pixel. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.

It is also preferable that the polymerizable compound contains a polyfunctional monomer having a caprolactone structure.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, Caprolactone obtained by esterifying a polyhydric alcohol such as propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylol melamine and the like with (meth) acrylic acid and epsilon -caprolactone, And lactone-modified polyfunctional (meth) acrylates. Among them, a polyfunctional monomer having a caprolactone structure represented by the following general formula (Z-1) is preferable.

(79)

In the general formula (Z-1), all six R's are groups represented by the following general formula (Z-2), or one to five of the six R's are groups represented by the general formula (Z-2) And the remainder is a group represented by the following general formula (Z-3).

(80)

In the general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[Formula 81]

In the general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

Such a polyfunctional monomer having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., and DPCA-20 (m = 1 in the above formulas (1) (2) = 2, R ¹ are both a hydrogen atom), the group represented by, DPCA-30 (the same formula, m = 1, equation (2) of the group represented by = 3, R ¹ is hydrogen atom DPCA-120 (the same formula, m = 1, the number of groups represented by formula (2) = 6 and R ¹ are all hydrogen atoms), DPCA-120 The number of groups represented by formula (2) = 6, and R ¹ are all hydrogen atoms).

In the present invention, the polyfunctional monomers having a caprolactone structure may be used alone or in combination of two or more.

It is also preferable that the specific monomer in the present invention is at least one member selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

(82)

E in the general formulas (Z-4) and (Z-5) each independently represents - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) , Y represents independently an integer of 0 to 10, and X represents, independently of each other, an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the acryloyl group and the methacryloyl group is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is 0 to 40 It is an integer. Provided that when the sum of each m is 0, any one of X is a carboxyl group.

In the general formula (Z-5), the sum of the acryloyl group and the methacryloyl group is 5 or 6, each n independently represents an integer of 0 to 10, and the total of n is 0 to 60 It is an integer. Provided that when the sum of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The sum of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable.

In the general formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

The - ((CH ₂ ) yCH ₂ O) - or - ((CH ₂ ) yCH (CH ₃ ) O) - in the general formula (Z-4) or the general formula A form in which the terminal is bonded to X is preferable.

The compounds represented by the above general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the general formula (Z-5), all of the six X's are preferably acryloyl groups.

The total content of the compound represented by the formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to ring opening skeleton And (meth) acryloyl groups are introduced into the terminal hydroxyl groups of the ring-opening skeleton by reaction with, for example, (meth) acryloyl chloride. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.

(A), (b), (f), (f), (f) and (f) , (e) and (f) are preferable.

(83)

(84)

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 And the ethylene oxide described in JP-A-62-39418, JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, Also suitable are urethane compounds having a skeleton. Examples of the polymerizable compound include compounds having an amino or sulfide structure in the molecule, such as those described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238 By using the polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyowa Chemical Industry Co., Ltd.).

JER-827, JER-834, JER-1001, JER-1002, and JER-1003 as the bisphenol A type epoxy resin having an epoxy group as the cyclic ether (epoxy, oxetane) (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.) as the resin, and JER-806, JER-4007, JER-4005, JER- JER-152, JER-157S70, JER-157S65 (above, Japan Epoxy Resin Co., Ltd.) as the phenol novolak type epoxy resin, (EPICLON N-660, EPICLON N-665, EPICLON N-770, and EPICLON N-775 manufactured by DIC Corporation) EPICLON N-670, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (Manufactured by Nippon Kayaku Co., Ltd.), and aliphatic epoxy resins such as ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Side 2083, Celloxide 2085, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of EHPE-3150 (2,2-bis (hydroxymethyl) PB 3600 and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX- NC-2000, NC-3000, NC-7300, XD (manufactured by Nippon Shokubai Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP- -1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable when a pattern is formed by a dry etching method.

The details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the like can be arbitrarily set in accordance with the final performance design of the resin composition. For example, from the viewpoint of sensitivity, a structure having a large number of unsaturated groups per molecule is preferable, and in most cases, a bifunctionality or more is preferable. From the viewpoint of enhancing the strength of the cured film formed by the resin composition, it is preferable that the trifunctional or more functional group and the number of other functional groups and other polymerizable groups (e.g., acrylate ester, methacrylate ester, styrene- ) Can be used in combination to control both the sensitivity and the strength. In addition, it is preferable to use a polymerizable compound having three or more functional groups and having different ethylene oxide chain lengths in combination from the viewpoint that the developability of the resin composition can be controlled and excellent pattern forming ability can be obtained.

The compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersant, an alkali-soluble resin, and the like) contained in the resin composition are also important factors for selection and use of the polymerizable compound. For example, The compatibility may be improved by the use of a low-purity compound or by the combination of two or more species. In addition, a specific structure may be selected from the viewpoint of improving adhesion with a hard surface such as a support.

When the polymerizable compound is compounded in the resin composition of the present invention, the content of the polymerizable compound is preferably 5 to 35 mass%, more preferably 5 to 25 mass%, and more preferably 5 to 15 mass% with respect to the total solid content in the resin composition % By mass is particularly preferable.

The composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more kinds are included, the total amount is preferably in the above range.

<Polymerization Initiator>

The resin composition of the present invention preferably contains a polymerization initiator (preferably a photopolymerization initiator) from the viewpoint of further improving the sensitivity.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the monomer.

