WO2017150667A1

WO2017150667A1 - Colorant dispersion liquid, colored polymerizable composition, and color filter

Info

Publication number: WO2017150667A1
Application number: PCT/JP2017/008281
Authority: WO
Inventors: 豊史篠塚
Original assignee: 株式会社Adeka
Priority date: 2016-03-02
Filing date: 2017-03-02
Publication date: 2017-09-08
Also published as: TW201807082A; JPWO2017150667A1

Abstract

Provided is a colorant dispersion liquid with which a colored polymerizable composition capable of forming a highly precise pattern having a high light-shielding property and high resistivity can be produced. The colorant dispersion liquid (E) is characterized by containing a polymerizable compound (A) represented by general formula (I), a colorant (B), a dispersant (C), and a dispersion medium (D). In the colorant dispersion liquid (E), the colorant (B) is preferably a black pigment. As the dispersant (C), a polymeric dispersant made from polyurethane having a nitrogen atom as a basic functional group is preferable. The colorant (B) is preferably a black pigment.

Description

Colorant dispersion, colored polymerizable composition, and color filter

The present invention relates to a colorant dispersion, a colored polymerizable composition containing the colorant dispersion of the present invention, a cured product and a black matrix obtained by curing the colored polymerizable composition, and the cured product or the black matrix. The present invention relates to a color filter having

Conventionally, color filters are widely used for the purpose of colorization of liquid crystal display devices and the like, and generally, red, green, and blue pixels are arranged in a mosaic pattern. As a method for producing this color filter, a dyeing method, a printing method, an ink jet method, an electrodeposition method, a colorant dispersion method and the like are known. In particular, a colorant dispersion method in which fine pixels are formed by photolithography using a color polymerizable composition for a color filter in which a colorant is dispersed together with a photosensitive polymer and / or a photosensitive monomer is used to improve pixel flatness. Because of its superiority, it has become the mainstream color filter manufacturing method.

The color filter coloring composition contains a pigment, a solvent, a dispersant, a photopolymerizable unsaturated compound, a photopolymerization initiator, and the like. Since the coloring composition containing a photopolymerization initiator can be polymerized and cured by irradiation with ultraviolet rays or an electron beam, it is useful for a filter segment constituting a color filter. The filter segment is formed by removing excess solvent from a coated product obtained by applying a photosensitive material on a glass substrate or the like, and then exposing the coated material to active energy by exposure through a photomask for pixel formation. It is formed by applying a heat of 230 ° C. or more called post-baking after irradiating a wire, increasing the curing (negative type) or increasing the alkali solubility (positive type), and then removing the portion dissolved with an alkali solution or the like.
In the case of using a pigment in the color filter coloring composition, it is general to prepare a pigment dispersion in which the pigment is previously dispersed in a resin or a dispersion medium when the coloring composition is prepared.

In recent years, there has been a strong demand for high-definition display panels reflecting the high quality of color image sensors and color LCD televisions. Therefore, a colored polymerizable composition for a color filter that has a high light-shielding property and can form a high-definition and high-definition black matrix has been studied. However, the existing colored polymerizable composition for a color filter has a problem that a black matrix having both light shielding properties and high resistance cannot be obtained.

Patent Document 1 discloses a colored polymerizable composition using acid-modified novolak epoxy acrylate or acid-modified bisphenol A epoxy acrylate as a dispersion resin.
Patent Document 2 discloses a photocurable composition using novolak bisphenol A epoxy acrylate as a coating material for carbon black, and Patent Document 3 discloses an acid-modified product of novolac bisphenol A epoxy acrylate as an alkali-soluble resin. A photosensitive composition using the above is disclosed.
However, a colored polymerizable composition for a color filter that has a high light-shielding property, a high resistance, and a high definition, which is currently desired, has not been obtained.

JP 2010-014961 A JP 2003-015278 A WO2008 / 023675 pamphlet

Accordingly, an object of the present invention is to provide a colorant dispersion, a colored polymerizable composition containing the colorant dispersion of the present invention, a cured product and a black matrix obtained by curing the colored polymerizable composition, and the cured product. Another object is to provide a color filter having the black matrix. The object of the present invention is also a colored polymerizable composition having a high light-shielding property and capable of forming a high-definition and high-definition pattern, particularly when carbon black is used as a colorant, and has a high light-shielding property and high resistance. An object of the present invention is to provide a colored polymerizable composition capable of forming a high-definition pattern.

The present inventors diligently studied the above-mentioned problems, and as a result, a colorant containing a polymerizable compound (A) represented by the following general formula (I), a colorant (B), a dispersant (C) and a dispersion medium (D). A colored polymerizable composition containing an agent dispersion (E) and the colorant dispersion (E), an ethylenically unsaturated compound (F) and a polymerization initiator (G) can solve the above-mentioned problems. As a result, the present invention has been achieved.

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a methyl group,
If R ³ there are a plurality or multiple R ³ are each identical or different if also there if R ⁴ there are a plurality or multiple of R ⁴ are each identical or different case,
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ and Y ⁶ (hereinafter also referred to as Y ¹ to Y ⁶ ) are each independently a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring. Represents a group having 2 to 20 carbon atoms containing
If Y ³ there are multiple, or a plurality of Y ³ are respectively the same or different when there is also located if Y ⁴ there are a plurality, or a plurality of Y ⁴ are each the same or different case,
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ (hereinafter also referred to as Z ¹ to Z ⁶ ) each independently have 1 to 20 carbon atoms substituted with a hydrogen atom or a carboxyl group. Represents a group of 1 to 20 carbon atoms containing a heterocyclic ring substituted with a hydrocarbon group or a carboxyl group,
If Z ³ there are multiple, there are a plurality of Z ³ are each identical or different case, there if Z ⁴ there are a plurality, or more Z ⁴ are each identical or different case,
Y ¹ ~ ^{Y 6} and ^Z 1 ~ 2 carbon atoms containing a hydrocarbon group and heterocyclic ring represented by ^Y 1 ~ ^{Y 6} and ^Z 1 ~ ^{Z 6} having 1 to 20 carbon atoms represented by ^{Z 6} The hydrogen atom in the groups of 20 to 20 is a group containing a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, or heterocyclic ring complex in may be ^substituted, represented by Y 1 - ^{Y 6} and ^Z 1 hydrocarbon group and ^Y 1 of ~ 1 to 20 carbon atoms represented by ^{Z 6} ~ ^{Y 6} and ^Z 1 - ^{Z 6} The methylene group in the group having 2 to 20 carbon atoms containing a ring is —O—, —CO—, —COO—, —OCO—, —S—, —SO ₂ —, —SCO— or —COS—. May be replaced,
M ¹ , M ² and M ³ (hereinafter also referred to as M ¹ to M ³ ) are each independently an alkanediyl group having 1 to 5 carbon atoms, a cycloalkyldiyl group having 3 to 10 carbon atoms or a sulfonyl group Represents
Hydrogen atoms of a cycloalkyl-diyl group which M 1 ^~ 3 to 10 carbon atoms represented by alkanediyl group having 1 to 5 carbon atoms and M ^{1 ~} M ³ represented by M ³ represents a halogen atom, a carbon atom And may be substituted with an alkyl group of 1 to 5 or an aryl group of 6 to 12 carbon atoms,
If M ² there are a plurality, there are a plurality of M ² are each identical or different case,
m represents a positive number of 0 or 10 or less. )

The present invention also provides a cured product obtained by curing the colored polymerizable composition, a black matrix obtained by curing the colored polymerizable composition, and a color filter having the cured product or the black matrix. It is.

Hereinafter, the colorant dispersion (E) and the colored polymerizable composition of the present invention will be described based on preferred embodiments.

The colorant dispersion (E) of the present invention contains the polymerizable compound (A) represented by the general formula (I), the colorant (B), the dispersant (C) and the dispersion medium (D). The colorant dispersion is characterized.

<Polymerizable compound (A)>
The polymerizable compound (A) used in the colorant dispersion (E) of the present invention is not particularly limited as long as it is a compound represented by the above general formula (I). Since it is excellent in property, the compound shown by the following general formula (II) is especially preferable.

