WO2020195963A1

WO2020195963A1 - Colored curable resin composition

Info

Publication number: WO2020195963A1
Application number: PCT/JP2020/011135
Authority: WO
Inventors: 智博中山; 裕史濱木; 学栂井
Original assignee: 住友化学株式会社
Priority date: 2019-03-28
Filing date: 2020-03-13
Publication date: 2020-10-01
Also published as: TW202102617A; CN113316603A; KR20210149756A; JP2020164814A; CN113316603B

Abstract

A colored curable resin composition which comprises a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein the colorant (A) comprises an isoindoline pigment (A1) and a perylene compound (1) having an absorption maximum at 400-560 nm and having no absorption maximum in the range of 560-780 nm, excluding 560 nm.

Description

Color curable resin composition

The present invention relates to a colored curable resin composition. In particular, the present invention relates to a colored curable resin composition that can be suitably used for red color.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As the color curable resin composition for forming the color filter, a color curable resin composition capable of forming a dark color and thin color filter, particularly a dark color and thin film color filter that can be suitably used for red color. There is a demand for a colored curable resin composition capable of forming the above. As a coloring curable resin composition for red color, C.I. I. A composition containing Pigment Red 242 is known (Patent Document 1). However, C.I. I. Pigment Red 242 has a weak coloring power because it absorbs little at a wavelength of 525 nm, which exhibits red color characteristics, and it is necessary to increase the density of the color material in the color filter in order to obtain a dark color filter in order to widen the color reproduction range. was there. Increasing the concentration of the color material in the color filter is not preferable because the performance of the color curable resin composition deteriorates, such as deterioration of the pattern shape. Further, if the coloring power is weak, it is necessary to manufacture a color filter with a thick film in order to obtain the desired color characteristics, but when it is applied to a liquid crystal display device or a solid-state image sensor, it is connected to adjacent pixels. Thickening is also not preferable because color mixing of light occurs.

Patent Document 2 describes a photosensitive coloring composition for a color filter substrate containing a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). As a red photosensitive coloring composition, C.I. I. Pigment Red 179, and those containing isoindoline pigments are disclosed.

Japanese Unexamined Patent Publication No. 2010-24436 JP-A-2017-116767

However, the color filter formed from the red photosensitive coloring composition disclosed in Patent Documents 1 and 2 has weak absorption at a wavelength of 525 nm, which is required as a characteristic of the red color filter, and the coloring power is sufficiently satisfactory. It wasn't a thing.
An object of the present invention is to obtain a color curable resin composition which has strong absorption at a wavelength of 525 nm and can form a dark color and a thin film color filter.

That is, the gist of the present invention is as follows.
[1] Contains a colorant, a resin, a polymerizable compound and a polymerization initiator.
A color-curable resin composition in which the colorant contains a perylene compound having a maximum absorption at 400 nm to 560 nm and no maximum absorption at more than 560 nm to 780 nm, and an isoindoline pigment.
[2] The color-curable resin composition according to [1], wherein the colorant further contains a pigment other than the perylene compound and the isoindoline pigment.
[3] The colored curable resin composition according to [1] or [2], which further contains a solvent.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A solid-state image sensor including the color filter according to [4].

According to the present invention, it is possible to provide a color curable resin composition useful for producing dark color and thin film color filters. The color-curable resin composition of the present invention is particularly suitable as a color-curable resin composition for red.

The color-curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A)), a resin (hereinafter, may be referred to as a resin (B)), and a polymerizable compound (hereinafter, a polymerizable compound). (C) and a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)) are included.
The colorant (A) is a perylene compound (hereinafter, may be referred to as perylene compound (1)) and an isoindoline pigment (hereinafter, may be referred to as perylene compound (1)) having a maximum absorption in 400 nm to 560 nm and not having a maximum absorption in more than 560 nm to 780 nm. , May be referred to as isoindoline pigment (A1)).
The colorant (A) may contain a colorant other than the perylene compound (1) and the isoindoline pigment (A1) (hereinafter, may be referred to as a colorant (A2)).
The colorant (A) preferably further contains a pigment other than the perylene compound (1) and the isoindoline pigment (A1) (hereinafter, may be referred to as a pigment (A2-2)).
The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter, may be referred to as a solvent (E)).
The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as a polymerization initiation aid (D1)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as a leveling agent (F)).
In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of types unless otherwise specified.