It is also preferable that the photopolymerization initiator contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, An oxime compound such as an imidazole or an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoximeether, an aminoacetophenone compound, or a hydroxyacetophenone.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

More preferably, a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triarylimidazole dimer, a triarylimidazole compound, a benzimidazole compound , An onium compound, a benzophenone compound, and an acetophenone compound, and is a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triarylimidazole compound, a benzophenone compound, a triarylimidazole compound, And at least one compound selected from the group consisting of a thiol compound and a thiol compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.

Specifically, as the trihalomethyltriazine compound, the following compounds are exemplified. Ph is a phenyl group.

(85)

As the triarylimidazole compound and the benzimidazole compound, the following compounds are exemplified.

&Lt; EMI ID =

As the trihalomethyltriazine compound, a commercially available product may also be used, and for example, TAZ-107 (Midori Kagaku) may be used.

Particularly, when the resin composition of the present invention is used in the production of a color filter provided in a solid-state image pickup device, it is necessary to form a fine pattern in a sharp shape, and therefore it is important that the resin composition is cured and developed without residue on the unexposed portion Do. From this viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, although stepper exposure is used for curing exposure, this exposure device may be damaged by halogen, and the addition amount of the polymerization initiator also needs to be suppressed to a low level, Taking this into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator (D) for forming a fine pattern such as a solid-state image sensor.

As the halogenated hydrocarbon compound having a triazine skeleton, for example, see Wakabayashi et al., Bull. Chem. Soc. Japanese Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, the compound described in JP-A-3337024 by FC Schaefer et al. Org. Chem .; 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds disclosed in JP-A-5-34920, A compound described in Japanese Patent Publication No. 4212976, particularly a compound described in Japanese Patent Laid-Open Publication No. 2013-077009, paragraph No. 0075, and the like.

As other photopolymerization initiators other than the above, acridine derivatives are exemplified. Specific examples thereof include compounds described in paragraph [0076] of Japanese Laid-Open Patent Publication No. 2013-077009, and the contents thereof are incorporated herein by reference.

Examples of the ketone compound include compounds described in Japanese Patent Application Laid-Open No. 2013-077009, paragraph number 0077, and the contents thereof are herein incorporated by reference.

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

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm may be used. As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used.

Examples of the oxime compounds such as oxime derivatives suitably used as the photopolymerization initiator in the present invention include 3-benzoyloxyiminobutain-2-one, 3-acetoxyiminobutain-2- 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane 1-one, 3- (4-toluenesulfonyloxy) iminobutain-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

As oxime compounds, see J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

As commercial products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used. Commercially available products such as TRONLY TR-PBG-304, TRONLY TR-PBG-309 and TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) have.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Laid-Open Patent Publication No. 2010-15025 and US Patent Publication No. 2009-292039 in which nitro groups are introduced, ketoxime compounds described in WO 2009-131189, triazine skeleton and oxime skeleton in the same molecule A compound described in U.S. Patent Publication No. 7556910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.

Preferably, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can be suitably used. Of the cyclic oxime compounds, cyclic oxime compounds which are condensed in the carbazol dye described in JP-A-2010-32985 and JP-A-2010-185072 are particularly preferable from the viewpoint of high light absorbability and high sensitivity.

The compound described in Japanese Unexamined Patent Application Publication No. 2009-242469 having an unsaturated bond at a specific site of an oxime compound can also be suitably used because high sensitivity can be achieved by regenerating active radicals from polymerization inert radicals.

Particularly preferred are oxime compounds having a specific substituent group as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

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

[Chemical Formula 87]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent nonmetal atomic 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. These groups may have one or more substituents. The substituent described above may be 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 is preferably an alkyl group having from 1 to 30 carbon atoms and specific examples thereof include 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, , a sec-butyl group, a tert-butyl group, a 1-ethylpentyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group, a 2-ethylhexyl group, a phenacyl group, , 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group , 3-trifluoromethylphenacyl group, and 3-nitrophenacyl group.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, Naphthacenylene group, a 5-naphthacenylene group, a 1-indenyl group, a 2-azulenyl group, a 9-fluorenyl group, a terphenyl group, a quaterphenyl group, an o- tolyl group, Dienes, m-cumene dienes and p-cumene dienes, mesityl groups, pentalene dienes, binaphthalenylene dienes, terenaphthalene dienes, quaternaphthalenylene dienes, heptalenylene dienes, biphenylene dienes, indacene dienes, A phenanthryl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, a pyrenyl group, A naphthacene group, a phenanthrene group, a perylene group, a pentaphenyl group, a pentacene group, a tetraphenylene group, Examples of the alkylene group include a methylene group, a dihexyl group, a hexaphenyl group, a hexacene group, a rubisene group, a coronenyl group, a trinaphthylene group, a heptaphenyl group, a heptacene group, a pyranthrene group and an ovalvenyl group.