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or a methyl group,
If R ¹³ there are a plurality There are several R ¹³ are each identical or different case,
If R ¹⁴ there are a plurality There are several R ¹⁴ are each identical or different case,
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ (hereinafter also referred to as Z ¹ to Z ⁶ ) each independently have 1 to 20 carbon atoms substituted with a hydrogen atom or a carboxyl group. Represents a group of 1 to 20 carbon atoms containing a heterocyclic ring substituted with a hydrocarbon group or a carboxyl group,
When there are a plurality of Z ¹³ , the plurality of Z ³ may be the same or different,
When there are a plurality of Z ¹⁴ , the plurality of Z ⁴ may be the same or different,
Z ¹¹ of ~ 1 to 20 carbon atoms represented by ^{Z 16} hydrogen atoms of the hydrocarbon group and ^Z 11 ^~ 2 to 20 carbon atoms containing heterocyclic ring represented by ^{Z 16} is a halogen atom, a nitro May be substituted with a group containing a group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, or a heterocyclic group, and Z ¹¹ to Z The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by ¹⁶ and the group having 2 to 20 carbon atoms containing the heterocyclic ring represented by Z ¹¹ to Z ¹⁶ is —O—, —CO—. , -COO -, - OCO -, - S -, - SO 2 -, - SCO- or -COS- with may be substituted,
n represents a positive number of 0 or 10 or less. )

Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ in the general formulas (I) and (II) each contain a single bond, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic ring. Represents a group having 2 to 20 carbon atoms. When Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ represent a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, Y ¹ to Y ^6, ^Z 1 of ~ ^{Z 6} and ^Z 11 ^~ 1 to 20 carbon atoms represented by ^{Z 16} hydrogen atoms of the hydrocarbon group, and in ^{^{^{Y 1 ~ Y 6, Z 1}}} ~ Z 6 and ^Z 11 ^{~ Z 16} The hydrogen atom of the group having 2 to 20 carbon atoms containing the heterocyclic ring represented is a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, It may be substituted with a mercapto group, an isocyanate group or a group containing a heterocyclic ring. Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ each represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and carbon When the hydrocarbon group having 1 to 20 atoms or the group having 2 to 20 carbon atoms containing a heterocycle has a methylene group, the methylene group is —O—, —CO—, —COO—, —OCO—. , -S-, -SO _2- , -SCO- or -COS-.

The hydrocarbon group having 1 to 20 carbon atoms represented by Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ is not particularly limited, but preferably has 1 to 20 carbon atoms. An alkanediyl group having 2 to 20 carbon atoms, a cycloalkanediyl group having 3 to 20 carbon atoms, a cycloalkylalkanediyl group having 4 to 20 carbon atoms, an aryldiyl group having 6 to 20 carbon atoms, and Represents an arylalkanediyl group having 7 to 20 carbon atoms.

Examples of the alkanediyl group having 1 to 20 carbon atoms include methanediyl, ethanediyl, propanediyl, isopropanediyl, butanediyl, isobutanediyl, s-butanediyl, t-butanediyl, pentanediyl, isopentanediyl, t-pentanediyl, hexane Diyl, heptanediyl, octanediyl, isooctanediyl, 2-ethylhexanediyl, t-octanediyl, nonanediyl, isononanediyl, decanediyl, isodecanediyl, undecanediyl, dodecanediyl, tetradecanediyl, hexadecanediyl and octadecanediyl.

Examples of the alkenediyl group having 2 to 20 carbon atoms include ethanediyl, propenediyl, 3-butenediyl, 2-butenediyl, 4-pentenediyl, 3-pentenediyl, 2-hexenediyl, 3-hexenediyl, 5-hexenediyl, and 2-heptenediyl. 3-heptenediyl, 4-heptenediyl, 3-octenediyl, 3-nonenediyl, 4-decenediyl, 3-undecenediyl, 4-dodeceninediyl, 3-cyclohexenediyl and the like.

The above-mentioned cycloalkanediyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the cycloalkanediyl group having 3 to 20 carbon atoms include cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, cyclononanediyl, cyclodecandidiyl, adamantanediyl, Examples include decahydronaphthalenediyl, octahydropentanediyl, bicyclo [1.1.1] pentanediyl, and tetradecahydroanthracenediyl.

The cycloalkyl alkanediyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkanediyl group is substituted with a cycloalkyl group. Examples of the cycloalkylalkanediyl group having 4 to 20 carbon atoms include cyclopropylmethanediyl, cyclobutylmethanediyl, cyclopentylmethanediyl, cyclohexylmethanediyl, cycloheptylmethanediyl, cyclooctylmethanediyl, and cyclononylmethanediyl. , Cyclodecylmethanediyl, 2-cyclobutylethanediyl, 2-cyclopentylethanediyl, 2-cyclohexylethanediyl, 2-cycloheptylethanediyl, 2-cyclooctylethanediyl, 2-cyclononylethanediyl, 2-cyclodecyl Ethanediyl, 3-cyclobutylpropanediyl, 3-cyclopentylpropanediyl, 3-cyclohexylpropanediyl, 3-cycloheptylpropanediyl, 3-cyclooctylpropaprop Diyl, 3-cyclononylpropanediyl, 3-cyclodecylpropanediyl, 4-cyclobutylbutanediyl, 4-cyclopentylbutanediyl, 4-cyclohexylbutanediyl, 4-cycloheptylbutanediyl, 4-cyclooctylbutanediyl, 4 -Cyclononylbutanediyl, 4-cyclodecylbutanediyl, 3-3-adamantylpropanediyl, decahydronaphthylpropanediyl and the like.

Examples of the aryldiyl group having 6 to 20 carbon atoms include benzenediyl, toluenediyl, xylenediyl, ethylbenzenediyl, naphthalenediyl, anthracenediyl, phenanthrenediyl and biphenyldiyl.

The arylalkanediyl group having 7 to 30 carbon atoms means a group having 7 to 30 carbon atoms in which a hydrogen atom of the alkanediyl group is substituted with an aryl group. Examples of the arylalkanediyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl, etc., and the aryl having 7 to 20 carbon atoms. An alkyl group means a group having 7 to 30 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.

The group having 2 to 20 carbon atoms containing a heterocyclic ring represented by Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ includes at least one heterocyclic ring, and the carbon of the entire group It means a group having 2 to 20 numbers. Examples of the group having 2 to 20 carbon atoms containing a heterocyclic ring include pyrrole diyl, pyridinediyl, pyridylethanediyl, pyrimidinediyl, piperazinediyl, piperidinyl, pyrandiyl, pyranylethanediyl, pyrazolinediyl, triazinediyl, triazyl Methanediyl, quinolinediyl, isoquinolinediyl, imidazolinediyl, benzimidazolonedilyl, frangyl, benzofurandyl, thiophenediyl, benzothiophenediyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolediyl, isoxa Examples include zondiryl, indoyl diyl, morpholine diyl and thiomorpholine diyl. When the heterocyclic ring in a group containing a heterocyclic ring has a substituent, the total number of carbon atoms in the group may exceed 20. When the heterocyclic ring in a group having 2 to 20 carbon atoms containing a heterocyclic ring has a substituent, examples of the substituent include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, Examples include an acryloyl group, an epoxy group, a vinyl group, a mercapto group, or an isocyanate group.

Examples of the alkanediyl group having 1 to 5 carbon atoms represented by M ¹ to M ³ include methanediyl, ethanediyl, propanediyl, butanediyl and butanediyl. In view of good compatibility with the colorant (B), the alkanediyl group having 1 to 5 carbon atoms represented by M ¹ to M ³ is preferably methanediyl, ethanediyl or propanediyl. Most preferred is diyl.

The cycloalkyldiyl group having 3 to 10 carbon atoms represented by M ¹ to M ³ means a saturated monocyclic or saturated polycyclic alkyldiyl group having 3 to 10 carbon atoms. Examples of the cycloalkyldiyl group having 3 to 10 carbon atoms represented by M ¹ to M ³ include cyclopropyldiyl, cyclobutyldiyl, cyclopentyldiyl, cyclohexyldiyl, cycloheptyldiyl, cyclooctyldiyl, and cyclononyl. Diyl, cyclodecyldiyl, adamantyldiyl, decahydronaphthyldiyl, octahydropentalenediyl, bicyclo [1.1.1] pentanyldiyl, etc. are mentioned, and the compatibility with the colorant of the polymerizable compound (A) is good. In addition, bicyclo [1.1.1] pentanyldiyl is more preferable because of good dispersibility.

Examples of the alkyl group having 1 to 5 carbon atoms that can replace the hydrogen atom of the alkanediyl group having 1 to 5 carbon atoms and the cycloalkyldiyl group having 3 to 10 carbon atoms represented by M ¹ to M ³ above. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl and t-pentyl.

Examples of the aryl group having 6 to 12 carbon atoms that can replace the hydrogen atoms of the alkanediyl group having 1 to 5 carbon atoms and the cycloalkyldiyl group having 3 to 10 carbon atoms represented by the above M ¹ to M ³ Examples thereof include phenyl, tolyl, xylyl, ethylphenyl and naphthyl.

A hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms represented by Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ , Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to hydrogen atom of the group having 2 to 20 carbon atoms containing heterocyclic ring represented by Z ^{^16,} alkanediyl group having 1 to 5 carbon atoms represented by ^M 1 ~ M ^3, as well as in ^M 1 ~ ^{M 3} Examples of the halogen atom that can replace the hydrogen atom of the cycloalkyldiyl group having 3 to 10 carbon atoms include fluorine, chlorine, bromine, and iodine.

A hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms represented by Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ to Z ¹⁶ , and Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ¹¹ Examples of the group containing a heterocyclic ring capable of substituting a hydrogen atom of a group having 2 to 20 carbon atoms containing a heterocyclic ring represented by ˜Z ¹⁶ include Y ¹ to Y ⁶ , Z ¹ to Z ⁶ and Z ^11. include those exemplified as the group ~ having 2 to 20 carbon atoms containing heterocyclic ring represented by Z ^16.

In the above general formula (I), m is a positive number of 0 or 10 or less. M is preferably 2 to 10 because of good compatibility with the dispersion medium (D) and good dispersibility of the colorant. When m is less than 2, the dispersibility of the colorant is poor, and when m is greater than 10, the solubility in the dispersant is poor.

In the general formula (II), n is a positive number of 0 or 10 or less. N is preferably 2 to 10 because of good compatibility with the dispersion medium (D) and good dispersibility of the colorant (B). When n is smaller than 2, the dispersibility of the colorant (B) is poor, and when n is larger than 10, the solubility in the dispersant (C) is poor.

The polymerizable compound (A) can be produced according to the following reaction formula [Chemical Formula 3]. That is, the production method of the polymerizable compound (A) is known, and the following compound A-1 can be obtained by reacting a commercially available epoxy compound with an unsaturated monobasic acid such as acrylic acid. By further reacting the obtained compound A-1 with a polybasic acid such as phthalic anhydride, the following compound A-2 can be obtained.

Examples of the unsaturated monobasic acid to be reacted with the epoxy compound include acrylic acid, methacrylic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, -Methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-acryloxyethyl-2-hydroxyethylphthalic acid, 2-methacryloxyethyl-2-hydroxyethylphthalic acid, 2-acryloxyethyl hexahydrophthalic acid, 2-methacryloxyethyl hexahydrophthalic acid, pentaerythritol pentaacrylate succinic acid modified product, pentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol pentaacrylate Succinic acid-modified products, and pentaerythritol pentaacrylate phthalic acid-modified products, and the like.
As the unsaturated monobasic acid, acrylic acid and methacrylic acid are preferable because they are easy to handle and the reaction rate is high, and acrylic acid is most preferable because the resulting polymerizable compound (A) has good reactivity.
A commercial item can be used as said unsaturated monobasic acid. Commercially available unsaturated monobasic acids include NK ester A-SA, SA, CB-1 (manufactured by Shin-Nakamura Chemical Co., Ltd.), light ester A, HOA-MS, HO-MS, HOA-MPE, HOA-HH. , HOA-MPL, DPE6A-MS, PE3A-MS, DPE6A-MP and PE3A-MP (manufactured by Kyoeisha) and Aronix M-5300 (Toagosei).

Examples of the polybasic acid anhydride to be reacted with the compound A-1 include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride. 2,2′-3,3′-benzophenone tetracarboxylic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, dodecenyl succinic anhydride and the like.

The colorant dispersion (E) of the present invention may contain an ethylenically unsaturated compound (F) described later in addition to the polymerizable compound (A). The content of the ethylenically unsaturated compound (F) in the colorant dispersion (E) of the present invention is not particularly limited, but is 10 parts by mass or less with respect to 100 parts by mass of the polymerizable compound (A). Is preferred.

In the colorant dispersion (E) of the present invention, the content of the polymerizable compound (A) is not particularly limited, but it is colored in a total of 100 parts by mass of the solid content of the colorant dispersion (E). From the viewpoint of good dispersibility of the agent, the amount is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass. When the content of the polymerizable compound (A) is smaller than 1 part by mass, the dispersibility of the colorant may be inferior, and when it is larger than 30 parts by mass, sufficient coloring may not be expressed.
For example, in the case of producing a black matrix coloring composition using the colorant dispersion (E), the content of the polymerizable compound (A) in the colorant dispersion (E) is determined according to the colorant dispersion ( E) The total solid content is 100 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass.

<Colorant (B)>
As the colorant (B) used in the colorant dispersion (E) of the present invention, pigments and dyes can be used. As the pigment and the dye, an inorganic color material or an organic color material can be used, respectively, and these can be used alone or in admixture of two or more. Here, the pigment refers to a colorant that is insoluble in the dispersion medium (D) described below, and among inorganic or organic colorants or inorganic or organic dyes, those that are insoluble in the dispersion medium (D), or inorganic or organic dyes The raked version is also included.

Examples of the pigment include carbon black obtained by a furnace method, a channel method or a thermal method, or carbon black such as acetylene black, ketjen black or lamp black, the carbon black prepared or coated with an epoxy resin, the carbon Black previously dispersed with a resin in a solvent and coated with 20 to 200 mg / g of resin, an acid or alkaline surface treated carbon black, an average particle size of 8 nm or more, and a DBP oil absorption of 90 ml / Carbon black, graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotubes having a total oxygen amount of 9 mg or more per 100 m ^{2 of} surface area, calculated from CO and CO ₂ in volatile matter at 950 ° C. at 100 g or less , Carbo Black pigments such as microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, perylene black, lactam black, pigment black 7, titanium black, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, Russianide, phosphate ultramarine, bituminous, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red pepper (red iron (III) oxide), cadmium red, synthetic iron black, amber, lake Examples thereof include organic or inorganic pigments such as pigments, and it is preferable to use a black pigment because of its high light shielding properties, and it is more preferable to use carbon black.

Among the above carbon blacks, carbon black having a sulfonic acid group on the surface of carbon black can provide a colorant dispersion excellent in dispersibility, has excellent light shielding properties, and has good adhesion to substrates such as glass. Since a thing is obtained, it is preferable.

Examples of the method for imparting a sulfonic acid group to the surface of carbon black include a method of oxidizing carbon black with peroxodisulfuric acid or a salt thereof (1), and a method of treating carbon black with a sulfonating agent (2).

The method (1) for oxidizing carbon black with peroxodisulfuric acid or a salt thereof can be performed by any known method. For example, carbon black, peroxodisulfuric acid or a salt thereof, and an aqueous medium (water or a mixture of water and a water-soluble solvent) are mixed with a surfactant or a dispersant as necessary, and the mixture is less than 100 ° C. It can be carried out by heating at 40 to 90 ° C. for less than 24 hours, preferably 2 to 20 hours, and neutralizing to pH ≧ 7 as necessary.
Examples of the salt of peroxodisulfuric acid include metal salts such as lithium, sodium, potassium, and aluminum, or ammonium salts.
The amount of peroxodisulfuric acid or a salt thereof used is preferably in the range of 0.5 to 5 parts by mass with respect to 1 part by mass of carbon black.

The method (2) for treating the carbon black with the sulfonating agent can be carried out by any known method. For example, the carbon black and the sulfonating agent are mixed or dissolved in a solvent, and 200 ° C. or less, preferably Stir at 0-100 ° C.
As the sulfonating agent, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, halogenated sulfate, amide sulfate, bisulfite, sulfite, SO 3 _- dioxane complex, SO 3 _- ketone complexes, sulfamic acid, sulfonated pyridine salt Etc.
Examples of the solvent include water; acidic solvents such as sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid and acetic anhydride; basic solvents such as pyridine, triethylamine and trimethylamine; ethers such as tetrahydrofuran, dioxane and diethyl ether; dimethylformamide Polar solvents such as dimethylacetamide, N-methylpyrrolidone, sulfolane, nitromethane, acetone, acetonitrile and benzonitrile; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, xylene and nitrobenzene; methanol, Alcohol solvents such as ethanol and isopropanol; chlorine solvents such as chloroform, trichlorofluoromethane, methylene chloride, and chlorobenzene can be used, and a mixed solvent thereof may be used.
The amount of the sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass with respect to 1 part by mass of carbon black. When a plurality of sulfonating agents are used, the total amount is within the above range. preferable.
In addition, in order to suppress the production of a known sulfone produced as a side reaction of the sulfonation reaction, a known sulfone inhibitor such as a fatty acid, an organic peracid, an acid anhydride, acetic acid, a ketone, etc. is used as long as the reaction is not inhibited. In some cases, 0.01 to 5 parts by mass is added to 1 part by mass of carbon black.

