TW201303499A - Colored composition and color filter using the same - Google Patents

Abstract

According to an embodiment, the present invention relates to a colored composition, including a coloring agent, a resin, a monomer and an organic solvent.The monomer includes a polyfunctional monomer having an acidic group.The coloring agent includes a halo-chemical, which is obtained by reacting the resin whose side chain containing a cation group with an anion die.

Description

Coloring composition and color filter using the same

The present invention relates to a coloring composition and a color filter formed therewith, and the coloring composition is used for a color filter for manufacturing a color liquid crystal display device and a color image pickup device.

In recent years, liquid crystal display devices have been highly evaluated for their space saving, light weight, power saving, and the like due to their thinness. Therefore, television receivers including liquid crystal display devices have recently become popular.
The liquid crystal display device includes, for example, a pair of polarizing plates, and a liquid crystal layer sandwiched by them. In the liquid crystal display device, the state of polarization passing through a polarizing plate is controlled, and the amount of light passing through the other polarizing plate is controlled.
The display modes of the liquid crystal display device include a VA (Vertical Alignment) mode, an IPS (Plane Switching) mode, and a TN (Twisted Nematic) mode. Among them, the TN mode is the mainstream.
The liquid crystal display device can perform color display by providing a color filter between polarizing plates. The color liquid crystal display device has been used in recent years in television receivers, personal computer monitors, and the like. Therefore, the color filter requires a performance improvement necessary for high luminance, high contrast, and high chroma of the liquid crystal display device, for example, an increase in the transmittance increase.
The color filter has a structure in which two or more sections having different hue are arranged on the surface of a transparent substrate such as glass. This structure is, for example, a structure in which a fine band (striped) filter segment is arranged in parallel or in a crosswise manner, or a structure in which fine filter segments are arranged in a certain arrangement. Each of the filter segments is fine to several μm to several hundreds μm. The filter segments are arranged neatly in accordance with the respective hue.

It is an object of the present invention to provide a technique that is advantageous for the performance improvement of a color filter, or a colored composition used in its manufacture.
The inventors of the present invention have focused on the cumulative study, and have found that a coloring composition for a color filter contains a halogenated compound as a coloring agent obtained by reacting a resin having a cationic group in a side chain with an anionic dye, and has an acidity. The polyfunctional monomer is excellent in storage stability, does not cause foreign matter to the coating film, and has strong adhesion to a transparent substrate such as glass, and has good developability. Then, based on this discretion, the inventions of the first and second aspects below are completed.
That is, the first aspect of the present invention relates to a coloring composition for a color filter comprising a coloring agent, a resin, a monomer, and an organic solvent; and the coloring agent contains a halogenated compound which is contained by a side chain. A reaction between a cationic group-based resin and an anionic dye; the aforementioned monomer comprising a polyfunctional monomer having an acidic group.
The resin having a cationic group in the side chain may be a vinyl resin, and includes a structural unit represented by the general formula (1).
General formula (1):
Formula (I)
(wherein R ¹⁸ represents a hydrogen atom, or a substituted or non-substituted alkyl group;
R ¹⁹ to R ²¹ each independently represent a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted alkenyl group, or a substituted or non-substituted aryl group; and two of R ¹⁹ to R ²¹ are bonded to each other to form Ring can also be
Q ¹ represents an alkylene group, an arylene group, -CONH-R''- or -COO-R''-, and R'' represents an alkylene group;
The Y ^- line represents an inorganic or organic anion. )
The aforementioned acidic group may also be a carboxyl group.
The coloring composition for a color filter may further contain a photopolymerization initiator.
The resin may also contain an alkali-soluble photosensitive resin.
Further, a second aspect of the present invention relates to a color filter comprising a filter segment which is formed on a substrate and which is formed by the coloring composition for the color filter.
Further, the inventors of the present invention focused on cumulative research, and as a result, it was found that color reproduction of high brightness and wide color gamut can be achieved by using a halogenated product composed of a xanthene-based basic dye and a xanthene-based acid dye. And excellent tolerance can be achieved. Then, based on this discretion, the invention of the following third aspect and fourth aspect is completed.
That is, the third aspect of the present invention relates to a photosensitive coloring composition comprising a colorant, a resin, a monomer, and a photopolymerization initiator; the monomer comprises a polyfunctional monomer having an acidic group; 100 parts by mass of the nonvolatile component of the photosensitive coloring composition, the content of the monomer is 20 to 50 parts by mass, and the photopolymerization initiator contains an acetophenone-based compound and a fluorenylphosphorus oxide-based compound; acetophenone The mass ratio of the compound to the fluorenylphosphorus oxide-based compound (acetophenone-based compound/phosphorylphosphorus oxide-based compound) is in the range of 60/40 to 90/10.
The total amount of the acetophenone-based compound and the content of the above-mentioned fluorenylphosphine oxide-based compound may be 3 to 20 parts by mass, based on 100 parts by mass of the nonvolatile component.
The ratio of the above polyfunctional monomer to the total monomer may also be 30 to 60 parts by mass.
The above polyfunctional monomer may also be a compound represented by the general formula (3).


(wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents an organic group having a carbon number of 3 to 60 of (n+o), and n represents 2; An integer of ～18, o represents an integer from 1 to 3.)
Further, a fourth aspect of the invention relates to a color filter comprising a filter segment formed of the photosensitive coloring composition.
In other words, the inventors of the present invention focused on the cumulative research, and as a result, it was found that when a high-density color filter is simultaneously produced with higher penetration, a coloring composition remaining on the non-line portion on the substrate after development occurs (developing Residue), or a method of attaching a foreign matter such as an undissolved release sheet to a line portion, a line defect caused by a pattern peeling or defect of a line portion, and a yellowing change in a baking step such as post-baking, In the coloring composition for a color filter, the amount of the alkali-soluble photosensitive resin and the polyfunctional monomer having an acidic group is set within a specific range with respect to the total of the resin and the polyfunctional monomer, and is oxidized. It is effective to set the amount of the preventive agent to a specific range with respect to the nonvolatile component of the coloring composition for a color filter. Then, based on this discretion, the invention of the following fifth aspect and sixth aspect is completed.
That is, the fifth aspect of the present invention relates to a photosensitive coloring composition comprising a coloring agent, a resin, a monomer, and a photopolymerization initiator; the resin comprising an alkali-soluble photosensitive resin component and an alkali-soluble non-photosensitive At least one selected from the group consisting of resin components; the monomer comprises a polyfunctional monomer having an acidic group; and the total amount of the resin and the content of the polyfunctional monomer is 100 parts by mass, alkali-soluble photosensitive The total content of the resin component and the content of the polyfunctional monomer having an acidic group is 20 to 70 parts by mass, and the content of the oxidation preventing agent is 0.1 to 5 with respect to 100 parts by mass of the nonvolatile component of the colored composition. Quality Department.
The non-volatile content of the coloring composition for color filter, the binding of the ethylene contained in the alkali-soluble photosensitive resin component and the polyfunctional monomer concentration molar mass may also be ^{2.00 × 10 - 3 mol / g} ~ ^{2.75 × 10 - 3 mol / g} ; mass with respect to the non-volatile components, the acid value of the non-volatile component of the resin and the sum of the non-volatile components of the monomer may also be an acid value ratio of 8.0 ~ 40.0mgKOH / g.
At least one of the alkali-soluble photosensitive resin component and the alkali-soluble non-photosensitive resin component includes a first repeating unit of 2.0 to 60 parts by mass, a second repeating unit of 0.2 to 80 parts by mass, and a third repeating unit of 2.0 to 30 parts by mass. The first repeating unit includes a carboxyl group; and the second repeating unit has at least one cyclic structure selected from the group consisting of aromatic ring groups represented by the general formulas (12) and (13);
General formula (12):
Formula (12)
(In the general formula (12), R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group may be replaced by a benzene ring.)
General formula (13):
Formula (13)
(In the general formula (13), R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group may be replaced by a benzene ring.)
The third repeating unit has at least one cyclic structure selected from the group consisting of aromatic ring groups represented by the general formulas (14) and (15).
General formula (14):
Formula (14)
General formula (15):
Formula (15)
The oxidation inhibitor may also contain a hindered phenol-based oxidation inhibitor.
Further, a sixth aspect of the invention relates to a color filter comprising a filter segment formed of the coloring composition for a color filter.

The aspects of the invention are described in detail below.
In addition, when one or both of "acrylic acid and methacrylic acid" are shown in this specification, it may be described as "(meth)acrylic acid." Similarly, when one or both of "acrylonitrile and methacryl" are indicated, "(meth)acrylofluorene" may be described. Also, "C.I." means a color index (C.I.).
○The first aspect
First, a first aspect of the present invention will be described.
The method for producing a color filter is known to include: a dyeing method for dyeing a pattern after patterning by a resist; or a transparent electrode having a specific pattern formed in advance, and dissolving and dissolving in a solvent by applying a voltage A plating method in which a pigment-containing resin is ionized to form a pattern, and a pigment dispersion method in which a color resist obtained by dispersing a coloring agent such as a pigment in a resist material is used, and a pigment dispersion method is mainly used as a production method. However, the color filter used as a coloring agent is caused by light scattering or the like by the pigment particles, so that the degree of polarization controlled by the liquid crystal is disordered, and as a result, the brightness or contrast of the color liquid crystal display device is easily lowered. .
As a technique for solving this problem, for example, a review of a dye-based curable composition using a dye as a colorant is proposed in the Japanese Patent Publication No. Hei 6-75375, and the dye can be present in a dissolved state in the curability. In the medium of the composition. However, as for the color filter using a dye in the colorant, the dye used for the color resist is required to have heat resistance, light resistance, and solubility to the resin and the organic solvent used for the resin.
Therefore, in order to improve solubility and to improve heat resistance and light resistance, a color filter using a salt of an anionic dye and a cationic surfactant as a colorant has been proposed. Such a color filter is described in, for example, Japanese Laid-Open Patent Publication No. Hei 5-333207 and No. 2004-307391. In general, it is known to use sodium sulfonate (-SO) as an anionic dye.₃Na) is changed to a salt of an organic amine to enhance the solubility of the anionic dye in an organic solvent. The above coloring agent enhances the solubility of the anionic dye for the organic solvent by changing the sodium sulfonate group of the anionic dye to the matrix salt of the cationic surfactant, and enhances heat resistance by increasing the molecular weight. Lightfastness. However, these methods are incapable of obtaining sufficient solubility for the solvent used for producing the color filter, and are not compatible with the resin, so that it is difficult to impart long-term storage stability to the coloring composition for a color filter. Further, it is difficult to impart strong adhesion between the coating film and a transparent substrate such as glass.
Further, as a halogenated compound of an anionic dye, for example, JP-A-2005-350648, a cationic resin is used as a counter-charged substance as a crystalline aqueous coloring material, and the purpose is to use a dye. Used in the state of particles, the use of color filters that are required to be used in a dissolved state has not been reviewed in detail.
Further, for example, Japanese Laid-Open Patent Publication No. 2000-352815 proposes a coloring resin composition in which an anionic dye is added to a copolymer solution obtained by copolymerizing a monomer having a guanamine structure. This is achieved by the action of the guanamine structure as a dyeing point on the anionic dye to stabilize the dye in the coating film and improve the tolerance. However, the method disclosed herein is a problem in which a foreign matter is produced by mixing a copolymer and an anionic dye in an organic solvent, so that a dye having a high polarity is not sufficiently dissolved.
The present inventors focused on cumulative research in order to solve the various problems described above, and as a result, found a coloring composition for a color filter which, if used as a coloring agent, contains a resin having a cationic group in a side chain and an anionic dye. The halogenated compound or a polyfunctional monomer having an acidic group is excellent in storage stability, does not cause foreign matter to the coating film, and has strong adhesion to a transparent substrate such as glass, and has good developability. The residue of the colored composition or the like is generated in the non-pixel portion on the substrate after development. Then, according to the discretion, the completion of this aspect.
That is, the second aspect of the present invention is a coloring composition for a color filter containing a colorant, a resin, a monomer, and an organic solvent; and the coloring agent contains a halogenated compound which contains a cation by a side chain. The reaction of a resin of a base with an anionic dye; the aforementioned monomer comprises a polyfunctional monomer having an acidic group.
In the color filter of the second aspect, the coloring composition for a color filter used includes a halogenated compound obtained by reacting a resin having a cationic group in a side chain with an anionic dye; and a polyfunctional group having an acidic group; By using a single color filter, a color filter having high storage stability can be obtained, and foreign matter is not generated when the coating film is formed, and the adhesion is excellent and the developability is good, and the non-pixel on the substrate after development can be suppressed. The residue of the coloring composition or the like is generated.
Specifically, it is considered that the colored composition is formed of a halogenated compound contained as a coloring agent to form a salt having a cation in a side chain and a salt structure obtained by reacting with an anionic dye, thereby reacting with a resin binder, a monomer, and a solvent. The compatibility is improved, so that the stability of the coloring composition is improved, and the generation of foreign matter is also suppressed.
Further, since the alkali developability is improved by the polyfunctional monomer having an acidic group contained as a monomer, no residue is generated.
Further, it has been judged that the adhesion to the glass surface is enhanced by the influence of the acidic functional group of the polyfunctional monomer having an acidic group.
It has been found that the stability of the colored composition is improved by the combination, and the generation of foreign matter can be suppressed, and the development residue does not occur, and the substrate adhesion becomes high.
<<Coloring composition for color filter>>
As described above, the coloring composition for a color filter according to the first aspect of the present invention contains a coloring agent, a resin binder, a monomer, and an organic solvent; and the coloring agent contains a halogenated compound which has a cationic group by a side chain. The reaction of the resin with an anionic dye; the monomer contains a polyfunctional monomer having an acidic group.
<colorant>
The colorant contains a halogenated compound as an essential component, and the aforementioned halogenated compound is obtained by reacting a resin having a cationic group in a side chain with an anionic dye. The colorant may further contain a pigment as needed.
<halogenated compound>
The halogenated compound is a halogenated compound obtained by reacting a resin having a cationic group in a side chain with an anionic dye.
(resin having a cationic group in the side chain)
The resin having a cationic group in the side chain may be any one having at least one onium salt group in the side chain, and is not particularly limited as long as it is difficult to obtain, and the resin having a cationic group in the side chain is preferably a suitable ruthenium. Ammonium salt, iodized salt, sulfur salt, diazonium salt and barium salt of salt structure. Further, from the viewpoint of preserving stability (thermal stability), the resin having a cationic group in the side chain is preferably an ammonium salt, an iodide salt or a phosphonium salt, and further preferably an ammonium salt.
When a coloring composition for a color filter containing a halogenated compound is prepared, and the characteristics of the color filter are exhibited, it is preferable to use a resin which is the same as the resin binder constituting the coloring composition for a color filter. In the present embodiment, the acrylic resin is preferably used as the coloring composition for the color filter. Therefore, the resin having a cationic group in the side chain for obtaining the halogenated compound is preferably an acrylic resin.
Further, as the resin having a cationic group in the side chain, a vinyl-based resin containing a structural unit represented by the following general formula (1) is preferably used.
General formula (1):
Formula 1)
[General formula (1), R¹⁸It is a hydrogen atom, or a substituted or non-substituted alkyl group. R¹⁹~R^{twenty one}Each independently represents a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted alkenyl group, or a substituted or non-substituted aryl group;¹⁹~R^{twenty one}The two can be combined to form a ring. Q¹It means an alkylene group, an arylene group, -CONH-R''- or -COO-R''-, and R'' means an alkylene group. Y^-It is an inorganic or organic anion. ]
In general formula (1), R¹⁹It is a hydrogen atom, or a substituted or non-substituted alkyl group. R¹⁹The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group or a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is particularly suitable.
By R¹⁹When the alkyl group shown has a substituent group, the substituent group may, for example, be a hydroxyl group, an alkoxy group or the like.
Among the above, R¹⁹It is most suitable to use a hydrogen atom or a methyl group.
In the general formula (1), R¹⁹~R^{twenty one}Examples thereof include a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted alkenyl group, or a substituted or non-substituted aryl group.
Here, R¹⁹~R^{twenty one}The alkyl group may, for example, be a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-dodecyl, n-tetradecyl, n-hexadecanyl and n- Octadecyl, etc., branched alkyl (isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.), and bridged cyclic alkyl (norbornyl, adamantane) Base and base). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
R¹⁹~R^{twenty one}The alkenyl group may, for example, be a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl) , 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc., cycloalkenyl (2-ring) Hexyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkyl group having 2 to 18 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms.
R¹⁹~R^{twenty one}Examples of the aryl group include a monocyclic aryl group (such as a phenyl group), a condensed polycyclic aryl group (naphthyl group, an anthracenyl group, a phenanthryl group, an anthranquinolyl group, an anthracenyl group, a naphthylquinolyl group, etc.), and Aromatic heterocyclic hydrocarbon group (thienyl group (derived from thiophene)), furyl group (derived from furan), pipenyl (group derived from piper), pyridyl (group derived from pyridine) , 9-carbonyl fluorenyl (based on xanthene) and 9-carbonyl thioxyl (based on thioxan).
By R¹⁹~R^{twenty one}When the alkyl group, the alkenyl group and the aryl group shown have a substituent group, the substituent group may, for example, be a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group, a decyl group, an alkoxycarbonyl group, a carbonyl group or a benzene group. The substituent selected by the base or the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxy group or a phenyl group is particularly preferable.
From the perspective of stability, R¹⁹~R^{twenty one}Preferably, it is a substituted or non-substituted alkyl group, more preferably a non-substituted alkyl group. Also, R¹⁹~R^{twenty one}Two of them are combined to form a ring.
In the general formula (1), the Q of the vinyl group and the ammonium salt group is bonded.¹It means an alkylene group, an arylene group, -CONH-R''- or -COO-R''-, and R'' represents an alkylene group. Among them, from the viewpoint of polymerization and difficulty in obtaining, it is preferable to be -CONH-R''- or -COO-R''-. Further, R'' is more preferably a methyl group, an ethane group, a propane group or a butylene group, and particularly preferably an ethane group.
Y in the general formula (1) constituting the counter anion of the foregoing resin^-The component is an inorganic or organic anion. The counter anion can be used without any limitation, and specific examples thereof include halide ions such as hydroxide ions, chloride ions, bromide ions, and iodide ions; acid ions such as formic acid ions and acetate ions; and carbonate ions. , inorganic acid ions such as hydrogencarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromic acid ions, potassium dichromate ions, phosphate ions, permanganic ions, etc.; cyanide ions; and further, such as hexacyanoferrate ( III) complex ions such as acid ions. From the viewpoint of synthetic suitability or stability, it is preferably a halide ion and a carboxylate ion, and is most preferably a halide ion. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ions in the resin may be combined to form an intramolecular salt.
In order to obtain a vinyl resin having a structural unit represented by the general formula (1), a method of copolymerizing not only a monomer having an ammonium salt group and ethylene as a monomer component but also a method can be used. It is obtained by copolymerizing a monomer having an amine group and ethylene as a monomer component, and reacting the obtained acrylic resin having an amine group with a hydrazine chlorinating agent to carry out ammonium chlorination.
When a monomer having an ammonium salt group and an ethylene bond is copolymerized as a monomer component, a monomer having a 4-stage ammonium salt group and ethylene bonding may, for example, be (meth)acryloyloxyethyltrimethyl chloride. Ammonium, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylammonium chloride, (meth)acryloyloxyethylmorphoammonium chloride, etc. Alkyl (meth) acrylate type 4th ammonium salt; (meth) acrylamide propyl trimethyl ammonium chloride, (meth) acrylamide ethyl triethyl ammonium chloride, (methyl An alkyl (meth) acrylamide amine grade 4 ammonium salt such as acrylamide ethyl dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl sulfate; and trimethyl vinyl Phenyl ammonium chloride and the like.
When an acrylic resin having an amine group is obtained, and the hydrazine chlorinating agent is reacted to be ammonium chlorinated, the monomer having an amine group and ethylene bonding may, for example, be dimethylaminoethyl (meth) acrylate or the like. Ethylamine ethyl (meth) acrylate, dipropyl amine ethyl (meth) acrylate, diisopropyl amine ethyl (meth) acrylate, dibutyl amine ethyl (meth) acrylate Ester, diisobutylamine ethyl (meth) acrylate, di-tert-butylamine ethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylamine B (meth) acrylate, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl propyl propyl (meth) acrylamide , dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-tertiary-butylaminopropyl (meth) acrylamide, etc. with dioxane a (meth) acrylate or (meth) acrylamide; and a styrene having a dialkylamine group such as dimethylamine styrene or dimethylamine methyl styrene; Diene such as diene methylamine or dienamine An amine compound; an aromatic vinyl monomer containing an amine group such as N-vinylpyrrolidine, N-vinylpyrrolidone or N-vinylcarbazole.
The hydrazine chlorinating agent may, for example, be an alkylsulfate such as dimethylsulfuric acid, diethylsulfonic acid or dipropylsulfuric acid; a sulfonic acid ester such as p-toluenesulfonic acid methyl or benzenesulfonic acid methyl; methyl chloride or chlorine chloride; An alkyl bromide such as an alkane, a chloropropane or a chlorooctane; an alkyl bromide such as methyl bromide, ethyl bromide, propane bromide or octyl bromide; or benzyl chloride or benzyl bromide.
The reaction of the amine group with the hydrazine chlorinating agent can generally be carried out by dropping a polymer solution having an amine group and dropping the hydrazine chlorinating agent in an amount equal to or less than the amine group. The temperature at the time of the ammonium chlorination reaction is about 90 ° C or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C or less, and the reaction time is about 1 to 4 hours.
Further, an alkoxycarbonylalkyl halide can also be used as the hydrazine chlorinating agent. The alkoxycarbonylalkyl halide can be represented by the following general formula (2).
General formula (2):
Z-R^{twenty two}-COOR^{twenty three}
In the general formula (2), Z is a halogen such as chlorine or bromine, and is preferably bromine;^{twenty two}An alkylene group having 1 to 6, preferably 1 to 5, more preferably 1 to 3 carbon atoms;^{twenty three}It is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
The reaction of an amine group with an alkoxycarbonylalkyl halide can be carried out by reacting the above-mentioned hydrazine chlorinating agent with an alkoxycarbonylalkyl halide having an amine group of less than or equal to an amine group, and then -COOR' 'Transfer to carboxylate ion (-COO)^-) and get. Thereby, a polymer having a carbonyl betaine structure represented by the general formula (2) and having an ammonium salt group can be obtained.
In addition, as another monomer having ethylene coupling which can be used together with a structural unit having a cationic group in forming a side chain and a monomer having ethylene bonding, crotonate, vinyl ester, and cisplatin are mentioned. Oleic acid diesters, phthalic acid diesters, itaconic acid diesters, vinyl alcohol esters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (Meth)acrylonitrile or the like. Further, it may contain a copolymerization unit derived from a monomer having an acidic group.
Examples of the crotonate include crotonate butyl and crotonate hexyl groups.
Examples of the vinyl esters include vinyl ethyl ester, ethylene propyl ester, vinyl butyl carbonate, vinyl methoxyethyl ester, and benzoic acid ethylene.
Examples of the maleic acid diesters include dimethyl maleic acid, diethyl maleate, and dibutyl maleate.
Examples of the phthalic acid diesters include dimethyl phthalate, diethyl phthalate, and dibutyl phthalate.
Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl ( Methyl) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-ring Hexyl (meth) acrylamide, N-(2-methoxyethyl)(meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl ( Methyl) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene morpholine, diacetone acrylamide, and the like.
Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxystyrene, ethoxylated styrene, fluorostyrene, difluorostyrene, bromostyrene, fluoromethylstyrene, protected by an acid-removable group (eg tertiary Boc) Etc.) Protected hydroxystyrene, ethylene benzoic acid methyl, and α-methylstyrene.
Examples of the monomer having an acidic group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, phthalic acid, and clothing. Unsaturated dicarboxylic acid or its anhydrides such as benic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; unsaturated polyvalent carboxylic acids having three or more valences or anhydrides thereof; succinic acid mono(2- Propylene oxiranyl ethyl), succinic acid mono(2-methylpropenyloxyethyl), phthalic acid mono(2-propenyl oxiranyl), phthalic acid mono(2-methylpropene oxime) Mono[(methyl)acryloxyalkylene] esters of polyvalent carboxylic acids of two or more valences such as ethyl); omega-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylic acid A mono(meth)acrylate such as a methyl ester or the like having a terminal carboxyl group.
As a method of obtaining a structural unit having a cationic group having a side chain, particularly a copolymer comprising a structural unit represented by the general formula (11), anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, or radical can be employed. A conventional method such as polymerization and living radical polymerization. Among them, radical polymerization or living radical polymerization is preferred.
In the case of living radical polymerization, a polymerization initiator is preferably used. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compound include 2, 2'-azobisisobutyronitrile, 2, 2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane). 1–carboxonitrile), 2, 2'-azobis(2,4-dimethylvaleronitrile), 2, 2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl 2, 2'-azobis(2-methylpropionate), 4, 4'-azobis(4-cyanovaleric acid), 2, 2'-azo double (2– Hydroxymethylvaleronitrile) and 2, 2'-azobis[2-(2-imidazoline-2-yl)propane]. Examples of the organic peroxides include benzammonium peroxide, tertiary hydrogen peroxide butadiene, diisopropyl peroxycarbonate, di-n-propyl peroxycarbonate, and di(2-ethoxyethyl). Peroxycarbonate, tertiary butyl peroxy neoacetate, (3, 5, 5 - trimethylhexyl) peroxide, dipropyl hydrazine peroxide and diethyl hydrazine peroxide . These polymerization initiators may be used singly or in combination of two or more. The polymerization temperature is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C, and the reaction time is preferably from 3 to 30 hours, more preferably from 5 to 20 hours.
The living radical polymerization method suppresses side reactions which occur in general radical polymerization, and since the polymerization growth occurs on average, it is easy to synthesize a block polymer or a resin having a uniform molecular weight.
Among them, an atomic mobile radical polymerization method using an organic halide or a halogenated fluorenyl compound as a starting agent and a transition metal complex as a catalyst can be adapted to a wide range of monomers. It is more suitable in terms of the polymerization temperature of the equipment. The atomic mobile radical polymerization method can be carried out by the methods described in the following References 1 to 8.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) International Publication No. 96/030421
(Reference 6) International Publication No. 97/018247
(Reference 7) Japanese Patent Laid-Open No. 9-208616
(Reference 8) Japanese Patent Laid-Open No. 8-41117
It is preferred to use an organic solvent for the above polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexanone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether B can be used. Ester, dipropylene glycol monomethyl ether ethyl ester, ethylene glycol monoethyl ether ethyl ester, ethylene glycol monobutyl ether ethyl ester, diethylene glycol monoethyl ether ethyl ester or ethylene glycol monobutyl ether Ester and the like. These polymerization solvents can be used by mixing two or more types.
The amount of the ammonium salt group in the vinyl resin containing the structural unit represented by the general formula (2) which is preferably in this aspect is not particularly limited, but the ammonium salt of the resin preferably has a valence of 10 to 200 mgKOH/g, more preferably 20 to ～. 130 mg KOH / g.
The molecular weight of the vinyl resin which is preferably present in the structural unit represented by the general formula (2) is not particularly limited, but the converted weight average molecular weight measured by the gel permeation chromatography (GPC) is preferably 1,000. ～500,000, more preferably 3,000 to 150,000.
Moreover, it is preferable that the vinyl resin containing the structural unit represented by the general formula (2) in the present aspect has a property of being dissolved in a solvent widely used for the coloring composition for a color filter. Thereby, a coating film which does not generate foreign matter can be obtained. In particular, the aforementioned vinyl resin preferably has a property of being dissolved in propylene glycol monomethyl ether ethyl ester.
In the resin having a cationic group in the side chain, the total content of the structural unit represented by the above general formula (2) is not particularly limited, but the total structural unit contained in the resin having a cationic group in the side chain is set to When it is 100% by mass, it is preferably 5 parts by mass or more, and more preferably 10 to 50 parts by mass from the viewpoint of solvent solubility and coloring power of the halogenated product.
(anionic dye)
As the anionic dye, the above-described coloring compound in combination with the above copolymer and ion is used. The coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group or a metal salt thereof in the molecule, and the solubility in an organic solvent or a developer can be considered. The salt forming property, the absorbance, the other interaction with the composition, the light resistance, the heat resistance and the like are appropriately selected.
Examples of the anionic dye include an anthraquinone anionic dye, a monoazo anionic dye, a diazo anionic dye, an oxazine anionic dye, an amine ketone anionic dye, and a xanthene anionic dye. a quinoline anionic dye, a triphenylmethane anionic dye, or the like. Further, an anionic dye is preferably an acid dye or a direct dye. Specific examples of the anionic dye which can be used for the synthesis of the halogenated compound are shown below.
The red dyes include CI acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22 , 23, 24, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44 , 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80 , 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120 , 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161 ,163,164,167,170,171,172,173,175,176,177,181,229,231,237,239,240,241,242,249, 252,253,255,257 , 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 334, 335, 336, 337, 340, 343, 344, 347, 348 , 350, 351, 353, 354, 356, 388 and so on.
Also, CI direct red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23 can also be used. 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54 55, 56, 57, 58, 59, 60, 61, 62, 7, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127:1 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. .
The yellow dyes include CI acid yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17 : 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43 , 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115 , 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187 , 189, 190, 191, 192, 199, etc.
Also, CI direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, and the like.
The orange dyes include CI acid orange 1, 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23 , 24, 24, 1, 25, 27, 28, 28: 1, 30, 31, 33, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83 , 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138, and the like.
Also, CI direct orange 1, 2, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114, and the like.
The blue dye may be CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 18, 19, 21, 22, 23, 24, 25 , 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57 , 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90:1 , 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127 : 1,128,129,135,137,138,143,145,147,150,155,159,169,174,175,176,183,198,203,204,205,206,208,213,227 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, and the like.
Also, CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8, 1:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 244, 253, 254, 260, 263, and the like.
The purple dye may be CI acid violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.
Also, CI Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27 may also be used. 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, and the like.
The green dye may be CI Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25:1. 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95, and the like.
Further, C.I. Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. may also be used.
(production of halogenated compounds)
The halogenated compound used in the present aspect can be easily stirred or vibrated to cause a resin having a cationic group in a side chain, an aqueous solution dissolved in an anionic dye, or an aqueous solution of a resin having a cationic group in a side chain under stirring or vibration. Obtained by mixing an anionic dye aqueous solution. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and the ion-bonding portion is precipitated as water-insoluble. Conversely, since the salt composed of the reverse anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain and the anionic dye system may be used in a single type or in a plurality of types having different structures.
The solvent used in the formation of the salt is a resin having a cationic group in the side chain and is dissolved in the anionic dye. Therefore, a mixed solution of water and a water-soluble organic solvent can also be used. The water-soluble organic solvent may, for example, be methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol or 2-( Methoxymethoxy)ethanol, 2 -butoxyethanol, 2 - (isopropoxy)ethanol, 2 - (hexyloxy) ethanol, 2 - (hexyloxy) ethanol, diethylene glycol, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol , dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, propyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl hydrazine, tetrahydrofuran (THF), Dioxane, 2-oxanone, 2-methylxanthone, N-methyl-2-indole ketone, 1,2-hexanediol, 2,4,6-hexanetriol, Tetrafuranmethanol, 4-methoxy-4-pentanone, and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50 parts by mass, and preferably 5 to 20 parts by mass, based on the total weight of the aqueous solution (100 parts by mass).
The content of the dye component derived from the anionic dye in the halogenated compound is in the mass portion of the halogenated compound 100, and is preferably in the range of 10 to 60 parts by mass, more preferably in the range of 15 to 55 parts by mass. By controlling within this range, a halogenated compound excellent in solvent solubility can be obtained.
Further, the mass portion of the effective dye component (except for the counter ion such as an alkali metal ion) in the anionic dye contained in the halogenated compound can be measured by the spectroscopic spectrum of the halogenated compound solution and the anionic dye solution adjusted to the same concentration. Calculated by calculating the spectral intensity ratio of the maximum absorption wavelength.
For example, a halogenated compound solution and an anionic dye solution can be prepared at a certain concentration by using a solvent (N-methyl-2-oxacandone or the like) which dissolves both the halogenated compound and the anionic dye, and the halogenation obtained by measuring the absorbance is used. The absorbances of the maximum absorption wavelengths of the compound solution and the anionic dye solution were set to Xa and Xb, respectively. Many anionic dyes contain a counter ion such as an alkali metal ion. In this case, if the number of counter ions present in one molecule is Na, the atomic weight of the counter ion is set to Ma, and the molecular weight of the xanthene acid dye is set to In Mb, the mass portion of the effective dye component in the anionic dye is imparted by the following formula (iv).
(1-Ma×Na×Mb)×100[mass part] (iv)
Then, by using this formula, the mass portion of the effective dye component in the anionic dye contained in the halogenated compound can be calculated by the following formula (v).
(Xa/Xb) × (1-Ma × Na / Mb) × 100 [mass part] ... (v)
The ratio of the resin having a cationic group in the side chain to the anionic dye may be appropriately adjusted if the molar ratio of the total anionic group of the total cationic unit of the resin to the anionic dye is in the range of 10/1 to 1/4. The halogenated compound is preferably in the range of 2/1 to 1/2.
(pigment)
The coloring composition for a color filter of this aspect may further contain a pigment as a coloring agent.
The pigment may be used singly or in combination of two or more organic or inorganic pigments. The pigment is preferably a pigment having high color rendering property and high heat resistance, and particularly preferably a pigment having high heat decomposition resistance, and an organic pigment is generally used. The following is a specific example of the organic pigment which can be used for a color filter by using a color index number.
For the red coloring composition used to form the red filter segments, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81 can be used. : 2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223 Red pigments such as 224, 226, 227, 228, 240, 242, 246, 254, 255, 264 and 272.
In addition to these red pigments, it can also be used together with the yellow pigment or the orange pigment shown below.
In the red coloring composition, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34 can be used simultaneously. , 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86 , 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128 , 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175 Yellow pigments and/or CI pigments such as 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. 36, 43, 51, 55, 59, 61, 71 , 73 and other orange pigments.
For the green coloring composition for forming the green filter segment, a green pigment such as C.I. Pigment Green 7, 10, 36, 37, 58 or the like can be used. Further, in the green coloring composition, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32 can be used at the same time. , 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83 , 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127 , 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174 Yellow pigments such as 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219 or 220.
For the blue colored composition for forming the blue filter segment, for example, CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10 can be used. , 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56 : 1,57, 58, 59, 60, 61, 62, 64 and other blue pigments. Further, in the blue coloring composition, a purple pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 45 may be used at the same time.
For the cyan coloring composition for forming the cyan filter section, for example, CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81, etc. may be used alone or in combination. Color pigments.
The magenta coloring composition for forming the magenta filter segment may be used alone or in combination, for example, a purple pigment such as C.I. Pigment Violet 1, 19, C.I. Pigment Red 144, 146, 177, 169, 81, and a red pigment. In the magenta colored composition, a yellow pigment can be used at the same time.
The inorganic pigments are, for example, titanium oxide, palladium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, purple red paint (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, cobalt green, brown earth and Synthetic iron black. The inorganic pigment is used in combination with an organic pigment in order to achieve a balance between chroma and brightness while ensuring good coatability, sensitivity, developability, and the like.
[Pigment Refining]

