JP2007057658A - Thermosetting composition, color filter and its manufacturing method, and image recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition which is capable of maintaining etching performance and forming a satisfactory rectangular pattern, has a sufficient curing property and can provide excellent solvent resistance and adhesiveness with an adjacent layer. <P>SOLUTION: The thermosetting composition contains a dye having a weight average molecular weight of 5,000 or more as a colorant. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermosetting composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device, a solid-state imaging device, etc., a color filter using the thermosetting composition, and a dry etching method. The present invention relates to a method of manufacturing a color filter that is suitable for forming a colored image that is used and that constitutes a color filter used in a liquid crystal display element, a solid-state imaging element, or the like.

  As a method for producing a color filter used for a liquid crystal display element (LCD) or a solid-state image sensor (CCD, CMOS, etc.), a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A colored filter is formed, and a color filter is obtained by repeating this operation for each color according to the desired number of hues. As such a pigment dispersion method, there is one in which an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, Patent Documents 1 to 4). reference).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In view of such a problem, a technique for using a dye instead of a pigment has been proposed (for example, see Patent Document 5). However, a curable composition using a dye has a problem that it is generally inferior to a pigment in various performances such as light resistance, heat resistance, solubility and coating uniformity. In addition, since a film thickness of 1.5 μm or less is required for use in the production of a color filter for a solid-state image sensor, a large amount of a dye must be added to the curable composition, and therefore, it is in close contact with the substrate. In addition, there is a problem that the pattern forming property is remarkably deteriorated such that the degree of curing is insufficient or the dye is removed from the exposed portion forming the filter.

In addition, as a colorant, regardless of whether it is a pigment or a dye, when producing a color filter using a photolithography method, it is necessary to use a considerable amount of components other than the colorant, that is, a binder resin, a photopolymerizable compound, and a polymerization initiator. There is a drawback that the film thickness cannot be reduced.
On the other hand, in recent years, further thinning of color filters has been demanded from the viewpoint of improving image quality by reducing shading.

In comparison with the color filter manufacturing method using the photolithography method, a dry etching method has been known for a long time as a method effective for forming a finer pattern with a thinner film. This dry etching method has been conventionally employed as a method for forming a pattern on a dye-deposited thin film (see, for example, Patent Document 6). Compared to a photolithographic system, the thickness of the thin film is reduced while maintaining the same spectral characteristics. Thin film formation of 1/2 or less is possible.
JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP-A-55-146406

  However, in the above-described thin film formation by vapor deposition, contamination of the vapor deposition apparatus is unavoidable, and it becomes a heavy load for the production of the color filter, and the pixels are mainly formed with pigments or dyes. It was also one of the reasons why the yield did not increase.

  The present invention has been made in view of the above, maintains etching performance, can form a good rectangular pattern, has good curability, excellent spectral characteristics, solvent resistance, and substrate and adjacent Thermosetting composition that provides adhesion to the layer, excellent in rectangularity, spectral characteristics, and solvent resistance, and suitable for forming images with high adhesion between the substrate and adjacent layers. A color filter with excellent rectangularity, no color mixing, good spectral characteristics and solvent resistance, and high adhesion between the substrate and the adjacent layer, and the spectral characteristics, solvent resistance, and substrate and adjacent layer of the color filter It is an object of the present invention to provide a method for producing a color filter with high cost performance using a dry etching method, and to achieve the purpose.

Specific means for achieving the above object are as follows.
<1> A thermosetting composition containing a dye having a weight average molecular weight of 5,000 or more.
<2> A color filter using the thermosetting composition according to <1>.
<3> An image recording material having a photosensitive resin layer on the thermosetting composition according to <1>.
<4> A step of forming a pattern in at least the photosensitive resin layer of an image recording material having a photosensitive resin layer on the thermosetting composition according to <1>, and the image recording in which the pattern is formed. And a step of forming a colored pattern on the thermosetting composition by subjecting the material to a dry etching process.

  According to the present invention, etching performance can be maintained, a good rectangular pattern can be formed, curability is good, and excellent spectral characteristics, solvent resistance, and adhesion to a substrate and an adjacent layer are obtained. Thermosetting composition, excellent in rectangularity, spectral characteristics and solvent resistance, image recording material suitable for forming images with high adhesion between the substrate and adjacent layers, and excellent in the rectangularity of the pattern and color mixing Color filter with good spectral characteristics and solvent resistance and high adhesion between the substrate and adjacent layers, and spectral characteristics of solvent, solvent resistance, and adhesion between the substrate and adjacent layers Therefore, it is possible to provide a method for manufacturing a color filter with high cost performance using a dry etching method.

  Hereinafter, the thermosetting composition of the present invention, an image recording material using the same, a color filter, and a method for producing the same will be described in detail.

<Thermosetting composition>
The thermosetting composition of the present invention includes at least a dye having a weight average molecular weight of 5,000 or more, preferably includes a thermosetting compound, and optionally includes a binder, a curing agent, and a curing catalyst. , And other components can be used. Hereinafter, each component will be described in detail.

-Dye-
The thermosetting composition of the present invention contains at least one dye having a weight average molecular weight of 5,000 or more (hereinafter sometimes referred to as “high molecular weight dye according to the present invention”) as a colorant. In particular, by selecting a dye having a large molecular weight as the colorant, good rectangularity can be obtained without impairing the etching performance during the etching process, curability, solvent resistance after curing, spectral characteristics, and substrate. And adhesion between adjacent layers can be effectively improved.

  The weight average molecular weight is measured by gel permeation chromatography (GPC).

The high molecular weight dye according to the present invention can be appropriately selected from known dyes. For example, JP-A-2-104289, JP-A-5-271567, JP-A-2-3448, and JP-A-3- A dye selected from those described in Japanese Patent Publication No. 95183 and the like and a group of compounds having a structural unit represented by the following general formula (I) is preferable.
In addition, the high molecular weight dye according to the present invention may be used in combination of two or more in addition to the single use.

  Hereinafter, a compound having a structural unit represented by the following general formula (I) and / or a tautomer thereof will be described in detail as a colorant suitable for the thermosetting composition of the present invention. This compound and its tautomer are pigment compounds that satisfy both high light resistance and high heat resistance at the same time and can be freely dissolved in water or an organic solvent when necessary. In particular, by taking the form of a (meth) acrylic polymer or copolymer, it has good solubility in water and various solvents of pyridone azo dyes which are generally poor in solubility.

In the general formula (I), R ⁵ represents a divalent linking group which may have a substituent, R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a group containing a pyridoneazo structure. .

In the general formula (1), R ⁵ represents a divalent linking group which may have a substituent.
R ⁵ is not particularly limited as long as it is a divalent linking group, and examples thereof include a substituent derived from a linking group portion of amino alcohol: HO—R ⁵ —N (R ³ ) H. Amino alcohol: HO—R ⁵ —N (R ³ ) H will be described later.
R ⁶ represents a hydrogen atom or a methyl group, and both are preferable.
R ⁷ represents a group containing a pyridone azo structure. Examples of the group containing a pyridone azo structure include a group containing a pyridone azoaryl structure or a group containing a pyridone azoheteroaryl structure. Among them, a group containing a pyridone azophenyl structure is preferable, and the following general formula (II) Or the compound which has a structural unit represented by general formula (III) is still more preferable.