As the inorganic color material or organic color material, known dyes can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, And dyes such as phthalocyanine dyes and cyanine dyes.

Examples of the inorganic or organic colorant include, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, Examples include quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids, azo dyes, and cyanine dye metal complex compounds. .

As the inorganic color material or organic color material, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180 and 185; Pigment Green 7, 10, 36 and 58; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62 and 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

In the colorant dispersion liquid (E) of the present invention, the content of the colorant (B) is not particularly limited. From the viewpoint of goodness, it is preferably 30 to 90 parts by mass, and more preferably 50 to 90 parts by mass. If the content of the colorant (B) is less than 30 parts by mass, a colored polymerizable composition having a sufficient colorant concentration may not be formed. If the content is greater than 90 parts by mass, the colorant (B) In some cases, the colorant dispersion (E) cannot be sufficiently dispersed.
For example, when a colored polymerizable composition for a color filter is produced using the colorant dispersion (E), the content of the colorant (B) in the colorant dispersion (E) is determined by the colorant dispersion. (E) In a total of 100 parts by mass of the solid content, it is preferably 30 to 90 parts by mass, and more preferably 50 to 90 parts by mass.

<Dispersant (C)>
Although it does not specifically limit as a dispersing agent (C) used for the coloring agent dispersion liquid (E) of this invention and the coloring polymeric composition mentioned later, it can disperse | distribute and stabilize a coloring agent (B). A polymer dispersant made of polyester, polyether or polyurethane having a basic functional group, a nitrogen atom as the basic functional group, the functional group having a nitrogen atom being an amine, and / or a quaternary salt thereof And those having an amine value of 1 to 100 mgKOH / g can be used. Since the dispersibility of carbon black is excellent, the dispersant (C) is particularly preferably a polymer dispersant made of polyurethane having a nitrogen atom as a basic functional group.

As the dispersant (C), commercially available dispersants can also be used. For example, DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-167, DISPERBYK-168, DISPERBYK. -170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2020, 70 DISPERBYK-2096 DISPERBYK-2150, DISPERBYK-LPN21116, DISPERBYK-LPN6919 (manufactured by BYK-Chemie GmbH), Ajisper PB711, Adisper PB821, Adisper PB822, Adisper PB814, Adisper PN411 and Ajisper PA111 (Ajinomoto Co., Inc.), and the like.

In the colorant dispersion (E) of the present invention, the content of the dispersant (C) is not particularly limited, but the colorant dispersion is contained in a total of 100 parts by weight of the solid content of the colorant dispersion (E). Since the dispersibility of the colorant in the liquid (E) becomes better, it is preferably 5 to 40 parts by mass, more preferably 5 to 20 parts by mass. If the content of the dispersant (C) is less than 5 parts by mass, the dispersibility of the colorant may be inferior. If it is greater than 40 parts by mass, a colorant dispersion having a sufficient colorant concentration may not be produced. is there.
For example, when a colored polymerizable composition for a color filter is produced using the colorant dispersion (E), the content of the dispersant (C) in the colorant dispersion (E) is determined by the colorant dispersion. (E) The total solid content is 100 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 5 to 20 parts by mass.

<Dispersion medium (D)>
The dispersion medium (D) used in the colorant dispersion (E) of the present invention is usually a solvent that can dissolve or disperse the above components as necessary. Examples thereof include methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc. Ether solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; ethylene glycol monomethyl ether and ethyl Cellosolve solvents such as glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol and amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol Ether ester solvents such as 1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; hexane, Aliphatic hydrocarbon solvents such as heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, Paraffinic solvents such as Wazol # 310 (manufactured by Cosmo Matsuyama Petroleum) and Solvesso # 100 (manufactured by Exxon Chemical); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include methyl pyrrolidone, dimethyl sulfoxide and water, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents and the like, particularly PGMEA and cyclohexanone are preferable because the colorant dispersion and the compatibility between the resist and the polymerization initiator are good in the colorant dispersion (E) and the color polymerizable composition. .

In the colorant dispersion liquid (E) of the present invention, the content of the dispersion medium (D) is not particularly limited, but it is colored with respect to a total of 100 parts by weight of the solid content of the colorant dispersion liquid (E). In view of good handling of the agent dispersion (E), the amount is preferably 100 to 1900 parts by mass, and more preferably 200 to 900 parts by mass. When the amount is larger than 1900 parts by mass, there may be a case where a colored polymerizable composition having a sufficient colorant concentration cannot be obtained. When the amount is less than 100 parts by mass, sufficient colorant dispersibility may not be obtained.
For example, when forming a colored polymerizable composition for a color filter using the colorant dispersion (E), the content of the dispersion medium (D) in the colorant dispersion (E) is particularly limited. Although it is not a thing, since it is easy to handle the colorant dispersion (E) with respect to a total of 100 parts by weight of the solid content of the colorant dispersion (E), it is preferably 100 to 1900 parts by weight, More preferably, it is 200 to 900 parts by mass.

The colorant dispersion (E) of the present invention is a mixture of a polymerizable compound (A), a dispersant (C), a dispersion medium (D), etc., and a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, etc. Can be obtained by dispersing the colorant (B).

The colorant dispersion (E) of the present invention is a gravure ink, offset ink, ink for inkjet printer, colored polymerizable composition for color filter, various general paints for automobile, wood, metal, etc., magnetic tape back It can be used for various applications such as coat paints and radiation cure inks, and there are no particular restrictions on the applications.

The colorant dispersion (E) of the present invention can be used for a color filter black matrix coloring composition when a black pigment typified by carbon black is used as the colorant (B). The colored composition for a matrix for a color filter is particularly useful for a color filter for a display device for an image display device such as a liquid crystal display panel.

<Coloring polymerizable composition>
An ethylenically unsaturated compound (F) and a polymerization initiator (G) can be added to the colorant dispersion (E) to obtain the colored polymerizable composition of the present invention.

In the colored polymerizable composition of the present invention, the content of the colorant dispersion liquid (E) is not particularly limited. For example, a colorant dispersion having a solid content of 25% by mass in the production of the colored polymerizable composition is used. When the liquid (E) is used, it is preferably 10 to 80 parts by mass, more preferably 30 to 80 parts by mass, because the colorability is good in a total of 100 parts by mass of the colored polymerizable composition. When the content of the colorant dispersion (E) having a solid content of 25% by mass is less than 10 parts by mass, sufficient coloring may not be obtained. May decrease.
When the colored polymerizable composition is, for example, a colored polymerizable composition for a color filter, the content of the colorant dispersion (E) having a solid content of 25% by mass is that of the colored polymerizable composition for the color filter. The total content is 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 30 to 80 parts by mass.

Preferred contents of the polymerizable compound (A), the colorant (B) and the dispersant (C) in the colored polymerizable composition are shown below.

In the colored polymerizable composition of the present invention, the content of the polymerizable compound (A) is not particularly limited, but the dispersibility of the colorant in the total 100 parts by mass of the solid content of the colored polymerizable composition. Is preferably 1 to 20 parts by mass, and more preferably 1 to 10 parts by mass. If the content of the polymerizable compound (A) is less than 1 part by mass, the dispersibility of the colorant may be inferior, and if it is greater than 20 parts by mass, sufficient coloring may not be expressed.
When the colored polymerizable composition is, for example, a colored composition for color filters, the content of the polymerizable compound (A) in the colored polymerizable composition for color filters is the solid content of the colored composition for color filters. Is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass.

In the colored polymerizable composition of the present invention, the content of the colorant (B) is not particularly limited, but the colorability is good in a total of 100 parts by mass of the solid content of the colored polymerizable composition. Therefore, the amount is preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass. When the content of the colorant (B) is less than 20 parts by mass, sufficient light shielding properties may not be obtained, and when it is greater than 80 parts by mass, the chemical resistance of the cured product described later may be reduced. .
When the color polymerizable composition is, for example, a color polymerizable composition for color filters, the content of the colorant (B) in the color polymerizable composition for color filters is the same as that of the color polymerizable composition for color filters. The total solid content is 100 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass.

In the colored polymerizable composition of the present invention, the content of the dispersant (C) is not particularly limited, but in a total of 100 parts by mass of the solid content of the colored polymerizable composition, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass. If the content of the dispersant (C) is less than 0.1 parts by mass, the dispersibility of the colorant may be inferior, and if it is greater than 20 parts by mass, the chemical resistance may be deteriorated.
When the colored polymerizable composition is, for example, a colored polymerizable composition for a color filter, the content of the dispersing agent (C) in the colored polymerizable composition for a color filter is the colored polymerizable composition for a color filter. The total solid content is 100 to 100 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass.