As the acyl group, an acyl group having 2 to 20 carbon atoms is preferable, and specific examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, a 1-naphthoyl group, A 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2-methylbenzoyl group, a 2- Trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-fluorobenzoyl group, 4-chlorobenzoyl group, A cyanobenzoyl group and a 4-methoxybenzoyl group.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group , A decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, a 4-phenylsulfanylphenyloxycarbonyl group, A 4-dimethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, a 2-methylphenyloxycarbonyl group, a 2-methoxyphenyloxycarbonyl group, a 2-butoxyphenyloxy 3-chlorophenyloxycarbonyl, 3-chlorophenyloxycarbonyl, 3-trifluoromethylphenyloxycarbonyl, 3-cyanophenyloxycarbonyl, 3-nitrophenyloxycarbonyl, 4-fluorophenyloxycarbonyl, 4- Cyanophenyloxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specific examples thereof include a cyano group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thianthrenyl group, a furyl group, a pyranyl group, an isobenzofuranyl group, A pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizine group, an isoindolyl group, a 3H-indolyl group, a pyrazolyl group, a pyrazolyl group, , Indolyl group, 1H-indazolyl group, purine group, 4H-quinolyl group, isoquinolyl group, quinolyl group, phthalazine group, naphthyridyl group, quinoxalinyl group, quinazolinyl group, A pyranyl group, a phenanthryl group, a phenarazyl group, an isothiazole group, an imidazolyl group, an imidazolyl group, an imidazolyl group, a pyrimidinyl group, A diazonium, a phenothiazine diazonium, an isoxazoline diazonium, a furazanil diazonium, a phenoxazoi diazonium, an isochroman diazonium, , Pyrrolidinyl, pyrrolinyl, imidazolinyl, imidazolinyl, pyrazolidinyl, pyrazolyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidine, A diazo group, a morpholine diazo group, and a thioxantholyl group.

Specific examples of the alkylthiocarbonyl group include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, A trifluoromethylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, a 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2 3-chlorophenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-chlorophenylthiocarbonyl group, 4-chlorophenylthiocarbonyl group, -Fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group and a 4-methoxyphenylthiocarbonyl group.

In the general formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent.

Among them, particularly preferred is the structure shown below.

Y, X, and n in the following structures are synonymous with Y, X, and n in the general formula (OX-2) to be described later, and preferred examples are also the same.

[Formula 88]

Examples of the divalent organic group represented by A in formula (OX-1) include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent.

Among them, A in the formula (OX-1) is preferably an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group An alkylene group substituted with an alkenyl group (e.g., a vinyl group or an allyl group), an aryl group (e.g., a phenyl group, a p-tolyl group, a xylyl group, a cumene group, Anthryl group, phenanthryl group, styryl group) is preferable.

In the formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. The substituent may be the same as the substituent introduced into the substituted aryl group as a specific example of the aryl group which may have a substituent.

Among them, a substituted or unsubstituted phenyl group is preferable in that the sensitivity is increased and coloration due to heating over time is suppressed.

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

(89)

The oxime compound is preferably a compound represented by the following general formula (OX-2).

(90)

In the formula (OX-2), each of R and X independently represents a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents an integer of 0 to 5 Lt; / RTI &gt; R, A and Ar in formula (OX-2) are synonymous with R, A and Ar in formula (OX-1), and preferred examples are also the same.

Examples of the monovalent substituent represented by X in formula (OX-2) include an alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, amino group, heterocyclic group, . These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified. The substituent described above may be substituted with another substituent.

Among them, an alkyl group is preferable as X in the general formula (OX-2) in view of solubility in solvents and improvement of absorption efficiency in a long wavelength region.

In the formula (OX-2), n represents an integer of 0 to 5, preferably an integer of 0 to 2.

Examples of the divalent organic group represented by Y in the general formula (OX-2) include the following structures. In the groups shown below, "*" represents a bonding position of Y and adjacent carbon atoms in formula (OX-2).

[Formula 91]

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

&Lt; EMI ID =

The oxime compound is preferably a compound represented by the following general formula (OX-3) or (OX-4).

&Lt; EMI ID =

In the formula (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, It is an integer.

R, X, A, Ar and n in the general formula (OX-3) or (OX-4) Agreement, and the preferred example is the same.

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

(94)

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

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

Specific examples of the molar extinction coefficient of the compound include an ultraviolet visible spectrophotometer (Varian Carry-5 spectrophotometer), an ethyl acetate solvent at a concentration of 0.01 g / L .

When the photopolymerization initiator is contained in the resin composition of the present invention, the content of the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, 1 to 10% by mass. Within this range, more excellent sensitivity and pattern formability can be obtained.

The composition of the present invention may contain only one type of photopolymerization initiator or two or more types of photopolymerization initiators. When two or more kinds are included, the total amount is preferably in the above range.

<Surfactant>

Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the applicability.

As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the composition of the present invention contains a fluorine-containing surfactant, the uniformity of liquid coating thickness and the liquid-repellency (liquid-repellency) can be improved by improving the liquid property Can be improved.

That is, in the case of forming a film by using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, . Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine 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. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the lyophobic property, and the solubility in the composition is also good.

Examples of the fluorochemical surfactant include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101 (manufactured by Sumitomo 3M Co., Ltd.), F- , SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Garas Co., Ltd.) .

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerine ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diisostearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF) Ltd.) and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

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

Examples of silicone based surfactants include fluorine-based surfactants such as TORAY Silicon DC3PA, TORAY Silicone SH7PA, TORAY Silicon DC11PA, TORAY Silicone SH21PA, TORAY Silicone SH28PA, TSF-4440 "," TSF-4445 "," TSF-4460 "," TSF-4440 "," TSF- KP341 ", " KF6001 ", "KF6002 ", manufactured by Shin-Etsu Silicone Co., Ltd., BYK307, BYK323 and BYK330 manufactured by Big Chemie.

When the surfactant is contained in the composition of the present invention, the addition amount of the surfactant is preferably 0.001 to 5 mass%, more preferably 0.005 to 3 mass%, based on the total mass of the composition.