<Colorant (A)>
The colorant (A) contains a perylene compound (1) and an isoindoline pigment (A1).

<< Perylene compound (1) >>
The perillene compound (1) is a perillene compound having a maximum absorption at 400 nm to 560 nm and no maximum absorption at more than 560 nm to 780 nm, and examples thereof include a compound represented by the following formula (1-A). Be done. The perylene compound (1) may be a dye or a pigment. Further, the perillene compound (1) may have maximum absorption in a plurality of wavelength regions in 400 nm to 560 nm, for example, one maximum absorption in 400 nm to 470 nm and one maximum absorption in more than 470 nm to 510 nm. And one maximal absorption may be provided above 510 nm to 570 nm, respectively.

[In formula (1-A),
R ¹ and R ² each independently represent a methyl group having a substituent or a hydrocarbon group having 2 to 30 carbon atoms which may have a substituent.
R ³ to R ¹⁰ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a hydrogen atom, a hydroxy group, or a substituent. ]

The hydrocarbon groups having 2 to 30 carbon atoms represented by R ¹ and R ² may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated. It may be a chain type or an alicyclic type.

Saturated or unsaturated chain hydrocarbon groups represented by R ¹ and R ² include linear alkyl groups such as ethyl group, propyl group, butyl group and pentyl group; isopropyl group and (2-methyl) propyl group. , Isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl) pentyl group, (1-ethyl) pentyl group, ( 1-Hexyl) Branched chain alkyl group such as heptyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, (1-methyl) ethenyl group, 2-butenyl group, 3 -Alkenyl groups such as butenyl group and 1,3-butadienyl group; and the like.

Saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ and R ² include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and 1-methylcyclohexyl. Cycloalkyl groups such as groups, 1,2-dimethylcyclohexyl groups, 2,4,6-trimethylcyclohexyl groups, 2,2,6,6-tetramethylcyclohexyl groups; cyclohexenyl groups (eg, cyclohex-2-ene, Cyclohexa-3-ene), cycloalkenyl groups such as cycloheptenyl group, cyclooctenyl group; norbornan group, adamantyl group and the like can be mentioned.

The saturated or unsaturated hydrocarbon group represented by R ¹ and R ² may be a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined, for example, a cyclopropylmethyl group and a cyclopropylethyl group. Examples thereof include an alkyl group to which one or more alicyclic hydrocarbon groups such as a group, a cyclobutylmethyl group and a cyclobutylethyl group are bonded.

The aromatic hydrocarbon groups represented by R ¹ and R ² include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-isopropylphenyl group, m-isopropylphenyl group and p-isopropyl. Phenyl group, 2,3-dimethylphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-trimethylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6 , 7,8-Tetrahydro-2-naphthyl group, fluorenyl group, phenyl tril group, anthryl group and the like.

The aromatic hydrocarbon group represented by R ¹ and R ² is not particularly limited as long as it is a hydrocarbon group having an aromatic hydrocarbon ring, and is a chain hydrocarbon group, an alicyclic hydrocarbon group, and aromatic carbide. At least one of the hydrogen groups may be a group combined with an aromatic hydrocarbon group, and aralkyl such as a benzyl group, a 2-methylbenzyl group, a 3,4-methylbenzyl group, a phenylethyl group, and a phenylpropyl group. Group; arylalkenyl group such as phenylethenyl group (phenylvinyl group); arylalkynyl group such as phenylethynyl group; phenyl group to which one or more phenyl groups such as biphenylyl group and terphenylyl group are bonded; cyclohexylmethylphenyl group, Examples thereof include a benzyl phenyl group and a (dimethyl (phenyl) methyl) phenyl group.

The substituents contained in the methyl group represented by R ¹ and R ² and may be contained in the hydrocarbon group having 2 to 30 carbon atoms include halogens such as fluorine atom, chlorine atom, iodine atom and bromine atom. Atomic; nitro group; cyano group; amino group; hydroxy group; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; sulfanyl group; alkylsulfanyl having 1 to 6 carbon atoms such as methyl sulfanyl group and ethyl sulfanyl group. Group; carboxy group; carbamoyl group; alkoxycarbonyl group having 2 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; sulfo group; sulfamoyl group; alkoxysulfonyl group having 1 to 6 carbon atoms such as methoxysulfonyl group and ethoxysulfonyl group. Group; etc.