<Ethylenically unsaturated compound (F)>
The ethylenically unsaturated compound (F) used in the colored polymerizable composition of the present invention is not particularly limited as long as it is a compound having a carbon-carbon double bond in the compound. Can be used. The polymerizable compound (A) can be further added as an ethylenically unsaturated compound (F) when preparing the colored polymerizable composition.

Examples of the ethylenically unsaturated compound (F) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2- (meta ) Acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate, etc., polymer mono (meth) having a carboxy group and a hydroxyl group at both ends Acrylate; hydroxyethyl (meth) acrylate malate, H Unsaturated monobasic acids such as roxypropyl (meth) acrylate malate, dicyclopentadiene malate and polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound no. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Enoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate and tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomers; Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-none Acid anhydrides of unsaturated polybasic acids such as hydromaleic acid adduct, dodecenyl succinic anhydride and methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meta ) Unsaturated monobasic acids and amides of polyvalent amines such as acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; Unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene chloride and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoate Unsaturated aromatic compounds such as perfume acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinyl Unsaturated amine compounds such as pyrrolidone and vinyl piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; maleimide, N-phenyl Unsaturated imides such as maleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; 1,3-butadiene, isoprene and chloroprene Aliphatic conjugated dienes such as polystyrene; macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; vinyl Chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer, polyisocyanate Examples of the compound include a vinyl urethane compound, a hydroxyl group-containing vinyl monomer, and a vinyl epoxy compound of a polyepoxy compound.
Commercially available products can be used as the ethylenically unsaturated compound (F). For example, Kaylad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku), SPC- 1000, SPC-3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350, M-450 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD-N A-9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of the ethylenically unsaturated compound (F) include a copolymer of acrylic ester, a product obtained by reacting phenol and / or cresol novolac epoxy resin with an unsaturated monobasic acid, and a polyfunctional epoxy group. What reacted phenyl phenyl type epoxy resin and unsaturated monobasic acid can also be used.

Among the ethylenically unsaturated compounds (F), when a compound having an acid value is used, alkali developability can be imparted to the colored polymerizable composition of the present invention. When the compound having the acid value is used, the amount used should be 50 to 99% by mass of the entire polymerizable compound having an ethylenically unsaturated bond including the ethylenically unsaturated compound (F). preferable.
The compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. The alkali developability of the curable resin can be improved by adjusting the acid value of the compound having the acid value. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl A , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, compound No.A2 and No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored curable resin composition with better characteristics can be obtained.
As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, and 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds and dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane Compound; Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and dimer acid glycidyl; tetraglycidyl di Glycidylamines such as minodiphenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

Preferred examples of the ethylenically unsaturated compound (F) include ethylenically unsaturated compounds having an indane skeleton.
The ethylenically unsaturated compound having an indane skeleton is obtained by epoxidizing a bisphenol compound having an indane skeleton and then reacting with an unsaturated basic acid; after epoxidizing a novolak compound having an indane skeleton, an unsaturated base A product reacted with an acid; an alkylene oxide added to a bisphenol compound having an indane skeleton, followed by epoxidation and a reaction with an unsaturated basic acid; an alkylene oxide added to a novolak compound having an indane skeleton Thereafter, epoxidation and reaction with an unsaturated basic acid are exemplified.

Specifically, examples of the ethylenically unsaturated compound having an indane skeleton include 1,1-bis [4-[(4-ethylenephenyl) methoxy] phenyl] -2,3-dihydro-3-phenyl- 1H-indene, (3-phenyl-2,3-dihydro-1H-indene-1,1-diyl) bis (4,1-phenylene) diacrylate and (3,5-phenyl-2,3-dihydro-1H -Indene-1,1-diyl) bis (4,1-phenylene) diacrylate and the like.

Examples of the ethylenically unsaturated compound having an indane skeleton include an epoxy adduct obtained by reaction of an epoxy compound represented by the following general formula (III) with an ethylenically unsaturated monobasic acid, a polybasic acid anhydride, An ethylenically unsaturated compound, which is a reaction product obtained by the esterification reaction, is preferred because of good colorant dispersibility and curability.

Wherein Y represents a substituent selected from the group represented by the following formulas (A) and (B), and R ²¹ to R ²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms or a halogen atom, and k is a number from 0 to 10. When k is a number from 1 to 10, a plurality of R ²¹ to R ²⁸ present in the compound and Y may be the same or different.)

(Wherein R ²⁹ to R ⁴⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon atom) Represents an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group is an unsaturated bond, —O— or —S—. R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ and R ³⁹ and R ⁴⁰ are bonded to form a ring. May form.)

In the general formula (III), the alkyl group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁸ includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, trifluoromethyl, difluoromethyl, monofluoro Methyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, Ropenchiru, cyclohexyl, cycloheptyl, cyclooctyl, etc. cyclononyl and cyclodecyl and the like.

In the general formula (III), the alkoxy group having 1 to 10 carbon atoms represented by R ²¹ to R ²⁸ is methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyl. Oxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, trifluoromethyloxy, difluoromethyloxy, monofluoromethyloxy, pentafluoroethyloxy, tetrafluoroethyloxy, trifluoroethyloxy, difluoroethyloxy, hepta Fluoropropyloxy, hexafluoropropyloxy, pentafluoropropyloxy, tetrafluoropropyloxy, trifluoropropyloxy, perfluorobutyloxy, cyclopropyloxy, Black butyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy include cyclo-nonyl oxy and cycloalkyl decyloxy and the like.

In the general formula (III), examples of the halogen atom represented by R ²¹ to R ²⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the substituent selected from the group represented by the above formulas (a) and (b) that is Y in the general formula (III), an alkyl group having 1 to 20 carbon atoms represented by R ²⁹ to R ⁴⁴ As methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl , Isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoro Ethyl, trifluoroethyl, difluoroethyl, Data fluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. cyclononyl and cyclodecyl and the like.

In the substituent selected from the group represented by the above formulas (a) and (b) that is Y in the general formula (III), an alkoxy group having 1 to 20 carbon atoms represented by R ²⁹ to R ⁴⁴ As methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, undecyl Oxy, dodecyloxy, tridecyloxy, isotridecyloxy, myristyloxy, palmityloxy, stearyloxy, trifluoromethyloxy, difluoromethyloxy, monofluoromethyloxy, pentafluoroethyloxy, tetrafluoroethyloxy, trifluoro Tiloxy, difluoroethyloxy, heptafluoropropyloxy, hexafluoropropyloxy, pentafluoropropyloxy, tetrafluoropropyloxy, trifluoropropyloxy, perfluorobutyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, Examples include cycloheptyloxy, cyclooctyloxy, cyclononyloxy, and cyclodecyloxy.

In the substituent selected from the group represented by the above formulas (A) and (B) that is Y in the general formula (III), an aryl group having 6 to 20 carbon atoms represented by R ²⁹ to R ⁴⁴ As phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl 2,4-di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di -T-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluorophenyl, etc.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ²⁹ to R ⁴⁴ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl and 4-chlorophenylmethyl. .

In the substituent selected from the group represented by the above formulas (a) and (b), which is Y in the general formula (III), a heterocyclic group having 2 to 20 carbon atoms represented by R ²⁹ to R ⁴⁴ As pyrrolyl, pyridyl, pyrimidyl, pyridadyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl , Benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimi Zorijin-3-yl and 2,4-dioxy-oxazolidinedione-3-yl, and the like.

In the substituent selected from the group represented by the above formulas (A) and (B) which is Y in the general formula (III), the halogen atom represented by R ²⁹ to R ⁴⁴ includes a fluorine atom, chlorine An atom, a bromine atom, and an iodine atom are mentioned.

In the substituent selected from the group represented by the above formulas (A) and (B) which is Y in the general formula (III), R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³² , R ³⁷ and R ³⁸ , R ³⁸ and R ³⁹ and R ³⁹ and R ⁴⁰ are, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, Examples thereof include 5- to 7-membered rings such as tetrahydropyridine, lactone ring and lactam ring, and condensed rings such as naphthalene and anthracene.

The ethylenically unsaturated monobasic acid to be reacted with the epoxy compound represented by the general formula (III) is a single hydrogen atom that has an unsaturated bond in the structure and can be ionized to form a hydrogen ion. It means an acid with one per unit.
Examples of the ethylenically unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid and hydroxyethyl methacrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / Examples thereof include malate, and acrylic acid and methacrylic acid are preferable because of high polymerizability.