The pigment used in this aspect is preferably refined by salt milling in order to correspond to high penetration and high contrast. From the viewpoint of good dispersion in the colorant carrier, the primary particle diameter of the pigment is preferably 10 nm or more. Further, it is preferably 80 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly suitable range is from 20 to 60 nm.
The primary particle diameter of the pigment was determined from an electron micrograph of the pigment obtained by TEM (transmission electron microscope). Specifically, first, from the TEM image, one pigment particle that can see the entire primary particle is selected. Next, the line segment having the largest length is selected from the line segments connecting the two points on the contour of the pigment particle image. This line segment is set to the first line segment. Next, from the line segments connecting the two points on the contour of the pigment particle image, a line segment orthogonal to the first line segment is selected. This line segment is set to the second line segment. Then, find the length L of the first line segment₁Length L with the second line segment₂Average, set it to the average length L_AvAnd further find the length of one side and the average length L_AvThe volume V of the equal cube. The above measurement and calculation are performed on 100 or more pigment particles, and the average of the volume V is obtained, and this is set as the average volume V._Av. With the average volume V_AvThe length of one side of the cube is set to the average primary particle size of the pigment particles.
The salt milling treatment refers to heating a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After mechanically mixing and stirring, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a pulverization aid. In salt milling, the high hardness of the inorganic salt is used to pulverize the pigment. By optimizing the conditions in which the pigment is subjected to a salt milling treatment, it is possible to obtain a pigment having a very fine primary particle diameter, or a narrow distribution range thereof and a clear particle size distribution.
As the water-soluble inorganic salt, for example, sodium chloride, cesium chloride, potassium chloride or sodium sulfate can be used. From the price point of view, sodium chloride (salt) should be used. From the viewpoint of the treatment efficiency and the production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment.
The water-soluble organic solvent functions as a wet pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and the inorganic salt used is substantially insoluble in water. However, in the salt milling treatment, the temperature rises and the solvent is in a state of easy evaporation. Therefore, from the viewpoint of safety, it is preferably a high boiling point solvent having a boiling point of 120 ° C or higher. For example, 2-methoxymethoxyethane, 2-butoxyethane, 2-(isopropoxy)ethane, 2-(hexyloxy)ethane, 2-(hexyloxy)ethane can be used. , diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid poly Ethylene glycol, 1-methoxy-2-propane, 1-ethoxy-2-propane, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of from 5 to 1,000 parts by mass, and most preferably from 50 to 500 parts by mass, based on 100 parts by mass of the pigment.
When the pigment is subjected to salt milling, the resin may be added as needed. The kind of the resin to be used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified from a natural resin, or the like can be used. The resin to be used is preferably solid at room temperature and insoluble in water, and a part is soluble in the above organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by weight based on 100 parts by weight of the pigment.
<Resin Adhesive>
The resin binder is a coloring agent, in particular, a substance in which a halogenated product is dispersed, or a halogenated product is dyed and/or infiltrated. The resin binder is preferably in the entire wavelength range of 400 to 700 nm in the visible light region, and has a transmittance of 80% or more, more preferably 95% or more. The resin binder is, for example, a thermoplastic resin and a thermosetting resin. The resin binder may be used singly or in combination of two or more. Moreover, when the coloring composition of this aspect is used in the form of an alkali-developing type coloring resist, it is preferable to use an alkali-soluble resin obtained by copolymerizing a monomer having an acidic group-containing ethylene bond. Further, in order to further enhance the light sensitivity, a photosensitive resin having ethylene bonding may also be used.
Among the resin binders, an alkali-soluble photosensitive resin having both alkali-soluble and photo-curing properties is particularly preferable.
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, and polyurethane. Resin, polyester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, polybutadiene resin, polyimine Resin, etc. Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a phenol resin, and the like.
Examples of the thermosetting resin include a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a phenol resin, and the like.
The alkali-soluble resin obtained by copolymerizing a monomer having an acidic group and an ethylene bond may, for example, be a resin having an acidic group such as a carboxyl group or a sulfonic acid group.
Specifically, the alkali-soluble resin may, for example, be an acrylic resin having an acidic group, an α-olefin-(anhydride) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, or a styrene-(meth)acrylic acid. Copolymer and isobutylene-(anhydride) maleic acid copolymer. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene-styrenesulfonic acid copolymer having an acidic group is preferable, and an acrylic resin having an acidic group is particularly preferably used because it has high heat resistance and transparency.
The mass average molecular weight (Mw) of the resin binder is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, and still more preferably in the range of 5,000 to 30,000. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000. The value of Mw/Mn is preferably 10 or less.
When the mass average molecular weight Mw of the resin binder exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the colored filter for the color filter becomes high, so that it is easy to be difficult to handle. Moreover, when the mass average molecular weight Mw is less than 5,000, problems may occur in developability or adhesion to a substrate such as glass.
The acid value of the resin binder is preferably from 20 to 300 mgKOH/g from the viewpoints of dispersibility, permeability, developability and resistance of the pigment. When the acid value is less than 20 mgKOH/g, the solubility in the developer is not good, and it is difficult to form a fine pattern. When the acid value exceeds 300 mgKOH/g, a fine pattern is not left.
The resin binder can be used in an amount of 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition.
(alkali soluble photosensitive resin)
The resin binder preferably contains an alkali-soluble photosensitive resin.
As the alkali-soluble photosensitive resin of the present aspect, for example, a resin in which ethylene is bonded is introduced according to the method (a) or the method (b) shown below.
[method (a)]
As the method (a), for example, by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, the side chain epoxy group of the obtained copolymer is rendered unsaturated. An ethylenic double-bonded unsaturated carboxyl group of an unsaturated monovalent acid is subjected to an additional reaction, and a polyvalent acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group. Examples of the ethylenically unsaturated monomer having an epoxy group include epoxypropyl (meth)acrylate, methyl epoxypropyl (meth)acrylate, and 2-epoxypropoxy group (A). Acrylate, 3,4 epoxybutyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the standpoint of reactivity with an unsaturated monovalent acid in the next step, it is preferably a propylenepropyl (meth) acrylate.
Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and α-halogenane, alkoxy, halogen, and nitrate of (meth)acrylic acid. And a monocarboxylic acid such as a cyanide substituent. These may be used alone or in combination of two or more.
Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, and these may be used alone or in combination of two or more. If necessary, the number of carboxyl groups and the like may be increased, and a tricarboxylic acid anhydride such as trimellitic anhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, or the residual anhydride group may be hydrolyzed or the like. Further, when a polyvalent acid anhydride is used, tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond can further increase the ethylenic unsaturated double bond.
The method similar to the method (a) includes, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, and having a ring The ethylenically unsaturated ethylenic monomer is subjected to an additional reaction to introduce an unsaturated ethylenic double bond and a carboxyl group.
[method (b)]
As the method (b), comprising using an ethylenically unsaturated monomer having a hydroxyl group, copolymerizing with another unsaturated monovalent acid having a carboxyl group or another monomer, and having a side chain hydroxyl group of the obtained copolymer, having an isocyanate A method in which an isocyanate group of an ethylenically unsaturated monomer is reacted.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2 - or 3 - or 4 - hydroxy butyl A hydroxyalkyl (meth) acrylate such as a (meth) acrylate, a glycerol (meth) acrylate or a cyclohexane dimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. Further, it can also be used in the above-mentioned hydroxyalkyl (meth) acrylate, and polyether mono(meth)acrylic acid obtained by additionally polymerizing an ethylene peroxide, a propylene peroxide, and/or a butyl peroxide. Ester, or (poly)ester mono(meth)acrylate with (poly)γ-valerolactone, (poly)ε-caprolactone and/or (poly)12-hydroxystearic acid. From the viewpoint of suppressing the coating film foreign matter, it is preferably 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate.
Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acrylofluoreneoxy]ethyl isocyanate, but are not limited thereto. Alternatively, you can use two or more types at the same time.
The alkali-soluble photosensitive resin is, for example, a resin having a carboxyl group and having an ethylene bond; specifically, an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid or α-chlorinated acrylic acid, maleic acid, and benzene An unsaturated dicarboxylic acid such as formic acid. Alkali-soluble photosensitive resin precursors having other ethylene-bonding monomers are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( Methyl) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl ( Methyl) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, tertiary pentyl (meth) acrylate, 1-methyl butyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, Mercapto (meth) acrylate, sterol oxime (meth) acrylate, isosteid oxime (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate or oil The alkyl or alkenyl (meth) acrylate such as an alkenyl acrylate is not limited thereto, and a monomer having another ethylene bond may also be used depending on the purpose. The alkali-soluble photosensitive resin precursor may have two or more kinds of monomers having other ethylene bonds. From the viewpoint of pigment dispersibility, the monomer having other ethylene bonds in the precursor of the alkali-soluble photosensitive resin is preferably methyl (meth) acrylate or ethyl (meth) acrylate.
<monomer>
The single system of this aspect contains a polyfunctional monomer having an acidic group. The monomer of this aspect contains a monomer or oligomer which is hardened by ultraviolet rays or heat or the like to form a resin.
(multifunctional monomer having an acidic group)
Examples of the polyfunctional monomer having an acidic group include poly(meth)acrylates containing a polyvalent alcohol and (meth)acrylic acid, esterified products with dicarboxylic acids, and polyvalent carboxylic acids. An esterified product of a monohydroxyalkyl (meth) acrylate or the like. Specific examples thereof include trimethylolpropane diacrylate, trimethylolpropane diacrylate methyl ester, neopentyl alcohol triacrylate, neopentyl alcohol trimethyl acrylate, and dipentaerythritol. Monohydroxy oligoacrylate or monohydroxy oligo acrylate such as penta acrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta acrylate, and malonic acid, succinic acid, glutaric acid, p-benzene a monoester of a dicarboxylic acid such as dicarboxylic acid containing a free carboxyl group; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2 , 3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and other tricarboxylic acids, with 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate A monohydroxy monoacrylate such as a methyl ester, 2-hydroxypropyl acrylate or 2-hydroxypropyl acrylate or an oligoesteride containing a free carboxyl group of a monohydroxymethyl methacrylate or the like. The polyfunctional monomer may be used singly or in combination of two or more kinds at any ratio as needed.
Further, a compound represented by the following formula (3) can also be suitably used.


(where, R¹⁰Is a hydrogen atom or a methyl group, R¹¹Is a carbon number of 1 to 12 carbon atoms, X¹The system represents an organic group having a carbon number of 3 to 60 (n+o), n is an integer of 2 to 18, and o is an integer of 1 to 3. )
Here, the compound represented by the formula (3) can be easily obtained by, for example, the following method.
(1) a method of adding a ruthenium compound to a compound obtained by subjecting a compound having an organic group represented by X to acrylate with acrylate;
(2) a method in which a compound having an organic group represented by X is modified with a polyisocyanate compound, and an acrylate compound having a hydroxyl group is used to acrylize the obtained compound, and then a ruthenium compound is added to the obtained compound;
(3) A method in which a compound obtained by supplying an organic group represented by X is acrylated to be acrylated, and then modified with a polyisocyanate compound to add a ruthenium compound to the obtained compound.
Examples of the compound which supplies the organic group represented by X include pentaerythritol, a caprolactone modification of pentaerythritol, a polyisocyanate modification of pentaerythritol, and dipentaerythritol and dioxon. A caprolactone modification of a tetraol, a polyisocyanate modification of dipentaerythritol.
Examples of the ruthenium compound include hydrazine acetic acid, 2-propionic acid, 3-propionic acid, o-benzoic acid, 2-nonylnic acid, and decanoic acid.
The content of the polyfunctional monomer having an acidic group is usually from 5 to 500 parts by mass, more preferably from 20 to 300 parts by mass, per 100 parts by mass of the resin binder. When the content of the polyfunctional monomer having an acidic group is less than 5 parts by mass, the pixel strength or the smoothness of the surface of the pixel tends to decrease, and if it exceeds 500 parts by mass, for example, the alkali developability is lowered, and the area other than the pixel portion tends to be formed. It is prone to substrate contamination or film residue.
(other polyfunctional monomers)
The monomer of this aspect may also contain other polyfunctional monomers other than the polyfunctional monomer having an acidic group.
Other polyfunctional monomers include, for example, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, epoxy (meth)acrylate, and EO modification. Bisphenol A di(meth)acrylate, 1,4-butanedi(di)di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanedipine (methyl) Acrylate, neopentyl glycol di(meth)acrylate, polyester (meth) acrylate, trimethylolpropane tri(meth) acrylate, tris(propylene oxyethyl) isocyanide, three (Propylene methoxyethyl) isocyanide, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate , pentaerythritol tetra (meth) acrylate, and the like.
These other polyfunctional monomers may be used singly or in combination of two or more kinds at any ratio as needed. When a polyfunctional monomer having an acidic group and other polyfunctional monomers are used at the same time, the content of the polyfunctional monomer having an acidic group is based on the total mass of all the monomers (100 mass parts), preferably 10 masses. More than 50 parts by mass or more. When the content of the polyfunctional monomer having an acidic group is 10 parts by mass or more, a filter segment excellent in adhesion to the substrate or no development residue can be obtained.
(monofunctional monomer)
The monomer of this aspect may also contain a monofunctional monomer.
Monofunctional monomers are, for example, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethyl acrylate, 2-propenyl oxyethyl succinic acid, 2-propene methoxyethyl succinyl Acid, 2-propenyloxypropyl succinic acid, 2-propenyl methoxymethoxy succinic acid, methoxyethylene glycol acrylate, methyl methacrylate methacrylate, methoxy diethylene glycol acrylate, A Oxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methyl acrylate, methoxypropylene glycol acrylate, methoxypropyl glycol methyl acrylate, methoxydipropylene glycol acrylate, methoxy Dipropylene glycol methyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methyl 2-hydroxy-3-phenoxypropyl acrylate, and commercially available 2-propenyl oxyethyl succinic acid (trade name M -5300).
The monofunctional monomers may be used singly or in combination of two or more kinds in any ratio.
<solvent>
The coloring composition of this aspect further comprises a solvent. The solvent may be contained so that the colorant is sufficiently dispersed and/or infiltrated into the colorant carrier, and the film is coated on the substrate to have a dry film thickness of 0.2 to 5 μm to easily form a filter segment.
The solvent may, for example, be ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol diacetate. , 1, 4 - dioxane, 2 - heptanone, 2-methyl-1, 3-propanediol, 3, 3, 5 - trimethyl-2, cyclohexene-1, ketone, 3, 5, 5 Trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methylacetate, 3-methoxybutyl Alcohol, butyl 3-methoxyacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamidine Amine, n-butanol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, di-n-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate , ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, two Ethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate Salt, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetic acid Salt, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, phenyl alcohol , methyl isobutyl ketone, methyl cyclohexanol, n-aminoacetic acid, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, divalent acid ester, and the like.
Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate are preferably used from the viewpoint of dispersion of the pigment and halogenated compound in this aspect, and dissolution. And an alcoholic acid ester such as ethylene glycol monoethyl ether acetate or an aromatic alcohol such as benzyl alcohol or a ketone such as cyclohexanone. Particularly, from the viewpoint of safety and hygiene and low viscosity, propylene glycol monomethyl ether acetate is preferably used. The organic solvent may be used singly or in combination of two or more kinds at any ratio as needed. When two or more organic solvents are used in combination, the above preferred organic solvent preferably contains 65 to 95 parts by mass.
The organic solvent is used to adjust the viscosity of the colored composition, and it is preferable to form a filter segment having a uniform film thickness as the target, and it is preferably used in an amount of 800 to 4,000 parts by mass with respect to the mass portion of the colorant 100.
Further, in addition to the above-mentioned components, a photopolymerization initiator, a sensitizer, an amine compound, a leveling agent, a curing agent, and a curing accelerator described below can be used as the coloring composition for a color filter.
<Photopolymerization initiator>
In the coloring composition for a color filter, the composition is cured by ultraviolet irradiation, and when a filter segment is formed by photolithography, a photopolymerization initiator may be contained. The composition can be prepared by adding a photopolymerization initiator in the form of a solvent development type or an alkali development type coloring resist material.
The photopolymerization initiator can be used: 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1–(4-isopropylbenzene) Base)–2–hydroxy- 2–methylpropane–1-ketone, 1-hydroxycyclohexylbenzophenone, 2-benzyldimethylamine-1–(4-morpholinylphenyl)–butane–1– An acetophenone compound such as a ketone; a benzo compound such as benzo, benzoxyl ether, benzoether, benzoisopropyl ether or benzyldimethylketal; benzophenone, benzoquinone benzoic acid, benzene Benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, propylene benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3, 3', a benzophenone compound such as 4, 4'-tetra(t-butylperoxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthiophene a thioxanthone compound such as ketone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone; 2, 4, 6-trichloro-o-triazine, 2-phenyl- 4, 6-bis(trichloromethyl)-o-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-o-triazine, 2–(pair Phenyl)-4,6-bis(trichloromethyl)-o-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-o-triazine, 2,4-bis(trichloromethane) —6– Styryl-o-triazine, 2–(naphtho-l-yl)-4,6-bis(trichloromethyl)-o-triazine, 2–(4-methoxynaphthalene –1–yl)–4, 6–bis(trichloromethyl)-o-triazine, 2,4-trichloromethyl-(piperidinyl)-6-triazine, 2,4-trichloromethyl ( Triazine-based compounds such as 4'-methoxystyryl-6-6-triazine; 1,2-octanedione, 1–[4–(phenylthio)–, 2(O–benzopyrene)] , O-(Ethyl)-N-(1-phenyl-2-carbonyl- 2–(4′-methoxy-naphthyl)ethylidene)hydroxylamine and other oxime ester compounds; bis (2, 4, Phosphate compounds such as 6-trimethylbenzo)epoxyphenylphosphine, 2,4,6-trimethylbenzoepoxyphenylphosphine; 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, etc. a compound; a borate ester compound; an oxazole compound; an imidazole compound; or a titanocene compound.
These photopolymerization initiators may be used singly or in combination of two or more kinds at any ratio as needed.
The content of the photopolymerization initiator is preferably from 5 to 200 parts by mass based on 100 parts by mass of the colorant. The content of the photopolymerization initiator is preferably from 10 to 150 parts by mass from the viewpoint of photocurability and developability.
<sensitizer>
In the colored composition for a color filter of the present aspect, a sensitizer may be further contained.
The sensitizer may, for example, be an unsaturated ketone represented by a flavonoid derivative or dibenzylideneacetone, a 1,2-dione derivative represented by benzyl or camphorquinone, a benzo derivative, or an anthracene. Derivatives, naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives Polymethine pigment, acridine derivative, azabenzene derivative, diene terpene derivative, oxazine derivative, porphyrin derivative, etc., such as a cyanine derivative, a merocyanine derivative, and a cyanine derivative , anthracene derivative, sulfonium salt derivative, squaric acid ylide derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazine porphyrin Derivative, phthalocyanine derivative, tetrazoporphyrin derivative, tetraquinoxaline porphyrin derivative, naphthalocyanine derivative, phthalocyanine derivative, pyridinium salt derivative, thiopyridinium salt derivative , Tetraphyrin derivatives, olefin derivatives, spiropyran derivatives, spirooxazine derivatives, thiospirone derivatives , metal aromatic hydrocarbon complex, organic ruthenium complex, Michler's ketone derivative. Further, in the present invention, the derivative means a compound which is substituted with another atom or a functional group, or which is oxidized or reduced, or a part of the compound, is changed to the original compound. The derivative may have a structure which contains most of the skeleton of the original compound, and only the structure similar to the original compound may exhibit a completely different property.
Specifically, the "Special Functional Materials" (1986, CMC) compiled by the "Pigment Handbook" compiled by Ohara Shinto and others, and the "Special Functional Materials" (1986, CMC) and Chisen-Sang Sanlang, etc. The sensitizer described in "Special Functional Materials" (1986, CMC) is not limited to these. Further, it may contain a sensitizer which exhibits absorption of light from the ultraviolet to the near-infrared region.
Among the above sensitizers, particularly suitable sensitizers are, for example, thioxanthone derivatives, methyl ketone derivatives, and carbazole derivatives. Further specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone can be used. Ketone, 1-chloro-4-propoxythioxanthone, 4,4''-bis(dimethylamine)benzophenone, 4,4''-bis(diethylamine)benzophenone, 4, 4''-bis(ethylmethylamine)benzophenone, N-ethylcarbazole, 3-benzylidene-N-ethylcarbazole, 3,6-dibenzoyl-N-B Carbazole and the like.
It is also possible that the sensitizer can be contained in two or more kinds at any ratio. The content of the sensitizer is preferably from 3 to 60 parts by mass based on 100 parts by mass of the photopolymerization initiator, and is preferably from 5 to 50 parts by mass from the viewpoint of photocurability and developability.
<Multifunctional thiol>
The coloring composition for a color filter may further contain a polyfunctional thiol.
The polyfunctional thiol can be used in the same manner as described in the third aspect below.
<leveling agent>
In the coloring composition of the present aspect, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to further add a leveling agent. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include, for example, FZ-2212 manufactured by TORAY‧Dow Corning Co., Ltd., BYK-333 manufactured by BYK Corporation, and the like. Specific examples of the dimethyl methoxy olefin having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Corporation. As the leveling agent, it is also possible to use dimethyl methoxyoxane having a polyether structure in the main chain and dimethyl methoxy oxane having a polyester structure in the main chain.
The leveling agent is particularly preferably a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and has hydrophilicity and low solubility in water, and when added to a colored composition, the surface tension reducing ability is low, even if The surface tension reducing ability is low, and the lubricity to the glass sheet is still good. As such a leveling agent, it is preferred to use, for example, dimethyloxane having a polyalkylene oxide unit. The polyalkylene oxide units are, for example, polyethylene oxide units and polyoxypropylene units. Dimethyloxane may also have both polyethylene oxide units and polypropylene oxide units. Further, the combination of the polyalkylene oxide unit and the dimethyloxane may be any of the following types: a pendant type in which a polyalkylene oxide unit is combined in a repeating unit of dimethyloxane; a polyepoxy a terminal unit modified with an alkane unit bonded to a terminal end of dimethyloxane; and a linear block copolymer in which a polyalkylene oxide unit is repeatedly and repeatedly bonded to dimethyloxane. The dimethyloxane having a polyalkylene oxide unit is, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203 and FZ- commercially available from TORAY‧Dow Corning. 2207, but is not limited to these.
The content of the leveling agent is preferably from 0.003 to 1.0 part by mass based on 100 parts by mass of the total mass of the coloring composition.
The leveling agent may also optionally comprise an anionic, cationic, nonionic or amphoteric surfactant. The leveling agent may comprise a mixture of two or more surfactants.
The anionic surfactant may, for example, be a polyethylene oxide ether sulfate, a sodium dodecylbenzenesulfonate, an acrylate of a styrene-acrylic acid copolymer, a sodium alkylnaphthalenesulfonate or an alkyl diphenyl ether. Sodium sulfonate, ethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer and polyethylene oxide Ether phosphate and the like.
The cationic surfactant may, for example, be an alkyl quaternary ammonium salt or the like.
Examples of the nonionic surfactant include polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyethylene oxide nonylphenyl ether, polyethylene oxide ether phosphate, and polyethylene oxide sorbitan. An alkyl quaternary ammonium carboxylate internal salt such as glyceryl stearic acid, polyethylene glycol monolauryl ester, alkyl dimethylamine acetic acid quaternary ammonium carboxylate, or an amphoteric surfactant such as alkyl imidazoline or a fluorine-based or Anthraquinone based surfactant.
The amphoteric surfactant may, for example, be an alkylbetaine such as an alkyldimethylamine acetate betaine or an alkylimidazoline. Further, a fluorine-based or sulfhydryl-based surfactant can be mentioned.
<Amine compound>
The coloring composition for a color filter of the present aspect may contain an amine compound. The amine compound reduces the dissolved oxygen.
The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamine benzoic acid methyl, 4-dimethylamine benzoic acid ethyl, 4-dimethylamine benzoin Acid isoamine, benzoic acid 2-dimethylaminoethyl, 4-dimethylamine benzoic acid 2-ethylhexyl, and N,N-dimethyl-p-toluidine.
<hardener, hardening accelerator>
The coloring composition of this aspect may also contain a curing agent and/or a hardening accelerator. The hardener and/or the hardening accelerator assist in hardening of the thermosetting resin.
Any hardener may be used if the hardener is reactive with the thermosetting resin. As the curing agent, for example, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, or the like can be effectively used, but it is not particularly limited thereto. Further, among these, a hardening agent is preferably a compound having two or more phenolic hydroxyl groups or an amine-based curing agent in one molecule.
The hardening accelerator is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N - dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.); a 4-stage ammonium chloride compound (for example, triethylbenzylammonium chloride, etc.); a blocked isocyanate compound (for example) Dimethylamine, etc.); imidazolyl derivative bicyclic oxime compounds and salts thereof (eg imidazolyl, 2-methylimidazolyl, 2-ethylimidazolyl, 2-ethyl-4-methylimidazolyl, 2-phenylimidazolyl, 4-phenylimidazolyl, 1-cyanoethyl-2-phenylimidazolyl and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolyl And other; phosphorus compounds (such as triphenylphosphine, etc.); guanamine compounds (such as melamine, guanamine, acetamide, benzoguanamine, etc.); S-triazine derivatives (such as 2,4-diamine - 6-Methyl propylene oxiranyl-S-triazine, 2-vinyl-2,4-diamine-6-triazine, 2-vinyl-4,6-diamine-S-triazine ‧ isocyanate Acid addenda and 2,4-diamine-6-methylpropenyloxyethyl-S-triazine ‧ isocyanate acid addenda). The hardening accelerator may be used alone or in combination of two or more. The content of the hardening accelerator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting resin.
<Dispersing Aid>
The coloring composition for a color filter of this aspect may further contain a dispersing aid. The dispersing aid promotes the dispersion of the pigment in a colorant carrier such as a resin binder or an organic solvent. The dispersing aid is, for example, a dye derivative, a resin type dispersant, and a surfactant. The dispersing aid has a great effect on dispersing the pigment well and preventing re-coagulation of the dispersing coloring agent. Therefore, when a coloring composition obtained by dispersing a coloring agent in a pigment carrier by using a dispersing aid is used, a high spectral transmittance can be obtained. Color filter.
In this aspect, the above halogenated compound can also function as a dispersing aid for the pigment used at the same time.
(pigment derivative)
The dye derivative is, for example, an organic pigment, anthracene, acridone or a triazine, and a compound having a basic substituent, an acidic substituent or a sulfhydryl methyl group which may have a substituent. The pigment derivative can be used, for example, in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5- In the case of the publication No. 9469 or the like, these may be used alone or in combination of two or more.
The content of the pigment derivative is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, based on 100 parts by mass of the pigment. Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 200 parts by mass or less, and more preferably 100 parts by mass or less.
In the color filter composition of the present aspect, when the coloring composition is contained in the blue pigment, as the pigment derivative for dispersing the blue pigment, it is particularly preferable to use a base of copper phthalocyanine in which a basic substituent is introduced into the phthalocyanine pigment. Sex compounds. The basic compound of copper phthalocyanine is preferably an ammonium compound of copper phthalocyanine, for example, a copper phthalocyanine sulfonate ammonium salt compound, a copper phthalocyanine tertiary amine compound, and a copper phthalocyanine ammonium amide compound.
Specifically, it is an amine compound of copper phthalocyanine represented by the following general formula (4). Further, an amine compound of copper phthalocyanine having a basic group represented by the following general formulas (5) to (7) can be suitably used.
By using a basic compound of copper phthalocyanine, especially an amine compound of copper phthalocyanine, in the blue coloring composition, high luminance and high contrast ratio can be achieved when a blue color filter is produced. This is because the basic compound of copper phthalocyanine suppresses the occurrence of fluorescence from the halogenated compound while enhancing the dispersion of the blue pigment. In particular, in the blue coloring composition, a basic compound of a halogenated compound and copper phthalocyanine is present, which is significant.
General formula (4):
P-Lq