In the general formulas (II) and (III), R ¹ , R ³ and R ⁴ are each independently a substituent having a hetero atom, a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, or 2 to 21 carbon atoms. An alkenyl group, an aryl group having 6 to 21 carbon atoms, and an aralkyl group having 7 to 21 carbon atoms. R ³ and R ⁴ may form a heterocyclic ring together with the nitrogen atom bonded thereto. R ² represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group. R ⁵ represents a divalent linking group which may have a substituent, and R ⁶ represents a hydrogen atom or a methyl group.

In the general formula (II), when the group represented by R ¹ is a “substituent having a hetero atom”, R ¹ is particularly limited as long as it is a group derived from an amine having a hetero atom that can be used for the synthesis of a pyridone ring. Not. R ¹ may be unsubstituted or may have a substituent. R ¹ is preferably a group having about 3 to 50 total atoms from the viewpoint of color value, more preferably a group having 3 to 40 total atoms, particularly preferably a group having 3 to 30 total atoms, a nitrogen atom, a sulfur atom And a group having 3 to 30 total atoms having at least one of oxygen atoms.
The substituent represented by R ¹ is introduced by, for example, closing an amide compound obtained by the reaction of a cyanoacetate ester with a primary amine on the pyridone ring, so that the group represented by R ¹ is “hetero In the case of the “substituent having an atom”, examples of R ¹ include a group derived from a primary amine containing a heteroatom described in the Aldrich Structure Index.

Specific examples of the “substituent having a hetero atom” represented by R ¹ include 2-methoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-butoxypropyl group, 2-methoxy- 1-methyl-ethyl group, tetrahydrofurfuryl group, hydroxyethyl group, hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidi) ) Propyl group, 3- isopropoxypropyl group, and the like.

  Among them, 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, hydroxyethyl group, hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1- Methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) ) A propyl group, a 3-isopropoxypropyl group, etc. are preferable, a 3-methoxypropyl group, a 2-methoxy- -Methyl-ethyl group, tetrahydrofurfuryl group, hydroxyethyl group, hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N- Pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl- N-piperidinyl) propyl group, 3-isopropoxypropyl group and the like are more preferable, and 3-methoxypropyl group, tetrahydrofurfuryl group, hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxyethyl group, 3-N-morpholino Propyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidino Rupropyl group, 3-dimethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3- An isopropoxypropyl group and the like are particularly preferable.

In the general formulas (II) and (III), when R ³ and / or R ⁴ represents a substituent having a hetero atom, R ³ and / or R ⁴ can be used for the synthesis of the corresponding sulfonamide. The group is not particularly limited as long as it is a group derived from an amine having an atom.
R ³ and / or R ⁴ may be unsubstituted or may have a substituent, and a group having about 3 to 50 total atoms is preferable from the viewpoint of color value, and a group having 3 to 40 total atoms. Is more preferable, a group having 3 to 30 total atoms is particularly preferable, and a group having 3 to 30 total atoms having at least one of a nitrogen atom, a sulfur atom and an oxygen atom is still more preferable.
Since the substituent represented by R ³ or R ⁴ is introduced, for example, by the reaction of nitrobenzenesulfonyl chloride with a primary or secondary amine, the group represented by R ³ and / or R ⁴ can be substituted with a hetero atom. when a substituent having, as the R ³ and / or R ^4, for example, and the groups or derivatives thereof derived from a primary or secondary amine containing heteroatoms that are described in Aldrich structure index Can do.

Specific examples of the “substituent having a hetero atom” represented by R ³ and / or R ⁴ include 2-methoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-butoxypropyl group. Group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl Group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2- N-pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2 -Methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolan-2-yl-methyl group, 3-hydroxypropyl group, 2- A mercaptoethyl group, and the like.

  Among them, 3-methoxypropyl group, 3-ethoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydrofurfuryl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 2- Hydroxy-1-methyl-ethyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 2-dimethylaminoethyl group, 3-dimethyl Aminopropyl group, 3-diethylaminopropyl group, 2-N-pyrrolidinylethyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl) -N-piperidinyl) propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxy ester Group, 1,3-dioxolan-2-yl-methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group, etc. are preferable, 3-methoxypropyl group, 2-methoxy-1-methyl-ethyl group, tetrahydro Furfuryl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonyl Propyl group, 3-dimethylaminopropyl group, 3-diethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group, 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) ) Propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3 More preferred are dioxolan-2-yl-methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group, etc., 3-methoxypropyl group, tetrahydrofurfuryl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxy Ethoxyethyl group, 3-N-morpholinopropyl group, 2-N-morpholinoethyl group, 3-N-pyrrolidinonylpropyl group, 3-dimethylaminopropyl group, 2- (N-methyl-2-pyrrolidinyl) ethyl group 2-N-piperidinylethyl group, 3- (2-methyl-N-piperidinyl) propyl group, 3-isopropoxypropyl group, diethylaminoethyl group, 2,2-dimethoxyethyl group, 1,3-dioxolane- 2-yl-methyl group, 3-hydroxypropyl group, 2-mercaptoethyl group, and the like are particularly preferable. .

In the case where R ¹ , R ³ and R ⁴ are groups containing no hetero atom, R ¹ , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, or an alkenyl having 2 to 21 carbon atoms. Group, an aryl group having 6 to 21 carbon atoms, and an aralkyl group having 7 to 21 carbon atoms. In the general formula (III), R ³ and R ⁴ may form a heterocyclic ring together with the nitrogen atom bonded thereto. In addition, the groups R ¹ , R ³ and R ⁴ may have a substituent.
The alkyl group having 1 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ may be unsubstituted or may have a substituent. As said alkyl group, a C1-C15 alkyl group is preferable and a C1-C10 alkyl group is more preferable.

The alkyl group having 1 to 21 carbon atoms represented by R ¹ , R ³ , and R ⁴ may be any of linear, branched, or cyclic alkyl groups, such as a methyl group, an ethyl group, and n-propyl. Group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group Group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl Group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t Amyl group, a 1,3-dimethylbutyl group, 3,3-dimethylbutyl group,

2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl Group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched octadecyl group, linear or Branched nonadecyl group, straight chain or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl Group, cyclododecyl group, Rubornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentyl Preferred examples include an ethyl group and a bicyclooctyl group.

  Among them, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- Undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2 -Methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2 -Ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, Nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl Group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, bicyclooctyl group are more preferable,

  Furthermore, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i -Propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched Heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl , Cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantylmethyl, adamantylmethyl The group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group and bicyclooctyl group are particularly preferred.

  Furthermore, among the above groups, from the viewpoint of improving heat resistance, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl Group, n-decyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl Group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2- Methylpropyl group, branched heptyl group, 1-methylheptyl group 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, Chlopropylmethyl, cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, cyclooctyl, cyclohexylpropyl, cyclododecyl, norbornyl, bornyl, noradamantyl, adamantyl A branched alkyl group and a cyclic alkyl group such as a group, an adamantylmethyl group, a 1- (1-adamantyl) ethyl group, a 3,5-dimethyladamantyl group, a cyclopentylethyl group, and a bicyclooctyl group are particularly preferable.