The polybasic acid anhydride to be esterified with the epoxy adduct obtained by the reaction of the epoxy compound represented by the general formula (III) and the ethylenically unsaturated monobasic acid includes biphenyltetracarboxylic dianhydride, Tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate , Glycerol trisanhydro trimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-si Rohekisen 1,2-dicarboxylic anhydride, trialkyl tetrahydrophthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound represented by the general formula (III) to the ethylenically unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the ethylenically unsaturated monobasic acid are added to one epoxy group of the epoxy compound, It is preferable that the polybasic acid anhydride has a polybasic acid anhydride structure in a ratio of 0.1 to 1.0 with respect to one hydroxyl group.
Although the reaction example of the said epoxy compound, the said ethylenically unsaturated monobasic acid, and the said polybasic acid anhydride is shown below, it is not limited to the following reaction scheme 1.

As the ethylenically unsaturated compound (F), among the above reaction products, it is possible to use an epoxy compound represented by the general formula (III) in which R ²¹ to R ²⁶ are hydrogen atoms. It is preferable from the viewpoint of further enhancing the ease of use and the effects of the present invention. From the same viewpoint, Y is a group represented by (A), R ²⁹ to R ³⁶ are a hydrogen atom or a phenyl group, or Y is a group represented by (B), and R It is also preferred to use those in which ³⁷ to R ⁴⁴ are a hydrogen atom or a phenyl group.
Moreover, since the polymerizable property of the colored polymerizable composition is high, those using 5 or less carbon atoms are preferable as the ethylenically unsaturated monobasic acid, and those using acrylic acid, methacrylic acid, etc. are particularly preferable. .
In addition, since the dispersibility of the colorant is excellent, those having a benzene ring or a saturated alicyclic ring as the polybasic acid anhydride are preferable. Those using anhydrides are preferred.

As the ethylenically unsaturated compound (F) used in the present invention, since the dispersibility and curability of the colorant are good, among the above reaction products, it is obtained by using the following compounds as raw materials, among others. Products are preferred, but not limited thereto.
Specifically, for example, 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane as an epoxy compound represented by the above general formula (III) is used as an ethylenically unsaturated monobasic acid. A product comprising acrylic acid and biphthalic anhydride as the polybasic acid anhydride;
1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane as an epoxy compound represented by the above general formula (I), acrylic acid as an unsaturated monobasic acid, polybasic acid anhydride The product obtained using tetrahydrophthalic anhydride as
1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane as an epoxy compound represented by the above general formula (I), acrylic acid as an unsaturated monobasic acid, and phthalate as a polybasic acid Products obtained using acid anhydrides;
1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane as an epoxy compound represented by the above general formula (I), acrylic acid as an unsaturated monobasic acid, polybasic acid anhydride A product obtained by using biphthalic anhydride and tetrahydrophthalic anhydride as: 1,1-bis [4- (2,3-epoxypropyloxy) as an epoxy compound represented by the above general formula (I) Products obtained using phenyl] -3-phenylindane, acrylic acid as the unsaturated monobasic acid, biphthalic anhydride and tetrahydrophthalic anhydride as the polybasic acid anhydride, and the like.

In the colored polymerizable composition of the present invention, the content of the ethylenically unsaturated compound (F) is not particularly limited, but the cured product described later in a total of 100 parts by weight of the solid content of the colored polymerizable composition. The chemical resistance is preferably 5 to 60 parts by mass, more preferably 5 to 50 parts by mass. When the content of the ethylenically unsaturated compound (F) is smaller than 5 parts by mass, the chemical resistance of the cured product described later may be inferior, and when it is larger than 60 parts by mass, sufficient coloring may not be obtained. is there.
When the colored polymerizable composition is, for example, a colored polymerizable composition for a color filter, the content of the ethylenically unsaturated compound (F) in the colored polymerizable composition for a color filter is the colored polymerization for the color filter. It is preferably 10 to 60 parts by mass, more preferably 5 to 50 parts by mass, in a total of 100 parts by mass of the solid content of the composition.

<Polymerization initiator (G)>
A conventionally known radical polymerization initiator can be used as the polymerization initiator (G) used in the colored polymerizable composition of the present invention. Conventionally known radical polymerization initiators include photopolymerization initiators and thermal polymerization initiators.
Examples of the photopolymerization initiator include benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2- Morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2- Hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloro Methane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2,2-bis (2-Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N -1717, N-1919, NCI-831, NCI-930 (made by ADEKA), IRGACURE369, IRGACURE907, IRGACURE XE 01 and IRGACURE OXE 02 (manufactured by BASF) and the like. Examples of thermal polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (methylisobutyrate), Azo initiators such as' -azobis-2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butylbenzoyl peroxide, t- Examples thereof include peroxide initiators such as butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

As the polymerization initiator (G) used in the colored polymerizable composition of the present invention, it is particularly preferable to use a compound represented by the following general formula (IV). The cured product obtained from the composition is preferable because of good heat resistance.

Wherein R ⁵¹ and R ⁵² are each independently a hydrogen atom, a nitro group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or the number of carbon atoms In some cases, it may represent an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, or R ⁵¹ or R ⁵² may be bonded to an adjacent benzene ring to form a ring containing X ¹ There is also
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkylalkyl group having 4 to 20 carbon atoms. , R ⁵⁵ , OR ⁵⁵ , SR ⁵⁵ , NR ⁵⁶ R ⁵⁷ , COR ⁵⁵ , SOR ⁵⁵ , SO ₂ R ⁵⁵ or CONR ⁵⁶ R ⁵⁷ ,
R ⁵⁵ to R ⁵⁷ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a complex having 2 to 20 carbon atoms. Represents a cyclic group,
X ¹ represents an oxygen atom, a sulfur atom, a selenium ^atom, CR ⁵⁸ R 59, CO, a ^{NR 60} or ^{PR 60,}
X ² represents a single bond or CO,
R ⁵⁸ to R ⁶⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
The methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, nitro group, cyan group, hydroxyl group, carboxyl group or heterocyclic group, and may be interrupted by —O—. Yes,
R ⁵⁸ and R ⁵⁹ may combine to form a ring,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

Examples of the alkyl group, aryl group, arylalkyl group and heterocyclic group represented by each symbol of the general formula (IV) include the alkyl group, aryl group, arylalkyl group represented by the above R ²⁹ to R ⁴⁴ , The thing similar to the example of a heterocyclic group is mentioned.

In the compound represented by the general formula (IV), the cycloalkyl group having 3 to 20 carbon atoms represented by R ⁵³ and R ⁵⁴ is a saturated monocyclic or saturated group having 3 to 20 carbon atoms. A polycyclic alkyl group is meant. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo [1.1.1] pentanyl and tetradecahydroanthracenyl Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl and the like.

In the compound represented by the general formula (IV), the cycloalkyl alkyl group having 4 to 20 carbon atoms represented by R ⁵³ and R ⁵⁴ is obtained by replacing the hydrogen atom of the alkyl group with a cycloalkyl group. Means a group having from 4 to 20 carbon atoms. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2- Cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl , 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl , Cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl , 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, etc. It is.

Examples of the ring containing X ¹ formed by combining R ⁵¹ or R ⁵² with an adjacent benzene ring include carbazole, xanthene, dibenzofuran and dibenzothiophene.

Examples of the ring formed by combining R ⁵⁸ and R ⁵⁹ include 5 to 5 such as cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring, and lactam ring. Examples thereof include 7-membered rings and condensed rings such as naphthalene and anthracene.

These polymerization initiators can be used alone or in combination of two or more according to the desired performance.

In the colored polymerizable composition of the present invention, the content of the polymerization initiator (G) is not particularly limited, but the curability is good in a total of 100 parts by mass of the solid content of the colored polymerizable composition. Therefore, the amount is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass. When the content of the polymerization initiator (G) is less than 0.1 parts by mass, the curability may be inferior, and when it is more than 20 parts by mass, the initiator may be precipitated in the resin composition.
When the colored polymerizable composition is, for example, a colored polymerizable composition for a color filter, the content of the polymerization initiator (G) in the colored polymerizable composition for a color filter is the color polymerization for the color filter. The total solid content of the composition is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass.

Further, in the colored polymerizable composition of the present invention, a solvent may be included for the purpose of improving the handling or controlling the thickness of the cured product, and as such a compound, the dispersibility of the colorant is good. Although it will not specifically limit if it is excellent in the solubility of an ethylenically unsaturated compound (F) and a polymerization initiator (G), The thing quoted by the said dispersion medium (D) can be used preferably.

In the colored polymerizable composition of the present invention, the content of the solvent is preferably such that the concentration of the composition other than the solvent is 5 to 30% by mass. When the concentration of the composition other than the solvent is less than 5% by mass, it is difficult to increase the thickness of the cured product, and sufficient colorability may not be obtained. Since the storage stability of the composition is lowered and the viscosity is improved, handling is lowered, which is not preferable.