The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more kinds are included, the total amount is preferably in the above range.

<Solvent>

The resin composition of the present invention may contain a solvent. The solvent is not particularly limited so long as it satisfies the solubility of each component and the coating property of the resin composition, but is preferably selected in consideration of solubility, coatability, and safety of an ultraviolet absorber, an alkali-soluble resin or a dispersant. In preparing the resin composition of the present invention, it is preferable to include at least two kinds of solvents.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate, Ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl methoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2- (2-methoxypropionate, Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, , Ethyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Lycol monobutyl ether, propylene Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone, and the like, and examples of the aromatic hydrocarbon include toluene, xylene, and the like.

From the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the shape of the coated surface, and the like, these solvents are preferably mixed with two or more kinds. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

The content of the solvent in the resin composition is preferably such that the total solid concentration of the composition is 5 to 50 mass%, more preferably 10 to 35 mass%, and more preferably 10 to 25 mass% Is particularly preferable.

The composition of the present invention may contain only one kind of solvent, or two or more types of the solvent. When two or more kinds are included, the total amount is preferably in the above range.

<Polymerization inhibitor>

In the composition of the present invention, it is preferable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during the preparation of the composition.

Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'- (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerium salt have. Among them, p-methoxyphenol is preferable.

The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the composition. The composition of the present invention may contain only one kind of polymerization inhibitor or two or more kinds thereof.

<Other ingredients>

The composition of the present invention may optionally contain a chain transfer agent such as an N, N-dialkylamino benzoic acid alkyl ester or 2-mercaptobenzothiazole, a thermal polymerization initiator such as an azo compound or a peroxide compound, Ultraviolet absorber such as polyfunctional thiol, epoxy compound, alkoxybenzophenone, plasticizer such as dioctyl phthalate, developing property improving agent such as low molecular weight organic carboxylic acid, other filler, Various additives such as a polymer compound other than a binder and an alkali-soluble resin, an antioxidant, and an anti-aggregation agent.

In addition, a thermosetting agent may be added after development to improve the degree of curing of the film. Examples of the heat curing agent include an azo compound, a thermal polymerization initiator such as a peroxide, a novolak resin, a resol resin, an epoxy compound, and a styrene compound.

&Lt; Preparation of Resin Composition >

The resin composition of the present invention can be prepared by stirring and mixing together the above-mentioned respective components and, if necessary, filtering as described below.

The resin composition of the present invention can be obtained by dispersing the above-mentioned red pigment and a pigment containing a blue pigment together with components such as a dispersant, a solvent and a pigment derivative, if necessary, to prepare a pigment dispersion, It is preferable to prepare them by mixing them.

The method of preparing the pigment dispersion is not particularly limited, and for example, the pigment and the dispersant are mixed in advance and dispersed in advance by a homogenizer or the like is finely dispersed using a beads disperser using zirconia beads or the like .

The resin composition of the present invention is preferably filtered with a filter for the purpose of eliminating foreign matters or reducing defects. So long as it is conventionally used for filtration applications and the like. For example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6, nylon-6,6 and the like, polyolefin resins such as polyethylene and polypropylene (including those having high density and ultrahigh molecular weight) ) And the like. Of these materials, polypropylene (including high-density polypropylene) is preferable.

The pore diameter of the filter is preferably about 0.01 to 7.0 mu m, preferably about 0.01 to 2.5 mu m, and more preferably about 0.01 to 2.0 mu m. This range makes it possible to reliably remove fine foreign matter which inhibits the preparation of a uniform and smooth resin composition in the subsequent step.

When using a filter, other filters may be combined. At this time, the filtering in the first filter may be performed once or two or more times.

It is also possible to combine the first filters having different pore sizes within the above-mentioned range. The pore diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include various filters provided by Nippon Polyurethane Industry Co., Ltd., Advantel Co., Ltd., Nippon Integrity Corporation (formerly Nippon Micrel Co., Ltd.) or Kitsch Microfilter of Kabushiki Kaisha, .

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

For example, the filtering in the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing the other components.

&Lt; Production of Infrared Transmissive Filter by Resin Composition >

Next, the infrared ray transmitting filter of the present invention and its manufacturing method will be described.

The infrared transmitting filter of the present invention is characterized by having a colored region (coloring pattern) (preferably a black region (black pattern)) formed by using the above-mentioned resin composition on a substrate.

Hereinafter, the infrared ray transmitting filter of the present invention will be described in detail with reference to its manufacturing method.

The method of forming the colored pixel constituting the infrared ray transmitting filter of the present invention may be a method of preparing the above resin composition by a photolithography method or a method of preparing the above resin composition by an inkjet method Can be adopted.

Among them, a method of preparing a resin composition and preparing it by a photolithography method is an easy and preferable embodiment of providing a fine pattern in an arbitrary shape.

Hereinafter, a method of preparing an infrared ray transmitting filter for use in a solid-state image pickup device by preparing a resin composition and providing each colored pixel by a photolithography method will be described, but the infrared ray transmitting filter of the present invention is limited to this It is not.

The method for producing an infrared ray transmitting filter of the present invention comprises a step of forming an infrared ray transmitting composition layer (colored layer) on a substrate (coloring layer forming step) using the above resin composition, a step of exposing the infrared ray transmitting composition layer in a pattern shape And a step of developing the exposed infrared transmitting composition layer to form a pattern (developing step).