[In general formula (4), P: an organic pigment residue, an anthracene residue, an acridone residue or a triazine residue; L: a basic substituent, an acidic substituent or an orthobenzene which may also have a substituent Dimethyl imine methyl; q: an integer from 1 to 4]
In the general formula (4), the organic pigment constituting the organic pigment residue of P may be, for example, the following.
The organic pigment constituting the organic pigment residue of P is, for example, a pyrrolopyrroledione pigment; an azo pigment such as azo, disazo, or polyazo; copper phthalocyanine, copper phthalocyanine, zinc phthalocyanine, a phthalocyanine pigment such as a zinc halide phthalocyanine or a metal-free phthalocyanine; an onion, a diamine, an onion, a pyrimidine, a ketone, an indolinone, a standard reduction blue, a furanone, an anthrone violet dye, etc. Lanthanide pigment; quinophthalone pigment; dithiazide pigment; anthraquinone pigment; anthraquinone pigment; thiazin indigo pigment; isoindane pigment; isoindolinone pigment; quinophthalone pigment Durene-based pigments; dioxazine-based pigments; and metal-compound pigments.
Among them, it is preferable to use a dye derivative having a basic substituent and a basic substituent in the general formula (4). By including a dye derivative having a basic substituent, even in the case of a pigment which is difficult to disperse without a dye derivative having a basic substituent, it is excellent in dispersibility, fluidity, and storage stability. The pigment composition is suitable. The additive effect of the acidic resin type dispersant and the dye derivative having a basic substituent can be a pigment composition which is effective for dispersing a pigment and excellent in fluidity and storage stability.
Among the basic substituents, L is particularly a substituent selected from the group represented by the general formulae (5), (6) and (7).
General formula (5):
Formula (5)
General formula (6):
Formula (6)
General formula (7):
Formula (7)
[In general formula (5) to formula (7),
X¹Department –SO₂–, –CO–, –CH₂–, –CH₂NHCOCH₂–, –CH₂NHSO₂CH₂– or directly combined;
Y¹Department-NH-, -O-, or direct combination;
X²Department –SO₂–, –CO–, –CH₂–, –CH₂NHCOCH₂–, –CH₂NHSO₂CH₂– or directly combined;
X³Department –SO₂–, –CO–, –CH₂–, –CH₂NHCOCH₂–, –CH₂NHSO₂CH₂– or directly combined;
Y³Department -NH-, -NR⁵⁸-Z'-NR⁵⁹- or directly combined;
R⁵⁸And R⁵⁹Each of which is independently a hydrogen-bonded, substituted or non-substituted alkyl group having 1 to 36 carbon atoms, a substituted or non-substituted alkenyl group having 2 to 36 carbon atoms, or a substituted or non-substituted phenyl group;
r is an integer from 1 to 10;
a Z'-substituted or non-substituted alkylene group, or a substituted or non-substituted arylene group;
R^{twenty four}And R²⁵Each of which is independently a hydrogen-bonded, substituted or non-substituted alkyl group having 1 to 30 carbon atoms, a substituted or non-substituted carbon number of 2 to 30, or R^{twenty four}With R²⁵a substituted or non-substituted heterocyclic ring that is integrated into a nitrogen, oxygen or sulfur atom;
R²⁶, R²⁷, R²⁸And R²⁹Each of which is independently a hydrogen atom, a substituted or non-substituted alkyl group having 1 to 20 carbon atoms, a substituted or non-substituted alkenyl group having 2 to 20 carbon atoms, or a substituted or non-substituted arylene group having 6 to 20 carbon atoms. ;
R³⁰a hydrogen atom, a substituted or non-substituted alkyl group having 1 to 20 carbon atoms, a substituted or non-substituted alkenyl group having 2 to 20 carbon atoms;
R³¹And a substituent represented by the above general formula (5) or a substituent represented by the above general formula (6);
Q²The hydroxyl group, the alkoxy group, the substituent represented by the above formula (5), or the substituent represented by the above formula (6). ]
Examples of the amine component used to form the substituents represented by the general formulae (5) to (7) include dimethylamine, diethylamine, N,N-ethylisopropylamine, and N,N-B. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisobutylamine, dipropylamine, N, N-t-butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, diisobutylamine, N, N-isobutyl second butylamine, diamylamine, diisoamylamine , dihexylamine, bis(2-ethylhexyl)amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diarylamine, N, N-methyl-1, 2-dimethyl Propylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylamine methylamine, N,N-dimethylamine ethylamine, N,N-dimethylamine propylamine, N, N-dimethylamine, N,N-diethylamine ethylamine, N,N-diethylamine propylamine, N,N-diethylamine hexylamine, N,N-diethylamine butylamine, N , N-diethylamine pentylamine, N,N-dipropylamine butylamine, N,N-dibutylamine propylamine, N,N-dibutylamine ethylamine, N,N-dibutylamine butylamine, N, N -Diisobutylamine pentylamine, N, N-methyl-lauramide, N, N-ethyl-hexylamine ethylamine, N, N-distearylamine Amine, N, N-dioleylamine, N,N-distearylamine, piperidine, 2-methylpiperidine, 4-methylpiperidine, 2,4-dimethylpiperidine, 2,6-Dimethylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, methylpiperidine acid, isopiperidinecarboxylic acid, isopiperidinecarboxylic acid methyl, isopiperidinecarboxylic acid ethyl , 2-piperidinemethanol, pyrrole, 3-hydroxypyrrole, N-amineethylpiperidine, N-aminoethyl-4-methylpiperidine, N-amineethylmorpholine, N-aminopropylpiper Pyridine, N-aminopropyl-2-methylpipecolic acid, N-aminopropyl-4-methylpipecolic acid, N-aminopropylmorpholine, N-methylpiperazine, N- Butyl piperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine or 1-cyclopentylpiperazine.
Pigment derivatives having a basic substituent can be synthesized in various synthetic routes. For example, after the organic dye is introduced into the substituent represented by the formulas (8) to (11), the substituent is reacted with the above-mentioned substituent, and the amine component of the substituent represented by the formula (5) to the formula (7) is, for example, N, N-dimethylaminopropylamino, N-methylpiperidine, diethylamino or 4-[4-hydroxy-6-[3(dibutylamino)propylamino]-1,3,5-triazine –2–amine] aniline and other reactions are obtained.
Equation (8): –SO₂Cl
Formula (9): –COCl
Equation (10): –CH₂NHCOCH₂Cl
Equation (11): –CH₂Cl
When the substituent represented by the formulae (8) to (11) is reacted with the above-mentioned amine component, one of the substituents of the formulae (8) to (11) is partially hydrolyzed, and a substance in which chlorine is substituted with a hydroxyl group may be mixed. In this case, the formula (8) and the formula (9) each become a decanoic acid group and a carboxylic acid group, but both may maintain a free acid or a salt of a valence of 1 to 3 or a salt of the above monoamine.
In addition, when the organic dye is an azo dye, the substituents represented by the general formulae (5) to (7) are introduced into the diazo component or the coupling component in advance, and then a coupling reaction is carried out, whereby the coupling can be produced. A nitrogen derivative.
Among the amine compounds of copper phthalocyanine, the substituent represented by the general formula (7) can be synthesized by various synthetic routes. For example, by using cyanogen chloride as a starting material and at least one chlorine of cyanogen chloride, an amine component such as N,N-dimethylamine propylamine which forms a substituent represented by formula (5) and (6) is formed. Or a reaction such as N-methylpiperidine, followed by reacting residual chlorine of cyanogen chloride with various amines or alcohols.
Among the amine compounds of copper phthalocyanine used in this aspect, the most preferable form is a copper phthalocyanine sulfonamide compound.
The copper phthalocyanine sulfonate compound is the above copper phthalocyanine sulfonate compound having a basic substituent, X¹, X²And X³For –SO₂–, –CH₂NHSO₂CH₂–, Y⁰For -NH- or direct combination, r is an integer from 1 to 10, Y³For -NH-, -NR⁵⁸-Z'-NR⁵⁹- the compound. [Here, R⁵⁸And R⁵⁹Each is independently a hydrogen-bonded, substituted or non-substituted alkyl group having 1 to 36 carbon atoms, a substituted or non-substituted alkenyl group having 2 to 36 carbon atoms, or a substituted or non-substituted phenyl group, and Z is a carbon number of 1 to The alkylene group of 20 is more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 1 to 20 carbon atoms, more preferably an arylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group. Base, vinyl, propenyl, phenylalkenyl. ]
The amine compound of copper phthalocyanine may be used singly or in combination of two or more. The blending amount of the copper phthalocyanine amine compound is preferably from 0.01 to 200 parts by mass, more preferably from 1 to 100 parts by mass, per 100 parts by mass of the total amount of the blue pigment. Further, in the case of the blue coloring composition, the compounding amount of the copper phthalocyanine amine compound is preferably from 0.3 to 1.5 by mass ratio of the halogenated compound (amine compound of halogen phthalocyanine/halogenated compound). By conforming to this range, it is possible to suppress the fluorescence generated from the halogenated compound while enhancing the dispersion of the blue pigment, and as a result, it is possible to obtain a blue coloring composition in which a color filter can achieve high brightness and high contrast ratio. If the mass ratio of the halogenated compound (the amine compound of the copper phthalocyanine/halogenated compound) is less than 0.3, since the fluorescence inhibition and the dispersibility of the amine compound of the copper phthalocyanine are insufficient, the contrast becomes low, and if it exceeds 1.5, It affects the color characteristics and sometimes becomes low brightness. The mass ratio of the halogenated compound (amine compound of a copper phthalocyanine/halogenated compound) is preferably from 0.4 to 1.2, and most preferably from 0.5 to 1.1.
(resin type dispersant)
The resin type dispersant has a pigment affinity site having a property of adsorbing to the added pigment and a site compatible with the colorant carrier, and is adsorbed to the added pigment to stabilize the dispersion of the colorant carrier. The resin type dispersant is, for example, a polycarboxylate such as a polyurethane or a polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylate ammonium salt, a polycarboxylic acid alkylamine salt, a poly a siloxane, a long-chain polyamine phthalamide phosphate, a hydrocarbon-containing polycarboxylate or a modified product thereof, formed by reacting with a polyester having a polymerized (lower alkylenimine) and a free carboxyl group An oily dispersant such as guanamine or a salt thereof, a (meth)acrylic acid-(meth) acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol, a polyvinylpyrrolol or the like, or The water-soluble polymer compound, the polyester-based, the modified polyacrylate-based, the ethylene oxide/propylene oxide-added compound, the phthalate-based compound, and the like are not limited thereto. The resin type dispersant may be used singly or in combination of two or more.
Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie. 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK – P104, P104S, 220S and 6919, or Lactimon, Lactimom-WS or Bykumen, etc., SOLSPERSE 3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, manufactured by Lubrizol, Japan. 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, manufactured by Chiba Corporation, Japan. 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine AJISPER-PA111, PB711, PB821, PB822, PB824, etc. manufactured by -Techno Corporation.
When the resin-type dispersant is added, the amount thereof is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, based on 100 parts by mass of the pigment. When the amount of the resin-type dispersant is less than 0.1 part by mass, it is difficult to obtain an effect of addition, and when the amount is more than 55 parts by mass, excessive dispersing agent may adversely affect dispersion.
(surfactant)
The surfactant may be, for example, sodium lauryl sulfate, polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, acrylate of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, alkyl diphenyl. Sodium ether disulfonate, ethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, ethanolamine of styrene-acrylic acid copolymer, polyepoxy Anionic surfactant such as alkyl ether phosphate; polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyethylene oxide decyl phenyl ether, polyethylene oxide ether phosphate, polyethylene oxide sorbitol a cationic surfactant such as an anhydride glyceryl stearate; a raw rubber dry-distillation surfactant such as an alkyl 4-grade ammonium salt or an ethylene oxide additive thereof; an alkyl dimethylamine acetate quaternary ammonium carboxylate internal salt, etc. An alkyl quaternary ammonium carboxylate inner salt; or an amphoteric surfactant such as an alkyl imidazoline, but is not limited thereto. The surfactants may be used singly or in combination of two or more.
When the surfactant is added, the amount thereof is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, based on 100 parts by mass of the pigment. When the amount of the surfactant is less than 0.1 part by mass, it is difficult to obtain an effect of addition, and when the amount is more than 55 parts by mass, excessive dispersion may adversely affect dispersion.
<Other additive ingredients>
The coloring composition of this aspect may also contain a storage stabilizer in order to stabilize the viscosity of the composition over time.
Storage stabilizers are, for example, 4-grade ammonium chlorides such as benzyltrimethyl chloride and dimethylhydroxylamine; organic acids such as lactic acid and oxalic acid and ethyl ether thereof; tertiary butyl pyrocatechol; tetraethylphosphine And an organic phosphine such as tetraphenylphosphine; and a phosphite.
The content of the storage stabilizer is, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.
Further, in order to improve the adhesion to the transparent substrate, the coloring composition of the present aspect may contain a adhesion improving agent such as a decane coupling agent.
The adhesion promoter is a decane coupling agent such as ethylene tris (β-methoxy-oxy) decane, ethylene ethoxy decane and ethylene trimethoxy decane; γ-methacryloxy propylene (meth)acrylic acid decane such as trimethoxydecane; β-(3,4-epoxycycloalkyl)ethyltrimethoxydecane, β-(3,4-epoxycycloalkyl)methyltrimethoxy Baseline, β–(3,4-epoxycycloalkyl)ethyltriethoxydecane, β–(3,4-epoxycycloalkyl)methyltriethoxydecane, γ–epoxypropyl Epoxy decanes such as oxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N–β (Amineethyl) γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ– Amino decanes such as aminopropyltrimethoxydecane, N-phenyl-gamma-aminopropyltrimethoxydecane, N-phenyl-gamma-aminopropyltriethoxydecane; and gamma-mercaptopropyltrimethyl Oxydecane, γ-mercaptopropyltrimethylethyl decane Isothioguananes.
The content of the adhesion enhancer is, for example, 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant.
<Method for Producing Colored Composition for Color Filter>
Hereinafter, a method of producing a coloring composition for a color filter of the present aspect will be described. First, the halogenated compound is stirred and dissolved in a resin binder and/or an organic solvent to obtain a halogenated compound solution. A resin binder, a polyfunctional monomer, and a photopolymerization initiator are added to the halogenated compound solution, and further, an organic solvent and other additives are added as needed, and a solvent-developing type or an alkali-developing type photosensitive coloring composition (anti-resistance) is obtained. Etch material).
When the colorant contains a pigment, various pigments such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor are used to finely disperse the pigment together with the pigment dispersant shown below. , a pigment dispersion is obtained. This is mixed with a halogenated compound solution, a polyfunctional monomer, a photopolymerization initiator, an organic solvent, or the like to obtain a coloring composition for a color filter.
The colorant solution and the pigment dispersion may be separately prepared, and then mixed and used, or the halogenated compound and the pigment may be mixed and dispersed.
When the pigment is dispersed in a resin binder and/or an organic solvent, a dispersion aid may be appropriately added.
[Remove coarse particles]
From the coloring composition for a color filter, coarse particles of 5 μm or more are removed by means of centrifugation, a sintered filter, a membrane filter, or the like, and coarse particles of 1 μm or more are preferably removed, and coarse particles of 0.5 μm or more are preferably removed. And mixed dust. Thus, the colored composition is preferably substantially free of coarse particles of 0.5 μm or more. Further, the colored composition is substantially more preferably free of coarse particles of 0.5 μm or more.
<<Color filter>>
Next, a color filter according to a first aspect of the present invention will be described.
The color filter of the first aspect includes a filter segment formed of the coloring composition for the color filter described above. A color filter of one form includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Another aspect of the color filter includes at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.
<Method of Manufacturing Color Filter>
The color filter of this aspect can be manufactured by, for example, a printing method or photolithography.
The patterned filter segments can be formed by printing and drying only the coloring composition prepared as the printing ink by the printing method. Therefore, the printing method is low in cost and excellent in mass productivity. Further, by the development of printing technology, it is possible to form a fine pattern having high dimensional accuracy and smoothness by printing.
When using ink in printing, it is preferable that the ink does not dry and solidify on the printing plate or on the felt cloth. Moreover, the control of the fluidity of the ink on the printing press is also important. The ink fluidity can be controlled by adjusting the ink viscosity by using a dispersant or an extender pigment.
When the filter segment is formed by the photolithography method, the solvent development type or the alkali development type coloring composition is applied to the transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. The colored composition prepared by the object is applied to a dry film thickness of, for example, 0.2 to 10 μm, more preferably 0.2 to 5 μm. A dry coating film such as a vacuum dryer, a convection oven, an IR oven, or a hot plate is used as needed, and the coating film is exposed to ultraviolet rays through a mask having a specific pattern which is provided in contact or non-contact with the coating film. . Thereafter, the coating film is immersed in a solvent or an alkali developer, or the developer is sprayed to remove the uncured portion from the coating film. Thereby, a film pattern corresponding to a filter segment of a certain color is obtained. The same operation as described above was repeated except that the coloring composition for the color filter segments of other colors was used to form a film pattern corresponding to the remaining filter segments. Thereafter, a color filter is obtained by firing the film patterns. Further, the firing may be performed each time a film pattern is formed.
At the time of development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.
Further, in order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied onto the colored resist film obtained by applying and drying the colored resist. The coating film is dried, and then ultraviolet exposure is also possible. A coating film composed of a water-soluble or alkali-soluble resin prevents oxygen from inhibiting polymerization of the colored resist film.
The color filter can also be manufactured by a method other than printing or photolithography. For example, a color filter can be manufactured by an electrodeposition method or a transfer method. The above colored composition can be utilized in any method.
Further, in the manufacture of a color filter using an electrodeposition method, a substrate having a transparent conductive film on one main surface is prepared, and the transparent conductive film is used as an electrode to cause colloidal particles to be electrophoresed on the transparent conductive film. Thereby a filter segment is formed. Further, in the manufacture of a color filter using a transfer method, a filter segment is formed in advance on a previous main surface of a transfer substrate having a release surface on a main surface, and the filter region is formed. The segment is transferred from the transfer substrate to the substrate.
On the transparent substrate, a black matrix in which a light-shielding pattern is formed before forming the filter segment may be used. The black matrix is made of, for example, a metal film such as a chromium film, a multilayer film such as a chromium/chromium oxide film, an inorganic compound film such as titanium nitride, or a resin film in which a light shielding material is dispersed in a resin.
An electrical circuit, such as an active matrix circuit including a thin film transistor (TFT), may also be formed prior to forming the filter segments on the transparent substrate. Further, on the color filter, other layers such as a film or a transparent conductive film may be further formed as needed.
The substrate on which the color filter is formed is not transparent. For example, a color filter may also be formed on the reflective substrate. When the substrate on which the color filter is formed is transparent, the substrate may be a glass plate such as soda lime glass, low alkali borosilicate glass, alkali-free aluminoborosilicate glass, or polycarbonate, polymethyl methacrylate, or poly. A resin plate such as ethylene glycol. Further, the surface of the glass plate or the resin plate may be formed of a transparent electrode composed of indium oxide, tin oxide or the like for driving the liquid crystal after the panel formation.
The color filter is bonded to the counter substrate by using a sealant. Thereafter, the liquid crystal is injected from the injection port provided in the sealing portion, and the injection port is sealed, and if necessary, a polarizing film or a retardation film is bonded to the outside of the substrate, whereby the liquid crystal display panel is manufactured. The liquid crystal display panel can be used for color filters using twisted nematic (TN), super twisted nematic (STN), planar switching (IPS), vertical alignment (VA), optical compensation bending (OCB), and the like. Colorized liquid crystal display mode.
The color filter of this aspect is excellent in storage stability by the coloring composition. In addition, the color filter composition of the color filter is excellent in developability, and no residual (developing residue) of the colored composition or pattern defect and/or peeling of the pixel portion is generated in the non-pixel portion on the substrate after development. The color filter manufactured by using the coloring composition for a color filter is a coating film which does not generate a foreign material, and has a strong adhesiveness with a transparent substrate, such as glass. Further, the color filter described above has high transmittance and high productivity.
○Second aspect
Next, a second aspect of the present invention will be described.
The color filter is formed on a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed, and a coloring layer is directly formed or a passivation film such as a tantalum nitride film is formed to form a colored layer on the surface thereof. A fine strip (striped) filter segment of two or more different hue is arranged in parallel or in a crosswise manner, or a fine filter segment is arranged in a certain arrangement. The filter segments are from a few micrometers to hundreds of micrometers, are very fine, and are arranged neatly in a specific arrangement for each hue.
The liquid crystal used in such a liquid crystal display device is susceptible to electrical characteristics of members such as color filters built in the liquid crystal display device, and may be disordered in liquid crystal alignment due to liquid crystal contamination or may cause poor switching performance. A problem such as an influence is displayed as a problem. In order to solve such problems, insulation is required for the color layer of the color filter, and the film thickness is increased to improve the insulation, and a color film having a low dielectric constant is formed. In order to solve such a problem, for example, in Japanese Laid-Open Patent Publication No. 2004-117537, a method of selecting a dielectric tangent of two layers in a color layer of a green (green) pixel in a specific range is examined.
In the COA method, which has recently been highlighted by the Japanese Patent Publication No. 2004-94263, a coloring layer or a passivation film such as a tantalum nitride film is directly formed on a driving substrate on which a thin film transistor (TFT) is disposed. Forming a coloring layer, bonding a substrate on which the colored layer is formed, and forming a substrate for driving a transparent electrode of liquid crystal by vapor deposition or sputtering; the COA method is driven by a thin film transistor (TFT) Since the coloring layer is directly formed on the substrate, the aperture ratio (opening ratio) of the pixel is greatly increased, and high luminance and low cost can be achieved. On the other hand, the mechanism is susceptible to color filtering. The effect of the electrical characteristics of the light sheet.
In order to solve this problem, the film thickness of the color filter segment is generally set to about 1.6 to 2 μm. In the COA method, the following method is often used, that is, a film thickness of about 3 μm or a bridge density is formed. A higher film, thereby reducing the effects of the electrical characteristics of the color filter. Further, since the structure of the color filter segment of the thick film is formed on the thin film transistor (TFT) instead of the insulating film, it is necessary to provide the connection between the transparent electrode and the thin film transistor (TFT) in the color filter section. Since the pores are formed, the photosensitive coloring composition forming the pixel must be more excellent in resolution than the general photosensitive coloring composition. The resolution of the photosensitive coloring composition is generally adjusted by the amount of the photopolymerization initiator and the monomer, and may be improved by selecting a photopolymerization initiator and a monomer having a low sensitivity or an adjustment amount. On the other hand, since the sensitivity is lowered, the adhesion between the photosensitive coloring composition and the glass substrate is lowered, and pattern peeling is likely to occur. Moreover, when a photopolymerization initiator having high sensitivity is used, the pattern tends to be thicker than the mask, and it is difficult to form minute contact holes. Further, in the COA method, the required characteristics of the profile angle, that is, the angle between the pattern profile and the substrate are very strict, and it is difficult to control the profile angle by the conventional photosensitive coloring composition.
In recent years, color filters have been required to have further high penetration and high concentrations. In order to produce a high-density color filter, the concentration of the coloring material in the colored composition to be used must be increased, but the coloring material concentration of the coloring composition is increased, the exposure sensitivity and the solubility during development are helpful for image formation. The characteristics will be relatively reduced. As a result, the solubility of the non-exposed portion in the developing process is deteriorated, and the coloring composition of the non-exposed portion remains in the developing process, and the resist remains undissolved and remains as a release sheet on the substrate, which may cause chromatic aberration or the like. s reason. As a result, the quality of the color filter is lowered and the yield at the time of production is lowered. In other words, when the liquid crystal is a material having a very high insulating property, if the polar compound remaining in the coloring composition for a color filter is dissolved in the liquid crystal cell, the voltage between the electrodes is lowered, resulting in a decrease in the voltage holding ratio. Display unevenness, poor alignment, and the like cause a decrease in the performance of the liquid crystal display element. Therefore, the coloring composition is required to be insoluble to liquid crystals. This resistance is referred to as a voltage holding ratio characteristic, which is an index indicating the electrical characteristics of the display performance of a liquid crystal display element (LCD).
A second aspect of the present invention is a photosensitive coloring composition comprising a colorant, a resin, a monomer, and a photopolymerization initiator; the monomer comprises a polyfunctional monomer having an acidic group; and is colored with respect to photosensitivity. 100 parts by mass of the nonvolatile component of the composition, the content of the monomer is 20 to 50 parts by mass, and the photopolymerization initiator contains an acetophenone-based compound and a sulfonium-based phosphorus oxide-based compound; an acetophenone-based compound and an anthracene The mass ratio of the phosphine oxide-based compound (acetophenone-based compound/phosphonium-based phosphorus oxide-based compound) is in the range of 60/40 to 90/10.
The photosensitive coloring composition having the above-described configuration is formed by using a polyfunctional monomer having an acidic group, adhesion to a glass substrate, solubility to an alkali developing solution, and high voltage holding ratio characteristics. Further, by setting the amount of the polyfunctional monomer having an acidic group to a specific range and containing a photopolymerization initiator of a specific component at a specific ratio, a pattern having a good profile angle can be formed.
According to this aspect, a thick film and a high resolution can be obtained, and the adhesion to the glass substrate is good, and the solubility in the alkali developing solution and the high voltage holding property are excellent, and the developability, in particular, the contour angle can be formed well. A photosensitive coloring composition of the pattern, and a color filter using the same.
<<Coloring composition for color filter>>
As described above, the photosensitive coloring composition of the second aspect contains a coloring agent, a resin, a monomer, and a photopolymerization initiator.
<colorant>
For red colorants, for example, Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2 can be used. 81:3, 81:4,122,146,166,168,169,176,177,178,179,184,185,187,200,202,208,210,221,242,246,254,255, Red pigments such as 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Further, a halogenated compound which exhibits a red basic dye, an acid dye or the like may also be used.
Also, in the red coloring agent, it is also possible to use CI pigment orange 36, 38, 43, 71 or 73 orange pigment, and/or CI pigment yellow 1, 2, 3, 4, 5, 6, 10, 12 , 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60 , 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116 , 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 1,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220 Or 221 and other yellow pigments. Further, a halogenated compound which exhibits an orange dye and/or a yellow basic dye, an acid dye or the like may also be used.
The green coloring agent may, for example, be C.I. Pigment Green 7, 10, 36, 37, 58, and the like. Among them, as a green pigment, it is preferable to use C.I. Pigment Green 58 from the viewpoint of achieving high brightness. C.I. Pigment Green 58 has a high acidity, and therefore it is difficult to ensure dispersion stability as compared with other pigment types. However, by using the coloring composition for a color filter of the present aspect, crystal foreign matter of the coating film can be suppressed.
Also, in the green coloring agent, a yellow pigment can be used at the same time. The yellow pigments which can be used at the same time are CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, A yellow pigment such as 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a halogenated compound which exhibits a yellow basic dye, an acid dye or the like may also be used.
As the blue coloring agent, for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 or 64 or the like can be used. In the blue coloring composition, a purple pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 or 50 may also be used. Further, a halogenated compound which exhibits a purple basic dye, an acid dye or the like may also be used.
[Micronization of pigments]
The pigment used in this aspect can be refined by salt milling. The salt milling treatment can be carried out, for example, by the same method as the description of the first aspect. Further, as the salt milling treatment, for example, the same aqueous solution inorganic salt, water-soluble organic solvent, and resin as those described in the first aspect can be used. The amount of each material used should be set to the range described in the first aspect. The amount of each material used should be set to the range described in the first aspect. The primary particle size of the pigment is in the same range as the description of the first aspect. The primary particle diameter of the pigment can be measured by the same method as described in the first aspect.
When the pigment is subjected to salt milling, a resin may also be added. The resin used is the same as that described in the first aspect. The amount of the resin used should also be within the range described in the first aspect.
From the viewpoint of good dispersion in the colorant carrier, the primary particle diameter of the pigment is preferably 20 nm or more. Further, it is preferably 100 nm or less from the viewpoint of forming a filter segment having a high contrast ratio. A particularly suitable range is in the range of 25 to 85 nm. The primary particle diameter of the pigment can be measured by the same method as described in the first aspect.