R ¹ and R ² are preferably methyl groups having substituents or hydrocarbon groups having 8 to 20 carbon atoms which may have substituents, respectively, and methyl groups having substituents. , Or a hydrocarbon group having 10 to 15 carbon atoms which may have a substituent, a methyl group having a substituent and a chain having 10 to 15 carbon atoms which may have a substituent. It is more preferably an aromatic hydrocarbon group having 10 to 15 carbon atoms which may have a like hydrocarbon group or a substituent, and a methyl group having a substituent and saturated chain carbide having 10 to 15 carbon atoms. It is more preferably a hydrogen group or an aromatic hydrocarbon group having 10 to 15 carbon atoms, a methyl group having a carboxy group as a substituent, a branched alkyl group having 10 to 15 carbon atoms, or a branched alkyl group having 10 to 15 carbon atoms. It is particularly preferable that it is a monocyclic aromatic hydrocarbon group.
Further, it is preferable that R ¹ and R ² have the same group.

The hydrocarbon groups having 1 to 10 carbon atoms represented by R ³ to R ¹⁰ are represented by R ¹ and R ² except that they contain a methyl group and do not contain a group having 11 or more carbon atoms. The same as the hydrocarbon group can be mentioned.

Examples of the substituent which the hydrocarbon group represented by R ³ to R ¹⁰ may have are the same as the substituent which the hydrocarbon group represented by R ¹ and R ² may have. Be done.

R ³ to R ¹⁰ are preferably hydrocarbon groups having 1 to 10 carbon atoms, which may independently have a hydrogen atom or a substituent, and have a hydrogen atom or a substituent. It is more preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a hydrogen atom, or a hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom.
Further, R ³ to R ¹⁰ are preferably the same group.

To measure the maximum absorption of a perillene compound, a chloroform solution containing 0.001% by mass of the perillene compound is prepared, and then the solution is placed in, for example, a measuring container having an optical path length of 1 cm (for example, a cuvette) and spectrally measured. It can be done by.

The content of the perillene compound (1) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass, and 1 to 1 to 40 parts by mass with respect to 100 parts by mass of the resin (B). It is more preferably 35 parts by mass, and even more preferably 5 to 30 parts by mass.

The content of the perillene compound (1) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and 20 to 70% by mass in the total amount of the colorant (A). Is more preferable, and 25 to 65% by mass is particularly preferable. When the content of the perillene compound (1) is within the above range, a color-curable resin composition capable of forming a color filter having good red color characteristics can be obtained.

<< Isoindoline Pigment (A1) >>
The isoindoline pigment (A1) is not particularly limited as long as it is an isoindoline pigment, and known isoindoline pigments can be used.

Examples of the isoindoline pigment (A1) include isoindoline pigments classified as pigments by the Color Index (The Society of Dyers and Colorists Publishing), and specifically, C.I. I. Pigment Yellow 109, 110, 137, 139, 173, 177, 179, 185, C.I. I. Pigment Orange 61, 69 and the like.

The isoindoline pigment (A1) may be an isoindoline pigment other than those classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing), and examples thereof include compounds represented by the following formula (Y). Be done.

[In formula (Y), R ¹¹ to R ¹⁵ are independent of each other and may have a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, and a substituent. Represents a heterocyclic group which may have a hydrocarbon group or a substituent of the number 1 to 20.
M represents a hydrogen atom or an alkali metal atom.
R ¹⁶ and R ¹⁷ represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
L ¹¹ and L ¹² represent -CO- or -SO _2- . ]

The hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹¹ to R ¹⁷ are represented by R ¹ and R ² except that they contain a methyl group and do not contain a group having 21 or more carbon atoms. The same as the hydrocarbon group can be mentioned.

The heterocyclic group represented by R ¹¹ to R ¹⁷ may be monocyclic or polycyclic.

The hydrocarbon group represented by R ¹¹ to R ¹⁷ or the substituent which may be contained in the heterocyclic group may be contained in the hydrocarbon group represented by R ¹ and R ^2. The same thing can be mentioned.