&Lt; Coloring layer forming step &

In the coloring layer forming step, a colored layer (infrared transmitting composition layer) comprising a resin composition is formed on a substrate by using a resin composition.

Examples of the substrate that can be used in the present process include a photoelectric conversion element substrate in a CCD, a CMOS, an organic CMOS used in a solid-state imaging element, a non-alkali glass used in a silicon substrate, , Pyrex (registered trademark) glass, quartz glass, and those having a transparent conductive film adhered thereto. In these substrates, a black matrix for isolating each pixel may be formed.

If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the surface of the substrate.

As the method of forming the infrared transmitting composition layer on the substrate, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

Drying (prebaking) of the colored layer (infrared transmitting composition layer) coated on the substrate can be performed at a temperature of 50 to 140 캜 for 10 to 300 seconds in a hot plate, an oven or the like.

The thickness of the colored layer after drying (after prebaking) is in the range of 0.55 μm to 1.8 μm, preferably 0.60 μm or more and less than 1.8 μm, more preferably 0.70 μm or more and 1.6 μm or less, more preferably 0.80 μm or more and 1.4 μm Or less is particularly preferable.

<Exposure Step>

In the exposure step, the colored layer (infrared transmitting composition layer) formed in the coloring layer forming step is exposed in a pattern shape.

In the exposure in this step, the exposure of the colored layer is preferably performed by exposing through a predetermined mask pattern and curing only the part of the colored layer that has been irradiated with light. As the radiation which can be used at the time of exposure, radiation such as g line, h line and i line is preferably used, and i line is particularly preferable. Radiation amount is most preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2 are preferred, and ^{50mJ / cm 2 ~ 1000mJ / cm} 2 are more ^{preferred, 80mJ / cm 2 ~ 500mJ /} cm 2 (a)

<Development Process>

Subsequent to the exposure step, an alkali development treatment (development step) is carried out to elute the uncured portions after exposure to the developer to leave the photocured portions. By this developing step, a patterned film made of colored pixels can be formed.

The developing method may be any one of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined with these methods.

Before the developer comes in contact with the developer, the surface to be developed may be wetted with water or the like in advance to prevent development unevenness.

As the developing solution, an organic alkali developing solution which does not cause damages to the underlying circuit or the like is preferable. The developing temperature is usually 20 to 30 占 폚, and the developing time is 20 to 90 seconds.

Examples of the alkaline agent to be used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide And organic alkaline compounds such as benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5.4.0] -7-undecene. Is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 1% by mass, based on the total amount of the aqueous alkaline solution. When a developing solution comprising such an alkaline aqueous solution is used, it is generally preferable to rinse the developing solution with pure water after development to wash away the excess developing solution, followed by drying.

Further, in the production method of the present invention, after the above-described coloring layer forming step, the exposing step and the developing step are carried out, a curing step of curing the formed coloring pattern by post-heating (post-baking) . The post-baking is a post-development heat treatment for making the curing to be complete, and usually a heat curing treatment is performed at 100 ° C to 270 ° C.

In the case of using light, it can be performed by g-line, h-line, i-line, excimer laser such as KrF or ArF, electron beam, X-ray or the like, but it is preferably performed at a low temperature of about 20 to 50 ° C , And the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of combined use of post exposure and post heating, it is preferable to perform post exposure first.

By performing the above-described coloring layer forming step, the exposure step and the developing step (and, if necessary, the curing step) described above, an infrared ray transmitting filter is produced.

The infrared transmitting filter may be constituted by only the colored pixels showing the specific spectral characteristics of the present invention. The infrared transmitting filter may be composed of the colored pixels showing the above-described spectral characteristics and the coloring of red, green, blue, magenta, yellow, cyan, A color filter having pixels may be configured. When a color filter is formed with pixels of different colors, a colored pixel showing the specific spectral characteristic of the present invention may be provided first or may be provided later.

The resin composition of the present invention can be easily cleaned and removed by using a known cleaning liquid even when it is adhered to, for example, a nozzle of a coating device discharging portion, a pipe portion of a coating device, a coating device or the like. In this case, it is preferable to use the above-mentioned organic solvent as the cleaning liquid for the organic solvent contained in the resin composition in order to perform cleaning and removal with better efficiency.

Also, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102, JP-A-2007-281523, etc., It can be suitably used as a cleaning liquid.

As the cleaning liquid, it is preferable to use an alkylene glycol monoalkyl ether carboxylate or an alkylene glycol monoalkyl ether.

These organic solvents which can be used as a cleaning liquid may be used alone or in combination of two or more kinds.

When two or more kinds of organic solvents are mixed, a mixed solvent obtained by mixing an organic solvent having a hydroxyl group and an organic solvent having no hydroxyl group is preferable. The mass ratio of the organic solvent having a hydroxyl group to the organic solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is preferably a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio thereof is particularly preferably 60/40.

In order to improve the permeability of the cleaning liquid to the resin composition, the above-mentioned surfactant may be added to the cleaning liquid as a surfactant that the resin composition may contain.

The infrared ray transmitting filter of the present invention manufactured by the manufacturing method of the infrared ray transmitting filter of the present invention can be suitably mounted on a solid-state image sensor such as a CCD sensor, a CMOS sensor, an organic CMOS sensor, and a CIGS image sensor. Particularly, it is suitable to be mounted on a solid-state image sensor of CCD sensor, CMOS sensor or organic CMOS sensor with high resolution exceeding 1 million pixels. The infrared ray transmitting filter of the present invention can be disposed, for example, between a light receiving portion of each pixel constituting a CCD element and a microlens for condensing.