  Of the alkyl groups exemplified above, an alkyl group substituted with fluorine is particularly suitable. As the fluorine-substituted alkyl group, trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, A tridecafluorooctyl group, a nonadecafluorononyl group, a heptadecafluorodecyl group, and a perfluorodecyl group are preferable, and among them, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group , A tridecafluorohexyl group and a pentadecafluoroheptyl group are more preferable, and a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and a tridecafluorohexyl group are particularly preferable.

The alkenyl group having 2 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ may be unsubstituted or may have a substituent. As said alkenyl group, a C2-C15 alkenyl group is preferable and a C2-C10 alkenyl group is more preferable.
Examples of the alkenyl group having 2 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ include a vinyl group, an isopropenyl group, a 2-propenyl group, a 2-methyl-propenyl group, and 1-methyl-1 -Propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1- Pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl- 2-cyclohexenyl group, 1,4-dihydro-2-methylphenyl group, octenyl group, citronellyl group, oleyl group, geranyl group, farnesyl group, 2- (1-cyclohexyl group) Yl) ethyl group, and the like preferably.

  Among them, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1 , 1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl Group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2-methylphenyl group are more preferable, and further vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group Group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group Group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclo A hexenyl group and a 1,4-dihydro-2-methylphenyl group are particularly preferred.

The aryl group having 6 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ may be unsubstituted or may have a substituent. As said aryl group, a C6-C15 aryl group is preferable and a C6-C10 aryl group is more preferable.
Examples of the aryl group having 6 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, and a pyrenyl. Among them, a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, and an anthracenyl group are more preferable, and a phenyl group, a naphthyl group, a biphenylenyl group, and a fluorenyl group are particularly preferable.

The aralkyl group having 7 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ may be unsubstituted or may have a substituent. As the aralkyl group, an aralkyl group having 7 to 15 carbon atoms is preferable, and an aralkyl group having 7 to 10 carbon atoms is more preferable.
Examples of the aralkyl group having 7 to 21 carbon atoms represented by R ¹ , R ³ and R ⁴ include benzyl group, diphenylmethyl group, 1,2-diphenylethyl group, phenyl-cyclopentylmethyl group and α-methyl. Benzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, 3,3-diphenylpropyl group, 4-phenylbutyl group, naphthylmethyl group, styryl group, Preferred examples include cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, indanyl group, piperonyl group, pyrenemethyl group and the like.

  Among them, benzyl group, phenyl-cyclopentylmethyl group, α-methylbenzyl group, phenylethyl group, α-methyl-phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, 4-phenylbutyl group, styryl Group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group, 1,2,3,4-tetrahydronaphthyl group, more preferably benzyl group, α-methylbenzyl group, phenylethyl group, α-methyl- Particularly preferred are phenylethyl group, β-methyl-phenylethyl group, 3-phenylpropyl group, styryl group, cinnamyl group, fluorenyl group, 1-benzocyclobutenyl group and 1,2,3,4-tetrahydronaphthyl group.

The groups represented by R ¹ , R ³ and R ⁴ may contain an ether group, and for example, a tetrahydrofurfuryl group and a 2,5-dihydro-2,5-dimethoxyfurfuryl group are also preferable.

R ³ and R ⁴ may form a heterocyclic ring together with the nitrogen atom bonded thereto, and examples of the heterocyclic ring in this case include a 2-methylaziridine ring, an azetidine ring, a pyrrolidine ring, 3 -Pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane ring, decahydro Quinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring, indoline ring, isoindoline ring, 1,2,3,4-tetrahydrocarbazole ring, 1,2,3,4-tetrahydroquinoline ring, 1,2 , 3,4-tetrahydroisoquinoline ring, iminodibenzyl ring, phenoxazine ring, phenothiazine ring, phenazine ring, etc. are preferred. Yes.

  Among them, pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, hexamethyleneimine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, thiomorpholine ring More preferred are pyrrolidine ring, 3-pyrroline ring, piperidine ring, 1,2,3,6-tetrahydropyridine ring, piperazine ring, decahydroquinoline ring, oxazolidine ring, morpholine ring, thiazolidine ring, and thiomorpholine ring. preferable.

In the case where the group represented by R ¹ , R ³ , R ⁴ and the heterocyclic ring formed by R ³ and R ⁴ and a nitrogen atom have a substituent, the substituent includes an acyl group, an acylamino group, Acylaminocarbonylamino group, aralkylaminocarbonylamino group, arylaminocarbonylamino group, methacryloylaminocarbonylamino group, alkoxycarbonyl group, trifluoromethyl group, fluoro group, chloro group, bromo group, iodo group, hydroxy group, nitro group , Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl Group, methoxy group, ethoxy group, butoxy group, isopropoxy group, t-butoxy group, cyclohexyloxy group, Aryloxy group, a methylthio group, an ethylthio group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an amino group, dimethylamino group, diethylamino group, a phenyl group, -SO ₃ M group, -COOM group (M represents a hydrogen atom, a metal atom or containing Represents a cation composed of a nitrogen compound).

Among them, acyl group (especially acetyl group), acylamino group, acylaminocarbonylamino group, alkoxycarbonyl group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, vinyl group, methoxy group, ethoxy group, butoxy group, isopropoxy group , T-butoxy group, cyclohexyloxy group, vinyloxy group, methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, piperazinyl group, amino group, dimethylamino group, diethylamino group, phenyl group, —SO ₃ M group, —COOM group (M represents a cation composed of a hydrogen atom, a metal atom or a nitrogen-containing compound) More preferably, further an acyl group (particularly acetyl group), acylamino group, acylaminocarbonylamino group, alkoxycarbonyl group, trifluoromethyl group, fluoro group, chloro group, bromo group, hydroxy group, nitro group, methyl group, ethyl Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, vinyl group, methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, vinyloxy group, Methylthio group, ethylthio group, pyrrolidinyl group, piperidinyl group, piperazinyl group, amino group, dimethylamino group, diethylamino group, phenyl group, —SO ₃ M group, —COOM group (M is a hydrogen atom, metal atom or nitrogen-containing compound) Are particularly preferred.

The above substituents may be further substituted several times with the same substituents as described above.
In particular, when the substituent is a group having an active hydrogen such as a hydroxy group or an amino group, it is reacted with various acid chlorides, acid anhydrides, halides or various isocyanates to give an acetyl group, an acyl group, (meth) It may be substituted with a group such as acryloyl group, alkylaminocarbonyl group, arylaminocarbonyl group (for example, butylaminocarbonyl group, phenylaminocarbonyl group, etc.), alkyl group, aralkyl group and the like.

Wherein R ^1, R ^3, the alkyl group represented by R ^4, an alkenyl group, aryl group and aralkyl group, and a heterocyclic ring formed by the R ³ and R ⁴ and the nitrogen atom, further said R ^1, R ³ and may be substituted with each group represented by R ⁴ .