Hydrogen atoms are preferable as R ¹¹ to R ¹⁵ .

As R ¹⁶ and R ¹⁷ , an aromatic hydrocarbon group having a substituent and having 6 to 20 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent is more preferable, and a carboxy group is used as a substituent. An aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable.

-CO- is preferable as L ¹ and L ² .

As the isoindoline pigment (A1), a yellow isoindoline pigment is preferable from the viewpoint of obtaining a color curable resin composition capable of forming a color filter having good red color characteristics, and C.I. I. Pigment Yellow 139, 185 or the compound represented by the formula (Y) is more preferable, and C.I. I. Pigment Yellow 139 or 185 is more preferred. I. Pigment Yellow 139 is even more preferred.
These isoindoline pigments (A1) may be used alone or in combination of two or more.

The content of the isoindoline pigment (A1) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 40 parts by mass with respect to 100 parts by mass of the resin (B). It is more preferably to 30 parts by mass.

The content of the isoindoline pigment (A1) is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and 30 to 70% by mass based on the total amount of the colorant (A). More preferably, it is particularly preferably 35 to 65% by mass. When the content of the isoindoline pigment (A1) is within the above range, a color curable resin composition capable of forming a color filter having good red color characteristics can be obtained.

<< Colorant (A2) >>
In the color curable resin composition of the present invention, as the colorant (A2), a dye other than the perylene compound (1) and the isoindoline pigment (A1) (hereinafter, may be referred to as a dye (A2-1)) and / or The pigment (A2-2) may be contained, and it is preferable that the pigment (A2-2) is contained.

The dye (A2-1) is not particularly limited as long as it does not include the perillene compound (1), and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dye include compounds classified as having a hue other than pigment in the Color Index (The Society of Dyers and Colorists Publishing), and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Be done. According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acrydin dyes, styryl dyes, coumarins. Examples thereof include dyes, perylene dyes (excluding perylene compound (1)), and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

As the pigment (A2-2), a known pigment can be used without particular limitation as long as the perylene compound (1) and the isoindoline pigment (A1) are not included. For example, the color index (The Society of Dyers and) can be used. Pigments classified as pigments by Colorists (published by Colorists).
Pigments classified as pigments include, for example, C.I. I. Pigment Yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,117,125,128,147,148,150,153,154, Yellow pigments such as 166, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 43, 51, 55, 59, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 166, 168, 176, 177, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, 291 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

As the pigment (A2-2), a red pigment is preferable from the viewpoint of obtaining a color curable resin composition capable of forming a color filter having good red color characteristics, and C.I. I. Pigment Red 254 is more preferred.

When the color curable resin composition of the present invention contains a colorant (A2), the content of the colorant (A2) (dye (A2-1) and / or pigment (A2-2)) is determined by the colorant (A2-2). Of the total amount of A), it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, and further preferably 20% by mass or more. It is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less. When the content of the colorant (A2) is within the above range, a color curable resin composition capable of forming a color filter having good red color characteristics can be obtained. In particular, the content of the pigment (A2-2) is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total amount of the coloring agent (A). Is more preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 55% by mass or less.

The perylene compound (1), the isoindoline pigment (A1), and the pigment used as a pigment (A2-2) as needed preferably have a uniform particle size, and are subjected to a dispersion treatment by containing a pigment dispersant. By doing so, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include surfactants, which may be cationic, anionic, nonionic, or amphoteric surfactants. Specific examples thereof include polyester-based, polyamine-based, and acrylic-based dispersants. These dispersants may be used alone or in combination of two or more. Dispersants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (BASF). (Manufactured by), Azisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), and the like. As the dispersant, the resin (B) described later may be used.
When a pigment dispersant is used, the amount used is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

When two or more pigments are used, each may be mixed as a dispersion at the time of use.