<Resin>
The resin disperses the colorant. The resin is, for example, a thermoplastic resin or a thermosetting resin.
The resin is preferably in the entire wavelength region of 400 to 700 nm in the visible light region, and the spectral transmittance is 80% or more, more preferably 95% or more. When a coloring composition is used in the form of an alkali-developing type colored resist, an alkali-soluble vinyl-based resin obtained by copolymerizing a monomer containing an acidic group and ethylene is preferably used. Further, in order to further enhance the light sensitivity, an energy ray-curable resin having ethylene bonding may also be used.
In addition, from the viewpoints of pigment dispersibility, developability, and heat resistance, a pigment adsorbing group and a carboxyl group serving as an alkali-soluble group during development, a colorant carrier, and an aliphatic group functioning as an affinity group for a solvent and The balance of aromatic groups is very important. The resin is preferably a resin binder having an acid value of 20 to 300 mgKOH/g. When a resin having an acid value of less than 20 mgKOH/g is used, the solubility in the developer is deteriorated, and it may be difficult to form a fine pattern. Further, when a resin having an acid value of more than 300 mgKOH/g is used, a fine pattern may not remain.
The amount of the resin is preferably 30 parts by mass or more based on 100 parts by mass of the coloring agent, and it is preferable to set a good color characteristic because the coloring agent has a high concentration. It is 500 mass parts or less. The blending amount of the resin is preferably 40 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the coloring agent.
(thermoplastic resin)
The thermoplastic resin may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyacetic acid. Ethylene, urethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), Polybutadiene and polyimine resin.
The alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group and a monomer containing an ethylene group may, for example, be a resin having an acidic group such as a carboxyl group or a sulfo group. Specifically, the alkali-soluble resin may, for example, be an acrylic resin having an acidic group, an α-olefin-(anhydride) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, or a styrene-(meth)acrylic acid. Copolymer or isobutylene-(anhydride) maleic acid copolymer or the like. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer having an acidic group, particularly an acrylic resin having an acidic group, is preferably used because it has high heat resistance and high transparency.
The energy ray-curable resin having ethylene bonding may, for example, be a resin in which ethylene bonding is introduced by the method (i) or (ii) described in the first aspect.
(thermosetting resin)
Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.
<monomer>
The monomer contains at least a polyfunctional monomer having an acidic group. By including a polyfunctional monomer having an acidic group in the monomer, the adhesion to the glass substrate, the solubility to the alkali developing solution, and the high voltage holding ratio characteristics can be simultaneously achieved. The monomer preferably further contains an oligomer which can be reacted by ultraviolet rays or heat. Further, the monomer may simultaneously use a monomer having no acidic group and/or an oligomer having no acidic group.
The amount of the monomer is preferably from 20 to 50 parts by mass in the non-volatile component of the colored composition, and is preferably from 30 to 45 parts by mass from the viewpoint of photocurability, resolution, and grating shape.
(multifunctional monomer having an acidic group)
As the polyfunctional monomer having an acidic group, for example, the same as the description of the first aspect can be used. The polyfunctional monomer having an acidic group is also preferably a compound represented by the general formula (3) shown in the first aspect. By using the compound of the general formula (3), the solubility of the photosensitive coloring composition of the present aspect to the alkali developing solution can be improved, and in the developing process on the manufacturing line, by preventing the generation of insoluble matter with the developing solution, it can be prevented. The filter is clogged.
The polyfunctional monomer having an acidic group may be used singly or in combination of two or more.
The amount of the polyfunctional monomer having an acidic group is 20 to 50 parts by mass, more preferably 30 to 45 parts by mass, based on 100 parts by mass of the nonvolatile component of the photosensitive coloring composition. When the amount of the polyfunctional monomer having an acidic group is less than 5% by mass, the pixel strength or the smoothness of the surface of the pixel tends to decrease, and if it exceeds 500 parts by mass, for example, the alkali developability is lowered to form an area other than the pixel portion. It tends to cause substrate contamination or film residue.
The monomer includes the above polyfunctional monomer having an acidic group, and may further contain a polyfunctional monomer or a monofunctional monomer other than the polyfunctional monomer having an acidic group.
(other polyfunctional monomers)
Other polyfunctional monomers may be the same as those described in the first aspect.
(monofunctional monomer)
As the monofunctional monomer, for example, the same as the description of the first aspect can be used.
When a polyfunctional monomer having an acidic group and another monomer are used at the same time, the other monomers may be used alone or in combination of two or more. In this case, the amount of the other monomer used is 100 parts by mass, and usually 0 to 90 parts by mass, more preferably 0 to 50 mass, based on the total monomer amount, that is, the total amount of the polyfunctional monomer having an acidic group. unit.
Further, in this aspect, from the viewpoint of voltage holding ratio, it is preferred to use a monomer which does not use caprolactone as a raw material.
<Photopolymerization initiator>
The photopolymerization initiator is an acetophenone-based compound and a fluorenylphosphorus oxide-based compound. Further, the ratio of the acetophenone-based compound to the fluorenylphosphorus oxide-based compound is in the range of 60/40 to 90/10 in the acetophenone-based compound/fluorenylphosphorus oxide-based compound. A good pattern can be formed by combining a photopolymerization initiator and the aforementioned polyfunctional monomer having an acidic group.
The acetophenone-based compound may, for example, be 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone or p-dimethylaminophenylbenzene. Ketone, 1–(4-isopropylphenyl)–2–hydroxy-2–methylpropane–1-ketone, 1-hydroxycyclohexylbenzophenone, 2-benzyldimethylamine-1–(4– Morpholine phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) Phenyl]-1-butanone and the like.
Examples of the fluorenylphosphine oxide-based compound include bis(2,4,6-trimethylbenzo)epoxyphenylphosphine and 2,4,6-trimethylbenzoepoxyphenylphosphine.
The photopolymerization initiator may further use a photopolymerization initiator other than the acetophenone-based compound and the fluorenylphosphine oxide-based compound. Specific examples of the photopolymerization initiator other than the acetophenone-based compound and the fluorenylphosphine oxide-based compound include 1,2-octanedione, 1–[4–(phenylthio)-, 2(O). - an oxime ester compound such as benzopyrene)], O-(acetylene)-N-(1-phenyl-2, carbonyl-2, (4'-methoxy-naphthyl)ethylidene)hydroxylamine; Benzene compounds such as benzo, benzomethyl ether, benzoether, benzoisopropyl ether, benzyl dimethyl ketal; benzophenone, benzoquinone benzoic acid, benzoquinone benzoic acid methyl, 4– Phenylbenzophenone, hydroxybenzophenone, propylene benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3, 3', 4, 4'-four (t a benzophenone compound such as butyl peroxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4–2 Thiophenone compounds such as isopropyl thioxanthone, 2,4-diethylthioxanthone; 2, 4, 6-trichloro-o-triazine, 2-phenyl-4, 6-bis (trichloro) Methyl)-orthotriazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-o-triazine, 2-(p-tolyl)-4, 6-bis (three Chlorine ) - o-triazine, 2 - piperonyl - 4, 6 - bis (trichloromethyl) - o-triazine, 2, 4 - bis (trichloromethyl) - 6 - styryl - o-triazine, 2 –(naphtho-l-yl)-4,6-bis(trichloromethyl)-o-triazine, 2–(4-methoxynaphthalenyl-l-yl)-4,6-bis(trichloro) Methyl)-orthotriazine, 2,4-trichloromethyl-(piperidinyl)-6-triazine, 2,4-trichloromethyl (4'-methoxystyryl)-6-three Triazine-based compound such as azine; 2, 2'-bis(o-chlorophenyl)-4, 5, 4', 5'-tetraphenyl-1, 2'-biimidazole, 2, 2'-double (ortho) Methoxyphenyl)-4, 5, 4', 5'-tetraphenylbiimidazole, 2, 2'-bis(o-chlorophenyl)-4, 5, 4', 5'-tetra(p-methyl An imidazole compound such as phenyl)biimidazole; an anthraquinone compound such as phenanthrenequinone, camphorquinone or ethylhydrazine; a borate ester compound; an oxazole compound; and a titanocene compound. These photopolymerization initiators may be used singly or in combination of two or more kinds at any ratio as needed.
In this aspect, the photopolymerization initiator is used in a specific amount to improve the adhesion. Specifically, the amount of the photopolymerization initiator to be added is preferably from 3 to 20 parts by mass, more preferably from 8 to 13 parts by mass, based on 100 parts by mass of the nonvolatile component of the photosensitive coloring composition.
As a characteristic when the photosensitive coloring composition is used for COA, the profile angle is preferably in the range of 35 to 65°, more preferably in the range of 40 to 60°. Further, the taper length is preferably 7 μm or less. By setting the blending amount of the monomer and the blending amount of the initiator in the above range, the contour angle and the taper length can be controlled to a desired value, and a color filter suitable for the COA method can be manufactured.
<sensitizer>
The coloring composition may also contain a sensitizer.
For the sensitizer, for example, the same as the description of the first aspect is used. The amount of the sensitizer to be formulated can be, for example, the same range as the description of the first aspect.
<Multifunctional thiol>
The colored composition of the present aspect may contain a polyfunctional thiol. As the polyfunctional thiol, for example, the same as the description of the third aspect below can be used.
<leveling agent>
The colored composition of this aspect may contain a leveling agent. For the leveling agent, for example, the same as the description of the first aspect can be used.
<polymerization inhibitor>
The colored composition of this aspect may contain a polymerization inhibiting agent. As the polymerization inhibiting agent, for example, the same as the description of the first aspect can be used.
<solvent>
The photosensitive coloring composition may contain a solvent so that the coloring agent is sufficiently dispersed and/or infiltrated into the coloring agent carrier, and is applied to a substrate such as a glass substrate to have a dry film thickness of 0.5 to 5.0 μm to easily form a filter. Section.
As the solvent, for example, the same as the description of the first aspect can be used. Moreover, it is preferable to use the thing similar to description of a 1st aspect from the viewpoint of the storage stability of a coloring composition.
The amount of the solvent to be added is preferably in the range of 800 to 4,000 parts by mass with respect to 100 parts by mass of the colorant. By setting the blending amount within this range, the viscosity of the colored composition can be adjusted to an appropriate value to form a filter segment having a uniform film thickness as a target.
<Dispersing Aid>
When the colorant is dispersed in the colorant carrier, a dispersing aid such as a dye derivative, a resin type dispersant, or a surfactant can be suitably used in the same manner as in the first embodiment.
As the pigment derivative, for example, the same as the description of the first aspect can be used.
Further, the pigment derivative can be used, for example, in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5. -9469 bulletin and the like. The pigment derivative may be used alone or in combination of two or more.
When the pigment derivative is used, it is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, based on 100 parts by mass of the coloring agent. Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to the mass portion of the coloring agent 100.
As the resin type dispersant, for example, the same as the description of the first aspect can be used.
As the surfactant, the same as the description of the first aspect can be used. When a resin-type dispersing agent and/or a surfactant is added, the total amount of the dispersing agent and the surfactant is preferably in the range of 0.1 to 55 parts by mass, and more preferably in the range of 0.1 to 45 parts by mass. Inside. When the amount of the resin-type dispersant and the surfactant is small, it is difficult to obtain an effect of addition. Further, when the total amount of the compound is large, the dispersion may be affected by the excessive dispersant.
<leveling agent>
In order to improve the leveling property of the photosensitive coloring composition on the transparent substrate, it is preferred to further add a leveling agent to the photosensitive coloring composition.
For the leveling agent, for example, the same as the description of the first aspect can be used. When a leveling agent is used, the compounding amount is generally in the photosensitive coloring composition, and it is preferably set to 0.003 to 0.5 part by mass.
The leveling agent may also be auxiliaryly added to an anionic, cationic, nonionic or amphoteric surfactant. The surfactants may be used alone or in combination of two or more. For the surfactants, for example, the same as the description of the first aspect can be used.
<hardener, hardening accelerator>
In order to assist the hardening of the thermosetting resin, the photosensitive coloring composition may contain a curing agent, a curing accelerator, and the like. As the curing agent and the curing accelerator, for example, the same as the description of the first aspect can be used. When a hardening accelerator is used, the compounding amount is also set to be the same as that of the first aspect.
<Other additive ingredients>
In order to stabilize the viscosity of the composition over time, the coloring composition may also contain a storage stabilizer. Further, the colored composition may contain a adhesion enhancer such as a decane coupling agent in order to improve the adhesion to the transparent substrate.
For the storage stabilizer and the adhesion enhancer, for example, the same as the description of the first aspect can be used. When the storage stabilizer and/or the adhesion enhancer are used, the amount of the stabilizer is preferably the same as that described in the first aspect.
<Method for Producing Photosensitive Coloring Composition>
The photosensitive coloring composition of this aspect can be produced, for example, by the same method as the description of the <Coloring composition for color filters> in the first aspect.
[Remove coarse particles]
From the photosensitive coloring composition, it is preferable to remove the coarse particles and the mixed fine dust in the same manner as the description of the first aspect. For example, it is preferable to remove coarse particles of 5 μm or more from the photosensitive coloring composition, and it is preferable to remove coarse particles of 1 μm or more, and it is preferable to remove coarse particles of 0.5 μm or more and fine dust mixed therein. That is, it is preferable that the coloring composition does not substantially contain coarse particles of 0.5 μm or more, and substantially does not contain coarse particles of 0.3 μm or more.
<<Color filter>>
Next, a color filter according to a second aspect of the present invention will be described.
An aspect of the color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter of the second aspect, at least one of the filter segments is formed of the photosensitive coloring composition. The filter section is formed on the substrate by applying the photosensitive coloring composition of the present aspect by a spin coating method or a die coating method.
<Method of Manufacturing Color Filter>
Examples of the substrate of the color filter include a glass plate such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass having high visible light transmittance, or polycarbonate or polymethyl. A transparent substrate or a reflective substrate of a resin plate such as methyl acrylate or polyethylene glycol. An appropriate pretreatment such as a drug treatment such as a decane coupling agent, a plasma treatment, an ion plating, a sputtering, a vapor phase reaction method, or a vacuum vapor deposition may be applied in advance to the substrates. Further, on the surface of the glass plate or the resin plate, a transparent electrode composed of indium oxide, tin oxide or the like may be formed in order to drive the liquid crystal after the panel is formed.
Before the filter segments are formed on the transparent substrate or the reflective substrate, if a black matrix is formed in advance, the contrast of the liquid crystal display panel can be further improved. The black matrix is a multilayer film using chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed, but is not limited thereto. Further, a thin film transistor (TFT) may be formed on the transparent substrate or the reflective substrate in advance, and then a filter segment may be formed. By forming the filter segments on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased, and the brightness can be improved.
Here, a method of forming a filter segment on a TFT substrate will be described. First, on the surface of the TFT substrate, or on the surface of the substrate on which the passivation film such as a tantalum nitride film is formed on the surface of the TFT substrate, a light shielding layer is formed to form a pixel portion, and the color of the present invention is coated on the substrate. After the composition, prebaking is performed to evaporate the solvent to form a coating film. Next, after the exposure film is exposed to the coating film, development is carried out using an alkali developing solution to dissolve and remove the unexposed portion of the coating film, followed by post-baking to form a pixel array in which pixels are arranged in a specific arrangement. The mask used at that time was provided with a pattern of through holes or "コ"-shaped depressions in addition to the pattern for forming pixels.
At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkali developer, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.
As the development treatment method, a shower development method, a spray development method, a dropping (dipping) development method, a stirring (liquid) development method, or the like can be applied. Among them, from the viewpoint of simultaneously achieving a good profile angle and opening of a contact hole, a spray development method or a spray development method is preferred.
Further, in order to increase the ultraviolet exposure sensitivity, the photosensitive coloring composition may be applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to prevent oxygen. After the film which is inhibited by the polymerization, ultraviolet exposure is performed. However, since the polymerization is prevented, the contact hole is difficult to be opened if the sensitivity is too high. Therefore, it is not preferable to apply a resin or the like to the coating film of the coloring composition.
The coating thickness when forming the filter segments on the transparent substrate or the reflective substrate is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm.
Further, in particular, when the coloring composition of the present aspect is used in the COA method, insulation is required to prevent crosstalk caused between the gate electrode and the transparent electrode, and since a thick film is preferable, it is preferable to use a dry film thickness of 0.1 to 10 μm, more preferably 0.5 to 5 μm.
On the color filter, a film or a column spacer, a transparent conductive film, a liquid crystal alignment layer, or the like is formed as needed.
The color filter is bonded to the counter substrate by a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, the polarizing film or the retardation film is bonded to the outside of the substrate, thereby preparing the color filter. LCD panel.
The liquid crystal display panel can be used for color filters using twisted nematic (TN), super twisted nematic (STN), planar switching (IPS), vertical alignment (VA), optical compensation bending (OCB), and the like. Colorized liquid crystal display mode.
The photosensitive coloring composition of this aspect is excellent in developability, and in particular, a pattern having a good contour angle can be formed. Further, the color filter thick film produced by using the photosensitive coloring composition has a high resolution. Further, the adhesion to the glass substrate is good, and the solubility in the alkali developing solution and the high voltage holding ratio characteristics are excellent.
○3rd aspect
Next, a third aspect of the present invention will be described.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal on a color filter is formed by vapor deposition or sputtering, and is formed thereon to form a liquid crystal in a certain direction. Orientation film. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, it is generally required to be formed at a temperature of 200 ° C, more preferably 230 ° C or higher. Therefore, as a method of producing a color filter, a method called a pigment dispersion method is a mainstream method, and a pigment having excellent light resistance and heat resistance is used as a colorant. In the pigment dispersion method, the filter section is formed by using a color resist coating liquid in which a photopolymerization initiator or a photopolymerizable monomer is blended in a pigment dispersion.
In recent years, color filters have been required to have further high penetration and high concentrations. In order to produce a high-density color filter, the concentration of the coloring material in the colored composition to be used must be increased, but the coloring material concentration of the coloring composition is increased, the exposure sensitivity and the solubility during development are helpful for image formation. The characteristics will be relatively reduced. As a result, the solubility of the non-exposed portion in the developing process is deteriorated, and the coloring composition of the non-exposed portion remains in the developing process, and the photoresist remains undissolved and remains as a release sheet on the substrate, which may cause chromatic aberration or the like. s reason. As a result, the quality of the color filter is lowered and the yield at the time of production is lowered.
As a countermeasure against such a problem, by using a polyfunctional monomer having an acidic group, it is possible to prevent undissolved matter (developing residue) from remaining in the color filter manufacturing, and to prevent the undissolved release sheet of the resist from adhering to the development. For example, Japanese Patent Laid-Open No. Hei 10-332929, JP-A-2005-148717, JP-A-2007-34119, and JP-A-2007-34119 Japanese Patent Publication No. 2007-328148, Japanese Patent Publication No. 2007-163890, and International Publication No. WO2007/102474.
Further, as a method of obtaining a color filter having a higher transmittance, Japanese Patent Laid-Open Publication No. 2009-122650 discloses that a coloring composition can be prevented from being used in a coloring composition by using a specific photopolymerization initiator and an oxidation preventing agent. The photopolymerization initiator contained in the yellowing of the firing process such as post-baking. Here, "yellowing" means that the color filter is colored due to heating by a baking process such as post-baking, and the transparency of the color filter is lowered.
However, in such a method, even if the problem of the residue of the undissolved matter (developing residue) or the adhesion of the undissolved release sheet is avoided, the problem that the pattern peeling or the defect of the line portion occurs due to excessive solubility is not solved at the same time. . Moreover, the development range is narrowed, that is, the manufacturing efficiency of the color filter is also poor. Further, in the above method, since the coloring of the color filter is lowered by using a baking process such as post-baking or a heating process of a color filter and a processing process, the penetrability of the color filter is lowered, so that it cannot be solved. The problem of developability or pattern defect of the line portion is achieved while achieving high penetration.
Further, the method described in Japanese Laid-Open Patent Publication No. 2009-122650 fails to sufficiently solve the yellowing caused by post-baking during the production of a high-density color filter or the formation of the transparent electrode and the alignment film at 200 ° C. The problem of a decrease in the penetration rate of the firing process. In addition, the problem of pattern peeling or defect of the line portion has not been solved. As a result, the method is not sufficient as a means of obtaining a color filter having high penetration and high productivity.
The inventors of the present invention have found that, as a result of simultaneously solving the production of a color filter having a higher permeability and a high concentration, a coloring composition (developing residue) remains on the non-line portion on the substrate after development, or is caused by a method in which the dissolving release sheet adheres to the foreign matter in the line portion, the line defect caused by the pattern peeling or the defect of the line portion, and the yellowing of the baking process such as post-baking, and the coloring composition The total amount of the alkali-soluble photosensitive resin component and the content of the polyfunctional monomer having an acidic group is 20 to 70 in total of 100 parts by mass of the resin content and the content of the polyfunctional monomer. In the mass portion, the content of the oxidation preventing agent is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the nonvolatile component of the colored composition for a color filter.
That is, the third aspect of the present invention relates to a coloring composition for a color filter comprising a coloring agent, a resin, a monomer, a photopolymerization initiator, a solvent, and an oxidation preventing agent; and the foregoing resin comprises a base At least one selected from the group consisting of a soluble photosensitive resin component and an alkali-soluble non-photosensitive resin component; the monomer comprises a polyfunctional monomer having an acidic group; and a content relative to the resin and a polyfunctional monomer 100 parts by mass of the total amount, the total amount of the alkali-soluble photosensitive resin component and the content of the polyfunctional monomer having an acidic group are 20 to 70 parts by mass, and the coloring composition is used for the color filter. The non-volatile component is 100 parts by mass, and the content of the oxidation preventing agent is 0.1 to 5 parts by mass.
According to the above configuration, by optimizing the amount of the alkali-soluble resin and the polyfunctional monomer having an acidic group, sensitivity, photocurability, and transparency at the time of exposure can be simultaneously achieved, and oxidation can be performed by an appropriate amount. The preventive agent can suppress the decrease in transparency and further increase the concentration of the colorant.
In addition, the coloring composition for a color filter having a high concentration of the coloring agent can provide a color filter which is excellent in productivity, is excellent in developability represented by image line formation property, and has good transparency. .
<<Coloring composition for color filter>>
The colored composition for a color filter according to a third aspect of the present invention contains a colorant, a resin, a monomer, a photopolymerization initiator, a solvent, and an oxidation inhibitor.
<colorant>
The coloring agent for coloring the color filter used in the present embodiment can be used by mixing two or more kinds of organic or inorganic pigments, and it is preferable to use an organic having high color rendering property and heat resistance.
The coloring agent for the red coloring composition can be used, for example, Pig Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1. , 81:2, 81:3, 81:4, 122, 146, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246 Red pigments such as 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Further, a halogenated compound which exhibits a red basic dye, an acid dye or the like may also be used.
Further, in the red coloring composition, it is also possible to use an orange pigment such as CI pigment orange 43, 71 or 73, and/or CI pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14 , 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62 , 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 , 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 , 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221 pigment. Further, a halogenated compound which exhibits an orange dye and/or a yellow basic dye, an acid dye or the like may also be used.
The coloring agent used for the green coloring composition may, for example, be C.I. Pigment Green 7, 10, 36, 37, 58, and the like.
Further, in the green coloring composition, a yellow pigment can be used at the same time. The yellow pigments which can be used at the same time are CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, A yellow pigment such as 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a halogenated compound which exhibits a yellow basic dye, an acid dye or the like may also be used.
As the coloring agent for the blue coloring composition, for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 or 64 or the like can be used. In the blue coloring composition, a purple pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 or 50 may also be used. Further, a halogenated compound which exhibits a purple basic dye, an acid dye or the like may also be used.
[Micronization of pigments]
The pigment used in this aspect can be refined by salt milling. The salt milling treatment can be carried out, for example, by the same method as the description of the first aspect. Further, as the salt milling treatment, for example, the same aqueous solution inorganic salt, water-soluble organic solvent, and resin as those described in the first aspect can be used.
The primary particle size of the pigment is in the same range as the description of the second aspect. The primary particle diameter of the pigment can be measured by the same method as described in the first aspect.
When the pigment is subjected to salt milling, a resin may also be added. The resin used is the same as that described in the first aspect. The amount of the resin used should also be within the range described in the first aspect.
In the case of producing a pigment dispersion, in order to prevent the pigment from coagulating, it is preferable to add a dye derivative by maintaining a state in which the pigment is finely dispersed and producing a color filter having high color purity with high brightness and high contrast ratio. The content of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, based on 100 parts by mass of the pigment. Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to the mass portion of the coloring agent 100.
The pigment derivative is a compound in which an organic pigment is introduced with a basic or acidic substituent. The organic pigment generally also contains a pale yellow aromatic polycyclic compound which is not called a pigment, such as naphthalene, anthracene, acridone or the like. The pigment derivative can be used, for example, in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5- In the case of the above-mentioned Japanese Patent Publication No. 9-176511, the above-mentioned ones can be used singly or in combination of two or more.
<Resin>
The resin disperses the colorant, particularly the halogenated compound, or functions as a colorant carrier for dyeing and penetrating the halogenated compound. The resin is preferably a transparent resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region.
The resin contains an alkali-soluble photosensitive resin and/or an alkali-soluble non-photosensitive resin.
(alkali-soluble photosensitive resin and alkali-soluble non-photosensitive resin)
The alkali-soluble photosensitive resin is a resin which is soluble in an alkali developing solution, and may be any resin which is classified into a thermoplastic resin and a thermosetting resin, and may have, for example, a carboxyl group. The acidic functional group such as a mercapto group has a mass average molecular weight of 1,000 to 500,000, more preferably 3,000 to 100,000. Hereinafter, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylate type means acrylate or methyl acrylate.
Specific examples thereof include an acrylic resin, an α-olefin-(anhydride) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, a styrene-(meth)acrylic acid copolymer, and an isobutylene-(anhydride). a maleic acid copolymer. Among these, at least one resin selected from the group consisting of an acrylic resin, an α-olefin-(anhydride) maleic acid copolymer, and a styrene-styrenesulfonic acid copolymer is preferable. Among these, an acrylic resin obtained by copolymerizing a monomer having an ethylene group containing an acidic group is preferably used because it has high heat resistance and penetrability.
Among the alkali-soluble resins, in particular, a resin having one or more ring structures selected from the group consisting of the aromatic ring groups represented by the general formulas (12) and (13) is used as the coloring layer. The agent or the coloring agent and the affinity component of the coloring agent composition composed of the dispersing agent and the like function, and therefore it is suitably used.
General formula (12):