In terms of color value (epsilon / Mw), the formula weight of the group represented by the R ^1, R ^3, R ⁴ is preferably 500 or less in total of said R ^1, R ^3, R ^4, is 400 or less More preferred is 300 or less.
As a number of the said substituent, 0-4 are preferable, 0-3 are more preferable, and 0-2 are especially preferable.

The group represented by R ¹ , R ³ , R ⁴ and the —SO ₃ M group mentioned as the substituent when the heterocyclic ring formed by R ³ and R ⁴ and a nitrogen atom has a substituent. , -COOM group M represents a cation comprising a hydrogen atom, a metal atom cation, or a nitrogen-containing compound. Among M, a cation composed of H, Li, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Ni, Cu, Co, or Fe, or a nitrogen-containing compound is preferable. , H, Na, K, Rb, Cs, Ag, Mg, Ca, Sr, Ba, Zn, Al, Cu, or Fe cations, or cations made of nitrogen-containing compounds are more preferable, and H, Na, K, Mg Rb, Ca, Ba, Sr, Zn, Al, Cu, or Fe cations, or cations composed of nitrogen-containing compounds are particularly preferred.

  The cation composed of the nitrogen-containing compound represented by M is selected in consideration of all of solubility in organic solvents and water, salt formation, absorbance / color value of the dye, heat resistance as a colorant, and light resistance. Is done. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible, preferably a molecular weight of 300 or less, more preferably a molecular weight of 280 or less, and a molecular weight of 250 or less. Is particularly preferred.

  Hereinafter, specific examples of the nitrogen-containing compound forming “a cation comprising a nitrogen-containing compound” will be given. However, the present invention is not limited to these. The cation here refers to a cation that has been protonated with one or more of the following nitrogen-containing compounds.

The pyridone azo compound having the structural unit represented by the general formula (I), (II) or (III) is bonded at the R ¹ , R ³ and R ⁴ portions, and has two or more dye skeletons. May be.

In the general formulas (II) and (III), R ² represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group, and may have a substituent.
R ² is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a methoxymethyl group, or a trifluoromethyl group. Among them, a methyl group, an ethyl group, an isopropyl group, t- A butyl group, a methoxymethyl group, and a trifluoromethyl group are more preferable, and a methyl group, an isopropyl group, a methoxymethyl group, and a trifluoromethyl group are particularly preferable.
The substituent for R ² is preferably a halogen atom, an alkyl group, or an alkenyl group, and more preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, a butyl group, or a 2-butenyl group, A group, ethyl group, propyl group, butyl group and 2-butenyl group are particularly preferred.

As described above, R ⁵ in the general formula (I) is derived from a linking group portion of amino alcohol: HO—R ⁵ —N (R ³ ) H described below (R ³ and R ⁵ are Can be linked to form a ring).

When synthesizing a pyridone azo compound having the structural unit represented by the general formula (I), (II) or (III), it is useful to use amino alcohol: HO—R ⁵ —N (R ³ ) H. is there.
The amino alcohol and / or R ⁵ derived therefrom may be unsubstituted or may have a substituent. The amino alcohol is preferably a group having a total number of atoms of about 3 to 50 from the viewpoint of color value, more preferably a group having a total number of atoms of 3 to 40, and particularly preferably a group having a total number of atoms of 3 to 30.
The amino alcohol: HO—R ⁵ —N (R ³ ) H is not particularly limited as long as it is an amino alcohol having a corresponding structure described in the Aldrich Structure Index, for example.

Specific examples of amino alcohol: HO—R ⁵ —N (R ³ ) H include ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, and 4-amino. -1-butanol, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2-amino-3-methyl -1-butanol, 6-amino-1-hexanol, 2-amino-1-hexanol, isoleucinol, leucinol, tertiary leucinol, 6-amino-2-methyl-2-heptanol, 1-amino-1-cyclopentane Methanol, 2-amino-3-cyclohexyl-1-propanol, 2-aminocyclohexanol, 4-aminocyclohexyl Sanol, 1-aminomethyl-1-cyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ) Ethanol, 2- (propylamino) ethanol, 2- (tertiary-butylamino) ethanol, 3-pyrrolidinol, 2-pyrrolidinemethanol, 2-piperidinemethanol, 2-piperidineethanol, 3-hydroxypiperidine, 3-piperidinemethanol, 4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] -piperazine, 2-anilino Ethanol, 2-aminophenol, 2 Aminobenzyl alcohol, 2-aminophenethyl alcohol, 3- (1-hydroxyethyl) aniline, 4-aminophenol, 4-aminophenethyl alcohol, 2-amino-3-methylbenzyl alcohol, 3-amino-2-methylbenzyl alcohol , 2-amino-M-cresol, 5-amino-2-methoxyphenol, 3-amino-O-cresol, etc., and the R ⁵ is a linkage between a nitrogen atom and an oxygen atom of these amino alcohols. Part.

Among them, examples of amino alcohols that provide the linking group R ⁵ include ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 2- Amino-1-butanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2-amino-3-methyl-1-butanol, 6- Amino-1-hexanol, 2-amino-1-hexanol, isoleucinol, leucinol, tertiary leucinol, 6-amino-2-methyl-2-heptanol, 1-amino-1-cyclopentanemethanol, 2-amino-3 -Cyclohexyl-1-propanol, 2-aminocyclohexanol, 4-aminocyclohexano 1-aminomethyl-1-cyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ) Ethanol, 2- (propylamino) ethanol, 2- (tertiary-butylamino) ethanol, 3-pyrrolidinol, 2-pyrrolidinemethanol, 2-piperidinemethanol, 2-piperidineethanol, 3-hydroxypiperidine, 3-piperidinemethanol, 4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidinol, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] -piperazine and the like are preferable.

  Among them, ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-2 -Methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2-amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino-1 -Hexanol, isoleucinol, leucinol, tertiary leucinol, 6-amino-2-methyl-2-heptanol, 1-amino-1-cyclopentanemethanol, 2-amino-3-cyclohexyl-1-propanol, 2-aminocyclo Hexanol, 4-aminocyclohexanol, 1-aminomethyl-1-cyclohexanol 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (propylamino) ethanol, 3 -Pyrrolidinol, 2-pyrrolidinemethanol, 2-piperidinemethanol, 2-piperidineethanol, 3-hydroxypiperidine, 3-piperidinemethanol, 4-hydroxypiperidine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2 -Hydroxyethoxy) ethyl] -piperazine, etc. are more preferred,

Ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-2-methyl -1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2-amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino-1-hexanol 6-amino-2-methyl-2-heptanol, 2-amino-3-cyclohexyl-1-propanol, 4-aminocyclohexanol, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2 -(Ethylamino) ethanol, 2- (propylamino) ethanol, 3-pyrrolidinol, 2-pyrrolidine methanol 2-piperidinemethanol, 2-piperidineethanol, 3-hydroxypiperidine, 3-piperidinemethanol, 4-hydroxypiperidine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl]- Piperazine and the like are particularly preferred.

  The Tg of the high molecular weight dye according to the present invention having the structural unit represented by the general formula (I) is preferably in the range of −100 to 400 ° C., and more preferably in the range of −80 to 350 ° C. Preferably, it is in the range of -70 to 300 ° C.