The content of the colorant (A) is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, based on the total solid content of the color-curable resin composition. More preferably, it is 1 to 30% by mass. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of the resin (B) can be contained in the composition, so that it is mechanical. It is preferable because it can form a pattern having sufficient strength.
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (a) (hereinafter, "(a)). A resin having a structural unit derived from) is more preferable. The resin (B) is further a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). , A structural unit derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and , It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the side chain.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, oxalic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

In (b), a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group is preferable. ..
In addition, in this specification, "(meth) acrylic acid" represents at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, and 3-ethyl-3-. Examples thereof include (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( Meta) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-8. -Il (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like can be mentioned, with preference given to styrene. , Vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding (b) to the copolymer of (a) and (c) or by adding (b) to the copolymer of (b) and (c). It can be manufactured by adding (a) to. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
The molecular weight dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 30 to 160 mg-KOH / g, more preferably 40 to 140 mg-KOH / g, and even more preferably 50 to 130 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titrating with an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 5 to 65% by mass, more preferably 8 to 60% by mass, and even more preferably 10 to 10% by mass, based on the total solid content of the color-curable resin composition. It is 57% by mass.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa ( Meta) acrylate and the like can be mentioned.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 15% by mass, based on the total solid content of the colored curable resin composition. It is 20 to 40% by mass.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- (4-phenyl) Sulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-) Morphorinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-Phenylglycine and the like.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). (Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Specific examples of the solvent include ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone. Ester solvent (solvent containing -COO- in the molecule and not containing -O-);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule and not containing -COO-). );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (intramolecular-COO- Solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), heptanone, 4-methyl-2-pentanone, cyclohexanone (containing -CO- in the molecule, -COO -Free solvent);
Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-);
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and the like.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and cyclohexanone are more preferable.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. Is. In other words, the content of the total solid content of the color-curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, based on the total amount of the color-curable resin composition of the present invention. Is. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed. ..

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK) ..

Examples of the above-mentioned fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.%, based on the total amount of the colored curable resin composition. It is 002 to 0.1% by mass. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The color curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) used as necessary, and leveling. It can be prepared by mixing the agent (F) and other components.
The perylene compound (1), the isoindoline pigment (A1) and the pigment as the pigment (A2-2) used as needed are mixed in advance with a part or all of the solvent (E), and the average particle size of the pigment is increased. It is preferable to disperse using a bead mill or the like until the thickness becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. A color-curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit, or the like may be formed on these substrates. Further, a substrate obtained by subjecting the silicon substrate to HMDS (1,1,1,3,3,3-hexamethyldisilazane) treatment may be used.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
First, the coloring composition is applied onto a substrate and dried by heating (prebaking) and / or under reduced pressure to remove volatile components such as a solvent to obtain a smooth coloring composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature at the time of heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.
It is preferable to use an exposure apparatus because it is possible to uniformly irradiate the entire exposed surface with parallel light rays and to accurately align the photomask with the substrate on which the coloring composition layer is formed. As the exposure apparatus, a mask aligner such as a stepper (reduced projection exposure machine) or a proximity exposure machine is preferable.

A coloring pattern is formed on the substrate by developing the coloring composition layer after exposure in contact with a developing solution. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Furthermore, it is preferable to post-bake the obtained coloring pattern. The post-baking temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 150 ° C. or higher, further preferably 160 ° C. or higher, preferably 250 ° C. or lower, and more preferably 235 ° C. or lower. The post-baking time is preferably 1 minute or more, more preferably 2 minutes or more, further preferably 10 minutes or more, preferably 120 minutes or less, more preferably 60 minutes or less, still more preferably 30 minutes or less.

The film thickness of the coating film after post-baking is, for example, preferably 3 μm or less, and more preferably 2.5 μm or less. The lower limit of the film thickness of the coating film is not particularly limited, but is usually 0.1, and may be 0.5 μm or more, or 1.0 μm or more.

The color filters formed from the color curable resin composition of the present invention are dark colors and thin films. In particular, the absorption at a wavelength of 525 nm, which is required as a characteristic of the red color filter, is C.I. I. It is stronger than a color filter formed from a color curable resin composition containing Pigment Red 242 as a colorant. The absorption strength, that is, the absorbance of the color filter formed from the color curable resin composition of the present invention at a wavelength of 525 nm is determined by C.I. I. 1. The absorbance of a color filter (particularly the filter of Comparative Example 1 described later) formed from a color curable resin composition containing Pigment Red 242 as a colorant is preferably 1.1 times or more the absorbance at a wavelength of 525 nm. It is more preferably 2 times or more, and the upper limit is not particularly limited. For example, it may be 5.0 times or less, 4.0 times or less, or 3.0 times or less. .. Further, in the colored curable resin composition, in addition to strong absorption at a wavelength of 525 nm, absorption at a wavelength of more than 560 nm to 780 nm, particularly absorption at a wavelength of 565 nm is preferably suppressed. Good color reproducibility can be achieved by suppressing absorption at wavelengths of more than 560 nm to 780 nm.
Specifically, the absorbance of the color filter formed from the color curable resin composition at 525 nm is preferably 0.65 or more, more preferably 0.70 or more, and more preferably 0.75 or more. Is even more preferable. Further, the absorbance of the color filter formed from the color curable resin composition at 565 nm is preferably 1.0 or less, more preferably 0.8 or less, and further preferably 0.7 or less.