The infrared transmittance filter of the present invention preferably has a light transmittance of 20% or less, more preferably 15% or less, and more preferably 10% or less at a wavelength of 400 nm, a wavelength of 520 nm, and a wavelength of 700 nm.

In the infrared ray-permeable filter of the present invention, the size of the pattern is preferably 2 μm or less, more preferably 1.5 μm or less.

[Infrared sensor]

The infrared sensor of the present invention comprises the infrared ray transmitting filter of the present invention. The configuration of the infrared sensor of the present invention is not particularly limited as long as it has an infrared transmission filter and functions as a solid-state image sensing device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD sensor, a CMOS sensor, an organic CMOS sensor, or the like) and a transfer electrode composed of polysilicon or the like are provided on a substrate. On the photodiodes and transfer electrodes, A device shielding film made of silicon nitride or the like and formed on the light-shielding film so as to cover the entire light-shielding film and the photodiode light-receiving portion, and having a configuration with the infrared ray-permeable filter of the present invention to be.

In addition, a configuration having a condensing means (for example, a microlens or the like, hereinafter the same) below the infrared ray transmitting filter (on the side closer to the substrate) or a configuration having a condensing means on the infrared ray transmitting filter .

In addition, the organic CMOS sensor includes a thin-film fan-shaped photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and the organic material plays a role of capturing light and converting it into an electric signal, Layer structure in which an inorganic material takes charge of taking out a signal to the outside. In principle, the aperture ratio can be set to 100% with respect to incident light. Since the organic photoelectric conversion film can be laid on the CMOS signal readout substrate as a continuous film of free structure, it is suitable for pixel refinement without requiring an expensive fine processing process.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, "%" and "part" are on a mass basis unless otherwise specified.

Red pigment

Red-1; A mixture of the following compound and C.I. Pigment Red 254 (weight ratio 97: 3)

&Lt; EMI ID =

Red-2; C. I. Pigment Red 254

Red-3; A mixture of the following compound (A) and the following compound (B) (weight ratio 97: 3)

&Lt; EMI ID =

Blue pigment aluminum phthalocyanine-1

[Formula 97]

Aluminum phthalocyanine-2

(98)

Aluminum phthalocyanine-3

[Formula 99]

Aluminum phthalocyanine-4

(100)

Aluminum phthalocyanine-5

(101)

PB15: 6; C. I. Pigment Blue 15: 6

Pigment derivative 1

&Lt; EMI ID =

Derivative 2

&Lt; EMI ID =

Derivative 3

&Lt; EMI ID =

Derivative 4

&Lt; EMI ID =

Alkali-soluble resin 1: The ratio in the following repeating units is a molar ratio. Mw = 11,000

&Lt; EMI ID =

Alkali-soluble resin 2: The ratio in the following repeating units is a molar ratio. Mw = 14,000

&Lt; EMI ID =

Polymerizable compound 1: a mixture of the left compound and the right compound in a molar ratio of 7: 3

(108)

Dispersant 1: Mw = 24,000

(109)

Polymerization initiator 1

(110)

OXE01: IRGACURE-OXE01 (manufactured by BASF)

OXE02: IRGACURE-OXE02 (manufactured by BASF)

Preparation of Red Pigment Dispersion (Pigment Dispersion 1)

The mixed liquid of the following composition was mixed and dispersed for 3 hours using a 0.3 mm diameter zirconia beads with a bead mill (NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) equipped with a pressure reducing mechanism) To prepare a pigment dispersion.

Red pigment (Red-1) 13.5 parts

The dispersant 1 4.0 parts

The pigment derivative 1 10% by mass of the red pigment

· Organic solvent: PGMEA 82.5 parts

Preparation of Yellow Pigment Dispersion (Pigment Dispersion 2)

The mixed liquid of the following composition was mixed and dispersed for 3 hours with 0.3 mm diameter zirconia beads by a bead mill (NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) equipped with a pressure reducing mechanism) To prepare a pigment dispersion.

Yellow pigments (C. I. Pigment Yellow 139) 14.8 parts

The dispersant 1 5.2

The pigment derivative 1 10% by mass of the yellow pigment

· Organic solvent: PGMEA 80 parts

Preparation of Blue Pigment Dispersion (Pigment Dispersion 3)

The mixed liquid of the following composition was mixed and dispersed for 3 hours using a 0.3 mm diameter zirconia beads with a bead mill (NANO-3000-10 (manufactured by Nippon Express Co., Ltd.) equipped with a pressure reducing mechanism) To prepare a pigment dispersion.

· Blue pigment (aluminum phthalocyanine pigment-1) 10.8 part

The dispersant 1 3.2

The pigment derivative 1 10% by mass of the blue pigment

· Organic solvent: PGMEA 86

Preparation of Purple Pigment Dispersion (Pigment Dispersion 4)

The mixed liquid of the following composition was mixed and dispersed for 3 hours using a 0.3 mm diameter zirconia beads with a bead mill (NANO-3000-10 (manufactured by Nihon Baii KK) equipped with a pressure reducing mechanism) To prepare a pigment dispersion.

· Purple pigment (C.I. Pigment Violet 23) 14.8 parts

The dispersant 1 5.2

The pigment derivative 1 10% by mass of the purple pigment

· Organic solvent: PGMEA 80 parts

&Lt; Example 1 >

Preparation of resin composition

The following components were mixed to prepare the resin composition of Example 1.