Formula (12)
General formula (13):
Formula (13)
(In general formula (12), R¹a hydrogen atom or an alkyl group having a benzene ring having 1 to 20 carbon atoms, in the general formula (13), R²It may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms in the benzene ring. )
One or more selected from the group consisting of aromatic ring groups represented by general formulas (12) and (13), based on the mass of the total repeating unit of the alkali-soluble photosensitive resin or the alkali-soluble non-photosensitive resin. The repeating unit content of the cyclic structure is preferably from 2.0 to 80 parts by mass from the viewpoint of developability and dispersion stability. When the amount is less than 2.0 parts by mass, the coloring agent or the affinity component of the coloring composition composed of the coloring agent and the dispersing agent is insufficient, and coloring filters for high quality cannot be obtained, or coloring for color filters may occur. When the stability of the composition is deteriorated, if it exceeds 80 parts by mass, the dissolution rate of the alkali developer may be slow, the development time may be long, and the productivity of the color filter may be deteriorated. Since this resin exhibits an excellent dispersing effect for almost all pigments, it prevents the pigment from coagulating in the colored composition and functions to maintain the fine dispersion state of the pigment. Therefore, when a color filter composition in which the coloring agent is dispersed in the coloring agent carrier containing the above resin is used to form the filter segment, a filter segment having less colorant condensation can be formed and manufactured. High color transmittance, high brightness color filter.
Examples of the repeating unit having one or more ring structures selected from the group consisting of the aromatic ring groups represented by the general formulas (12) and (13) include styrene and α-methylstyrene. , divinylbenzene, hydrazine, acetamidine, benzo (meth) acrylate, phenol oxirane modified (meth) acrylate, p-cumyl phenol ethane modified (meth) acrylate , nonylphenol ethane modified (meth) acrylate, nonyl phenol propane modified (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, methylolated melamine ( A monomer such as a methyl acrylate or a oligomer or the like.
In order to disperse the colorant well, the mass average molecular weight of the resin (hereinafter sometimes referred to as Mw) is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 100,000. Further, the number average molecular weight (Mn) is preferably in the range of 1,000 to 50,000, and the Mw/Mn value is preferably 10 or less.
The alkali-soluble photosensitive resin or the alkali-soluble non-photosensitive resin functions as a colorant adsorbent and a carboxyl group or a sulfonic acid group which functions as a base-acceptable group during development, and functions as an affinity group for a pigment carrier and a solvent. The balance of the aliphatic group and the aromatic group to be used is important for pigment dispersibility, developability, and durability, and a resin having an acid value of 20 to 300 mgKOH/g is preferably used. When the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, the development time is long, and the productivity is lowered. On the other hand, if it exceeds 300 mgKOH/g, the pattern peeling or defect of the line portion may occur. The alkali-soluble photosensitive resin is an energy ray-curable resin in which ethylene is introduced by, for example, the method (a) and/or the method (b) described in the first aspect.
(alkali-soluble photosensitive resin (a) and alkali-soluble non-photosensitive resin (b))
The alkali-soluble photosensitive resin is preferably an alkali-soluble photosensitive resin (a) having the following repeating units (U1) to (U3) in the following amounts. The alkali-soluble photosensitive resin (a) further contains a repeating unit (U4) having ethylene bonding.
The alkali-soluble non-photosensitive resin preferably contains the alkali-soluble non-photosensitive resin (b) of the following repeating units (U1) to (U3) in the following amounts. The alkali-soluble non-photosensitive resin (b) may further contain components other than the repeating units (U1) to (U3).
By using such a resin, various characteristics of a coloring composition such as penetrability and image line formation property can be further improved.
(U1) repeating unit having a carboxyl group: 2.0 to 60 parts by mass
(U2) a repeating unit having one or more ring structures selected from the group consisting of the aromatic ring groups represented by the general formulas (12) and (13): 2.0 to 80 parts by mass
General formula (12):
Formula (12)
General formula (13):
Formula (13)
(In general formula (12), R¹a hydrogen atom or an alkyl group having a benzene ring having 1 to 20 carbon atoms, wherein the hydrogen atom of the alkyl group may be replaced by a benzene ring; in the general formula (13), R²It may be a hydrogen atom or an alkyl group having 1 to 20 carbon atoms of a benzene ring, and the hydrogen atom of the alkyl group may be replaced by a benzene ring. )
(U3) a repeating unit having one or more ring structures selected from the group consisting of the aliphatic ring groups represented by the general formulas (14) and (15): 2.0 to 30 parts by mass
Chemical formula (14):
Formula (14)
Chemical formula (15):
Formula (15)
(U4) A repeating unit having photosensitivity of ethylene bonding.
When a certain repeating unit is classified into two or more of (U1) to (U4), the repeating unit is classified according to the priority order indicated by (U1)>(U2)>(U3)>(U4). For example, when a repeating unit contains a carboxyl group and an aliphatic cyclic group represented by the general formula (14), the repeating unit may be classified into a repeating unit (U1) when it conforms to (U1) and (U2). Further, for example, when a repeating unit includes an aliphatic ring group represented by the general formula (14) and an aromatic ring group represented by the general formula (12), the repeating unit may be classified into (U2) and (U3). Units are classified as repeat units (U2).
That is, the repeating unit (U2) does not have a carboxyl group; the repeating unit (U3) does not have a carboxyl group, and one or more rings selected from the group consisting of the aromatic ring groups represented by the general formulas (12) and (13) Any one of the structures; the repeating unit (U4) having no carboxyl group, one or more ring structures selected from the group consisting of the aromatic ring groups represented by the general formulas (12) and (13), and the general formula Any one or more of the ring structures selected from the group consisting of the aliphatic ring groups shown in (14 and (15).
The repeat unit (U1), the repeat unit (U2), the repeat unit (U3), and the repeat unit (U4) will be described in more detail below.
[repeating unit (U1)]
The carboxyl group contained in the repeating unit (U1) functions as a base-capable portion at the time of development. The content of the repeating unit (U1) is preferably 2.0 to ≤ the mass of the total repeating unit of the alkali-soluble photosensitive resin (a) or the alkali-soluble non-photosensitive resin (b) from the viewpoint of developability. 60 quality departments. When the content of the repeating unit (U1) is less than 2.0 parts by mass, the unexposed part removal property of the alkali developing solution may be insufficient, and if it exceeds 60 parts by mass, the dissolution rate to the alkali developing solution may become fast, and sometimes The exposed portion will dissolve.
The repeating unit (U1) precursor (U1-a) contains, for example, an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid or α-chloroacrylic acid, or an unsaturated carboxylic acid such as maleic acid or phthalic acid. A carboxyl group such as an acid, and having a compound in which ethylene is bonded. Further, the precursor (U1-a) is obtained by semi-esterifying an anhydride of an unsaturated carboxylic acid such as maleic anhydride with a (meth) propylene compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. Things. Among these, from the viewpoint of polymerizability (ease of control of molecular weight), (meth)acrylic acid is preferable, and methacrylic acid is more preferable. These may be used alone or in combination of two or more.
[repeating unit (U2)]
The repeating unit (U2) has a repeating unit of one or more ring structures selected from the group consisting of the aromatic ring groups represented by the above general formulas (12) and (13). The repeating unit (U2) functions as a coloring agent or a coloring composition containing a coloring agent and a dispersing agent as an affinity site. The content of the repeating unit (U2) is based on the mass of the total repeating unit of the alkali-soluble photosensitive resin (a) or the alkali-soluble non-photosensitive resin (b) from the viewpoint of developability and dispersion stability. It should be 2.0 to 80 parts by mass. When the content of the repeating unit (U2) is less than 2.0 parts by mass, the affinity of the coloring agent or the coloring composition composed of the coloring agent and the dispersing agent is insufficient, and it is difficult to obtain a high-quality color filter, or At the time, there is a problem that the storage stability of the coloring composition for a color filter is deteriorated. On the other hand, when it exceeds 80 parts by mass, the dissolution rate of the alkali developing solution may be slow, the development time may become long, and the productivity of the color filter may be deteriorated.
The repeating unit (U2) precursor (U2-b) is, for example, styrene, α-methylstyrene, stilbene, anthracene, acetamidine, benzyl acrylate, methyl benzyl acrylate, bisphenol A A monomer ‧ oligomer of glycidyl ether (meth) acrylate, methylolated melamine (meth) acrylate or the like and an ethylene-bonded monomer represented by the following general formula (16).
General formula (16):
Formula (16)
(In the above general formula (16), R³Is a hydrogen atom or a methyl group, R⁴Is an alkylene group having 2 or 3 carbon atoms, R⁵It is an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group may be replaced by a benzene ring, and k is an integer of 1 to 15. )
The monomer represented by the general formula (16) is, for example:
NEW-FRONTIER CEA made by First Industrial Pharmaceutical Co., Ltd. [EO modified cresol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:methyl, k=1 or 2], NP–2[n–nonylphenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k=2], N–177E[n–nonylphenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k=16～17] or PEH[phenoxyethyl acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1];
IRR169 [ethoxylated phenyl acrylate (EO 1mol), R by DAICEL³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1] or Ebecryl110 [ethoxylated phenyl acrylate (EO 2mol), R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=2];
ARONIX M-101A made by East Asia Synthetic Co., Ltd. [phenol EO modified (k≒2) acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒1], M–102 [phenol EO modified (k≒2) acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒4], M–110 [p-cumylphenol EO modified (k≒1) acrylate, R³: hydrogen atom, R⁴: vinyl, R³: p-cumyl, k≒1], M-111 [n-nonylphenol EO modified (k≒1) acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k≒1], M–113[n–nonylphenol EO modified (k≒4) acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k≒4] or M–117[n–nonylphenol PO modified (k≒2.5) acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–壬基,k≒2.5];
Co., Ltd. made light acrylate PO-A [phenoxyethyl acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1], P–200A [phenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒2], NP-4EA [nonylphenol EO add-on acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k≒4], or NP–8EA [nonylphenol EO addendum acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n-mercapto, k≒8] or light ester PO [phenol methyl acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1];
BLEMMER ANE–300 [Mercaptophenoxy Polyethylene Glycol Acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n–mercapto, k≒5], ANP–300[mercaptophenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: Acrylic, R⁵:n-mercapto, k≒5], 43ANEP–500[mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R³: hydrogen atom, R⁴: propylene and propylene, R⁵:n-mercapto, k≒5+5], 70ANEP–550[mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R³: hydrogen atom, R⁴: propylene and propylene, R⁵:n-mercapto, k≒9+3], 75ANEP–600[mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R³: hydrogen atom, R⁴: propylene and propylene, R⁵:n–mercapto, k≒5+2], AAE–50 [phenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1], AAE–300 [mercaptophenoxy polyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒5.5], PAE–50 [phenoxy polyethylene glycol methacrylate, R³:Methyl, R⁴: vinyl, R⁵: hydrogen atom, k=2], PAE–100 [phenoxy polyethylene glycol methacrylate, R³:Methyl, R⁴: vinyl, R⁵: hydrogen atom, k=2] or 43PAPE–600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R³:Methyl, R⁴: Vinyl and Propylene, R⁵: hydrogen atom, k≒6+6];
NK ESTER AMP–10G manufactured by Shin-Nakamura Chemical Co., Ltd. [phenoxyethylene glycol acrylate (EO 1mol), R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k = 1], AMP - 20G [phenoxy ethylene glycol acrylate (EO 2mol), R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒2], AMP–60G [phenoxy ethylene glycol acrylate (EO 6mol), R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k≒6] or PHE–1G [phenoxy ethylene glycol methacrylate (EO 1mol), R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1];
Osaka Organic Chemical Co., Ltd. made VISCOAT#192 [phenoxyethyl acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1]; and
Nippon Kayaku Co., Ltd. SR-339A [Phenoxyethylene glycol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵: hydrogen atom, k=1] or [ethoxylated decyl phenol acrylate, R³: hydrogen atom, R⁴: vinyl, R⁵:n-壬基]; However, it is not limited to these, and two or more types may be used at the same time.
In the monomer having ethylene bonding represented by the general formula (16), R⁵The alkyl group has a carbon number of from 1 to 20, more preferably from 1 to 10. The alkyl group may be not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. R⁵When the number of carbon atoms of the alkyl group is from 1 to 10, the alkyl groups are close to each other and the adsorption/alignment of the coloring agent is promoted. However, when the carbon number exceeds 10, the steric hindrance effect of the alkyl group becomes large, which tends to hinder the formation. Adsorption/alignment of the benzene ring to the colorant. This tendency follows R⁵The carbon chain of the alkyl group becomes long and becomes remarkable, and when the carbon number exceeds 20, the adsorption or alignment of the benzene ring is extremely lowered. R⁵The alkyl group having a benzene ring shown may be a benzyl group or a 2-phenyl (iso)propyl group. By adding one side chain benzene ring, solvent affinity and colorant alignment are improved, which not only improves dispersibility but also improves developability.
In the monomer having an ethylene bond represented by the general formula (16), k is preferably an integer of from 1 to 15. When k exceeds 15, the hydrophilicity is increased, the solvent and effect are small, and the viscosity of the vinyl resin is increased, and the viscosity of the colored composition using the same is also high, which may affect the fluidity. From the viewpoint of solvent and k, k is particularly preferably from 1 to 4.
From the viewpoint of copolymerizability with other precursors, and from the viewpoint of dispersibility of the colorant, the repeating unit (U2) precursor (U2-b) is preferably styrene, α-methylstyrene, phenylacrylic acid. An ester, a methyl phenyl acrylate, a monomer having an ethylene bond represented by the general formula (16). Among these, styrene, α-methylstyrene, phenyl acrylate, methyl phenyl acrylate, and a monomer having an ethylene bond represented by the general formula (16) may be used in the side chain of the vinyl resin. It is especially suitable to introduce a benzene ring. Since the side chain of the vinyl resin is introduced into the benzene ring, the side chain benzene ring is aligned to the colorant, thereby promoting the adsorption of the resin to the colorant and further suppressing the coagulation of the colorant. Further, from the viewpoint of developability and dispersion stability, phenyl acrylate and/or methyl phenyl acrylate are most suitable.
[repeating unit (U3)]
The repeating unit (U3) has one or more annular structures selected from the group consisting of the aliphatic cyclic groups represented by the above general formulas (14) and (15). The repeating unit (U3) functions as a coloring agent or a coloring composition containing a coloring agent and a dispersing agent, and functions as an affinity portion, and functions as a hydrophobic portion in the alkali developing solution. The content of the repeating unit (U3) is based on the mass of the total repeating unit of the alkali-soluble photosensitive resin (a) or the alkali-soluble non-photosensitive resin (b) from the viewpoint of developability and dispersion stability. It should be 2.0 to 30 parts by mass. When the content of the repeating unit (U3) is less than 2.0 parts by mass, the affinity of the coloring agent or the coloring composition composed of the coloring agent and the dispersing agent is insufficient, and it is difficult to obtain a high-quality color filter, or In the case where the storage stability of the coloring composition for a color filter is deteriorated, the hydrophobicity during development is insufficient, and thus the pattern peeling or defect of the line portion may occur. On the other hand, when the amount is more than 30 parts by mass, the dissolution rate of the alkali developer may be slow, the development time may be long, and the productivity of the color filter may be deteriorated.
The repeating unit (U3) precursor (U3-c) is, for example, a monomer having an ethylene bond represented by the following general formula (17) and a monomer having an ethylene bond represented by the following general formula (18).
General formula (17):
Formula (17)
(In the above general formula (17), R⁶Is a hydrogen atom or a methyl group, R⁷It is an alkylene group having 2 or 3 carbon atoms, and l is an integer of 0 to 2. )
General formula (18):
Equation (18)
(In the above general formula (18), R⁸Is a hydrogen atom or a methyl group, R⁹It is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 0 to 2. )
The monomer having an ethylene bond represented by the general formula (17) is, for example, FANCRYL FA-513A manufactured by Hitachi Chemical Co., Ltd. [dicyclopentyl acrylate, R⁶: hydrogen atom, R⁷: none, l=0] and FA–513M [dicyclopentyl acrylate, R⁶: hydrogen atom, R⁷: None, l = 0], but it is not limited to these, and two or more types may be used at the same time.
The monomer having an ethylene bond represented by the general formula (18) is, for example:
FANCRYL FA-511A [dicyclopentenyl acrylate, manufactured by Hitachi Chemical Co., Ltd., R⁸: hydrogen atom, R⁹: none, m=0], FA–512M [bicyclopentaoxyalkenyl acrylate, R⁸: hydrogen atom, R⁹:vinyl, m=1], FA–512A [bicyclopentaoxyalkenyl methacrylate, R⁸:Methyl, R⁹:vinyl, m=1], FA–512M [bicyclopentaoxyalkenyl methacrylate, R⁸:Methyl, R⁹: vinyl, m=1]; and
FA–512MT [bicyclopentaoxyalkenyl methacrylate, R⁸:Methyl, R⁹: vinyl, m=1], but it is not limited to these, and two or more types may be used simultaneously.
[repeating unit (U4)]
The repeating unit (U4) is a repeating unit containing photosensitivity of ethylene.
A method of preparing a resin having a photosensitive repeating unit (U4) includes a method of introducing ethylene by the above method (a) or method (b).
[repeating unit (ホ)]
The repeating unit (ホ) is a repeating unit other than the repeating unit (U1), the repeating unit (U2), the repeating unit (U3), and the repeating unit (U4). Repeating unit (ホ) precursors (ホ-e) precursors (U1-a), precursors (U2-b), precursors (U3-c), and precursors (U4-d) have ethylene bonding Monomer. The main function of the repeating unit (ホ) imparts developability and dispersion stability, and thus the side chain of the repeating unit (ホ) is larger than the aforementioned ring structure of the repeating unit (U2) side chain having a colorant dispersibility function. A smaller construction should be used. Addition by a repeating unit (U2) having a larger side chain having affinity for a colorant or a colorant composition, and a repeating unit (ホ) having a smaller affinity for a colorant carrier The effect is that the image and the dispersion stability will be improved.
The repeating unit (ホ) precursor (ホ-e) may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( Methyl) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, pentyl ( Methyl) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, trioctyl octyl (meth) acrylate, 1-methyl butyl (meth) acrylate, Hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, fluorenyl (Meth) acrylate, stearyl hydrazine (meth) acrylate, isostearyl hydrazine (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate or oleyl An alkyl or alkenyl (meth) acrylate such as acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (meth) acrylate Polyethylene glycol di(meth)acrylic acid 1,6-hexanediol diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate , various acrylates and methacrylates such as isobornene (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate; vinyl acetate, hydroxyethyl vinyl ether, ethylene Alcohol divinyl ether, neopentyl alcohol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl carbamide, dimethyl-2, 2'-[Oxyethyl (methene)] bis-2-ethyl acrylate, diethyl-2,2'-[oxyethyl(methylene)]bis-2-propenoic acid ethyl ester, dicyclohexyl- 2,2'-[oxyethyl (methene)] bis-2-ethyl acrylate, dibenzyl-2,2'-[oxyethyl (methene)] bis-2-ethyl acrylate and other monomers ‧ Oligomers, but depending on the purpose, it is not limited to these, and monomers having other ethylene bonds may be selected, or two or more types may be used at the same time. From the viewpoint of developability and dispersion stability, methyl (meth) acrylate or ethyl (meth) acrylate is preferable.
It can be used as a repeating unit (ホ) precursor (ホ-e) with other ethylene-bonded monomers, for example:
a (meth) acrylate having a heterocyclic substituent such as tetrahydroindenyl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
An alkoxy polyalkylene glycol (meth) acrylate such as methoxypolypropylene glycol (meth) acrylate or ethoxypolypropylene glycol (meth) acrylate; or
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide And (meth) acrylamide such as diacetone alcohol (meth) acrylamide and propylene morpholine.
Further, examples of the monomer other than the acrylic monomer include, for example:
a vinyl ether such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether; or
A fatty acid such as vinyl acetate or vinyl propionate. The aforementioned monomer other than the acrylic monomer may be used together with the aforementioned acrylic monomer.
Further, a monomer having an epoxy group and an ethylene bond or a monomer having a hydroxyl group may be used for the introduction of ethylene bonding as described later. However, depending on the quality of the modification, it may also be a repeating unit other than the repeating unit (ホ), so the quality ratio of the final repeating unit (U1), the repeating unit (U2), the repeating unit (U3), and the repeating unit (U4) must be considered. .
The alkali-soluble photosensitive resin (a) and/or the alkali-soluble non-photosensitive resin (b) preferably have an acid value of 20 to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility tendency to the developer is deteriorated, the development time is prolonged, and the productivity is lowered. On the other hand, if it exceeds 300 mgKOH/g, the pattern peeling or defect of the line portion may occur.
<Multifunctional monomer>
The polyfunctional monomer of this aspect contains a polyfunctional monomer having an acidic group, and a part thereof may also contain a monomer (other photopolymerizable monomer) which is induced by a radical.
Examples of such other polymerizable monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and epoxy. Ethylene is modified with various acrylates and methacrylates such as trimethylolpropane tri(meth)acrylate and propylene oxide-modified trimethylolpropane tri(meth)acrylate.
(multifunctional monomer having an acidic group)
As the polyfunctional monomer having an acidic group, for example, the same as the description of the first aspect can be used.
When the total amount of the resin and the polyfunctional monomer is 100 parts by mass, the total mass of the alkali-soluble photosensitive resin containing at least the alkali-soluble photosensitive resin (a) and the polyfunctional monomer having an acidic group is 20 to 70 parts by mass. .
When the total amount of the alkali-soluble photosensitive resin and the polyfunctional monomer having an acidic group is less than 20 parts by mass, the sensitivity at the time of exposure is insufficient, the curing is insufficient, and the pattern of the line portion is peeled off or damaged, and the solubility is lowered. The development residue causes problems such as a decrease in productivity due to a long development time. On the other hand, when the total amount exceeds 70 parts by mass, the sensitivity at the time of exposure is too high, and a good pattern shape cannot be obtained, or problems such as peeling or defect of the line portion due to excessive solubility may occur.
In the coloring composition, the alkali-soluble photosensitive resin and the polyfunctional monomer having an acidic group are preferably in a range of from 10.0 to 37.5 parts by mass in the mass portion of the non-volatile component of the colored composition for a color filter.
Further, in the non-volatile component of the coloring composition for the color filter, the mass-molar concentration of the ethylene-bonded alkali-soluble photosensitive resin component and the polyfunctional monomer is 2.00×10.^{- 3}Mol/g~2.75×10^{- 3}The molar ratio of mol/g to the acid content of the nonvolatile component of the resin and the acid value of the nonvolatile component of the monomer is preferably 8.0 to 40.0 mgKOH/g. In such cases, it is possible to produce a high-quality color filter having high penetrability and good productivity, and thus having few line defects caused by foreign matter. The total of the acid value of the nonvolatile component of the resin and the polyfunctional monomer is represented by the following formula (i).
Total acid value of non-volatile components = acid value of alkali-soluble photosensitive resin × ratio of alkali-soluble photosensitive resin + acid value of alkali-soluble non-photosensitive resin × ratio of alkali-soluble non-photosensitive resin + acid of polyfunctional monomer Price × polyfunctional monomer ratio
...(i)
Here, the ratio of the resin and the ratio of the polyfunctional monomer are the respective mass ratios when 100 parts by mass of the total of the resin and the polyfunctional monomer are used as a reference.
The alkali-soluble photosensitive resin component and the ethylene-bonded mass molar concentration contained in the polyfunctional monomer are preferably 2.00×10^{- 3}Mol/g~2.75×10^{- 3}Mol/g, more preferably 2.30×10^{- 3}Mol/g~2.70×10^{- 3}Mol/g. The mass molar concentration of the alkali-soluble photosensitive resin combined with the ethylene of the polyfunctional monomer is calculated from the following formula (ii).
(mass molar concentration of ethylene bond) = {mass of alkali-soluble photosensitive resin / double bond equivalent of alkali-soluble photosensitive resin + mass of polyfunctional monomer / double bond equivalent of polyfunctional monomer} / {quality of resin +The quality of polyfunctional monomers}
...(ii)
Further, the double binding equivalent is defined by the following formula (iii), which is a scale of double binding contained in the molecule. If the compound has the same molecular weight, the smaller the value of the double binding equivalent, the more the double binding is introduced. .
[Double Combination Equivalent] = [Molecular Weight of Repeating Unit] / [Double Binding Number in Repeating Units]
...(iii)
The ethylene binding mass molar concentration in the colored composition is less than 2.00×10^{- 3}In the case of mol/g, the sensitivity at the time of exposure is insufficient, and the hardening is insufficient to cause a problem that the pattern of the line portion is peeled off or missing. Moreover, the mass concentration of ethylene combined in the colored composition is greater than 2.75×10^{- 3}In the case of mol/g, the sensitivity at the time of exposure is too high, a problem of a good pattern shape cannot be obtained, or the dispersion stability is lowered, and a problem of a uniform coloring coating film cannot be obtained. In other words, when the total acid value of the nonvolatile content of the resin and the polyfunctional monomer is less than 8.0 mgKOH/g, the development residue is lowered to cause development residue, or the development time is often changed to cause a decrease in productivity. Further, when the total acid value of the nonvolatile component of the resin and the polyfunctional monomer is more than 40.0 mgKOH/g, there is a problem that the pattern is peeled off or defective in the line portion due to excessive solubility.
The degree of hardening of the line portion depends on the mass concentration of the ethylene bond in the coloring composition, and the content of the alkali-soluble photosensitive resin in the resin is blended into a mass concentration of ethylene combined in the colored composition. Within the aforementioned range. Meanwhile, the alkali developability depends on the total of the acid value of the nonvolatile component of the resin and the polyfunctional monomer, and the content of the polyfunctional monomer having an acidic group is compounded in the content of the polyfunctional monomer, and the resin and the multifunctional single The total acid value of the non-volatile components of the body is within the aforementioned range. As described above, the content of the alkali-soluble photosensitive resin and the polyfunctional monomer are mutually affected, and the content is appropriately adjusted within the above range depending on the colorant concentration, the desired alkali developability, and the pattern size of the line portion.
(other polyfunctional monomers)
The monomer of this aspect may also contain other polyfunctional monomers other than the polyfunctional monomer having an acidic group. Other polyfunctional monomers may be the same as those described in the first aspect.
<Photopolymerization initiator>
As the photopolymerization initiator, for example, a benzoin compound, a benzophenone compound, a thioxanthone compound, a triazine compound, an oxime ester compound, an oxazole compound, an anthraquinone compound, a boronic acid ester compound, or an imidazole system can be used. A compound, a titanocene compound, and a phosphine compound. Specific examples of the compounds include the same as those described in the first aspect. Further, as the photopolymerization initiator, the same acetophenone-based compound as described in the second aspect is used.
<sensitizer>
The coloring composition for a color filter may further contain a sensitizer. As the sensitizer, for example, the same as the description of the first aspect can be used.
Among the sensitizers, particularly preferred sensitizers are thioxanthone derivatives, methyl ketone derivatives, and carbazole derivatives. Further specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone can be used. Ketone, 1-chloro-4-propoxythioxanthone, 4,4''-bis(dimethylamine)benzophenone, 4,4''-bis(diethylamine)benzophenone, 4, 4''-bis(ethylmethylamine)benzophenone, N-ethylcarbazole, 3-benzylidene-N-ethylcarbazole, 3,6-dibenzoyl-N-B Carbazole and the like.
It is also possible that the sensitizer can be contained in two or more kinds at any ratio.
When the sensitizer is used, the amount of the photopolymerization initiator contained in the coloring composition is preferably in the range of 1.0 to 100 parts by mass.
<Multifunctional thiol>
The coloring composition for a color filter may further contain a polyfunctional thiol.
A polyfunctional thiol is a compound having two or more thiol (SH) groups. The polyfunctional thiol is used together with a photopolymerization initiator to act as a chain shifting agent in a radical polymerization process after light irradiation, thereby generating a sulfur-containing radical which is less susceptible to oxygen from being polymerized. The obtained color filter is used for the sensitivity of the coloring composition. The SH group is particularly preferably a polyfunctional aliphatic thiol group bonded to an aliphatic group such as a methene or a vinyl group. For example, hexathiophenol, decathiphenol, 1,4-butanediol dithiopropionic acid, 1,4-butanediol dithioacetic acid, ethylene glycol dithioacetic acid, ethylene glycol disulfide Propionic acid, trimethylolpropane trithioacetic acid, trimethylolpropane trithiopropionic acid, trimethylolpropane tris(3-thiol butyric acid), pentaerythritol tetrathioacetic acid, pentaerythritol tetrathio Propionic acid, trithiol propionate tris(2-hydroxyethyl)isocyanate, 1,4-dimethylthiol benzene, 2,4,6-trithiol-secondary triazine, 2–(N , N-dibutylamine) – 4, 6–dithiol – secondary triazine, etc. These polyfunctional thiophenols may be used alone or in combination of two or more.
When a polyfunctional thiol is used, the amount thereof is preferably in the range of 0.05 to 100 parts by mass, more preferably 0.1 to 50.0 parts by mass, based on 100 parts by weight of the coloring agent. When the compounding amount of the polyfunctional thiol is 0.05 parts by mass or more, more favorable development resistance can be obtained. When a monofunctional polythiol is used for the thiol (SH) group, such improvement in development resistance cannot be obtained.
<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter may further contain an ultraviolet absorber and/or a polymerization inhibitor. By including an ultraviolet absorber and/or a polymerization inhibiting agent, the pattern shape and resolution of the line portion can be controlled.
The ultraviolet absorber may, for example, be 2-[4-[(2-hydroxy-2-(tau and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl-4,6-bis (2, 4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-benzene Phenylphenyl)-1,3,5-triazine and other hydroxyphenyltriazines; 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazole- 2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro Benzotriazole series such as benzotriazole; 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4'-tetrahydroxydiphenyl a benzophenone system such as ketone; a phenyl sulphate; a p-cyl ester such as p-tert-butylphenyl sulphate; or a cyanide such as ethyl-2-cyano-3,3'-diphenyl acrylate. Propyl ester system; 2,2,6,6-tetramethylpiperidin-1-yloxy (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl- 4-piperidinyl)-sebacate, poly[[6-[(1,1,3,3-tetrabutyl)amine]-1,3,5-triazine-2,4-diyl][ A hindered amine system such as (2,2,6,6-tetramethyl-4-piperidinyl)amine]. These ultraviolet absorbers may be used singly or in combination of two or more kinds in any ratio.
As the polymerization inhibiting agent, for example, the same as the description of the first aspect can be used.
When the ultraviolet absorber and/or the polymerization inhibitor are used, the amount of the ultraviolet absorber and/or the polymerization inhibitor is in the range of 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass based on 100 parts by mass of the colorant. Within the scope of the Ministry. When the amount of the ultraviolet absorber and/or the polymerization inhibitor is 0.01 parts by mass or more, a better resolution can be obtained.
<oxidation inhibitor>
The coloring composition for a color filter may further contain an oxidation preventing agent.
By using the oxidation preventing agent together with the above-mentioned polyfunctional monomer having an acidic group, yellowing in the baking step such as baking after the conventional constitution problem can be suppressed. Further, it is possible to simultaneously solve the problem that the colored composition (developing residue) remains on the non-line portion on the substrate after development, or the foreign matter such as the undissolved release sheet adhered to the line portion, and the pattern peeling or defect of the line portion is caused. The problem of drawing line defects that occurred. Further, the oxidation preventing agent is judged to suppress deterioration of each component in the coloring composition for a color filter due to oxidation by a radical or peroxide generated by an oxidation reaction in the firing step.
The oxidation preventing agent is preferably, for example, a phenolic oxidation preventing agent, a phosphorus-based oxidation preventing agent, a hydroxylamine-based oxidation preventing agent, and a sulfur-based oxidation preventing agent.
The phenolic oxidation preventing agent may, for example, be 3,9-bis[2-[3-(3-tris-butyl-4-hydroxy-5-methylphenyl)propenyloxy]-1,1-di Methyl ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK STAB AO-80 manufactured by Adeka Co., Ltd., Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.), neopentyl alcohol ‧ four [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010 manufactured by BASF Corporation, ADK STAB AO-60 manufactured by ADEKA Co., Ltd., Sumilizer BP-101 manufactured by Sumitomo Chemical Co., Ltd.), 1,3,5-trimethyl-2,4,6-tris(3'5'-di-tertiarybutyl-4-hydroxybenzyl)benzene (IRGANOX 1330 manufactured by BASF Corporation, ADK STAB AO-made by ADEKA Corporation) 330), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (IRGANOX245 manufactured by BASF Corporation, ADK STAB AO-70 manufactured by ADEKA) 4,4'-thiobis(6-tris-butyl-3-methylphenol) (Sumilizer WX, Sumitomo Chemical Co., Ltd.), tris-(3,5-di-tertiary butyl-4-hydroxybenzyl) )-isocyanate (IRGANOX 3114 manufactured by BASF Corporation, ADK STAB AO-20 manufactured by ADEKA Co., Ltd.), 1,6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propane Oxime ester] (IRGANOX 259, manufactured by BASF Corporation), 2,2-thio-divinyl bis[3-(3,5-di-tertiary butyl-4-hydroxyl) Phenyl phenyl) propyl phthalate] (IRGANOX 1035, manufactured by BASF Corporation), N, N'-hexamethyl bis (3,5-di-tri-butyl-4-hydroxy-hydrocinnamylamine) (IRGANOX 1098, manufactured by BASF Corporation) , 2,4-bis[(octylthio)methyl]-O-cresol (IRGANOX 1520L, manufactured by BASF Corporation), octadecyl-[3-(3,5-di-tri-butyl-4-hydroxybenzene) Propyl propyl ester (IRGANOX 1076 manufactured by BASF Corporation, ADK STAB AO-50 manufactured by ADEKA Co., Ltd., Sumilizer BP-76 manufactured by Sumitomo Chemical Co., Ltd.), 4,4'-butylidene-bis(3-methyl-6-tridecyl) Phenol) (ADK STAB AO-40 manufactured by ADEKA Co., Ltd., Sumilizer BBM manufactured by Sumitomo Chemical Co., Ltd.), 1,1,3-tris(2-methyl-4-hydroxy-5-tributylphenyl)butane ( ADK STAB AO-30) made by ADEKA, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylanilino)-1,3,5- Triazine (IRGANOX 565 manufactured by BASF Corporation), 4,6-bis(dodecylthiomethyl)-o-cresol (IRGANOX 1726 manufactured by BASF Corporation), 2-tris-butyl-6-(3-tertiary butyl- 2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Sumilizer GM, Sumitomo Chemical Co., Ltd.), 2-[1-(2-hydroxy-3,5-di-triphenylbenzene) Ethyl]-4,6-di-tertiary benzyl phenyl acrylate (Sumilizer GS, Sumitomo Chemical Co., Ltd.), and 6-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldiphenyl[d,f][1,3, 2] dioxa phosphepine (Sumilizer GP, Sumitomo Chemical Co., Ltd.).
Among these, from the viewpoint of heat resistance and heat resistance and discoloration, 3,9-bis[2-[3-(3-tris-butyl-4-hydroxy-5-methylphenyl) is preferred. Propyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK STAB AO-80 manufactured by Adeka Co., Ltd., Sumilizer, Sumitomo Chemical Co., Ltd.) GA-80), pentaerythritol, tetrakis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] (IRGANOX1010, manufactured by BASF, ADK STAB AO-60, manufactured by ADEKA) Sumitomo Chemical Co., Ltd. Sumilizer BP-101), 1,3,5-trimethyl-2,4,6-tris(3'5'-di-tertiarybutyl-4-hydroxybenzyl)benzene (BASF Company's IRGANOX1330, ADEK STAB AO-330 made by ADEKA, and triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation) IRGANOX245, ADK STAB AO-70 manufactured by ADEKA Co., Ltd., tris-(3,5-di-tri-butyl-4-hydroxybenzyl)-isocyanate (IRGANOX 3114 manufactured by BASF Corporation, ADK STAB AO-20 manufactured by ADEKA Co., Ltd.), 1,6-hexanediol-bis[3-(3,5-di-tri-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 259 manufactured by BASF Corporation), N,N'-hexamethylene double ( 3,5-di-tertiary butyl-4-hydroxy-hydrocinnamylamine) (IRGANOX1098, manufactured by BASF Corporation), eight Base-[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate (IRGANOX1076 manufactured by BASF Corporation, ADK STAB AO-50 manufactured by ADEKA Co., Ltd., Sumilizer BP-76 manufactured by Sumitomo Chemical Co., Ltd.) 4,4'-butylidene-bis(3-methyl-6-tertiary butylphenol) (ADK STAB AO-40 manufactured by ADEKA Co., Ltd., Sumilizer BBM manufactured by Sumitomo Chemical Co., Ltd.), 1,1,3-three ( 2-methyl-4-hydroxy-5-tributylphenyl)butane (ADK STAB AO-30, manufactured by ADEKA), 2-tert-butyl-6-(3-tert-butyl-2- Hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Sumilizer GM, Sumitomo Chemical Co., Ltd.), 2-[1-(2-hydroxy-3,5-di-tertiary benzylphenyl) Ethyl]-4,6-di-tertiary benzyl phenyl acrylate (Sumilizer GS, Sumitomo Chemical Co., Ltd.). These may be used alone or in combination of two or more.
The phosphorus-based oxidation preventing agent may, for example, be 3,9-bis(2,6-di-tri-butyl-4-methylphenoxy)-2,4,8,10-tetraoxy-3,9-di Phosphorus [5.5] undecane (ADK STAB PEP-36 manufactured by ADEKA), bis(nonylphenyl) pentaerythritol diphosphite (ADK STAB PEP-4C manufactured by ADEKA), double (2, 4-di-tertiary butylphenyl) pentaerythritol diphosphite (ADK STAB PEP-24G, manufactured by ADEKA), 6-[3-(3-tert-butyl-4-hydroxy-5-methyl) Phenyl phenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzene [d,f][1,3,2]dioxa phosphepine (IRGAFOS12, manufactured by BASF Corporation), triphenyl phosphite (ADK STAB TPP made by ADEKA), bis-lipid pentaerythritol phosphite (ADK STAB PEP-8 made by ADEKA), tetrakis(trimethyl)-4,4'-butylene bis (3-A) -6-tertiary butyl phenol) diphosphite (ADK STAB 260, manufactured by ADEKA), 4,4'-butylene bis(3-methyl-6-tributylphenylditridecyl) Phosphite (trade name: JPH1200), tris(nonylphenyl) phosphite (ADK STAB 1178 manufactured by ADEKA), hexa(trimethyl)-1,1,3-tris(2-methyl-5) -Tributyl-4-hydroxyphenyl)butane-triphosphite (ADK STAB 522A, manufactured by ADEKA), 10-(3,5-di-tertiary 4-Hydroxybenzo)-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (trade name: SANKOHCA), tetra (C12-C15 mixed alkane)-4,4'-iso Propylene diphosphite (ADK STAB 1500 made by ADEKA) and tris(2,4-di-tert-butylphenyl) phosphite (IRGAFOS168 manufactured by BASF Corporation, ADK STAB 2112 manufactured by ADEKA Co., Ltd., Sumitomo Chemical Co., Ltd.) Sumilizer P-16), diphenyl monooctyl phosphite (ADK STAB C manufactured by ADEKA), diphenyl monodecyl phosphite (ADK STAB 135A manufactured by ADEKA), tridecyl phosphite ( ADEKA company ADK STAB 3010), triethyl phosphite (trade name: JP302), tri-n-butyl phosphite (trade name: JP304), tris(p-cresol) phosphite (trade name: Chelex-PC), diphenyl mono(trimethylene) phosphite (trade name: JPM308), tris(2-ethylhexyl) phosphite (trade name: JP308), phenyl dimercapto phosphite (ADK STAB 517 manufactured by ADEKA), tetraphenyldipropylene glycol diphosphite (trade name: JPP100), 2,2-methylenebis(4,6-di-triphenylphenyl)octylphosphoric acid Salt (ADK STAB HP-10 made by ADEKA), tetrakis(2,4-di-tert-butylphenyl)[1,1-diphenyl]-4, 4'-diylbisphosphite (IRGAFOS P-EPQ, manufactured by BASF Corporation), tris(tridecyl)phosphite (trade name: JP333E), bis[2,4-di(1-phenylisopropyl) Phenyl] pentaerythritol diphosphite (ADK STAB PEP-45 manufactured by ADEKA), trilauryl trisulfide (trade name: 312), tris(mono-didecylphenyl)phosphoric acid Salt (ADK STAB 329K manufactured by ADEKA), trioleyl phosphite (trade name: Chelex-OL), tristearate phosphite (trade name: JP318E), and double [2,4-double (1) , 1-dimethylethyl)]-6-methylphenylethyl ester, phosphorous acid (IRGAFOS38, manufactured by BASF Corporation), and the like.
Among these phosphate-based oxidation inhibitors, from the viewpoint of heat resistance and heat-resistant discoloration resistance, 3,9-bis(2,6-di-tri-butyl-4-methylphenoxy)- 2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane (ADK STAB PEP-36, manufactured by ADEKA), bis(nonylphenyl)neopentitol diphosphoric acid Salt (ADK STAB PEP-4C manufactured by ADEKA), bis(2,4-di-tert-butylphenyl)neopentitol diphosphite (ADK STAB PEP-24G manufactured by ADEKA), 6-[3 -(3-tertiary butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzene [d,f][1,3,2 ]dioxa phosphepine (IRGAFOS12 manufactured by BASF Corporation), distearyl neopentyl phosphite (ADK STAB PEP-8 manufactured by ADEKA), tetrakis(trimethyl)-4,4'-butylene bis (3- Methyl-6-tertiary butyl phenol) diphosphite (ADK STAB 260, manufactured by ADEKA), tris(nonylphenyl) phosphite (ADK STAB 1178 manufactured by ADEKA), and hexa(trimethyl)- 1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane-triphosphite (ADK STAB 522A, manufactured by ADEKA), and four (C12-C15 mixed alkane)- 4,4'-isopropylidene diphosphite (ADK STAB 1500 made by ADEKA), tris(2,4-di-tertiary butyl) Phenyl) phosphite (IRGAFOS 168 manufactured by BASF Corporation, ADK STAB 2112 manufactured by ADEKA Co., Ltd., Sumilizer P-16 manufactured by Sumitomo Chemical Co., Ltd.), diphenyl monooctyl phosphite (ADK STAB C manufactured by ADEKA Co., Ltd.), diphenyl Monodecyl phosphite (ADK STAB 135A, manufactured by ADEKA), tridecyl phosphite (ADK STAB 3010, manufactured by ADEKA), 2,2-methanebis (4,6-di-tributylphenyl) Octyl phosphite (ADK STAB HP-10 made by ADEKA), tetrakis(2,4-di-tert-butylphenyl)[1,1-diphenyl]-4,4'-diyl double Phosphite (IRGAFOS P-EPQ, manufactured by BASF Corporation), bis[2,4-bis(1-phenylisopropyl)phenyl]neopentanol diphosphite (ADK STAB PEP-45, manufactured by ADEKA) , trilauryl trithiophosphite (trade name: 312), tris(mono, dinonylphenyl) phosphite (ADK STAB 329K manufactured by ADEKA), and double [2,4-double (1,1) -Dimethylethyl)]-6-methylphenylethyl ester, phosphorous acid (IRGAFOS38, manufactured by BASF Corporation), and the like. These may be used alone or in combination of two or more.
The hydroxylamine-based oxidation preventing agent may, for example, be N,N-dioctadecylhydroxylamine (IRGASTAB FS 042, manufactured by BASF Corporation). The hydroxylamine-based oxidation inhibitor may be used singly or in combination of two or more.