  The molar fraction of the structural unit represented by the general formula (I) in the high molecular weight dye according to the present invention is preferably 99 to 1 mol%, more preferably 97 to 3 mol%, and 95 to 5 mol%. Particularly preferred.

  The component constituting the high molecular weight dye according to the present invention together with the structural unit represented by the general formula (I), a so-called copolymer component, is not particularly limited as long as copolymerization (two or more) is possible, For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, etc. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, (anhydrous) maleic acid copolymer, partially esterified maleic acid copolymer, partially amidated malein Monomers, (meth) acrylates, (meth) acrylamides, aromatic hydrocarbon rings having a vinyl group, heteroaromatic rings having a vinyl group, anhydrous monomers used in acid copolymers Inic acid, itaconic acid esters, crotonic acid esters, (meth) acrylonitrile, (meth) crotononitrile, various styrenes, various benzoyloxyethylenes, various acetoxyethylenes, vinylcarbazoles, vinylpyrrolidone, etc. .

  In addition to the above, there may be mentioned those copolymerized with the following conventional dye group homopolymers, acrylates represented by glycidyl acrylate, benzyl acrylate and the like.

  Specific examples of the pyridone azo compounds represented by the general formula (I), (II) or (III) [Exemplary compounds (1) to (18)] will be given below. However, the present invention is not limited to these.

The high molecular weight dye according to the present invention generally has an —OH group, for example, by reducing a nitrobenzene derivative having a desired substituent and then diazotizing it and adding a pyridone compound having the desired substituent to this. By synthesizing a pyridone azo dye and then polymerizing by (meth) acryloylation, a polymer having a structure represented by the general formula (I) to the general formula (III) can be synthesized.
A polymer having further desired physical properties can be synthesized by appropriately changing a desired nitrobenzene derivative, a substituent of a pyridone compound, and the like.

The high molecular weight dye according to the present invention is a high molecular weight dye having a molecular weight of 5,000 or more in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the etching performance is maintained and a good rectangular pattern can be formed, but there is no color mixing and excellent curability, solvent resistance, and adhesion to the substrate and adjacent layers. A color filter can be formed.
As a weight average molecular weight, 10,000 or more are preferable, More preferably, it is 20,000 or more. Moreover, as an upper limit, 500,000 or less is preferable. Furthermore, 5,000-100,000 are preferable and 5,000-50,000 are especially preferable. When a dye having a molecular weight within the above range is contained, color mixing is suppressed, curability and solvent resistance are good, spectral characteristics are excellent, and adhesion to a substrate or an adjacent layer is particularly effective. Depending on the application, a quantity oligomer may be preferred.

In the present invention, in addition to the high molecular weight dye according to the present invention, the following dye having a weight average molecular weight of less than 5000 may be used in combination. For example, conventionally known dyes for color filters can be used.
Specifically, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808. No. 5,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6- Examples thereof include dyes described in Japanese Patent No. 51115, Japanese Patent Laid-Open No. 6-194828, and the like.

  From the viewpoint of chemical structure, azo compounds such as pyrazole azo, anilino azo, pyrazolo triazole azo, pyridone azo, triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine , Xanthene, phthalocyanine, benzopyran, indigo, anthrapyridone and the like can be used, preferably pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, anthraquinone, anthrapyridone It is a dye.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing a binder and / or dye described later by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
Hereinafter, the acid dye and its derivative will be described in detail.

-Acid dyes and their derivatives-
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the above, acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63, 74;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25;
And the like and their derivatives are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. These acid dyes and derivatives of these dyes can also be suitably used.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developer, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

The method for forming the “salt of an acid dye and a nitrogen-containing compound” may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent), and improving heat resistance and light resistance.
Next, a nitrogen-containing compound that forms a salt with an acidic dye and a nitrogen-containing compound that forms an amide bond with an acidic dye will be described.

  The nitrogen-containing compound is a salt or amide compound in an organic solvent or developer, salt-forming property, dye absorbance / color value, interaction with other components in the curable composition, heat resistance as a colorant. Selected in consideration of all of light and light resistance. When selecting only from the viewpoint of absorbance and color value, the nitrogen-containing compound preferably has a molecular weight as low as possible. Among them, a molecular weight of 300 or less is preferable, a molecular weight of 280 or less is more preferable, and a molecular weight of 250 or less. Are particularly preferred.

The molar ratio (hereinafter referred to as n) of the nitrogen-containing compound / acid dye in the “salt of acid dye and nitrogen-containing compound” is a value that determines the molar ratio of the acid dye molecule and the amine compound that is a counter ion. And can be freely selected according to the salt forming conditions of the acid dye-amine compound.
Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting only from the viewpoint of absorbance, n preferably takes a numerical value between 0 <n ≦ 4.5, more preferably a numerical value between 0 <n ≦ 4, and 0 <n ≦ It is particularly preferred to take a numerical value between 3.5.

  Since the acidic dye is an acidic dye by introducing an acidic group in structure, it can be made a non-acidic dye by changing the substituent. In addition, the acid dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acid dye may be preferably used.

The concentration of the colorant in the thermosetting composition is preferably 0.5% by mass or more and less than 100% by mass, more preferably 0.5% by mass or more and 80% by mass or less, based on the total solid content. 5 mass% or more and 70 mass% or less are especially preferable.
When the concentration of the colorant is within the above range, it is possible to form a color filter having a desired hue and color density, and is preferable in terms of curability, solvent resistance, and adhesion between the substrate and the adjacent layer. .

The high molecular weight dye according to the present invention may be mixed with other types of dyes in addition to being used alone, or may be mixed with a dye having a molecular weight of less than 5,000, and the effects of the present invention can be achieved. The mixing ratio can be arbitrarily selected.
When two or more dyes are contained, not only when all the dyes are high molecular weight dyes according to the present invention, but also when some dyes are high molecular weight dyes according to the present invention, There is an effect.

-Thermosetting compound-
The thermosetting composition of this invention can be comprised suitably using at least 1 sort (s) of a thermosetting compound. The thermosetting compound is, for example, a compound responsible for curing the colored layer by applying heat when forming the colored layer, and is not particularly limited as long as the film can be cured by heating. It can be selected from compounds having a functional group (thermosetting group) to be cured.

  As a thermosetting compound, what has at least 1 group chosen from an epoxy group, a methylol group, an alkoxymethyl group, and an acyloxymethyl group as a thermosetting group is preferable, for example.

  More preferable thermosetting compounds include (a) epoxy resin, (b) melamine compound, guanamine compound, glycoluril substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Examples thereof include a compound or a urea compound, (c) a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. Of these, polyfunctional epoxy resins are particularly preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, and the like; Trivalent glycidyl group-containing low molecular weight compounds typified by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc .; similarly, pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether and the like; similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether; And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

Moreover, as what is marketed, alicyclic epoxy compound "CEL-2021", alicyclic solid epoxy resin "EHPE-3150", epoxidized polybutadiene "PB3600", flexible alicyclic epoxy compound "CEL-" 2081 ", lactone-modified epoxy resin" PCL-G "and the like (all are manufactured by Daicel Chemical Industries, Ltd.). In addition, “Celoxide 2000”, “Epolide GT-3000”, “GT-4000” (all manufactured by Daicel Chemical Industries, Ltd.) may be mentioned. Among these, the alicyclic epoxy resin has excellent curability, and “EHPE-3150” has excellent curability.
These compounds may be used individually by 1 type, may be combined 2 or more types, and the combination with the following other types is also possible.