Red pigment dispersion 32.8 parts

Yellow pigment dispersion 12.23 part

· Blue pigment dispersion 37.51 part

· Purple pigment dispersion 6.13 part

The alkali-soluble resin 1 1.218 part

The polymerizable compound 1 1.58 part

The polymerization initiator 1 0.758 part

Surfactant: 10.0 mass% PGMEA solution of Megafac F-781F manufactured by DIC K.K. 0.42 part

Polymerization inhibitor: p-methoxyphenol 0.0008 part

Organic solvent 1: PGMEA The amount in which the pigment concentration in the total solid content becomes 60 mass%

&Lt; Examples 2 to 15 and Comparative Examples 1 to 5 >

The resin compositions of Examples 2 to 15 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that each component was changed to that shown in the following table and amount in the preparation of the resin composition of Example 1 It was prepared.

&Lt; Evaluation of spectroscopic characteristics &

Each resin composition thus obtained was used to evaluate the spectroscopic characteristics (light shielding properties).

Each of the resin compositions was spin-coated on a glass substrate so as to have a film thickness of 0.8 mu m after post-baking, dried with a hot plate at 100 DEG C for 120 seconds, dried, Followed by heat treatment (post-baking) for 300 seconds.

The substrate having the colored layer was measured for a light transmittance of 400 nm, 520 nm and 700 nm with a spectrophotometer (ref. Glass substrate) of ultraviolet visible near infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). The evaluation criteria are as follows.

3: All the light transmittances of 400 nm, 520 nm and 700 nm were 10% or less

2: All the light transmittances of 400 nm, 520 nm and 700 nm exceed 10% and 15%

1: Both the light transmittances of 400 nm, 520 nm and 700 nm exceed 15%

<Fabrication of infrared ray transmission filter>

Each of the resin compositions of Examples and Comparative Examples was coated on a silicon wafer using a spin coater so that the film thickness after drying was 1.0 占 퐉 and subjected to heat treatment (prebaking) for 120 seconds using a hot plate at 100 占 폚 .

Next to, i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), 50mJ / cm ² step using a photomask which is a square pixel pattern of square 1.4μm formed up to 50 ~ 750mJ / cm ² by using By performing exposure, the optimum exposure amount for resolving the square pixel pattern was determined, and exposure was performed at this optimum exposure amount.

Thereafter, the silicon wafer on which the exposed coated film was formed was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by KEMITRONICS Co., Ltd.), and a CD-2060 (manufactured by Fuji Film Electronics Materials Co., ) At 23 DEG C for 60 seconds to form a colored pattern on the silicon wafer.

The silicon wafer having the colored pattern formed thereon was rinsed with pure water, and then spray-dried.

Further, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 占 폚 to obtain silicon wafers having coloring patterns as infrared transmission filters of Examples and Comparative Examples, respectively.

<< Evaluation of roughness >>

The value of the roughness when the infrared transmission filter was measured was evaluated. The value of the roughness was measured by the following method.

Evaluation boards were produced in the same manner as in the formation of solid-state imaging element coloring patterns, except that a glass substrate was used in place of the wafer with an undercoat layer and direct exposure was performed without using a mask. The luminance distribution was analyzed on the basis of the number of pixels whose deviation from the average was ± 10% or more by the following method.

A method of measuring the luminance distribution will be described. The evaluation substrate was placed between the observation lens of the optical microscope and the light source, and the light was irradiated toward the observation lens. The state of the transmitted light was observed with an optical microscope MX-50 (manufactured by Olympus Corporation) equipped with a digital camera. The film surface of the colored pattern was photographed for five arbitrarily selected areas. The luminance of the photographed image was stored as a concentration distribution of 256 gradations ranging from 0 to 255 and stored. The luminance distribution was analyzed from this image, and the color unevenness was evaluated by the number of pixels (the value of roughness) whose deviation from the average exceeded ± 10%.

The evaluation criteria are as follows.

5: The roughness value is less than 10,000

4: The roughness value is more than 1 million and less than 15,000

3: The roughness value is more than 15,000 and less than 20,000

2: The roughness value is more than 20,000 but less than 30,000

1: The value of roughness exceeds 3,000

<< Evaluation of adhesion (separation of coloring pattern) >>

The obtained silicon wafer with the infrared ray permeable filter was observed at 10 fields per wafer at random with an optical microscope (magnification: 100 times). The number of peeled patterns was actually counted and evaluated according to the following criteria.

~ Evaluation Criteria ~

3: Number of peeling defects 0 to 10

2: Number of peeling defects 11 to 20 (practically acceptable)

1: the number of peeling defects is 21 or more

In the following Tables, the red pigment ratio and the blue pigment ratio in the total coloring material represent the ratio (mass%) of the red pigment or blue pigment to the whole pigment in the composition.

[Table 1]

As is clear from the above table, it was found that in the examples, a resin composition excellent in roughness and adhesion can be provided. It was also found that the light-shielding property was also excellent. On the other hand, in the comparative example, it was found that it is difficult to provide a resin composition excellent in roughness and adhesion.