Examples of the sulfur-based oxidation preventing agent include dimercapto 3,3'-thiodipropionate (IRGANOX PS 800 FD manufactured by BASF Corporation) and octadecyl 3,3'-thiodipropionate (manufactured by BASF Corporation). IRGANOX PS 802 FD), ditridecylthiodipropionate (ADK STAB AO-503, manufactured by ADEKA), and neopentyltetrakis-(β-lauryl-thiopropionate) (ADK STAB AO, manufactured by ADEKA) -412S), dilauryl-3,3'-thiodipropionate (Sumilizer TPL-R, Sumitomo Chemical Co., Ltd.), dimyristyl-3,3'-thiodipropionate (Sumilizer, Sumitomo Chemical Co., Ltd.) TPM), diste oxime-3,3'-thiodipropionate (Sumilizer TPS manufactured by Sumitomo Chemical Co., Ltd.), neopentyl alcohol tetrakis(3-lauryl thiopropionate) (Sumilizer TP-made by Sumitomo Chemical Co., Ltd.) D), ditridecyl-3,3'-thiodipropionate (Sumilizer TL manufactured by Sumitomo Chemical Co., Ltd.), and 2-mercaptobenazole (Sumilizer MB manufactured by Sumitomo Chemical Co., Ltd.).
Among these sulfur-based oxidation inhibitors, from the viewpoint of heat resistance and heat-resistant discoloration resistance, dimercapto 3,3'-thiodipropionate (IRGANOX PS 800 FD manufactured by BASF Corporation), two or eight is preferable. Mercapto 3,3'-thiodipropionate (IRGANOX PS 802 FD, manufactured by BASF Corporation), ditridecylthiodipropionate (ADK STAB AO-503, manufactured by ADEKA), and neopentyl alcohol tetra-(beta) - lauryl-thiopropionate (ADK STAB AO-412S, manufactured by Adeka Co., Ltd.). These may be used alone or in combination of two or more.
The oxidizing agent is preferably a phenol-based oxidation preventing agent from the viewpoint of suppressing a decrease in permeability and achieving both penetrability and sensitivity. In particular, from the viewpoint of complementing the oxidation preventing ability of the peroxide radical, it is preferable to use a hindered phenol-based oxidation preventing agent in which carbon atoms on both sides of the carbon atom to which the phenolic hydroxyl group is bonded is replaced with a tertiary butyl group.
The amount of the oxidation preventing agent is preferably in the range of 0.1 to 5 parts by mass, more preferably in the range of 0.3 to 4 parts by mass, and particularly preferably 0.5 to 50 parts by mass of the total nonvolatile component in the coloring composition. 3 within the scope of the quality department. When the amount of the oxidation preventing agent is less than 0.1 part by mass, the desired effect cannot be obtained. On the other hand, when the amount of the oxidation preventing agent is more than 5 parts by mass, the degree of sensitivity is insufficient or insoluble matter and residue after development are generated.
<thermosetting compound>
The coloring composition for a color filter preferably further contains a thermosetting compound. By including a thermosetting compound, it is possible to prevent yellowing of the resin caused by a baking step such as post-baking. That is, a color filter having higher penetration can be obtained. Further, by including a thermosetting compound, the curing step is further progressed in a baking step such as post-baking, and the degree of hardening of the coating film is improved, so that a highly reliable color filter can be obtained.
The thermosetting compound is, for example, an epoxy resin, a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, a thermosetting resin such as a phenol resin, or the like. A monomer and an oligomer before heating polymerization of a thermosetting resin.
The thermosetting compound is preferably introduced with ethylene. By introducing ethylene bonding, the thermosetting compound can be provided with active energy hardening property, and the light sensitivity can be improved. The introduction of ethylene bonding to the thermosetting compound can be carried out by a known method.
Among the thermosetting compounds, the epoxy compound and the melamine compound are particularly excellent in penetrability, and have little influence on development speed and photosensitivity, and the coating film which is cured by baking is excellent in heat resistance, so it is suitable. . Among the melamine compounds, especially having a hydroxymethylimine group (-NHCH)₂The melamine compound of OH) is stereoscopic in the direction of thermosetting, and the coating film formed of the coloring composition containing the compound has a high thermal curing rate and an early starting point of thermal curing, which is preferable.
The content of the thermosetting compound is preferably from 0.5 to 10 parts by mass based on 100 parts by mass of the total nonvolatile component in the colored composition. When the amount is less than 0.5 part by mass, the film hardening density is low, and the effect on heat resistance and reliability is small. When the amount is more than 10 parts by mass, the amount of photopolymerizable monomer or photopolymerization initiator is limited, and the amount is not limited. In addition to ensuring sufficient developability, the stability over time sometimes poses a problem.
(epoxy compound)
The epoxy compound means a compound having an epoxy group. When the epoxy compound is fired in the color filter manufacturing process, the epoxy group initiates a thermosetting reaction, and the surface of the coating film is internally bridged to improve the heat resistance and/or drug resistance of the obtained coating film. The epoxy compound may be a low molecular compound or a polymer compound, and representative examples thereof include a bisphenol A epoxy resin, a brominated bisphenol A epoxy resin, a bisphenol F epoxy resin, and a brominated bisphenol F. Epoxy resin, phenolic epoxy resin, cyclic aliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, glycidylamine resin, epoxidized oil, etc., epoxy a brominated derivative of a resin, or tris(glycidylphenyl)methane or triglycidyl isocyanate. Among them, bisphenol A epoxy resin, brominated bisphenol A epoxy resin, phenolic epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester resin, glycidylamine resin, and tri (shrinkage) Glycerol phenyl) methane has a high film hardening density and has little adverse effect on the developability of the colored composition, and is preferable in this respect.
Examples of preferred commercially available epoxy compounds include EX111, EX201, EX411, EX611, EX901, EX212L, DA-111, DA-141 manufactured by Nagase ChemteX Co., Ltd., EPPN501H manufactured by Nippon Kayaku Co., Ltd., and Japanese epoxy resin. Company-made JER152, EHPE3150 made by Daycel Chemical Co., Ltd., etc. Among them, EX611, EHPE3150, etc. are particularly suitable for use in terms of the amount of addition, and the effect of improving the characteristics is very large.
Further, in order to promote the hardening of the epoxy compound, a hardener may be used at the same time. Typical examples of the curing agent include an acid anhydride-based curing agent and an amine-based curing agent. The amine-based curing agent has a disadvantage of being difficult to be stabilized by a one-liquid system because of a high reaction rate, and is considered to be a voltage if it is extracted into a liquid crystal phase. The retention rate is deteriorated, and the suitability with zinc phthalocyanine pigment is poor, and it is difficult to ensure dispersion stability. From the above points, an acid anhydride epoxy hardener is preferably used in this aspect. The acid anhydride-based epoxy curing agent may, for example, be maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or the like. An anhydride of phenyl ether tetracarboxylic acid or diphenylphosphonium tetracarboxylic acid. Among them, from the viewpoint of constructing a tight bridging structure, it is preferable to have an optical property of 2 or more anhydride groups in one molecule, good penetration from a short wavelength, or to maintain the voltage holding ratio of the liquid crystal. From a higher viewpoint, it is more preferably a saturated hydrocarbon-based polyfunctional acid anhydride such as cyclohexanone tetracarboxylic dianhydride.
(melamine compound)
The melamine compound is, for example, a melamine compound represented by the general formula (19) or a condensate thereof.
General formula (19):
Formula (19)
[where, R¹²~R¹⁷Respectively independent of each other to represent a hydrogen atom or CH₂OR' (R' represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), R¹²~R¹⁷Same or different. -CH₂The OR' group R' may be the same or different in the above formula (19). ]
The melamine compound represented by the general formula (19) lacks storage stability, and therefore it is preferred to use a condensate thereof. The mass average molecular weight of the condensate is preferably from 1.5 to 6.0.
Among the melamine compounds, there are hydroxymethylimine groups (-NHCH)₂The melamine compound of OH) has a thermosetting direction, and the coating film formed of the coloring composition containing the compound has a high thermal curing rate, and the starting point of the thermal curing starts early, so that the fastness to heat or medicine is increased. The reason is two. The first reason is that the number of reaction starting points can be increased by using a melamine compound having a hydroxymethylimine group. The melamine compound having a hydroxymethylimine group has a small molecular size, and many reaction starting points exist in a certain mass. Therefore, the heat hardening speed is fast, and the heat hardening is carried out throughout. The second reason is that the melamine compound having a hydroxymethylimine group exerts a magnifying effect of thermal energy when subjected to thermal energy. The thermal hardening of the melamine compound having a hydroxymethylimine group starts by receiving heat energy, and when the temperature is low, the thermal energy is small, and when the temperature is high, the thermal energy is increased. If the melamine compound having a hydroxymethylimine group is subjected to thermal energy, due to the influence of the unshared electron pair existing in the compound, energy due to the movement of the electron is generated, and since the heat energy is amplified, the heat hardening is performed even at a low temperature. It will still progress and the hardening speed will be faster.
The melamine compound having a hydroxymethylimine group is contained in the compound, and it is preferred to contain free formaldehyde in an amount of 0.5 to 4 parts by mass. The free formaldehyde in the melamine compound having a hydroxymethylimine group becomes a catalyst for thermosetting, thereby promoting a thermosetting reaction. When the amount of free formaldehyde is less than 0.5 part by mass, thermal hardening is not sufficiently promoted, and when it is more than 4 parts by mass, the melamine compound having a hydroxymethylimine group itself is unstable in storage stability, and it changes its function over time. Hardening effect. Further, the amount of free formaldehyde in the melamine compound having a hydroxymethylimine group can be measured by the method described in JIS-L1041 by the Japan Industrial Standards Survey.
Commercial products of the condensate of the melamine compound represented by the above formula (19) include NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-750, NIKALAC MX-706, and NIKALAC MX-0442 manufactured by Japan Carbide Industries Co., Ltd. NIKALAC MX–035 and so on.
<Storage stabilizer>
The coloring composition for a color filter of the present invention may further contain a storage stabilizer. By containing a storage stabilizer, the viscosity of the composition can be stabilized for a long period of time.
The storage stabilizer may, for example, be 2,6-bis(1,1-dimethylethyl)-4-methylphenol or neopentyltetrakis[3-(3,5-di-tertiary butyl) -4-carboxyphenyl)propionate], 2,4-bis-(n-octylsulfo)-6-(4-carboxy-3,5-di-tertiary butylanilino) 1,3,5 - a hindered phenol system such as triazine; an organophosphine system such as tetraethylphosphine, triphenylphosphine or tetraphenylphosphine; zinc dimethyl dithiophosphate, zinc dipropyl dithiophosphate, and manganese dibutyl dithiophosphate Such as phosphite system; 12-base sulfide, benzothiophene and other sulfur systems; benzyl trimethyl chloride, dimethyl hydroxylamine and other grade 4 ammonium chloride; lactic acid, oxalic acid and other organic acids and ethyl ether .
When the storage stabilizer is used, the amount thereof is preferably from 1 to 20 parts by mass, more preferably from 0.05 to 10 parts by mass, per 100 parts by mass of the colorant. When the amount of the storage stabilizer is 0.01 parts by mass or more, the stability of the coloring composition for color filters is improved over time.
<solvent>
The coloring composition for a color filter contains a solvent. By containing a solvent, the coloring agent is sufficiently dispersed and/or infiltrated into a dye carrier such as a resin or a photopolymerizable compound, and applied to a transparent substrate such as a glass substrate to have a dry film thickness of 0.2 to 5 μm, and it is easy to form a filter. Slice section or black matrix.
As the solvent, for example, the same as the description of the first aspect can be used. The solvent may be used alone or in combination of two or more. The amount of the solvent to be added is preferably in the range of 100 to 10,000 parts by mass, more preferably 500 to 5,000 parts by mass, based on 100 parts by mass of the colorant.
<Other additive ingredients>
In order to stabilize the viscosity of the composition over time, the colored composition may also contain a storage stabilizer. Further, the colored composition may contain a adhesion enhancer such as a decane coupling agent in order to improve the adhesion to the transparent substrate.
For the storage stabilizer and the adhesion enhancer, for example, the same as the description of the first aspect can be used. When the storage stabilizer and/or the adhesion enhancer are used, the amount of the stabilizer is preferably the same as that described in the first aspect.
When the decane coupling agent is used, the amount thereof is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.05 to 5.0 parts by mass, based on 100 parts by mass of the coloring agent.
<Amine compound>
Further, the coloring composition for a color filter may further contain an amine compound. The amine compound reduces the dissolved oxygen. The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminebenzoic acid methyl, 4-dimethylamine benzoic acid ethyl, 4-dimethylamine benzoic acid Isoamino group, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylamine benzoate, and N,N-dimethyl-p-toluidine.
<Dispersing Aid>
The coloring composition for a color filter of this aspect may further contain a dispersing aid. The dispersing aid is suitably, for example, a resin type colorant dispersant, a surfactant, and a dye derivative. The dispersing aid is used to disperse the colorant in a resin or a solvent. The dispersing aid has a great effect on dispersing the pigment and preventing the re-coagulation of the dispersing coloring agent. Therefore, when a coloring composition for a color filter obtained by dispersing a coloring agent in a resin or a solvent by a dispersing aid is used, a color filter having more excellent transmittance can be obtained.
When the dispersing aid is used, the amount thereof is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the coloring agent.
(resin type dispersant)
The resin type dispersant is adsorbed on the surface of the colorant by using an acidic group or a basic group as a anchor, and since the repellency effect of the polymer acts effectively and exhibits dispersion stability, it is preferable to have an acidic group or an alkaline group. Base polymer. The acidic group is preferably a mercapto group in terms of excellent adsorption characteristics, and the basic group is preferably an amine group in terms of excellent adsorption characteristics. Further, a coloring agent derivative having an acidic group is used together with a resin type dispersing agent having a basic group, or a coloring agent derivative having a basic group is used together with a resin type dispersing agent having an acidic group, due to compatibility with a resin Good, so it is more suitable.
As a resin type dispersant having an acidic group or a basic group, a comb-type polymer grafted with a branched polymer in a main polymer portion having an acidic group or a basic group is branched polymerization The product has excellent stereoscopic repulsion effect, so it is more soluble in organic solvent and is more suitable. Further, for the above reasons, a comb-shaped polymer having a molecular structure of one molecule of a backbone polymer and grafting a branched polymer of two or more molecules is more preferable.
As the resin type dispersant, for example, the same as the description of the first aspect can be used.
(pigment derivative)
As the pigment derivative, for example, the same as the description of the first aspect can be used. When the pigment derivative is used, the content of the pigment is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, based on the mass of the pigment. Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 200 parts by mass or less, and more preferably 100 parts by mass or less.
(surfactant)
As the surfactant, for example, the same as the description of the first aspect can be used. When a resin-type dispersing agent and/or a surfactant is added, the total amount of the dispersing agent and the surfactant is preferably in the range of 0.1 to 55 parts by mass, more preferably in the range of 0.1 to 45 parts by mass, based on 100 parts by mass of the coloring agent. Inside. When the amount of the resin-type dispersant and the surfactant is too small, it is difficult to obtain an additive effect. Further, when the total amount of the compound is too large, the excessive dispersant may adversely affect the dispersion.
<Method for Producing Colored Composition for Color Filter>
The coloring composition for a color filter of this aspect can be produced, for example, by the same method as the description of the first aspect.
[Remove coarse particles]
From the photosensitive coloring composition, it is preferable to remove the coarse particles and the mixed fine dust in the same manner as the description of the first aspect. For example, it is preferable to remove coarse particles of 5 μm or more from the photosensitive coloring composition, and it is preferable to remove coarse particles of 1 μm or more, and it is preferable to remove coarse particles of 0.5 μm or more and fine dust mixed therein. That is, the colored composition is preferably substantially free of coarse particles of 0.5 μm or more.
<<Color filter>>
Next, a color filter relating to the third aspect of the present invention will be described.
The color filter of the third aspect is attached to a transparent substrate and includes a filter segment or a black matrix formed of the coloring composition for the color filter described above. An aspect of the color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Other forms of color filters include at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.
<Method of Manufacturing Color Filter>
This color filter can be manufactured, for example, by the same method as the description of the first aspect.
The colored filter for the color filter of this aspect has good developability. Specifically, in the non-line portion on the substrate after development, there is little residue (developing residue) of the colored composition, and there is no pattern peeling or defect of the line portion, and the image forming property is excellent. The coloring composition is high in the concentration of the coloring agent, and can suppress the decrease in transparency after heating. Further, the color filter produced by using the colored composition has good penetrability and productivity.
[Examples]
The embodiments of the present invention are described below, but the present invention is not limited to the embodiments. In addition, unless otherwise specified, "part" means "quality department", and "%" means "mass%".
First, various measurement methods and the like performed in the examples and comparative examples will be described.
(mass average molecular weight of resin)
In the following test 1, a gel permeation chromatography measuring apparatus ("Shodex GPC System-21H" manufactured by Showa Denko Corporation) was used, and it measured by the polyethylene conversion.
In the following tests 2 and 3, a TSKgel column (manufactured by TOSOH Co., Ltd.) was used, and GPC (manufactured by TOSOH Co., Ltd., HLC-8120GPC) equipped with an RI detector was used, and THF was used as a developing solvent to measure the mass converted into polystyrene. Average molecular weight (Mw).
(acid price of resin)
0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added, and the mixture was uniformly dissolved by a stirring solution, and a 0.1 mol/K KOH aqueous solution was used as a titration solution, and titration was performed using an automatic titration apparatus ("COM-555", manufactured by Hiranuma Sangyo Co., Ltd.). The acid value of the resin solution. Then, the acid value of each nonvolatile component of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile component of the resin solution.
(the ammonium salt price of the resin)
After the 5% potassium chromate aqueous solution was used as a reagent and titrated with a 0.1 N aqueous solution of silver nitrate, the value was converted into the equivalent of potassium hydroxide, and the ammonium salt value of the solid portion was shown.
(amine price of resin)
The solution was determined by potentiometric titration using a 0.1 N aqueous hydrochloric acid solution, and converted to the equivalent of potassium hydroxide.
(relative surface area of the pigment)
It was determined by the BET method using nitrogen adsorption. In addition, an automatic steam adsorption amount measuring device ("BELSORP18" manufactured by BEL Japan Co., Ltd.) was used for the measurement.
(average primary particle size of pigment)
It is measured by a method of directly measuring the particle size from an electron microscope photograph. Specifically, the short axis diameter and the major axis diameter of the primary particles of each pigment are measured and averaged as the particle diameter of the pigment particles. Next, for the 100 or more pigment particles, the volume (mass) of each particle is obtained by approximating the cube of the obtained particle diameter, and the volume average particle diameter is defined as the average primary particle diameter. Furthermore, electron microscopy uses a penetrating type (TEM).
<<Test 1>>
Test 1 is about the first aspect. In the test 1, the example corresponding to the first aspect is described as "example", and the other example is described as "comparative example".
<Method for Producing Resin Adhesive>
<Method for Producing Alkali-Soluble Sensitive Resin Solution (A)>
(Preparation of alkali-soluble photosensitive resin solution (A-1))
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to the four separate flasks, and 100 parts of propylene glycol monomethyl ether acetate was placed in the reaction container. The reaction vessel was heated to 120 ° C while injecting nitrogen gas, and 5.2 parts of styrene, 35.5 parts of methyl glycidyl acrylate, 41.0 parts of methyl dicyclopentaacrylate, and even parts were dropped from the dropping tube over 2.5 hours at the same temperature. A mixture of nitrogen diisobutyronitrile 1.0.
Next, the inside of the reaction vessel was replaced with air, and 0.3 parts of trimethylamine phenol and 0.3 parts of hydroquinone were placed in 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C for 5 hours, when the solid content acid value was 0.8. The reaction was terminated to obtain an acrylic resin solution having a mass average molecular weight of about 12,000 (measured by GPC).
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were further added, and the reaction was continued at 120 ° C for 4 hours, and propylene glycol monomethyl ether acetate was added until the nonvolatile content became 40%, and an alkali-soluble photosensitive resin solution was obtained. (A-1).
(Preparation of alkali-soluble photosensitive resin solution (A-2))
A resin binder solution (A-2) was obtained in the same manner as the resin binder solution (A-1A) except that methyl dicyclopentenyl acrylate was used in place of methyl dicyclopentyl acrylate. The mass average molecular weight is 12,500.
(Preparation of alkali-soluble photosensitive resin solution (A-3))
370 parts of propylene glycol monomethyl ether acetate were placed in a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device. After the temperature was raised to 80 ° C and the inside of the flask was replaced with nitrogen, 18 parts of p-cumyl epoxide ethylene oxide modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and 10 parts of methyl benzyl acrylate were dropped from the dropping tube over 2 hours. A mixture of 18.2 parts of glycerol methyl acrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was further continued at 100 ° C for 3 hours, and then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour. Next, the inside of the reaction container was replaced with air, and 9.3 parts of the acrylic acid (equivalent to glycerol group), 0.5 parts of trimethylamine phenol and 0.1 part of hydroquinone were placed in a reaction container. The reaction was continued at 120 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the generated hydroxyl group) and 0.5 part of triethylamine were further added, and the reaction was continued at 120 ° C for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. The propylene glycol monomethyl ether acetate was added to the resin solution previously synthesized so that the nonvolatile content was 20 parts by mass, and the alkali-soluble photosensitive resin solution (1A-3) was obtained. The mass average molecular weight (Mw) was 19,000.
(Modulation of alkali-soluble non-photosensitive resin solution (B))
In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 70.0 parts of propylene glycol monomethyl ether acetate was placed. After raising the temperature to 80 ° C and replacing the inside of the reaction vessel with nitrogen, 13.3 parts of methyl n-butyl acrylate, 4.6 parts of 2-hydroxyethyl acrylate, 4.3 parts of methacrylic acid, and cumyl group were dropped from the dropping tube over 2 hours. A mixture of 7.4 parts of phenol oxirane modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a mass fraction of 30 parts by mass and a mass average molecular weight of 26,000. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to dry, and the nonvolatile component was measured. The propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20 parts by mass, and the alkali-soluble non-photosensitive resin solution (B-1) was obtained.
<Method for Producing Micronized Pigment>
(Production of blue fine pigment (p1))
100 pieces of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Ink Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were placed in a stainless steel 1 gallon. A kneading machine (manufactured by Inoue Seisakusho Co., Ltd.) was mixed and stirred at 70 ° C for 12 hours. Next, the kneaded material was placed in 3000 parts of warm water, and heated to about 70 ° C, and stirred in a high-speed mixer for about 1 hour to form a slurry. After repeating filtration and washing with water to remove diethylene glycol of salt and solvent, it was dried at 80 ° C for 24 hours to obtain 98 parts of blue fine pigment (p1). The average primary particle diameter of the obtained blue fine pigment (p1) was 28.3 nm.
(Production of purple fine pigment (p2))
120 pieces of CI Pigment Violet 23 ("Fast Violet RL" by Clariant Co., Ltd.), 1600 pieces of crushed salt, and 100 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.). ), mixing and stirring at 90 ° C for 18 hours. Next, the kneaded material was placed in 5000 parts of warm water, and heated to about 70 ° C, and stirred in a high-speed mixer for about 1 hour to form a slurry. After repeating filtration and washing with water to remove diethylene glycol of salt and solvent, it was dried at 80 ° C for 24 hours to obtain 118 parts of purple fine pigment (p2). The average primary particle diameter of the obtained purple fine pigment (p2) was 26.4 nm.
(generation of red fine pigment (p3))
120 parts of diketopyrrolopyrrole red pigment CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Corporation, Japan), 1000 parts of crushed salt and 120 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (Inoue The production system was mixed and stirred at 60 ° C for 10 hours. Next, the kneaded material was placed in warm water 2000, heated to about 80 ° C, and stirred in a high-speed mixer for about 1 hour to form a slurry. After repeating filtration and washing with water to remove diethylene glycol of the salt and the solvent, it was dried at 80 ° C for 24 hours to obtain 115 red fine pigments (p3). The average primary particle diameter of the obtained red fine pigment (p3) was 24.8 nm.
(generation of yellow fine pigment (p4))
100 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Co., Ltd.), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.). The mixture was stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in warm water 2000, heated to about 80 ° C, and stirred in a high-speed mixer for about 1 hour to form a slurry. After repeating filtration and washing with water to remove diethylene glycol of the salt and the solvent, it was dried at 80 ° C for 24 hours to obtain 95 yellow fine pigments (p4). The average primary primary particle diameter of the obtained yellow fine pigment (p4) was 39.2 nm.
(Production of green fine pigment (p5))
120 pieces of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 1600 parts of sodium chloride and 270 parts of diethylene glycol were placed in a 1 gallon kneading machine made of stainless steel (Inoue) The production system was mixed and stirred at 70 ° C for 12 hours. Next, the kneaded material was placed in 5000 parts of warm water, and heated to about 70 ° C, and stirred in a high-speed mixer for about 1 hour to form a slurry. After repeating filtration and washing with water to remove diethylene glycol of the salt and the solvent, it was dried at 80 ° C for 24 hours to obtain 117 green fine pigments (p5). The average primary particle diameter of the obtained green fine pigment (p5) was 32.6 nm.
<Manufacturing method of resin (c) having a cationic group in a side chain>
(modulation of resin (c1) having a cationic group in the side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In the reaction vessel, 34.0 parts of methyl methacrylate, 28.0 parts of methyl n-butyl acrylate, 28.0 parts of methyl 2-ethylhexyl acrylate, and 10.0 parts of methyl dimethylamine ethyl acrylate were placed. , a dropping funnel of 2'-a mixture of 5% azobis(2,4-dimethylvaleronitrile) and 25.1 portions of methyl ethyl ketone, and dropping the mixture over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% from the obtained solid component, and the mass average molecular weight (Mw) was 6,830. After cooling to 50 ° C, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the reaction was continued at 50 ° C for 2 hours, and then the mixture was heated to 80 ° C over 1 hour, and the reaction was further continued for 2 hours to obtain a resin component of 47 parts by mass. A resin (c1) having a cationic group in the chain. The ammonium salt value of the obtained resin was 34 mgKOH/g.
(modulation of resin (c2) having a cationic group in the side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 62.4 parts of isopropyl alcohol was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In the reaction vessel, 32.1 parts of methyl methacrylate, 25.1 parts of methyl propyl acrylate, 25.1 parts of methyl methacrylate, and 17.7 parts of methacrylamide propyl methacrylate were placed. A dropping mixture of 5.7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 15.6 parts of ethyl ethyl ketone was dropped over the funnel over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% from the obtained solid component, and the mass average molecular weight (Mw) was 7,420. The mixture was cooled to 50 ° C, and 72 parts of isopropyl alcohol was added to obtain a resin (c22) having a resin component in an amount of 40 parts in the side chain. The ammonium salt value of the obtained resin was 45 mgKOH/g.
(modulation of resin (c3) having a cationic group in the side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In the reaction vessel, 27.5 parts of methyl isopropyl acrylate, 25.0 parts of methyl benzyl acrylate, 27.5 parts of methyl 2-ethylhexyl acrylate, and N, N-dimethylamine methyl styrene 20.0 were placed. A dropping funnel of a homogeneous mixture of 2,2'-azobis(2,4-dimethylvaleronitrile) and 25.1 portions of methyl ethyl ketone was dropped over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% from the obtained solid content, and the mass average molecular weight (Mw) was 6,770. After cooling to 50 ° C, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, and the reaction was continued at 50 ° C for 2 hours, and then the mixture was heated to 80 ° C over 1 hour, and the reaction was further continued for 2 hours to obtain 50 parts by mass of the resin component. A resin having a cationic group (c3). The obtained ammonium salt value of the resin was 60 mgKOH/g.
(modulation of resin (c4) having a cationic group in the side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 62.4 parts of isopropyl alcohol was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In the reaction vessel, 25.0 parts of methyl methacrylate, 20.0 parts of stearin methyl acrylate, 20.0 parts of methyl cyclohexyl acrylate, and BLEMMER PE90 (made by Nippon Oil Co., Ltd., diethylene glycol monomethyl methacrylate) were placed. a dropping funnel of 15.0 parts, 20.0 parts of N-vinyl fluorenone, 4.7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and a homogeneous mixture of 15.6 parts of isopropyl alcohol. It dripped after 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% from the obtained solid component, and the mass average molecular weight (Mw) was 7,550. After cooling to 50 ° C, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, and the reaction was continued at 50 ° C for 2 hours. Thereafter, the mixture was heated to 80 ° C over 1 hour, and the reaction was further continued for 2 hours. Thereafter, 50 parts of isopropyl alcohol were added to obtain a resin (c4) having a resin component of 44 parts by mass and a cationic group in a side chain. The obtained ammonium salt value of the resin was 92 mgKOH/g.
(modulation of resin (c5) having a cationic group in the side chain)
In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 82.0 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In the reaction vessel, 23.5 parts of ethyl methacrylate, 26.0 parts of methyl butyl acrylate, 25.0 parts of methyl lauryl acrylate, and KAYAMAR PM-21 (made by Nippon Kayaku Co., Ltd., ε-make) were placed. Ester 1 molar added phosphate of 2-hydroxyethyl acrylate) 10.0 part, 18.5 part of diethylaminopropyl acrylate, 2,2'-azobis (2,4-dimethylvaleronitrile) The dropping funnel of a homogeneous mixture of 6.0 parts and 25.6 parts of methyl ethyl ketone was dropped over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% from the obtained solid content, and the mass average molecular weight (Mw) was 7010. After cooling to 50 ° C, a resin (c5) having a resin component of 48 parts by mass and a cationic group in a side chain was obtained. The obtained ammonium salt value of the resin was 49 mgKOH/g.
<Method for Producing Halogenated Compound>
(halogenated compound (C-1))
The halogenated compound (C-1) was produced from C.I. Acid Red 289 and a resin (c1) having a cationic group in a side chain by the following procedure.
To the water 2000, 51 resin (c1) having a cationic group in a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain water, and 32 parts of C.I. Acid Red 289 and a halogenated compound (C-1) of a resin (c1) having a cationic group in a side chain were obtained. At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (C-1) was 29 parts by mass.
(halogenated compound (C-2))
The halogenated compound (C-2) was produced from C.I. Acid Red 289 and a resin having a cationic group in the side chain (c2) by the following procedure.
88 parts of the resin (C-2) having a cationic group was added to 2000 parts of a 10% methanol aqueous solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain water, and 43 parts of C.I. Acid Red 289 and a halogenated compound (C-2) having a cationic group (c2) were obtained. At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (C-2) was 22 parts by mass.
(halogenated compound (C-3))
The halogenated compound (C-3) was produced from C.I. Acid Red 289 and a resin (c3) having a cationic group in a side chain by the following procedure.
To a portion of a 10% N,N-dimethylformamide aqueous solution, 46.7 parts of a resin (c3) having a cationic group in a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 70 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 70 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain a halogenated compound (C-4) of 19 parts of C.I. Acid Red 289 and a resin having a cationic group in the side chain (c4). At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (C-4) was 53 parts by mass.
(halogenated compound (C-4))
The halogenated compound (C-4) was produced from C.I. Acid Red 289 and a resin having a cationic group in the side chain (c4) by the following procedure.
To the water of 1000 parts, 20.0 parts of the cationic group-containing resin (c4) was added, and after sufficiently stirring and mixing, the mixture was heated to 70 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain a halogenated compound (C-4) of 19 parts of C.I. Acid Red 289 and a cationic group-containing resin (c4). At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (C-4) was 53 parts by mass.
(halogenated compound (C-5))
The halogenated compound (C-5) was produced from C.I. Acid Red 289 and a resin having a cationic group in the side chain (c5) by the following procedure.
63.2 parts of a resin having a cationic group (c5) having a side chain added thereto in 20 parts of acetic acid, and after sufficiently stirring and mixing, heating to 60 ° C, ammonium salting of the tertiary amine group of the side chain is prepared, and ammonium is prepared. Salted resin solution. The ammonium salted resin solution was gradually dropped into 90 parts of water, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by a dryer to obtain a halogenated compound (C-5) of 38 parts of C.I. Acid Red 289 and a resin (c5) having a cationic group in the side chain. At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (C-5) was 23 parts by mass.
(halogenated compound (C-6))
The halogenated compound (C-6) was produced from C.I. Acid Blue 112 and a resin (c1) having a cationic group in a side chain by the following procedure.
88 parts of the resin (c1) having a cationic group was added to 2000 parts of a 10% methanol aqueous solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Blue 112 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain a halogenated compound (C-6) of 43 parts of C.I. Acid Blue 112 and a resin (c1) having a cationic group in the side chain. At this time, the effective dye component content derived from C.I. Acid Blue 112 in the halogenated compound (c-6) was 22 parts by mass.
(halogenated compound (C-7))
The halogenated compound (C-7) was produced from C.I. Acid Blue 93 and a resin (c1) having a cationic group in a side chain by the following procedure.
To 4 parts of a 10% N,N-dimethylformamide aqueous solution, 46.7 parts of a resin (c1) having a cationic group in a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 70 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Acid Blue 93 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 70 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain a halogenated compound (C-7) of 29 parts of C.I. Acid Blue 93 and a resin (c1) having a cationic group in the side chain. At this time, the content of the effective dye component derived from C.I. Acid Blue 93 in the halogenated compound (C-7) was 30 parts by mass.
(halogenated compound (C-8))
The halogenated compound (C-8) was produced from C.I. Acid Red 249 and a resin (c1) having a cationic group in a side chain by the following procedure.
Adding 63.2 parts of a resin having a cationic group in a side chain of 63.2 parts of acetic acid to 2000 parts, and sufficiently stirring and mixing, heating to 60 ° C, ammonium salting of the tertiary amino group of the side chain, and preparing ammonium by ammonium Salted resin solution. The ammonium salted resin solution was gradually dropped into 90 parts of water, and 10 parts of C.I. Acid Red 249 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain water, and 38 parts of C.I. acid red 249 and a halogenated compound (C-8) having a cationic group (c1) were obtained. At this time, the content of the effective dye component derived from C.I. Acid Red 249 in the halogenated compound (C-8) was 23 parts by mass.
(halogenated compound (C-9))
The halogenated compound (C-9) was produced from C.I. Acid Yellow 5 and a resin having a cationic group in the side chain (c1) by the following procedure.
To the water 2000, 51 resin (c1) having a cationic group in a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. acid yellow 5 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain a halogenated compound (C-9) of 33 parts of C.I. Acid Yellow 5 and a resin having a cationic group in the side chain (c1). At this time, the content of the effective dye component derived from C.I. Acid Yellow 5 in the halogenated compound (C-9) was 33 parts by mass.
(halogenated compound (C-10))
The halogenated compound (C-10) consisting of C.I. Direct Blue 86 and Disperbyk-2000 (modified acrylic block copolymer, ammonium salt price: 61 mgKOH/g) was used in the following procedure.
50.9 parts of Disperbyk-2000 was added to the water 2000, and the mixture was thoroughly stirred and mixed, and then heated to 60 ° C to prepare a resin solution. The resin solution was gradually dropped into 90 parts of water one by one, and 10 parts of C.I. Direct Blue 86 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to remove water, and 31 parts of C.I. Direct Blue 86 and Disperbyk-2000 halogenated compound (C-10) were obtained. At this time, the effective dye component content derived from C.I. Direct Blue 86 in the halogenated compound (C-10) was 33 parts by mass.
(halogenated compound (AC-1))
The halogenated compound (AC-1) was produced from C.I. Acid Red 289 and distearyl dimethyl ammonium chloride (QUARTAMIN D86P) by the following procedure.
11.5 parts of QUARTAMIN D86P was added to 2000 parts of a 10% sodium hydroxide aqueous solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C to prepare a resin solution. To the solution, a small amount of water was gradually dropped in 90 parts, and 10 parts of C.I. Acid Red 289 was dissolved in the obtained aqueous solution. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 120 minutes to sufficiently react. The end point of the reaction is the time at which the reaction solution is dripped from the filter paper and does not bleed. That is, when the bleeding does not occur, it is judged that the halogenated compound has been obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the halogenated compound remaining on the filter paper was dried by using a dryer to obtain water, and 17 parts of C.I. Acid Red 289 and QUARTAMIN D86P halogenated compound (AC-1) were obtained. At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the halogenated compound (AC-1) was 42 parts by mass.
<Method for Producing Polyfunctional Monomer (OM) Having Acid Group>
(Polyfunctional monomer having an acidic group (OM-1))
578g of dipentaerythritol hexaacrylate, 20g of hydrazine acetate, 0.5g of N,N-dimethylbenzylamine and 0.6g of 4-methoxyphenol were placed in 4 flasks of 1L capacity, 50-60 The reaction was continued for 6 hours at a temperature of ° C to obtain a polyfunctional monomer (OM-1) having an acidic group. The acid value was 20, and the content of the polyfunctional monomer having an acidic group calculated from the results of gel permeation chromatography was 25% in terms of area. Further, the acid value of the polyfunctional monomer (OM-1) was 20 KOH-mg/g.
(Polyfunctional monomer having an acidic group (OM-2))
515 g of dipentaerythritol hexaacrylate, 50 g of tetrahydrophthalic anhydride, and 0.5 g of N,N-dimethylbenzylamine were placed in 4 flasks of 1 L capacity, and the temperature was continued at 80 to 100 ° C. After reacting for 10 hours, a polyfunctional monomer (OM-2) containing a polyfunctional monomer having an acidic group was obtained. The acid value was 38, and the content of the polyfunctional monomer having an acidic group calculated from the results of gel permeation chromatography was 40% in terms of area. Further, the acid value of the polyfunctional monomer (OM-2) was 38 KOH-mg/g.
<Method for Producing Pigment Dispersion>
(Modulation of blue pigment dispersion (P-B))
The mixture of the composition shown below was uniformly stirred, and then zirconia beads having a diameter of 1 mm were used, and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, it was filtered with a 5 μm filter to obtain a blue pigment dispersion (P-B).
Blue micronized pigment (p1): 18.0
Copper phthalocyanine derivative (chemical formula (20))
Chemical formula (20):
Formula (20)
Resin type pigment dispersant: 8.0
(BYK-111 made by BYK)
Resin binder solution (A-1): 60.0
Cyclohexanone: 12.0
(Modulation of Purple Pigment Dispersion (P-V))
A purple pigment dispersion (P-V) was obtained in the same manner as the blue pigment dispersion P-B from the mixture of the following composition.
Purple micronized pigment (p2): 20.0
Resin type pigment dispersant: 8.0
(BYK-111 made by BYK)
Resin binder solution (A-1): 60.0
Cyclohexanone: 12.0
(Red Pigment Dispersion (P-R))
A red pigment dispersion (P-R) was obtained in the same manner as the blue pigment dispersion (P-B) in the mixture of the following composition.
Red micronized pigment (p3): 10.0
Lanthanide pigment (C.I. Pigment Red 177): 2.0
("CHROMOPHTAL RED A2B" by Chiba Corporation, Japan)
Yellow micronized pigment (p4): 4.0
Diketopyrrolopyrrole pigment derivative (chemical formula (21)): 4.0
Chemical formula (21):
Formula (21)
Resin type pigment dispersant: 8.0
("Solsparz 20000" made by Lubrizol, Japan)
Resin binder solution (A-1): 60.0
Cyclohexanone: 12.0
(Green Pigment Dispersion (P-G))
A green pigment dispersion (P-G) was obtained in the same manner as the blue pigment dispersion (P-B) in the mixture of the following composition.
Green micronized pigment (p5): 13.5
Yellow micronized pigment (p4): 6.5
Resin type pigment dispersant: 8.0
("EFKA4300" manufactured by Chiba Corporation, Japan)
Resin binder solution (A-1): 60.0
Cyclohexanone: 12.0
<Method for Producing Halogenated Compound Solution>
(halogenated compound solution (Z-1))
The mixture of the following composition was stirred with a blade, and then filtered through a 5.0 mm filter to obtain a halogenated compound solution (Z-1).
Halogenated compound (C-1): 10.0 parts
Propylene glycol monomethyl ether acetate (PGMEA): 90.0
(halogenated compound solution (Z-2) to (Z-11))
The halogenated compound solutions (Z-2) to (Z-11) were produced in the same manner as the halogenated compound solution (Z-1) except that the halogenated compound shown in Table 1 was changed.
The content of the pigment component at this time is shown in Table 9.
Here, the "pigment component content A" and the "pigment component content B" respectively indicate the effective dye component content (mass portion) in the halogenated compound (C) and the effective dye component content in the halogenated compound solution (mass portion). ).