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in (b) that are substituted for each compound is 2 to 6 for melamine compounds, glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (b).

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds in (b) may be used alone or in combination.

  The compound in the above (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is a compound in the above (b). As in the case of, the intermixing with the overcoated photoresist is suppressed and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the compound in (c) is at least 2 per molecule, and from the viewpoints of thermosetting and storage stability, a phenolic compound that becomes a skeleton A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound serving as the skeleton are also preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound in (c) is a compound in which the phenolic OH group has a hydrogen atom at the 2nd or 4th position, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like in alcohol.
The acyloxymethyl group-containing compound in the above (c) can be obtained by reacting the methylol group-containing compound in the above (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in (c) include phenol compounds, naphthol compounds, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A and other bisphenols; 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the above (c) include, as a phenol compound or a naphthol compound, for example, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, tri (methoxymethyl) phenol, trimethylolphenol, or trimethylol. Compounds obtained by methoxymethylating one or two methylol groups of -3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol Tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl -4,4'-bishydroxybiphenyl, hexamethylol body of TrisP-PA, hexamethoxymethyl body of TrisP-PA, a compound obtained by methoxymethylating 1 to 5 methylol groups of the hexamethylol body of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include a part of the methylol group of the methylol group-containing compound, or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used singly or in combination of two or more.

  The total content of the thermosetting compound in the thermosetting composition varies depending on the material, but is preferably 0.1 to 70% by mass, and preferably 0.2 to 50% with respect to the total solid content (mass) of the layer. % By mass is more preferable, and 1 to 30% by mass is particularly preferable.

-Binder-
The thermosetting composition of this invention can be comprised suitably using at least 1 sort (s) of a binder. The binder is often added during the preparation of the pigment dispersion, does not require alkali solubility, and may be soluble in an organic solvent.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.

  Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

  As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Each copolymer such as benzyl methacrylate / benzylmethacrylamide, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

As the binder, not only a pigment dispersion resin but also a binder having a function as a thermosetting resin can be used. That is, among the thermosetting compounds, those having a binder function can be selected, and those described above having the thermosetting function can be used as they are. Those containing an epoxy group in the binder are preferred.
Among them, a resin obtained by copolymerizing an acrylic resin type such as glycidyl (meth) acrylate is preferable. For example, benzyl methacrylate / glycidyl methacrylate copolymer, hydroxyethyl methacrylate / benzyl methacrylate / glycidyl methacrylate copolymer, benzyl methacrylate / hydroxyethyl methacrylate / glycidyl methacrylate / isobutyl methacrylate copolymer, and Depending on the purpose, there may be mentioned various combinations of other monomers. Moreover, each copolymerization ratio, molecular weight, etc. can be selected arbitrarily.

  By dispersing the colorant in these binders at a high concentration, it is effective to impart adhesion to the lower layer and the like, and these also contribute to the coated surface shape during spin coating and slit coating.

As the binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to 5 × 10. The polymer of ⁴ is particularly preferred.

  The content of the binder in the thermosetting composition is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass with respect to the total solid content (mass).

-Curing agent-
The thermosetting composition of the present invention can be suitably configured using at least one curing agent. When using an epoxy resin as the thermosetting compound, it is preferable to add a curing agent. In this case, it reacts with an epoxy group by heating to undergo a polymerization reaction, and is cured by improving the crosslinking density.

  There are many types of curing agents for epoxy resins, and the properties, pot life of the resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used, An appropriate curing agent must be selected according to the purpose of use, usage conditions, working conditions, and the like of the curing agent. The curing agent is explained in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are given below.

  As those that act catalytically, tertiary amines, boron trifluoride-amine complexes react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc., and room temperature curing Examples thereof include diethylenetriamine and polyamide resin, examples of medium-temperature curing include diethylaminopropylamine and tris (dimethylaminomethyl) phenol, and examples of high-temperature curing include phthalic anhydride and metaphenylenediamine. From the viewpoint of chemical structure, in the case of amines, diethylenetriamine is used as an aliphatic polyamine, metaphenylenediamine is used as an aromatic polyamine, tris (dimethylaminomethyl) phenol is used as an acid anhydride, and anhydride is used as an acid anhydride. Phthalic acid, polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex, and synthetic resin initial condensate include phenol resin, other dicyandiamide, and the like.

  When adding a curing agent, a smaller amount is preferable from the viewpoint of thinning when the film is formed, specifically, 35% by mass or less is preferable with respect to the solid content (mass) of the thermosetting composition, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.

-Curing catalyst-
The thermosetting composition of the present invention can be suitably configured using at least one curing catalyst.
In order to achieve a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with the curing agent. In this case, it is preferable to use a curing catalyst without using a curing agent.

  Specific examples of the curing catalyst include those commercially available. For example, imidazole silane series IS-1000, IS-1000D, IM-1000, SP-1000, and IA manufactured by Japan Energy Co., Ltd. -1000A, the same IA-100P, the same IA-100F, the same IA-100AD, the same IA-100FD, the same IM-100F, the same IS-3000, the same IS-4000, etc. 1B2PZ made by Shikoku Kasei Co., Ltd., SFZ or the like is useful. However, it is not limited to these.

  When the curing catalyst is used, the addition amount of the curing catalyst in the thermosetting composition is preferably about 1/10 to 1/1000 on a mass basis with respect to an epoxy resin having an epoxy equivalent of about 150 to 200. More preferably, it is about 1/20 to 1/500, more preferably about 1/30 to 1/250, and it can be cured with a slight amount within the above range.

-Solvent-
In general, the thermosetting composition of the present invention can be prepared using a solvent. That is, the thermosetting composition can be used as a solution (for example, a coating solution) in which various components are dissolved in a solvent.

  The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the thermosetting composition, and is particularly selected in consideration of the solubility, applicability, and safety of the dye and binder. It is preferable.

  Specifically, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .;
Aromatic hydrocarbons such as toluene and xylene are preferred.

-Additives and other components-
The thermosetting composition of the present invention is within a range that does not impair the effects of the present invention, and various other additives as necessary, for example, dispersants, fillers, surfactants, adhesion promoters, antioxidants, An ultraviolet absorber, an aggregation inhibitor, etc. can be blended.

  The dispersant can be added to improve the dispersibility of the pigment. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.

  In addition, the graft copolymer described in JP-A-10-254133 having a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain has an action capable of finely dispersing the pigment. To the dispersant. When using the graft copolymer, it is possible to finely disperse the pigment while reducing energy and time consumption, and the dispersed pigment does not aggregate or settle over time, and can be dispersed for a long period of time. Can be maintained.