In the colored polymerizable composition of the present invention, the polymerizable compound (A), the colorant (B), the dispersant (C), the dispersion medium (D), the ethylenically unsaturated compound (F), and the polymerization initiator (G) Arbitrary components other than can be added as long as the effects of the present invention are not impaired.
Describe optional ingredients below

The colored polymerizable composition of the present invention as an optional component may not contain an ethylenically unsaturated bond and may contain a compound that imparts alkali developability, and such a compound has an acid value. The compound is not particularly limited as long as it is a compound soluble in an alkaline aqueous solution, but a representative example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5 Xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination of two or more.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p -N-butylbenzaldehyde is used, and among these compounds, form Aldehydes, acetaldehydes and benzaldehydes are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. Using amount of the acid catalyst, phenol per ^{mole, 1 × 10 -4 ~ 5 ×} 10 -1 mol is preferred. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

Examples of optional components other than the novolak resin include the resins shown below.

Resins used for the colored polymerizable composition include non-photosensitive resins such as thermoplastic resins and thermosetting resins and photosensitive resins. If necessary, the binder resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to form a binder resin.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, phenol resin and the like. Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxy group, and an amino group. A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. A linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

In addition, the colorant dispersion (E) and the colored polymerizable composition of the present invention include, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine; Adhesion promoter; Filler; Antifoaming agent; Leveling agent; Surface conditioner; Antioxidant; Ultraviolet absorber; Dispersion aid; Aggregation inhibitor; Catalyst; Effect promoter; Cross-linking agent and thickener Additives can be added.

Further, a chain transfer agent, a sensitizer, a surfactant, melamine, and the like can be used in combination with the colorant dispersion (E) and the colored polymerizable composition of the present invention.

As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate); iodo such as disulfide compounds obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4 Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, Karenz PE1 and NR1 manufactured by Showa Denko KK and the like.

Specific examples of the sensitizer include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′- tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine. Benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylaline Traquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7 -Dimethoxycarbonylcoumarin) and coronene.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different. In addition, methylol groups that are not alkyletherified may self-condense within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

In the colored polymerizable composition of the present invention, the polymerizable compound (A), the colorant (B), the dispersant (C), the dispersion medium (D), the ethylenically unsaturated compound (F), and the polymerization initiator (G) The content of the optional components other than is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 20 parts by mass or less in total with respect to 100 parts by mass of the solid content of the colored polymerizable composition.

The cured product obtained by curing the colored polymerizable composition of the present invention means a product obtained by polymerizing and curing the colored composition using heat or light. The method for curing the colored polymerizable composition will be described below, but the curing method is not limited to these in the cured product of the present invention.

The colored polymerizable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper and It can be applied on a supporting substrate such as plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

Further, as the active light source used for curing the colored polymerizable composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, Carbon arc and xenon arc can be used.

Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser beam, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

By using the colored polymerizable composition of the present invention, the following steps (1) to (4) are repeated, and a color filter used for a liquid crystal display panel or the like can be produced by combining patterns of two or more colors.

(1) A step of forming a coating film of the colored polymerizable composition of the present invention on a substrate (2) A step of irradiating the coating film with active light through a mask having a pattern shape (3) A film after curing Step of developing with developer (especially alkaline developer) (4) Step of heating the film after development

The colored polymerizable composition of the present invention (or a cured product thereof) is a color in a liquid crystal display panel of a color display such as a curable paint or varnish, an adhesive, a printed board, a color TV, a PC monitor, a portable information terminal, a digital camera, etc. Black column spacers in color display liquid crystal display panels such as filters and digital cameras, color filters for CCD image sensors, black column spacers for CCD image sensors, black partition materials for organic EL, touch panels, electrode materials for plasma display panels, powders Manufactures coatings, printing inks, printing plates, adhesives, gel coats, electronics photoresists, electroplating resists, etching resists, both liquid and dry films, solder resists, insulating films, and color filters for various display applications. Or to do Display panel, electroluminescent display device, resist for forming structure in LCD manufacturing process, composition for encapsulating electrical and electronic components, solder resist, magnetic recording material, micro mechanical component, waveguide, optical switch, Masks for plating, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, decolorizing materials Decolorizing material for image recording material, Decoloring material for image recording material using microcapsules, Photoresist material for printed wiring board, Photoresist material for UV and visible laser direct image system, Sequential lamination of printed circuit board Photoresist materials used for dielectric layer formation in Can be used for various applications such as protective film, there is no particular limitation on the application.

The colored polymerizable composition of the present invention can be preferably used for the purpose of forming a black matrix for a color filter when a black pigment is used as the colorant (B).

The above black matrix for color filter is particularly useful for a color filter for a display device for an image display device such as a liquid crystal display panel.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.

[Production Example 1] Polymerizable Compound No. Production of 1 50 g (0.036 mol) of bisphenol A type phenol novolak type epoxy compound manufactured by Japan Chemtech Co., Ltd., 31.0 g (0.36 mol) of methacrylic acid, 0.5 g of p-toluenesulfonic acid pyridinium salt, and solvent As a mixture, 100 g of THF was mixed, and these were stirred at room temperature overnight to be reacted. After neutralizing the reaction solution with sodium carbonate, the organic solvent-soluble matter in the reaction solution was extracted with ethyl acetate. After the solvent in the extract was distilled off with an evaporator, recrystallization was performed using an ethyl acetate / hexane mixed solvent, and the following polymerizable compound No. 1 was obtained.

[Production Example 2] Polymerizable Compound No. Production of 2
231.6 g of polymerizable compound No. 1 was dissolved in 230 g of PGMEA, 50 g of tetrahydrophthalic anhydride and 0.35 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 100 ° C. for 5 hours to be reacted. Thereafter, PGMEA was added so that the solid content concentration of the obtained PGMEA solution was 45% by mass. 2 PGMEA solution was obtained.

[Production Example 3] Polymerizable Compound No. Production of 231.6 g of polymerizable compound No. 3 1 was dissolved in 270 g of PGMEA, 80 g of tetrahydrophthalic anhydride and 0.57 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 100 ° C. for 8 hours to be reacted. Thereafter, PGMEA was added so that the solid content concentration of the obtained PGMEA solution was 45% by mass. 3 PGMEA solutions were obtained.

[Production Example 4] Carbon black no. Production of 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration 2.0 N) were mixed and stirred at 60 ° C. for 10 hours. Thereafter, the mixed solution is filtered, and the resulting slurry is neutralized with sodium hydroxide and treated by diafiltration to obtain a solid. The obtained solid is dried at 75 ° C. overnight to obtain carbon as a black powder. Black No. 1 was obtained.

[Production Example 5] Carbon black no. Production of 2 150 g of MA100 (Carbon Black manufactured by Mitsubishi Chemical Corporation) and 400 ml of sulfolane were mixed, 15 g of amidosulfuric acid was added, and the mixture was stirred at 140 to 150 ° C. for 10 hours. Thereafter, the resulting slurry was neutralized with lithium hydroxide and treated by diafiltration, and the resulting solid was dried at 75 ° C. overnight to obtain carbon black No. 4 as a black powder. 2 was obtained.

[Production Example 6] Ethylenically unsaturated compound No. 1 having an indane skeleton Preparation of 1 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] -3-phenylindane, 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol Then, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, PGMEA 128 g was added to obtain a PGMEA solution As polymerizable compound No. 1 was obtained.

[Production Example 7] Ethylenically unsaturated compound No. 1 having an indane skeleton Preparation of 2 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] -3-phenylindane 43 g, acrylic acid 11 g, 2,6-di-tert-butyl-p-cresol 0.05 g, Tetrabutylammonium acetate 0.11g and PGMEA 23g were prepared, and it stirred at 120 degreeC for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphthalic anhydride were added and stirred at 120 ° C. for 8 hours. Further, 6.0 g of tetrahydrophthalic anhydride was added and stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, and then PGMEA 27 g was added to prepare a PGMEA solution As polymerizable compound No. 2 was obtained.