The absorption at a wavelength of 525 nm is strong, and the absorption at a wavelength of more than 560 nm to 780 nm is suppressed. Therefore, according to the color curable resin composition of the present invention, the color material concentration can be increased particularly when forming a red color filter. A dark color filter can be obtained without increasing the height or thickening the film. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor, and is particularly useful for a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the example, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
In the following synthetic examples, the compounds were identified by mass analysis (LC; Agilent 1200, MASS; Agilent LC / MSD) or elemental analysis (VARIO-EL; Elemental, Inc.).

(Synthesis Example 1)
3,4,9,10-Perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.0 parts, 7-aminotridecane (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 parts, zinc acetate 1. 3 parts (manufactured by Kanto Chemical Co., Ltd.) and 314 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 150 ° C. for 3 hours. When 267 parts of 37% hydrochloric acid (manufactured by Kanto Chemical Co., Inc.) and 1300 parts of water prepared in advance were added while keeping the obtained mixture at 20 ° C. or lower, an orange-red precipitate was formed. The mixture containing the orange-red precipitate was filtered, and the filtered residue was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 12 parts of a compound represented by the formula (1-1) (hereinafter, also referred to as compound (1-1)) (yield 79%).

<Identification of compound (1-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 755
Exact Mass: 754

(Synthesis Example 2)
3,4,9,10-Perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.0 parts, glycine (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.8 parts, zinc acetate (Kanto Chemical (Kanto Chemical Industry Co., Ltd.) 1.3 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and 314 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 150 ° C. for 7 hours. When 267 parts of 37% hydrochloric acid (manufactured by Kanto Chemical Co., Inc.) and 1300 parts of water prepared in advance were added while keeping the obtained mixture at 20 ° C. or lower, an orange-red precipitate was formed. The mixture containing the orange-red precipitate was filtered, and the filtered residue was washed with 400 parts of water and 200 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C. to obtain 9.1 parts of a compound represented by the formula (1-2) (also referred to as compound (1-2)) (yield 88%).

<Identification of compound (1-2)>
(Mass Spectrometry) ionization mode = ESI-: m / z = [ M-H] - 505
Exact Mass: 506

(Synthesis Example 3)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A solution prepared by dissolving 289 parts of a mixture of decan-9-ylacrylate (content ratio 1: 1) in 125 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. .. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over about 6 hours using another dropping pump. did. After completion of the dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9200, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (B-2) has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0 mL / min
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

[Preparation of dispersion liquid 1]
2.5 parts of Lumogen F Orange 240 (manufactured by BASF), 2.5 parts of compound (1-2), 5 parts of dispersant (BYKLPN-6919 manufactured by BYK), resin (B-2) (solid content) (Conversion) was mixed with 4 parts of propylene glycol monomethyl ether acetate, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 1. The amount of propylene glycol monomethyl ether acetate in the dispersion liquid 1 is 186 parts, which is an amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

[Preparation of dispersion liquid 2]
C. I. 12 parts of Pigment Red 242, 4.3 parts of dispersant (BYKLPN-6919 manufactured by BYK), 2.7 parts of resin (B-2) (solid content equivalent), and propylene glycol monomethyl ether acetate are mixed. , 300 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 2. The amount of propylene glycol monomethyl ether acetate in the dispersion liquid 2 is 81 parts, which is the amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