【Table 1】


[Example 1]
(Photosensitive coloring composition (resist material R-1))
The mixture was stirred and mixed uniformly, and then filtered and mixed with a 5.0 μm filter to obtain a photosensitive coloring composition (resist material R-1).
Halogenated compound solution (Z-1): 30.0 parts
Resin binder solution (A-1): 22.8 parts
Resin binder solution (B-1): 5.7
Monomer (OM-1): 4.5
Photopolymerization initiator (I-1): 1.6
Sensitizer (S-1): 0.2
Propylene glycol monomethyl ether acetate (PGMEA): 35.2
Leveling agent (L-1): 0.005
[Examples 2 to 34]
(Photosensitive coloring composition (resist material (R-2) to (R-34)))
The photosensitive coloring compositions (R-2) to (R-) were obtained in the same manner as the photosensitive coloring composition (resist material R-1A) except that the components and the amounts of the components shown in Tables 2 and 3 were used. 34).
[Example 35]
In addition to the components and the amounts shown in Table 8, the photosensitive coloring composition (resist material R-6) was used except for the 35.2 portion of propylene glycol monomethyl ether acetate (PGMEA) in which the cyclopentanone 53.2 was substituted for the solvent. The photosensitive coloring composition (R-35) was obtained in the same manner.
[Comparative Examples 1 to 4]
(Photosensitive coloring composition (resist material (R-36) to (R-39)))
Resist materials (R-36) to (R-39) were obtained in the same manner as the resist material (R-6) except that the halogenated compound solution or the monomer was as shown in Table 8.

【Table 2】




【table 3】

The following are other abbreviations for Tables 2 and 3.
<Polyfunctional monomer (OM) having an acidic group>
‧ An acidic group-containing polyfunctional monomer (OM-3): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and a succinic acid derivative of dipentaerythritol pentaacrylate Mixture TO-1382 (manufactured by Toagosei Co., Ltd., acid price: 29)
‧ an acidic group-containing polyfunctional monomer (OM-4): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and a succinic acid derivative of dipentaerythritol pentaacrylate Mixture TO-2349 (manufactured by Toagosei Co., Ltd., acid price: 38)
<Polyfunctional monomer having no acidic group>
‧Multifunctional monomer (NM-1) without acid group: dipentaerythritol hexaacrylate ("ARONIX M-402" manufactured by Toagosei Co., Ltd.)
‧Multifunctional monomer (NM-2) without an acidic group: Trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator>
‧Photopolymerization initiator (I-1): 2-(dimethylamine)-2-[4-methylphenyl]methyl]-1-[4-(morpholinyl)phenyl]-1- Butanone ("IRGACURE-379" manufactured by Chiba Corporation, Japan)
‧Photopolymerization initiator (I-2): 2–Methyl-1–[4–(methylthio)]–2–morpholinylpropane-1 Ketone (IRGACURE 907, manufactured by Chiba Corporation, Japan)
‧Photopolymerization initiator (I-3): ketene, 1–[9-ethyl-6–(2-methylbenzo)–9H–carbazole–3-yl]–,1–(O–醯肟)) (IRGACURE OXE02, manufactured by Chiba Corporation, Japan)
<sensitizer>
‧ Sensitizer (S-1): 2,4-Diethylthioxanthone
(Kayakua DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
‧ Sensitizer (S-2): 4,4'-bis(diethylamine)benzophenone
("EAB-F" made by Hodogaya Chemical Co., Ltd.)
<Multifunctional thiol>
‧Multifunctional thiol (PT-1): Trimethylolethane tris(3-indolylbutyrate)
("TEMB" by Showa Denko Co., Ltd.)
‧Multifunctional thiol (PT-2): Trimethylolpropane tris(3-indolylbutyrate)
("DPMB" made by Showa Denko)
<Storage stabilizer>
‧ Storage stabilizer (SA-1): 2,6-bis(1,1-dimethylethyl)-4-methylphenol
("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
‧Storage stabilizer (SA-2): Triphenylphosphine
("TPP" manufactured by Beixing Chemical Industry Co., Ltd.)
<UV absorber>
‧UV absorber (UA-1): 2-[4-[(2-hydroxy-3-(dodecyl and thirteen)oxypropyl)oxy]-1,3,5-triazine
("TINUVIN400" made by Chiba Corporation, Japan)
‧UV absorber (UA-2): 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
("TINUVIN900" made by Chiba Corporation, Japan)
<polymerization inhibitor>
‧ Polymerization inhibitor (PI-1): N-nitrosophenylhydroxylamine aluminum salt
("Q-1301" made by Wako Pure Chemical Industries Co., Ltd.)
‧ Polymerization inhibitor (PI-2): methyl hydroquinone
(Seiko Chemical Co., Ltd. "MH")
<leveling agent>
‧Material dye (L-1): dimethyloxane
("FZ-2" made by TORAY‧Dow Corning)
[Evaluation of coloring composition]
With respect to the obtained photosensitive coloring compositions (resist materials (R-1) to (R-39)), tests for storage stability and coating foreign matter were carried out by the following methods. In the judgment of each evaluation result, ◎ indicates a very good level, ○ indicates a good level, △ indicates a level which is still usable, and ╳ indicates a level which is not suitable for use.
(Evaluation method for preservation stability)
For the coloring composition, the initial viscosity of the colored composition was measured by using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.) at a rotation number of 20 rpm, and after storage for 7 days in a thermostatic chamber at 40 ° C for 7 days. Time viscosity. The rate of change in viscosity over time was calculated from the measured viscosity according to the following formula (vii). Based on the calculated rate of change over time, the following criteria were used to evaluate the preservation stability.
Change rate of viscosity over time = ∣ ([initial viscosity] - [time-dependent viscosity]) / [initial viscosity] ∣ × 100 (%)
◎ : less than 10%
○ : 10% or more and less than 20%
△ : 20% or more and less than 50%
╳ : 50% or more (evaluation method for foreign matter on the film)
A test substrate was prepared using the newly formed coloring composition, and the number of particles was calculated. First, a resist material was applied onto a transparent glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater to a dry film thickness of about 2.0 μm, and dried at 70 ° C for 20 minutes. Thereafter, a mask having a stripe-shaped opening having a width of 100 μm was used, and an ultrahigh pressure mercury lamp was used for exposure to ultraviolet light having a total amount of light of 150 mJ/cm ² , and a non-exposed portion was washed with a 0.05% aqueous sodium hydroxide solution containing a surfactant. development. Subsequently, the film was placed in a hot air oven at 230 ° C for 20 minutes to form a stripe pattern having a width of 100 μm on the substrate to obtain a test substrate. Then, using a metal microscope "BX60" manufactured by Olympus Systems, the surface was observed at a magnification of 500 times, and the number of observable particles was calculated in any five fields by penetration. Based on the calculated number of particles, the following criteria were used to evaluate the foreign matter on the screen. In the evaluation results, ◎ and ○ series of foreign matter are small, and good; △ is a number of foreign substances, but there is a problem in the use of stratification; bismuth is uneven due to foreign matter (plaque), which is equivalent to an unusable state. .
◎ : ～ less than 5 ○ : 5 or more and less than 20 △ : 20 or more and less than 100 ╳ : 100 or more (evaluation method of glass adhesion)
A test film was formed on the substrate by the same procedure as the evaluation of the foreign matter on the above coating film to obtain a test substrate. The obtained test substrate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C for 30 minutes, and the adhesion to the glass before and after the immersion was visually observed. According to the observation results, the glass adhesion was evaluated in three stages by the following criteria.
○ : Peeling was not confirmed at all △ : Peeling was confirmed slightly ╳ : Peeling was confirmed (evaluation method for developing residue)
The photosensitive coloring composition was spin-coated on a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a film thickness of about 2.0 μm after drying, and dried at 70 ° C for 20 minutes. Thereafter, a mask having a stripe-shaped opening having a width of 100 μm was used, and an ultrahigh pressure mercury lamp was used for exposure to ultraviolet light having an integrated light amount of 150 mJ/cm ² . Next, the unexposed portion was washed with a 5% sodium carbonate aqueous solution to carry out development. The developed glass surface was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.), and the development residue was evaluated based on the following criteria.
○ : No residue ╳ : Residue The evaluation results are shown in Table 4 below.

【Table 4】

The coloring agent contains a halogenated compound obtained by reacting a resin having a cationic group in a side chain with an anionic dye, and a coloring composition for a color filter containing a polyfunctional monomer having an acidic group in the monomer, and the storage stability is uniform. It is excellent in coating film foreign matter, has good glass adhesion, and has no development residue, and is suitable for use as a color filter.
The coloring agent used in the photosensitive coloring compositions (resist materials (R-1) to (R-35)) is obtained by reacting a resin having a cationic group in a side chain with an anionic dye. The halogenated product is judged to have excellent compatibility with other components constituting the resist, and therefore the resist material exhibits stable coating liquid properties. Thereby, the storage stability of the resist material can be obtained, and the foreign matter of the coating film mainly caused by the coloring component or the like is not generated.
Further, in the photosensitive coloring compositions (resist materials (R-1) to (R-35)), halogenation obtained by reacting a resin having a cationic group in a side chain with an anionic dye is obtained. The product is used as a coloring agent, and further, by using a polyfunctional monomer having an acidic group as a resist material, the development characteristics are extremely excellent, and the pattern is peeled off from the glass substrate or the pattern end portion during development. Defect.
Further, it has been considered that by using the above-mentioned polyfunctional monomer having an acidic group, the solubility of the resist material coating film to the developer is improved, and the residue of the unexposed portion is greatly reduced.
Further, the photosensitive coloring composition (resist material (R-36)) of Comparative Example 1 was inferior in stability, and the viscosity of the composition was greatly increased. Moreover, a large amount of foreign matter is generated on the coating film. Further, there are many development residues, and the color filter fails to reach a usable level.
Thus, it is possible to determine the coloring component used in the resist material, and the halogenated product obtained by reacting the resin having a cationic group in the side chain with the anionic dye, and the compatibility with the components constituting the resist material. It is not good, so the coloring ingredients are coagulated and the various properties are not good.
The photosensitive coloring compositions (resist materials (R-37) and (R-38)) of Comparative Example 2 and Comparative Example 3 were good in terms of stability and foreign matter in the coating film, but there was a problem in development residue. From this, it is understood that by containing a polyfunctional monomer having an acidic group as a monomer, the colored composition can reduce the residue at the time of development, and an excellent color filter can be provided.
The resist material (R-39) of Comparative Example 4 does not contain a halogenated product obtained by reacting a resin having a cationic group in a side chain with an anionic dye, and does not contain a polyfunctional monomer having an acidic group. Each characteristic is greatly deteriorated.
<Manufacture of color filters>
The halogenated compound solution (Z-1) and the blue pigment dispersion (QB) were totaled 21.0 parts, and replaced with a red pigment dispersion (QR) in the case of a red resist material, and replaced with a green resist material in the case of a green resist material. Other than the pigment dispersion (QR), a red coloring composition for a color filter and a green coloring composition for a color filter were obtained in the same manner as the resist material (R-6).
The red colored composition was applied to a glass substrate of 100 mm × 100 mm by a die coater to a thickness of about 2 μm, and dried in an oven at 70 ° C for 20 minutes to remove the solvent. Next, the stripe pattern was exposed by ultraviolet rays using an exposure device. The exposure amount was set to 100 mJ/cm ² . Further, by a developing solution composed of an aqueous solution of sodium carbonate, spray development was carried out to remove unexposed portions, followed by washing with ion-exchanged water. Thereafter, the substrate was heated at 230 ° C for 30 minutes to form a red filter segment having a line width of about 50 μm. Next, by using the green coloring composition in the same manner, a green coloring composition is formed next to the red coloring composition, and then a blue color filter segment is formed using the resist material (R-6) to obtain the same substrate. Color filter for the 3-color filter section.
By using the photosensitive coloring composition of one aspect of the present invention, it is possible to produce a color filter which has a filter segment excellent in color characteristics over a wide range of chromaticity and excellent in heat resistance.
<<Test 2>>
Test 2 is about the second aspect. In the test 2, the example corresponding to the second aspect is described as "example", and the other example is described as "comparative example".
<Method for Producing Acrylic Resin Solution>
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to the four separate flasks, and 70.0 parts of propylene glycol monomethyl ether acetate was placed in the reaction container. After raising the temperature to 80 ° C and replacing the inside of the reaction vessel with nitrogen, 13.3 parts of methyl n-butyl acrylate, 4.6 parts of 2-hydroxyethyl acrylate, 4.3 parts of methacrylic acid, and cumyl group were dropped from the dropping tube over 2 hours. A mixture of 7.4 parts of phenol oxirane modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and 0.4 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a mass average molecular weight of 26,000. After cooling to room temperature, the acrylic resin solution was sampled at about 2 g. The mixture was dried at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. The propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution in accordance with the content of the nonvolatile component obtained in this manner so that the nonvolatile component was 20 parts by mass to prepare an acrylic resin solution.
<Method for Producing Resin-Type Dispersant Solution>
A commercially available resin type dispersant "EFKA 4300" manufactured by Chiba Corporation of Japan and ethylene glycol monomethyl ether acetate were used to prepare a solution of 40 parts by mass of a nonvolatile component, and used as a resin type dispersant solution.
<Method for Producing Pigment Dispersion>
(Modulation of Blue Pigment Dispersion (QB))
After the mixture of the composition shown below was stirred uniformly, the zirconia beads having a diameter of 0.5 mm were used, and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered through a 5.0 μm filter to prepare a blue pigment dispersion QB.
Ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6) ("Heliogen Blue L-6700" manufactured by BASF): 9.7 dioxazine violet pigment (CI Pigment Violet 23) ("Fast Violet RL" manufactured by Clariant): 1.1 Resin type dispersant solution: 8.3 acrylic resin solution: 18.9 parts of ethylene glycol monomethyl ether acetate: 62.0 parts (modulation of red pigment dispersion (QR))
In addition to replacing the pigment with a pyrrolopyrrolidone pigment (CI Pigment Red 254) ("IRGAFORRED B-CF" manufactured by Chiba Corporation, Japan) and a nickel azo complex pigment (CI Pigment Yellow 150), 3.0 parts. The red pigment dispersion QR was prepared in the same manner as the blue pigment dispersion QB described above.
(Modulation of Green Pigment Dispersion (QG))
In addition to replacing the pigment with 7.9 parts of a zinc halide phthalocyanine green pigment (CI Pigment Green 58) and 3.0 parts of a nickel azo-based complex pigment (CI Pigment Yellow 150) ("E4GN" manufactured by LANXESS Co., Ltd.), The blue pigment dispersion QB similarly modulates the green pigment dispersion QG.
[Example 36]
Photopolymerization initiator 2-(dimethylamine)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone 1.53 mass fraction and bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide 0.27 mass fraction, dissolved in solvent 3-ethoxypropionic acid ethyl 53.35 mass. Thereafter, a mixture of 13.45 parts by mass of the acrylic resin solution, 2.7 parts by mass of dipentaerythritol hexaacrylate, and a mixture of pentaerythritol triacrylate and dipentaerythritol triacrylate succinic anhydride addenda 2.7 were mixed. The mass portion was further mixed with 26.0 parts by mass of the above pigment dispersion, and the blade was stirred for 30 minutes. Thereafter, it was filtered with a filter of 1 μm to obtain a red colored composition (resist material (R-1A)).
[Examples 37 to 51 and Comparative Examples 5 to 15]
A blue, red or green colored composition (resist material (R-2A) to (R-28A) was obtained in the same manner as in Example 36 except that the respective materials were changed to the types and amounts shown in Tables 5 and 6. )).