  The said dispersing agent may be used individually by 1 type, and may combine 2 or more types. The addition amount of the dispersant in the thermosetting composition is preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

-Various additives-
In addition to dispersants, specific examples of various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonions , Cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethylto Adhesion promoters such as methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl) -6-t-butylphenol), 2,6-di-t-butylphenol antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone And an anti-aggregation agent such as sodium polyacrylate.

-Preparation of thermosetting composition-
Hereinafter, the preparation method of the thermosetting composition of this invention is demonstrated. However, the present invention is not limited to this.
The thermosetting composition of the present invention contains a dye having a weight average molecular weight of 5,000 or more (high molecular weight dye) as a colorant. When the high molecular weight dye is soluble in a solvent, By using a solvent, no dispersion treatment is required. For example, it can be dissolved in a desired solvent together with a binder or the like.

  Specifically, a dye-containing liquid (or a dispersion further containing a pigment as described below) containing a high molecular weight dye according to the present invention (preferably, a high molecular weight dye dissolved in a desired solvent) is heated. A curable compound (for example, epoxy resin) and a curing catalyst and / or a curing agent are added, or when the binder itself is already a thermosetting compound, a curing catalyst and / or a curing agent is added to achieve the thermosetting function. By applying, a thermosetting composition can be prepared. In addition to the high molecular weight dye according to the present invention, a dye other than the high molecular weight dye according to the present invention may further be contained, and in this case, the same applies.

When the high molecular weight dye according to the present invention is insoluble, or when the pigment further contains a pigment together with the high molecular weight dye according to the present invention, the pigment is used in such a manner that its particle size distribution falls within the range described above. Is preferred.
In this case, a dispersion method is important for the preparation, and suitable dispersion methods include, for example, dry dispersion (kneading dispersion treatment) in which the material is dispersed in a high-viscosity state using a roll mill such as a kneader or two rolls, and three Examples of the dispersion method include a combination of wet dispersion (fine dispersion treatment) in which the material is dispersed in a relatively low viscosity state using a roll or a bead mill. In addition, in the dispersion method, a method of co-dispersing two or more kinds of pigments or the like, or not using a solvent at the time of the kneading dispersion treatment or reducing the amount of use as much as possible, or using various dispersants is also suitable. Further, in order to relieve the solvent shock, it is preferable to add the resin component separately at the time of the kneading dispersion treatment and at the time of the fine dispersion treatment (use in two divisions), and shift from the kneading dispersion treatment to the fine dispersion treatment. In order to prevent re-aggregation of particles such as pigment, it is preferable to use a resin component having excellent solubility. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment. In addition, as said resin component, the above-mentioned alkali-soluble resin can be used, for example.

  In the present invention, it is preferable to use a dispersion obtained by dispersing in a high viscosity state of 50,000 mPa · s or more and then dispersing in a low viscosity state of 1,000 mPa · s or less.

  When a pigment is included as a colorant, a binder is added to the pigment so that the viscosity after the kneading and dispersing treatment is 50,000 mPa · s or more (preferably 50,000 to 100,000 mPa · s). A kneading and dispersing treatment is preferably performed. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion. Then, if necessary, a binder is additionally added to the dispersion after the kneading dispersion treatment, and the dispersion after the fine dispersion treatment is finely dispersed so that the viscosity becomes 1000 mPa · s or less (preferably 100 mPa · s or less). It is preferable to perform the treatment. The fine dispersion treatment may be low-viscosity dispersion or wet dispersion.

  In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. When dispersion is performed without using a large amount of solvent, the surface of the particles such as pigment can be promoted to wet with the constituent component mainly composed of the resin component of the vehicle, and the interface formed by the particle surface of the pigment or the like A solid / gas interface between particles and air can be converted to a solid / solution interface between particles and vehicle solution. When the interface formed by the surface of particles such as pigment is converted from air to a solution and mixed and stirred, the pigment and the like can be dispersed to a minute state close to primary particles.

  Thus, in order to disperse pigments and the like to a high degree, it is effective to convert the interface formed by the particle surfaces of pigments and the like from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the said kneading | mixing dispersion | distribution process, it is preferable to use the thing of high viscosity as a to-be-kneaded material using the kneader which can exhibit strong shearing force and compressive force.

  In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, it is necessary to uniformly and evenly distribute the particles such as pigments to a fine state, so that dispersion that can impart impact force and shear force to the aggregated pigment particles It is preferable to use a low-viscosity product as a material to be dispersed.

<Image recording material>
The image recording material of the present invention comprises the above-described thermosetting composition of the present invention and a photosensitive resin layer provided on the thermosetting composition. Preferably, a thermosetting colored layer using a thermosetting composition of the present invention and a photosensitive resin layer are laminated on a desired support in order from the support side.

-Thermosetting composition-
The image recording material of the present invention comprises a thermosetting composition, and is preferably provided as a colored layer containing a dye having a weight average molecular weight of 5,000 or more. The details of the thermosetting composition of the present invention are as described above.

  Moreover, when forming a colored layer on a support body, the thermosetting composition was provided on the support body (for example, applied and dried) to form a colored film (colored layer) (colored layer forming step) Thereafter, the film can be suitably formed by heating to cure the film (thermosetting process).

  Formation of the colored layer in the colored layer forming step can be performed by, for example, a method of coating and drying. In the case of coating, the thermosetting composition can be formed on the substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, and the like, and dried.

  Heating may be performed at the same time as drying after coating, or a step of separately heating and curing after coating and drying may be provided. The heating is performed using a known heating means such as an oven or a hot plate, preferably at 130 to 300 ° C., more preferably at 150 to 280 ° C., particularly preferably at 170 to 260 ° C., preferably 10 seconds to 3 hours, More preferably, it can be performed in a range of 30 seconds to 2 hours, particularly preferably 60 seconds to 60 minutes. However, considering the production, the time required for curing is preferably as short as possible.

The layer thickness when forming the colored layer is preferably 0.005 to 0.8 μm, more preferably 0.01 to 0.65 μm, and still more preferably 0.02 to 0.6 μm. Within this range, the concentration of the colorant can be adjusted to 65% or more, and in a system capable of thermosetting with an epoxy resin, the concentration can be adjusted to 70% or more. That is, it is possible to form a thin film in a range that cannot be performed by the photolithography method without affecting the spectral characteristics.
In other words, it can be formed into a thin film of 70% or less, preferably 60% or less, more preferably 50% or less of the film thickness of the photolithography method showing the same spectral characteristics.

-Photosensitive resin layer-
The image recording material of the present invention has at least one photosensitive resin layer as an upper layer of a thermosetting composition (preferably a colored layer). This photosensitive resin layer can be composed of a positive type or negative type photoresist, and functions as a pattern mask when a pattern is formed by subjecting the colored layer to dry etching.

  Formation of the photosensitive resin layer can be performed by, for example, a method of coating and drying. In the case of coating, it is preferably carried out using a coating method such as spin coating, slit coating, cast coating, roll coating or the like directly on the thermosetting composition (preferably a colored layer) or via another layer. Can do.