[Preparation of dispersion liquid 3]
C. I. 15 parts of Pigment Red 179, 3.8 parts of dispersant (BYKLPN-6919 manufactured by BYK), 3.0 parts of resin (B-2) (solid content equivalent), and propylene glycol monomethyl ether acetate are mixed. , 300 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 3. The amount of propylene glycol monomethyl ether acetate in the dispersion liquid 3 is 78.2 parts, which is an amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

[Preparation of dispersion liquid 4]
C. I. 12 parts of Pigment Yellow 139, 4.2 parts of dispersant (BYKLPN-6919 manufactured by BYK), 4.2 parts of resin (B-2) (solid content equivalent), and propylene glycol monomethyl ether acetate are mixed. , 300 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 4. The amount of propylene glycol monomethyl ether acetate in the dispersion liquid 4 is 79.6 parts, which is an amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

[Preparation of dispersion liquid 5]
C. I. 14.1 parts of Pigment Red 254, 4.2 parts of dispersant (BYKLPN-6919 manufactured by BYK), 4.9 parts of resin (B-2) (solid content equivalent), and propylene glycol monomethyl ether acetate. After mixing, 300 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 5. The amount of propylene glycol monomethyl ether acetate in the dispersion 5 is 76.8 parts, which is the amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

[Preparation of dispersion liquid 6]
C. I. Pigment Yellow 185 is 10.3 parts, dispersant (BYKLPN-6919 manufactured by BYK) is 4.1 parts, resin (B-2) (solid content equivalent) is 4.6 parts, and propylene glycol monomethyl ether acetate is added. After mixing, 300 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 6. The amount of propylene glycol monomethyl ether acetate in the dispersion liquid 6 is 81.0 parts, which is an amount containing propylene glycol monomethyl ether acetate derived from the resin (B-2).

Each compound was dissolved in chloroform so that the concentration was 0.001% by mass to obtain a solution. The solution was measured using an ultraviolet-visible near-infrared spectrophotometer V-650 (manufactured by JASCO Corporation). Table 1 shows the measurement results of the wavelength (maximum absorption wavelength) at the maximum absorption point of each compound.

[Examples 1 to 4, Comparative Examples 1 to 2]
<Preparation of Color Curable Resin Composition>
The components shown in Table 2 were mixed to obtain each colored curable resin composition.

Resin (B): Resin (B-2) (solid content conversion)
Polymerizable compound (C): Dipentaerythritol polyacrylate (“A9550” manufactured by Shin Nakamura Chemical Industry Co., Ltd .; solid content equivalent)
Polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanilphenyl) octane-1-one-2-imine (Irgacure® OXE 01; manufactured by BASF)
Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-2): Cyclohexanone leveling agent (F): Polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd .; solid content conversion)

<Preparation of colored coating film>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the colored composition layer was irradiated with light at an exposure amount of 60 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Then, it was post-baked in an oven at 230 ° C. for 20 minutes to obtain a colored coating film.

<Film thickness measurement>
The film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 3.

<Saturation evaluation>
The colored coating film on the obtained glass substrate was spectrophotometrically measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the absorbances at a wavelength of 525 nm and a wavelength of 565 nm were compared. The results are shown in Table 3. In Table 3, abs (525) represents the absorbance at a wavelength of 525 nm, and abs (565) represents the absorbance at a wavelength of 565 nm.

As shown in Table 3, from the colored curable resin compositions of Examples 1 and 2, it was possible to obtain a colored coating film having strong absorption at a wavelength of 525 nm and extremely suppressed absorption at a wavelength of 565 nm. Further, from the colored curable resin compositions of Examples 3 and 4, C.I. I. It was possible to obtain a colored coating film having very strong absorption at a wavelength of 525 nm while suppressing absorption at a wavelength of 565 nm caused by Pigment Red 254.

Claims

Contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
A color-curable resin composition in which the colorant contains a perylene compound (1) having a maximum absorption at 400 nm to 560 nm and no maximum absorption at more than 560 nm to 780 nm, and an isoindoline pigment (A1).
The color-curable resin composition according to claim 1, wherein the colorant (A) further contains a pigment (A2-2) other than the perylene compound (1) and the isoindoline pigment (A1).
The colored curable resin composition according to claim 1 or 2, further comprising a solvent (E).
A color filter formed from the colored curable resin composition according to any one of claims 1 to 3.
A solid-state image sensor including the color filter according to claim 4.