[Comparative Production Example 1] Comparative polymerizable compound No. 1 Production of 1 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g And 65.9 g of PGMEA, and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. The mixture was cooled to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 122.2 g of PGMEA was added, and a comparative polymerizable compound No. 1 as a target product as a PGMEA solution was added. Got 1

[Examples 1 to 9 and Comparative Examples 1 to 4] Preparation of Colorant Dispersion Liquid Each component was prepared according to the formulation of [Table 1] to [Table 3] and treated with a bead mill to obtain a colorant dispersion liquid (colorant dispersion). Dispersions Nos. 1 to 9 and comparative colorant dispersions Nos. 1 to 4) were obtained. In addition, the number in a table | surface represents a mass part.
Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 Polymerizable Compound No. 1
A-2 Polymerizable Compound No. 2
A-3 Polymerizable Compound No. 3
B-1 Carbon Black No. 1
B-2 Carbon Black No. 2
C-1 DISPERBYK-161 (manufactured by Big Chemie)
D-1 PGMEA
D-2 Cyclohexanone F-1 VR-60
(Bisphenol A epoxy acrylate, Showa Denko)
F-2 PR-300PG
(Showa Denko novolak epoxy acrylate)

[Examples 10 to 29 and Comparative Examples 5 to 8] Preparation of colored polymerizable composition Each component was mixed in accordance with the formulation of [Table 4] to [Table 8] to obtain a colored polymerizable composition (colored polymerizable composition No. 1 to 20 and comparative colored polymerizable compositions No. 1 to 4) were obtained. In addition, the number in a table | surface represents a mass part.
Moreover, the code | symbol of each component in a table | surface represents the following component.
Colorant dispersion (E) [Colorant dispersion No. 1-9] were used.
Comparative Colorant Dispersion [Comparative Colorant Dispersion No. 1-4] were used.
D-1 PGMEA
D-2 Cyclohexanone F-3 Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
F-4 Ethylenically unsaturated compound having an indane skeleton 1
F-5 ethylenically unsaturated compound having an indane skeleton 2
G-1 NCI-831 (made by ADEKA)
G-2 PBG-304 (manufactured by Troly)
H-1 EP-4100L (epoxy compound: manufactured by ADEKA)

[Evaluation Examples 10 to 29 and Comparative Evaluation Examples 5 to 8]
Polymerizable composition No. 1 to 20 and comparative colored polymerizable composition No. The following evaluation was performed for 1 to 4. The results are shown in [Table 9] and [Table 10].

Polymeric composition No. on glass substrate. 1 to 20 and comparative colored polymerizable composition No. 1-4 were spin-coated (1300 rpm, 50 seconds) and dried. After prebaking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol aqueous solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, using a predetermined photomask, using an ultra-high pressure mercury lamp, exposure was performed, followed by development by immersing in a 2.5% aqueous sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washing with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. About the obtained pattern, the following OD values, volume resistivity, and sensitivity were measured.

(OD value)
The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value was divided by the film thickness after post-baking to calculate the OD value per 1 μm film thickness.

(Volume resistivity)
Spin coating is performed on the chromium substrate so that the film thickness of the coloring composition is 4 μm, baking is performed at 110 ° C. for 2 minutes as a pre-baking, exposure is performed at 100 mJ / cm ^{2 with a} high-pressure mercury lamp, and baking is performed at 230 ° C. for 180 minutes as a post-baking. Thus, a cured film of the colored composition was prepared. A platinum electrode was formed on the cured film by sputtering. A lead wire was attached to the chromium portion and the platinum electrode, and a resistance measuring device was connected to measure the volume resistivity. The unit is Ω · cm.

(sensitivity)
The exposure amount was increased from 20 mJ / cm ² to 10 mJ / cm ² intervals, and the minimum exposure amount at which the pattern was fixed well after development was confirmed.

From the above results, the cured product of the colored polymerizable composition using the colorant dispersion (E) of the present invention is more sensitive than the cured product of the colored polymerizable composition using the colorant dispersion of the comparative example. As a result, both the OD value and the volume resistance are high. Therefore, the colorant dispersion (E) of the present invention and the color polymerizable composition of the present invention using the same are particularly useful as a color polymerizable composition for color filters and a color filter having excellent display quality.

The colored dispersion of the present invention is useful as a raw material for a colored polymerizable composition for forming a color filter or the like because it can provide a colored polymerizable composition having high light shielding properties and capable of forming a high-definition and high-definition pattern. .

Claims

A colorant dispersion comprising a polymerizable compound (A) represented by the following general formula (I), a colorant (B), a dispersant (C), and a dispersion medium (D).

(Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or a methyl group,
If R 3 there are a plurality or multiple R 3 are each identical or different if also there if R 4 there are a plurality or multiple of R 4 are each identical or different case,
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 (hereinafter also referred to as Y 1 to Y 6 ) are each independently a single bond, a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic ring. Represents a group having 2 to 20 carbon atoms containing
If Y 3 there are multiple, or a plurality of Y 3 are respectively the same or different when there is also located if Y 4 there are a plurality, or a plurality of Y 4 are each the same or different case,
Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 (hereinafter also referred to as Z 1 to Z 6 ) each independently have 1 to 20 carbon atoms substituted with a hydrogen atom or a carboxyl group. Represents a group of 1 to 20 carbon atoms containing a heterocyclic ring substituted with a hydrocarbon group or a carboxyl group,
If Z 3 there are multiple, there are a plurality of Z 3 are each identical or different case, there if Z 4 there are a plurality, or more Z 4 are each identical or different case,
Y 1 ~ Y 6 and Z 1 ~ 2 carbon atoms containing a hydrocarbon group and heterocyclic ring represented by Y 1 ~ Y 6 and Z 1 ~ Z 6 having 1 to 20 carbon atoms represented by Z 6 The hydrogen atom in the groups of 20 to 20 is a group containing a halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group, vinyl group, mercapto group, isocyanate group, or heterocyclic ring complex in may be substituted, represented by Y 1 - Y 6 and Z 1 hydrocarbon group and Y 1 of ~ 1 to 20 carbon atoms represented by Z 6 ~ Y 6 and Z 1 - Z 6 The methylene group in the group having 2 to 20 carbon atoms containing a ring is —O—, —CO—, —COO—, —OCO—, —S—, —SO 2 —, —SCO— or —COS—. May be replaced,
M 1 , M 2 and M 3 (hereinafter also referred to as M 1 to M 3 ) are each independently an alkanediyl group having 1 to 5 carbon atoms, a cycloalkyldiyl group having 3 to 10 carbon atoms or a sulfonyl group Represents
Hydrogen atoms of a cycloalkyl-diyl group which M 1 ~ 3 to 10 carbon atoms represented by alkanediyl group having 1 to 5 carbon atoms and M 1 ~ M 3 represented by M 3 represents a halogen atom, a carbon atom And may be substituted with an alkyl group of 1 to 5 or an aryl group of 6 to 12 carbon atoms,
If M 2 there are a plurality, there are a plurality of M 2 are each identical or different case,
m represents a positive number of 0 or 10 or less. )
2. The colorant dispersion according to claim 1, wherein the polymerizable compound (A) is a compound represented by the following general formula (II).

(Wherein R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each independently represents a hydrogen atom or a methyl group,
If R 13 there are a plurality There are several R 13 are each identical or different case,
If R 14 there are a plurality There are several R 14 are each identical or different case,
Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 (hereinafter also referred to as Z 1 to Z 6 ) each independently have 1 to 20 carbon atoms substituted with a hydrogen atom or a carboxyl group. Represents a group of 1 to 20 carbon atoms containing a heterocyclic ring substituted with a hydrocarbon group or a carboxyl group,
When there are a plurality of Z 13 , the plurality of Z 3 may be the same or different,
When there are a plurality of Z 14 , the plurality of Z 4 may be the same or different,
Z 11 of ~ 1 to 20 carbon atoms represented by Z 16 hydrogen atoms of the hydrocarbon group and Z 11 ~ 2 to 20 carbon atoms containing heterocyclic ring represented by Z 16 is a halogen atom, a nitro May be substituted with a group containing a group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group, or a heterocyclic group, and Z 11 to Z The methylene group in the hydrocarbon group having 1 to 20 carbon atoms represented by 16 and the group having 2 to 20 carbon atoms containing the heterocyclic ring represented by Z 11 to Z 16 is —O—, —CO—. , -COO -, - OCO -, - S -, - SO 2 -, - SCO- or -COS- with may be substituted,
n represents a positive number of 0 or 10 or less. )
The colorant dispersion according to claim 1 or 2, wherein the colorant (B) is a black pigment.
A colored polymerizable composition comprising the colorant dispersion (E) according to any one of claims 1 to 3, an ethylenically unsaturated compound (F), and a polymerization initiator (G).
A cured product obtained by curing the colored polymerizable composition according to claim 4.
A black matrix obtained by curing a colored polymerizable composition containing the colored dispersion (E), the ethylenically unsaturated compound (F) and the polymerization initiator (G) according to claim 3.
A color filter comprising the cured product according to claim 5 or the black matrix according to claim 6.