Claims (15)

Wherein the coloring material comprises at least a red pigment and a blue pigment represented by the following general formula (A1) and / or the following general formula (A2), wherein the content of the red pigment in the total coloring material is 20 To 50 mass%, and the content of the blue pigment is 25 to 55 mass%.
In formula (A1)
[Chemical Formula 1]

In the general formula (A1), X ¹ to X ⁴ each independently represent a substituent. R ^0A represents a hydrogen atom or a monovalent substituent. m1 to m4 each independently represent an integer of 0 to 4; When m1 to m4 are two or more, plural X ¹ to X ⁴ may be the same or different.
In general formula (A2)
(2)

In the general formula (A2), each of X ⁵ to X ¹² independently represents a substituent. R ^0B represents a divalent substituent. m5 to m12 each independently represent an integer of 0 to 4; When m5 to m12 are two or more, a plurality of X ⁵ to X ¹² may be the same or different. The method according to claim 1,
And further comprising a pigment derivative. The method of claim 2,
Wherein the pigment derivative has a triazine skeleton. The method according to claim 2 or 3,
Wherein the pigment derivative is represented by the following general formula (I) or the following general formula (II).
(3)

In the general formula (I), Dye represents an n-valent organic dye moiety, X is a single ^{bond, -CONH-Y 2 -, -SO} 2 NH-Y 2 - or ^{_{-CH 2 NHCOCH 2 NH-Y 2}} - represents a , Y ² represents an alkylene group or an arylene group, Y ¹ represents -NH- or -O-, Z represents a hydroxyl group, an alkoxy group when n represents 1, a group represented by the following general formula (I-1) X-Dye, X is the same as X in the general formula (I), and n represents an integer of 2 to 4, each represents a hydroxyl group, an alkoxy group, or a group represented by the following general formula (I-1) R ¹ and R ² each represent an alkyl group, and R ¹ and R ² may be bonded to each other to form a heterocycle containing a nitrogen atom. m represents an integer of 1 to 6, and n represents an integer of 1 to 4; When n is 2 or more, a plurality of X, Y ¹ , R ¹ and R ² may be the same or different.
[Chemical Formula 4]

In the general formula (I-1), Y ³ represents -NH- or -O-. R ¹ and R ² each represent an alkyl group, and R ¹ and R ² may be bonded to each other to form a heterocycle containing a nitrogen atom. m represents an integer of 1 to 6;
[Chemical Formula 5]

In the general formula (II), Dye represents a quinophthalone residue, X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR'COCH ₂ NR'-, or represent a -NR'CO-, X ² is an aryl group, or represents the number of carbon atoms is 4 to 20 heteroaromatic ventilation having the carbon number of 6 to 20, these groups, -NR'-, -O-, -SO ₂ - or -CO-. &Lt; / RTI &gt; X ³ represents -NR'- or -O-. R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. A and B are, respectively, groups represented by the following formula groups, represented by the following general formula (II-1) (II- 2), -O- (CH 2) n -R 8, -OR 9, -NR 10 R ¹¹ , -Cl, -F and -X ³ -X ² -X ¹ -Dye, R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and R ⁹ , R ¹⁰ , and R ¹¹ represent a group selected from Each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and n represents an integer of 0 to 20. Either one of A and B is a group represented by the following formula (II-1), a group represented by the following formula (II-2), -O- (CH ₂ ) nR ⁸ , -OR ⁹ or -NR ¹⁰ R ¹¹ , and t represents an integer of 1 to 3. When t is 2 or more, a plurality of X ¹ , X ² , X ³ , A and B may be the same or different.
[Chemical Formula 6]

Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkylene group having 6 to 20 carbon atoms, 20 represents an arylene of, these _{groups, -NR'-, -O-, -SO 2 -} , or may be coupled together by a divalent connecting group selected from -CO-. R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. R ¹ and R ² may be united to form a heterocyclic structure which may be substituted with an additional nitrogen atom, oxygen atom or sulfur atom.
In formula (II-2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-G-SO 2 -, -NR'-} G-SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO ₂ represents NR'-, G represents an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R 'and R "are each an alkyl group having 1 to 20 carbon atoms , An alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, Or an aryl group having 6 to 20 carbon atoms, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. The method according to any one of claims 1 to 4,
As the red pigment, a resin composition comprising a compound represented by the following general formula (4).
In general formula (4)
(7)

In the general formula (4), A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, ₃ , or -CON (R ¹ ) R ² . R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group. The method according to any one of claims 1 to 4,
A red pigment having a symmetrical structure and a red pigment having an asymmetric structure as the red pigment. The method according to any one of claims 1 to 6,
A resin composition, which further comprises a polymerizable compound and a polymerization initiator. The method according to any one of claims 1 to 7,
Wherein the content of the coloring material in the total solid content in the resin composition is 40 mass% or more. The method according to any one of claims 1 to 8,
A resin composition used for forming a color filter for a solid-state imaging element. A cured film obtained by curing the resin composition according to any one of claims 1 to 9. An infrared ray transmitting filter formed by the resin composition according to any one of claims 1 to 9. The method of claim 11,
Wherein the light transmittance at a wavelength of 400 nm, a wavelength of 520 nm, and a wavelength of 700 nm is 15% or less. A step of forming an infrared transmitting composition layer on a substrate by using the resin composition according to any one of claims 1 to 9, a step of exposing the infrared transmitting composition layer in a pattern shape, a step of forming the infrared transmitting composition layer Thereby forming a pattern. An infrared sensor comprising the infrared transmitting filter according to claim 11 or 12. An infrared sensor comprising an infrared ray transmitting filter obtained by the infrared ray transmitting filter manufacturing method according to claim 13.