【table 5】

[Table 6]

The abbreviations in Tables 5 and 6 are indicated below.
‧Monomer 1 (M1): Caprolactone-modified dipentaerythritol hexaacrylate ("KAYARAD DPCA-30" manufactured by Nippon Kayaku Co., Ltd.)
‧ monomer 2 (M2): dipentaerythritol hexaacrylate ("ARONIX M-402" manufactured by Toagosei Co., Ltd.)
‧ monomer 3 (a carboxyl group-containing polyfunctional monomer (OM-1A)): a succinic anhydride addition of a mixture of pentaerythritol hexaacrylate and dipentaerythritol triacrylate (ARONIX, manufactured by Toagosei Co., Ltd.) M-520") Acid value: 30mgKOH/g)
‧ monomer 4 (carboxyl-containing polyfunctional monomer (OM-2A)): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate A mixture of succinic acid derivatives ("TO-1382" manufactured by Toagosei Co., Ltd.) Acid value: 29 mgKOH/g)
‧ monomer 5 (carboxyl-containing polyfunctional monomer (OM-3A)): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate A mixture of succinic acid derivatives ("TO-2349" manufactured by Toagosei Co., Ltd.) Acid value: 68 mgKOH/g)
‧Photopolymerization initiator 1 (I-1A): acetophenone system: 2-(dimethylamine)-2-[4-methylphenyl]methyl]-1-[4-(morpholinyl) Phenyl]-1-butanone ("IRGACURE 379" manufactured by BASF Corporation)
‧Photopolymerization initiator 2 (I-2A): bismuth phosphide oxide system: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide ("IRGACURE 819" manufactured by BASF Corporation)
‧Photopolymerization initiator 3 (I-3A): acetophenone system: 2 - methyl - 1 - [4 - (methylthio)] - 2 - morpholinyl propane - 1 - ketone ("BASF" IRGACURE 907")
‧Photopolymerization initiator 4 (I-4A): oxime ester system: 1,2-octanedione, 1-[4-(phenylsulfanyl)-,2-(0-benzamide)] (BASF Company-made "IRGACURE OXE 01")
‧Solvent 1 (SL-1A): propylene glycol monomethyl ether acetate ‧ solvent 2 (SL-2A): 3-ethoxypropionic acid ethyl [Evaluation of photosensitive coloring composition]
<Evaluation method of adhesion, resolution, profile angle and taper length>
On a substrate having a tantalum nitride film formed on the surface of a TFT-type liquid crystal driving substrate of 100 mm × 100 mm and a thickness of 0.7 mm, the film thickness after drying was 3.0 μm in thickness using a spin coater, and the coating examples and comparative examples were applied. A photosensitive coloring composition. After drying under reduced pressure, an ultra-high pressure mercury lamp was used, and an intermediate mask was used for ultraviolet exposure of an integrated light amount of 50 mJ and an illuminance of 20 mW. A 0.2 mass% sodium carbonate aqueous solution was used as a developing solution, and a developing pressure of 0.1 mPa was applied, and the uncured portion of the coating film was removed by a spray developing method to form a pattern including a regular octagonal through hole having a diameter of 30 μm and a fine line having a line width of 50 μm. Thereafter, post-baking was performed at 230 ° C to prepare a test substrate. Regarding the post-baking time, red is 60 minutes, green is 40 minutes, and blue is 20 minutes.
Using the prepared substrate, evaluation of adhesion, resolution, and cross-sectional shape was performed using the following criteria. Further, the substrate having poor adhesion is not evaluated for resolution and cross-sectional shape.
(closeness)
The film adhesion was visually observed, and a three-stage evaluation was performed using the following criteria. Furthermore, Δ and ○ are practical levels.
○ : Pattern peeling was not confirmed at all △ : Pattern peeling was confirmed slightly ╳ : Pattern peeling was confirmed (resolution)
The pore size was measured by an analytical software (Image-Pro, manufactured by Planetron Co., Ltd.) using an optical microscope, and based on the measurement results, the following criteria were carried out, and the resolution was evaluated in three stages. Furthermore, Δ and ○ are practical levels.
○ : A pore of 25 μm or more was formed with respect to the maximum pore diameter of 30 μm. Δ: a pore of 15 μm or more to less than 25 μm was formed with respect to the maximum pore diameter of 30 μm: a pore of 15 μm or more was not formed with respect to the maximum pore diameter of 30 μm (contour angle)
The pattern thin line portion was cut together with the substrate, and a pattern cross section was taken from the cut surface direction of the substrate at a magnification of 10,000 times using a scanning microscope (SEM). The angle (θ) formed by the substrate and the edge portion of the pattern was obtained from the captured pattern cross section using the pattern analysis software. Furthermore, when the pattern is bent, a straight line connecting the external contact to the substrate contact and an angle formed by the substrate are used. The profile angle is evaluated based on the following criteria.
◎ : 40° or more and less than 60°
○: 35° or more, less than 40° or more, and less than 65°
╳ : Less than 35° or more (cone length)
The pattern thin line portion was cut together with the substrate, and a pattern cross section was taken from the cut surface direction of the substrate at a magnification of 10,000 times using a scanning microscope (SEM). The distance between the pattern edge portion and the intersection of the perpendicular line drawn from the pattern shoulder portion with respect to the substrate and the substrate is obtained from the captured pattern cross section using the pattern analysis software. Based on the measured distance, the following criteria were used to evaluate the taper length.
○: The above distance is less than 7μm
△ : The above distance is 7 μm or more and less than 10 μm
╳ : The above distance is 10 μm or more <Evaluation method of developer solubility>
The photosensitive coloring composition was applied to a glass substrate of 10 cm × 10 cm by a spin coater to have a film thickness of 3.0 μm. Thereafter, the substrate was dried under reduced pressure to obtain a test substrate. Four sheets of such a substrate were produced. Next, the test substrate was dissolved in 50 g of a developing solution composed of a 0.2 mass% sodium carbonate aqueous solution. The solution was allowed to stand, and it was confirmed whether or not there was a precipitate after 1 day. The developer solubility was evaluated according to the following criteria.
○ : No sediment ╳ : Precipitate <Evaluation method of voltage retention rate (VHR)>
The alkali-developing resist material was applied to a glass substrate (10 cm × 10 cm) by a spin coater to have a film thickness of 1.8 μm, which was exposed to an exposure amount of 50 mJ/cm ² at 23 ° C. A 0.2 mass aqueous solution of sodium carbonate was spray-developed for 30 seconds, and fired at 230 ° C in an oven to obtain a coated substrate of each resist material. From the obtained coated substrate, 0.05 parts of the resist coating film was scraped off, and then immersed in 1.5 parts of liquid crystal (manufactured by Merck Co., Ltd., MLC-2041), and aged in an oven at 120 ° C for 60 minutes. Thereafter, centrifugation was carried out at 4000 rpm for 15 minutes. After centrifugation, the upper clear liquid was collected to prepare a resist liquid-drawing liquid sampling liquid.
Further, two glass substrates having an ITO transparent electrode having an effective electrode size of 10 cm × 10 cm were placed so that the ITO transparent electrode faces faced each other, and a small amount of cells were produced by using a sealant to make the cell gap 9 μm. For the small cells, a resist liquid crystal sampling liquid was injected between the cell gaps, and a voltage was applied at 60 ° C for 60 μsec at a voltage of 5 V. The cell voltage [V _l ] of 16.67 m after the voltage was released was measured by VHR-1S manufactured by Toyo Corporation. The measurement was repeated 5 times, and the measured cell voltage was averaged. Then, using the obtained cell voltage, the voltage holding ratio (%) was obtained from the following formula (iii).
Voltage holding ratio (%) = ([V _l ]/5) × 100 ... (viii)
The obtained voltage holding ratio (%) was evaluated based on the following evaluation criteria. Further, Δ, ○, and ◎ are practical levels.
◎ : 95% or more ○ : 90% or more and less than 95%
△ : 85% or more and less than 90%
╳ : less than 85%
The evaluation results are shown in Table 7.

[Table 7]

The color filters formed of the photosensitive coloring compositions of Examples 36 to 51 were evaluated as good as Comparative Examples 5 to 15, and various characteristics were simultaneously achieved. Moreover, the contour angle is also an optimum range, and a color filter suitable for the COA method is obtained.
<<Trial 3>>
Test 3 is about the third aspect. In the test 3, the example corresponding to the third aspect is described as "example", and the other example is described as "comparative example".
<Method for Producing Alkali-Soluble Sensitive Resin Solution (A)>
(Preparation of alkali-soluble photosensitive resin solution (A-1B))
A cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to four separate flasks, and 370 parts of propylene glycol monomethyl ether acetate (PGMAc) were placed in the reaction container. The container was heated to 120 ° C while injecting nitrogen gas, and 18 parts of cumyl phenol ethylene oxide modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and benzylacrylic acid were dropped from the dropping tube for 2 hours at the same temperature. 10 parts of methyl ester, 18.2 parts of glycerol methyl acrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued at 100 ° C for 3 hours. Thereafter, a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C for 1 hour. Next, the inside of the reaction vessel was replaced with air, and 9.3 parts of the acrylic acid (equivalent to glycerol group), 0.5 parts of trimethylamine phenol and 0.1 part of hydroquinone were placed in the above container, and the reaction was continued at 120 ° C. 6 hours. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of the hydroxyl group formed) and 0.5 parts of triethylamine were added, and the reaction was continued at 120 ° C for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Propylene glycol monomethyl ether acetate (PGMAc) was added to the previously synthesized resin solution to prepare a non-volatile component to 20 parts by mass to prepare an alkali-soluble photosensitive resin solution (A-1B). ). The nonvolatile content had an acid value of 35.4 mgKOH/g and a mass average molecular weight of 19,000.
(Modulation of alkali-soluble photosensitive resin solution (A-2B))
In a separate four-stage flask, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached, and 800 parts of propylene glycol monomethyl ether acetate (PGMAc) were placed in the reaction container. The container was heated to 120 ° C while injecting nitrogen gas, and 60 parts of cumyl phenol ethylene oxide modified acrylate (ARONIX M110 manufactured by Toagosei Co., Ltd.) and methacrylic acid were dropped from the dropping tube for 2 hours at the same temperature. 40 parts, 40 parts of n-butyl methacrylate, 60 parts of 2-hydroxyethyl methacrylate and 0.4 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued at 80 ° C for 4 hours. Thereafter, 45 parts of methacryloxyethyl isocyanate was added, and the reaction was further continued at 60 ° C for 8 hours to obtain an acrylic resin solution. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Propylene glycol monomethyl ether acetate (PGMAc) was added to the resin solution previously synthesized so that the nonvolatile content was 20 parts by mass, and the alkali-soluble photosensitive resin solution (A-2B) was prepared. ). The nonvolatile content had an acid value of 52.8 mgKOH/g and a mass average molecular weight of 25,000.
<Method for Producing Alkali-Soluble Sensitive Resin Solution (a)>
(Modulation of alkali-soluble photosensitive resin solution (a-1B))
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to the four separate flasks, and 100 parts of propylene glycol monomethyl ether acetate (PGMAc) was placed in the reaction container. The reaction vessel was heated to 120 ° C while injecting nitrogen gas, and 5.2 parts of styrene, 35.5 parts of methyl glycidyl acrylate, 41.0 parts of methyl dicyclopentaacrylate, and even parts were dropped from the dropping tube over 2.5 hours at the same temperature. A mixture of nitrogen diisobutyronitrile 1.0.
Next, air was exchanged in the reaction vessel, and 0.3 parts of trimethylamine phenol and 0.3 parts of hydroquinone were placed in 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C for 5 hours.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were further added, and the reaction was continued at 120 ° C for 4 hours. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Propylene glycol monomethyl ether acetate (PGMAc) was added to the resin solution previously synthesized so that the nonvolatile content was 20 parts by mass, and the alkali-soluble photosensitive resin solution (a-1B) was prepared. ). The nonvolatile content had an acid value of 58.6 mgKOH/g and a mass average molecular weight of 12,000.
(Modulation of alkali-soluble photosensitive resin solution (a-2B))
An alkali-soluble photosensitive resin solution was prepared in the same manner as the alkali-soluble photosensitive resin solution (a-1B) except that methyl dicyclopentenyl acrylate was used in place of methyl dicyclopentyl acrylate (a- 2B). The nonvolatile content had an acid value of 58.4 mgKOH/g and a mass average molecular weight of 12,500.
(Modulation of alkali-soluble photosensitive resin solution (a-3B))
In addition to the use of p-cumyl epoxide ethylene oxide modified acrylate to replace methyl benzyl acrylate, methyl n-butyl acrylate is used in place of methyl dicyclopentyl acrylate, and other alkali-soluble photosensitive resin solutions are used. (A-2B) The same method was used to prepare an alkali-soluble photosensitive resin solution (a-3B). The nonvolatile content had an acid value of 59.7 mgKOH/g and a mass average molecular weight of 24,000.
(Modulation of alkali-soluble non-photosensitive resin solution (B-1B))
A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to the four separate flasks, and 70.0 portions of propylene glycol monomethyl ether acetate (PGMAc) were placed in the reaction vessel, and the temperature was raised to 80 ° C to transfer the reaction vessel. After nitrogen substitution in the inside, 13.3 parts of methyl n-butyl acrylate, 4.6 parts of 2-hydroxyethyl acrylate, 4.3 parts of methacrylic acid, and acrylic acid of p-cumyl phenol ethylene oxide were dropped from the dropping tube over 2 hours. A mixture of ester 7.4 and 2,2'-azobisisobutyronitrile 0.4. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a mass fraction of 30 parts by mass. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to dry, and the nonvolatile component was measured. Propylene glycol monomethyl ether acetate (PGMAc) was added to the previously synthesized resin solution to prepare a non-volatile component to 20 parts by mass to prepare an alkali-soluble photosensitive resin solution (B-1B). ). The nonvolatile content had an acid value of 46.8 mgKOH/g and a mass average molecular weight of 32,000.
(Modulation of alkali-soluble non-photosensitive resin solution (b-1B))
A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to the four separate flasks, and 70.0 portions of propylene glycol monomethyl ether acetate (PGMAc) were placed in the reaction vessel, and the temperature was raised to 80 ° C to transfer the reaction vessel. After nitrogen substitution, 67.2 parts of methyl benzyl acrylate, 18.4 parts of methacrylic acid, 14.4 parts of methyl dicyclopentyl acrylate, and 0.4 parts of 2,2'-azobisisobutyronitrile were dropped from the dropping tube over 2 hours. a mixture. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a mass fraction of 30 parts by mass. After cooling to room temperature, the resin solution was sampled to about 2 g. The mixture was dried at 180 ° C for 20 minutes to dry, and the nonvolatile component was measured. Propylene glycol monomethyl ether acetate (PGMAc) was added to the previously synthesized resin solution so that the nonvolatile content was 20 parts by mass, and the alkali-soluble photosensitive resin solution (b-1B) was prepared. ). The nonvolatile content had an acid value of 62.2 mgKOH/g and a mass average molecular weight of 26,000.
Table 8 shows the weight average molecular weight, solid content acid value, and double bond equivalent of the obtained alkali-soluble photosensitive resin solution and alkali-soluble non-photosensitive resin solution.

[Table 8]

<Method for Producing Polyfunctional Monomer (OM) Having Acid Group>
(Modulation of polyfunctional monomer (OM-1B) having an acidic group)
578g of dipentaerythritol hexaacrylate, 20g of hydrazine acetate, 0.5g of N,N-dimethylbenzylamine and 0.6g of 4-methoxyphenol were placed in 4 flasks of 1L capacity, 50-60 The reaction was continued for 6 hours at a temperature of ° C to obtain a polyfunctional monomer (OM-1) having an acidic group. The acid value was 20, and the content of the polyfunctional monomer having an acidic group calculated from the results of gel permeation chromatography was 25% in terms of area. Further, the acid value of the polyfunctional monomer (OM-1) was 20 KOH-mg/g.
(Polyfunctional monomer having an acidic group (OM-2B))
515 g of dipentaerythritol hexaacrylate, 50 g of tetrahydrophthalic anhydride and 0.5 g of N,N-dimethylbenzylamine were placed in 4 flasks of 1 L capacity, and the temperature was continued at 80 to 100 ° C. After reacting for 10 hours, a polyfunctional monomer (OM-2B) containing a polyfunctional monomer having a carboxyl group was obtained. Its acid price is 38. The content of the carboxyl group-containing polyfunctional monomer calculated from the results of the gel permeation chromatography was 40% in terms of area, and the double bond equivalent of the carboxyl group-containing polyfunctional monomer was 135.
<Method for Producing Pigment Dispersion>
[Modulation of Red Pigment Dispersion (OR)]
After the mixture of the following composition was uniformly stirred, zirconia beads having a diameter of 1 mm were used, and dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered through a 5 μm filter to obtain a red pigment dispersion OR.
Pyrrolopyrroledione pigment (CI Pigment Red 254): 3.5 parts ("IRGAFORRED B-CF" manufactured by Chiba Corporation, Japan)
蒽醌-based pigment (CI Pigment Red 177): 1.0 ("CHROMOPHTAL RED A2B" manufactured by Chiba Corporation, Japan)
Nickel azo complex pigment (CI Pigment Yellow 150): 0.5 ("E4GN" manufactured by LANXESS)
Resin-type colorant dispersant: 1.0 ("Solsparz 20000" manufactured by Lubrizol, Japan)
Pyrrolopyrroledione pigment derivative (chemical formula (22)): 0.5 part Chemical formula (22):
Equation (22)
Alkali-soluble non-photosensitive resin solution (b-1B): 5.0 parts Cyclohexanone: 26.0 parts [Modulation of green pigment dispersion (OG)]
A green pigment dispersion OG was produced in the same manner as the red pigment dispersion (OR) from the mixture of the following composition.
Copper phthalocyanine pigment (CI Pigment Green 36): 4.0 (Lionol Green 6YK, manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150): 1.0 ("E4GN" manufactured by LANXESS)
Resin type colorant dispersant: 1.5 parts ("Solsparz 20000" manufactured by Lubrizol, Japan)
Alkali-soluble non-photosensitive resin solution (b-1B): 5.0 parts Cyclohexanone: 26.0 parts [Modulation of blue pigment dispersion (OB)]
A blue pigment dispersion (OB) was produced in the same manner as the red pigment dispersion (OR) from the mixture of the following composition.
Ε-type copper phthalocyanine pigment (CI Pigment Blue 15:6): 5.0 ("Heliogen Blue L-6700F" manufactured by BASF)
Resin type colorant dispersant: 1.5 parts ("Solsparz 20000" manufactured by Lubrizol, Japan)
Alkali-soluble non-photosensitive resin solution (b-1B): 5.0 parts Cyclohexanone: 26.0 parts [Examples 53 to 80 and Comparative Examples 16 to 24]
(Example 1: Resist material (R-1B))
The components were blended in the amounts shown in Tables 9 and 10, stirred well, and then filtered through a 5 μm filter to obtain resist materials (R-1B) to (R-37B).
The abbreviations shown in Tables 9 and 10 are shown below.
Polyfunctional monomer having an acidic group (OM-1B): the above synthesis (acid value 20, double bond equivalent weight 128)
Polyfunctional monomer having an acidic group (OM-2B): the above synthesis (acid price 38, double binding equivalent 135)
Polyfunctional monomer (OM-3B) with an acidic group:
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, and succinic acid derivative of dipentaerythritol pentaacrylate: TO-1382 (manufactured by Toagosei Co., Ltd., acid value) :29, double combined equivalent 125)
Polyfunctional monomer (NM-1B) having no acidic group: dipentaerythritol hexaacrylate ("ARONIX M-402" manufactured by Toagosei Co., Ltd., double bond equivalent 119)
A polyfunctional monomer (NM-2B) having no acidic group: trimethylolpropane triacrylate ("NK ESTER ATMPT", manufactured by Shin-Nakamura Chemical Co., Ltd., double-binding equivalent 99)
Photopolymerization initiator (I-1B): 2 - methyl - 1 - [4 - (methylthio)] - 2 - morpholinyl propane - 1 - ketone (IRGACURE 907, manufactured by Chiba Corporation, Japan)
Photopolymerization initiator (I-2B): 2-(dimethylamine)-2-[4-methylphenyl]methyl]-1-[4-(morpholinyl)phenyl]-1-butene Ketone ("IRGACURE-379" manufactured by Chiba Corporation, Japan)
Photopolymerization initiator (I-3): ketene, 1–[9-ethyl-6–(2-methylbenzo)–9H–carbazole–3-yl]–, 1–(O–B醯肟)
("IRGACURE OXE02" made by Chiba Corporation, Japan)
Sensitizer (S-1B): 2,4-Diethylthioxanthone (Kayakua DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer (S-2B): 4,4'-bis(diethylamine)benzophenone ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
Polyfunctional thiol (PT-1B): Trimethylolethane tris(3-indolylbutyrate)
("TEMB" by Showa Denko Co., Ltd.)
UV absorber (UA-1B): 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN900, manufactured by Chiba Corporation, Japan) ")
Polymerization inhibitor (PI-1B): methyl hydroquinone ("MH" manufactured by Seiko Chemical Co., Ltd.)
Oxidation inhibitor (AO-1B): pentaerythritol ‧ tetra [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate]
(IRGANOX1010 made by BASF)
Oxidation inhibitor (AO-2B): 1,3,5-trimethyl-2,4,6-tris(3'5'-di-tertiarybutyl-4-hydroxybenzyl)benzene (manufactured by BASF Corporation) IRGANOX1330)
Oxidation inhibitor (AO-3B): tris[2-[[2,4,8,10tetrakis(1,1-dimethylethyl)diphenyl[d,f][1,3,2]dioxa phosphepine -6-yl]oxy]-ethyl]amine (IRGAFOS12 manufactured by BASF Corporation)
Oxidation inhibitor (AO-4B): tetrakis(2,4-di-tert-butylphenyloxy) 4,4'-biphenyl-di-phosphine (IRGAFOS P-EPQ, manufactured by BASF Corporation)
Thermosetting compound (T-1B): epoxy compound (EX611 manufactured by Nagase ChemteX)
Thermosetting compound (T-2B): melamine compound (NIKALAC MX-750, manufactured by Carbide Industries, Japan)
Storage stabilizer (SA-1B): Triphenylphosphine ("TPP" manufactured by Behind Chemical Industry Co., Ltd.)
Organic solvent (SL-1B): cyclohexanone

[Table 9]

[Table 10]

   

[Evaluation of resist material]
The coloring composition obtained was evaluated in the following manner.
(evaluation method of penetration)
On a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm, the colored compositions (R-1B) to (R-37B) obtained by spin coating were rotated at a film thickness of about 2.5 μm after drying to 70 ° C. Dry over 20 minutes. Thereafter, a mask having a stripe-shaped opening portion having a width of 100 μm was used, and an ultrahigh pressure mercury lamp was used for exposure to ultraviolet light having an integrated light amount of 150 mJ/cm ² . Next, the unexposed portion was washed with a 5% sodium carbonate aqueous solution to obtain a test substrate. The tristimulus values X, Y, and Z of the CIE color system were measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) for the pattern portion of the formed line portion. Further, the substrate was fired at 230 ° C for 60 minutes in a dust-free oven, and the tristimulus values X, Y, and Z of the CIE color system were measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). The change in permeability before and after post-baking was calculated from the following formula (vi). Then, according to the change in penetration, the permeability was evaluated in the following four stages. Furthermore, Δ~◎ is a practical level.
ΔY=∣ (Y before post-baking) - (Y after post-baking)∣
...(vi)
◎ : ΔY is less than 0.3
○ : ΔY is 0.3 or more and less than 0.6
△ : ΔY is 0.6 or more and less than 1.0
╳ : ΔY is 1.0 or more (evaluation method for developing residue)
On a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm, the resist material (R-1B) to (R-37B) was spin-coated at a film thickness of about 2.0 μm after drying, and the film was passed at 70 ° C for 20° C. Dry in minutes. Thereafter, a mask having a stripe-shaped opening portion having a width of 100 μm was used, and an ultrahigh pressure mercury lamp was used for exposure to ultraviolet light having an integrated light amount of 150 mJ/cm ² . Next, the unexposed portion was washed with a 5% sodium carbonate aqueous solution to obtain a test substrate. The developed glass surface was measured using a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.), and the development residue was evaluated based on the following criteria.
○ : No residue ╳ : Residue (evaluation method for foreign matter on the film)
On a transparent glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm, the film thickness after drying was 2.5 μm, and each of the resist materials (R-1B) to (R-37B) was spin-coated at 70 ° C. Dry over 20 minutes. Thereafter, a mask having a stripe-shaped opening portion having a width of 100 μm was used, and an ultrahigh pressure mercury lamp was used for exposure to ultraviolet light having an integrated light amount of 150 mJ/cm ² . Next, the unexposed portion was washed with a 5% aqueous sodium carbonate solution, and then heated in a hot air oven at 230 ° C for 20 minutes to form a stripe pattern having a width of 100 μm on the substrate. The surface of the substrate was observed at a magnification of 500 times using a metal microscope "BX60" manufactured by Olympus System, and the number of observable particles was calculated in any five fields by penetration. The foreign matter on the coating film was evaluated based on the number of particles by the following criteria. In the evaluation results, the number of foreign matter ◎ and ○ is small, and it is good; the number of △-based foreign matter is large, but the level of the problem is not used; the bismuth is unevenly coated due to foreign matter, and is an unusable level.
◎ : less than 5 ○ : 5 or more and less than 20 △ : 20 or more and less than 100 ╳ : 100 or more (evaluation method for linearity)
The pattern of the 100 μm mask portion of the filter segment formed by the above method was observed using an optical microscope. The evaluation of linearity was evaluated based on the following criteria. Furthermore, Δ and ○ are practical levels.
○ : Good linearity △ : The pattern section of the line drawing section is partially uneven, and/or at least one partial peeling and defect (a partial defect of linearity) occurs.
╳ : The pattern of the line drawing is uneven, and/or at least one partial peeling and defect (straight line defect) occurs.
(Evaluation method of pattern shape of line drawing)
The pattern cross section of the 100 μm mask portion of the filter segment formed by the above method was observed using an electron microscope. The pattern shape was evaluated based on the following criteria. Furthermore, Δ and ○ are practical levels.
○ : The profile is a forward tapered shape △ : The profile is slightly tapered from the vertical ╳ : The profile is a reverse tapered shape (Evaluation method for resolution)
The pattern of the 25 μm mask portion of the filter segment formed by the above method was observed using an optical microscope. Based on the observations, the following criteria were used to evaluate the resolution. Here, the poor resolution means that adjacent stripe patterns are connected, that is, the width of the stripe pattern is excessively larger than 25 μm. Conversely, insufficient sensitivity means that the width of the stripe pattern is excessively less than 25 μm. The evaluation level is as follows. Further, Δ, ○, and ◎ are practical levels.
◎ : The resolution and sensitivity are good ○ : The sensitivity is slightly poor, but the resolution is good △ : Some of the resolution is poor ╳ : The resolution is poor (Evaluation method for development tolerance)
At the time of spray development, development was carried out at twice the appropriate time, and the film thickness of the formed filter segment or the 100 μm mask portion of the black matrix was measured. The difference between the film thickness and the thickness of the pattern formed by development with an appropriate development time was evaluated as development resistance based on the following criteria. Further, Δ, ○, and ◎ are practical levels.
◎ : The film thickness difference is within 5% ○: The film thickness difference is more than 5% but within 10% Δ: The film thickness difference is more than 10% but within 20% ╳: peeling or defect occurs at twice as much as in Table 11 and 12 indicates the evaluation results.

[Table 11]

[Table 12]

From Tables 11 and 12, it is shown that according to one aspect of the present invention, a coloring composition suitable as a color filter material with high penetration and high productivity can be provided, and a color filter formed using the same can be provided. Further, the coloring composition was excellent in developability, and the non-lined portion on the substrate after development did not have any remaining (developing residue) of the colored composition or the pattern of the line portion peeled or broken.

(no)

(no)

Claims (13)

A colored composition comprising a colorant, a resin and a monomer;
The aforementioned monomer comprises a polyfunctional monomer having an acidic group;
The coloring composition described above meets one of the following requirements (1) to (3):
(1) further comprising an organic solvent;
The coloring agent includes a halogenated compound obtained by reacting a resin having a cationic group in a side chain with an anionic dye;
(2) further comprising a photopolymerization initiator;
The content of the monomer is 20 to 50 parts by mass with respect to 100 parts by mass of the nonvolatile component of the colored composition;
The photopolymerization initiator includes an acetophenone-based compound and a ruthenium-based phosphorus oxide-based compound; and a mass ratio of the acetophenone-based compound to the fluorenylphosphorus oxide-based compound (acetophenone-based compound/sulfonium-based phosphorus oxide-based compound) Within the range of 60/40 to 90/10;
(3) further containing a photopolymerization initiator, a solvent, and an oxidation preventing agent;
The resin includes at least one selected from the group consisting of an alkali-soluble photosensitive resin component and an alkali-soluble non-photosensitive resin component;
The aforementioned monomer comprises a polyfunctional monomer having an acidic group;
The total amount of the content of the alkali-soluble photosensitive resin component and the content of the polyfunctional monomer having an acidic group is 20 parts by mass in total of 100 parts by mass of the content of the resin and the content of the polyfunctional monomer. 70 parts by mass; the content of the oxidation preventing agent is 0.1 to 5 parts by mass with respect to 100 parts of the nonvolatile component of the coloring composition. For example, the colored composition of claim 1 of the patent scope, which meets the requirements of (1) above;
The resin having a cationic group in the side chain includes a vinyl-based resin having a structural unit represented by the general formula (1);
Formula 1)
(wherein R ¹⁸ represents a hydrogen atom, or a substituted or non-substituted alkyl group;
R ¹⁹ to R ²¹ each independently represent a hydrogen atom, a substituted or non-substituted alkyl group, a substituted or non-substituted alkenyl group, or a substituted or non-substituted aryl group; and two of R ¹⁹ to R ²¹ are bonded to each other to form Ring can also be
Q ¹ represents an alkylene group, an arylene group, -CONH-R''- or -COO-R''-, and R'' represents an alkylene group;
The Y ^- line represents an inorganic or organic anion. ) The coloring composition of claim 2, wherein the acidic group is a carboxyl group. The colored composition of claim 2, further comprising a photopolymerization initiator. The colored composition of claim 2, wherein the resin comprises an alkali-soluble photosensitive resin. For example, the colored composition of claim 1 of the patent scope, which meets the requirements of (2) above;
The total amount of the acetophenone-based compound and the content of the above-described fluorenylphosphine oxide-based compound is 3 to 20 parts by mass based on 100 parts by mass of the nonvolatile component. The coloring composition of claim 6, wherein the polyfunctional monomer accounts for 30 to 60 parts by mass of all monomers. The coloring composition of claim 6, wherein the polyfunctional single system is a compound represented by the general formula (3).

(wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, and X represents an organic group having a carbon number of 3 to 60 of (n+o) valence, and n represents An integer from 2 to 18, where o is an integer from 1 to 3.) For example, the colored composition of claim 1 of the patent scope, which meets the requirements of the foregoing (3);
In the nonvolatile component of the coloring composition, the molar concentration of ethylene in the alkali-soluble photosensitive resin component and the polyfunctional monomer is 2.00 × 10 ^-3 mol / g to 2.75 × 10 ^-3 mol / g; the total ratio of the acid value of the nonvolatile component of the resin to the acid value of the nonvolatile component of the monomer relative to the mass of the nonvolatile component is 8.0 to 40.0 mgKOH/g. The coloring composition of claim 9, wherein at least one of the alkali-soluble photosensitive resin component and the alkali-soluble non-photosensitive resin component comprises:
The first repeating unit is 2.0 to 60 parts by mass, the second repeating unit is 0.2 to 80 parts by mass, and the third repeating unit is 2.0 to 30 parts by mass;
The first repeat unit comprises a carboxyl group;
The second repeating unit has at least one annular structure selected from the group consisting of aromatic ring groups represented by the general formulas (12) and (13);
Formula (12)
(In the general formula (12), R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group may be replaced by a benzene ring.)
Formula (13)
(In the general formula (13), R ² is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group may be replaced by a benzene ring.)
The third repeating unit has at least one cyclic structure selected from the group consisting of aromatic ring groups represented by the general formulas (14) and (15).
General formula (14):
Formula (14)
General formula (15):
Formula (15) The coloring composition of claim 9, wherein the oxidation preventing agent comprises a hindered phenol-based oxidation preventing agent. A color filter comprising: a substrate; and a filter segment disposed on at least one main surface of the substrate, and the colored composition of any one of claims 1 to 11 Formed by. The color filter of claim 12, wherein the substrate is a substrate for driving a thin film transistor (TFT) color liquid crystal display device.