  The positive photosensitive resin composition is sensitive to radiation such as ultraviolet rays such as g rays, h rays and i rays, far ultraviolet rays including excimer lasers, electron rays, ion beams and X rays. A positive photosensitive resin composition suitable as a mold photoresist can be used. In this case, g-line or i-line is preferable as light or radiation, and exposure with i-line is particularly preferable.

  Specifically, as the positive photosensitive resin composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. The positive type photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin is decomposed from a quinonediazide group by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group, and from an alkali-insoluble state to an alkali-soluble state. It can be used as a positive-type photoresist utilizing change. Note that this positive type photoresist is remarkably excellent in resolving power, and is therefore used in the manufacture of integrated circuits such as ICs and LSIs. A preferred example of the quinonediazide compound is a naphthoquinonediazide compound.

  In recent years, with respect to integrated circuits, the width of wiring has become finer as the degree of integration increases, and for this reason, dry etching has become the mainstream in place of conventional wet etching. In this dry etching, the shape of the resist is directly reflected in the shape of the layer to be etched. Therefore, if the shape of the resist is poor, etching is performed up to a portion that does not require etching, which may cause defective integrated circuits and poor yield. For this reason, a resist having a good profile with little development residue (scum) or the like is required more than ever. Further, in dry etching, the temperature of the substrate rises, and the resist pattern may be thermally deformed to reduce the dimensional accuracy. For this reason, the heat resistance of a resist is requested | required more than before. From this point of view, many positive photoresists satisfying various performances such as profile, scum, resolution, and heat resistance are commercially available. As a suitable one, for example, FUJIFILM Electronics Materials Co., Ltd. FH-6000 series, such as FH-6400L, FH-6800L, FHi-3000 series, such as FHi-3200, FHi-3950, etc., FHi-600 series, such as FHi-644, FHi, etc. -645, Fi-SP series made by the same company, for example, Fi-SP2 and the like. However, the present invention is not limited to this, and it can be used as a positive-type photosensitive resin composition regardless of whether it is commercially available as long as it has a mask shape preferable for pattern formation.

  Examples of the negative photosensitive resin composition include negative sensitive to ultraviolet rays such as g rays, h rays and i rays, far ultraviolet rays, X rays, electron rays, molecular rays, gamma rays, synchrotron radiation and the like. Type photoresist. Furthermore, a negative photoresist which is excellent in resolving power and sensitivity and in which minute defects due to residual development is not substantially generated is preferable.

For example, a negative photoresist is applied on the colored layer to a thickness of, for example, 0.5 to 3 μm by the above-described application method, and then heated and dried, and then cured into a desired pattern by irradiating the desired pattern with ultraviolet rays through an exposure mask. If necessary, after the exposure, a heating step (PEB) is further performed, followed by development to obtain a negative image obtained by processing a photoresist (photosensitive resin layer) into a pattern. It can be used as a mask for exposure in the process.
Typical examples include semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photo application processes. Moreover, it can also be applied to a lithographic printing plate by utilizing the difference in affinity between the image and the support substrate for ink. With higher integration of semiconductor substrate processing, higher resolution of the photoresist is required.

  The negative photosensitive resin layer is preferably a layer containing a photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond. A negative photosensitive resin composition that can be used to form such a photosensitive resin layer is shown below. For example, Japanese Patent Publication No. 54-23574 discloses a technique for photocuring a novolak resin in combination with a photoacid generator composed of an organic halide, and West German Published Patent No. 2057473 discloses a photoacid generator composed of a diazo compound. A phenolic resin such as novolak can be applied as a binder between the photocurable composition comprising methylolated melamine and the like, and JP-A-60-263143 discloses a photoacid generator and an acid such as melamine resin. A composition comprising a curable aminoblast resin and a general novolak resin is disclosed, and it is said that a negative image capable of aqueous development and having high thermal stability can be obtained. JP-A-62-164045 describes that an organic halide having light absorption in the far ultraviolet region can be advantageously used as a photoacid generator, and similarly, JP-A-2-52348 discloses. Describes that an organic halide having a pKa value in a specific region is advantageous as a similar photoacid generator. Furthermore, JP-A-2-154266 describes that oxime sulfonic acid esters are effective as a photoacid generator for a photocurable composition. As another example, in JP-A-2-146444, a composition comprising a photoacid generator having a specific trichlorotriazine group and a novolak resin containing 30% or more of m-cresol in alkoxylated melamine, It is described that it is useful for high energy beam exposure. Further, European Patent No. 396460A also describes the use of a novolak resin having a high degree of branching in a similar composition.

  There are commercially available negative photosensitive resin compositions such as those described above, such as the SC series (for example, SC-60, SC-450, etc.) manufactured by FUJIFILM Electronics Materials Co., Ltd. HR series (for example, HR-100, HR-200, etc.) made by the company, HNR series (for example, HNR-80, HNR-120, etc.) made by the same company, etc. are mentioned. However, the present invention is not limited thereto, and any mask having a shape preferable for pattern formation can be used regardless of whether it is commercially available.

  The layer thickness of the photosensitive resin layer is preferably 0.01 to 3 μm, more preferably 0.1 to 2.5 μm, and still more preferably 0.15 to 2 μm.

-Support-
The image recording material according to the present invention can be constituted using a support. As the support, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and a transparent conductive film attached thereto, or a photoelectric conversion element substrate used for an imaging element or the like (For example, silicon substrate), complementary metal oxide semiconductor (CMOS), and the like. These substrates may have black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports as needed for the purpose of improving adhesion with a layer (for example, a colored layer), preventing diffusion of a substance, or flattening the surface.

<Color filter and manufacturing method thereof>
The method for producing a color filter of the present invention uses the image recording material of the present invention described above, and a step of forming a pattern on at least the photosensitive resin layer constituting the image recording material of the present invention (hereinafter, “ And a process of forming a colored pattern on the thermosetting composition by subjecting the image recording material on which the pattern is formed (hereinafter, referred to as an “etching process”). .). Other steps may be further included as necessary.
Since the image recording material of the present invention described above is used, the etching performance is maintained, a favorable rectangular pattern can be formed, and the spectral characteristics, solvent resistance, and adhesion between the substrate and the adjacent layer are improved. A color filter can be produced.

  The color filter of the present invention is formed using the above-described thermosetting composition of the present invention, and can be most suitably produced by the method for producing a color filter of the present invention. Since the color filter of the present invention is produced using the thermosetting composition of the present invention, it has excellent pattern rectangularity, high molecular weight, no color mixing, good spectral characteristics and solvent resistance. It is excellent in adhesion between the substrate and the adjacent layer that are in contact with each other.

  In the pattern forming step, at least the photosensitive resin layer is exposed and developed imagewise, and a pattern (etching mask) made of the photosensitive resin layer is formed on the colored layer by photolithography.

  The exposure can be suitably performed by selecting a light source that emits light having a wavelength corresponding to at least the photosensitive wavelength of the photosensitive resin layer. The g-line, h-line, i-line, etc., particularly preferably the i-line is preferably a predetermined mask pattern. It can be performed in a pattern by irradiating via, for example.

  In the development, the photosensitive resin layer after the exposure is alkali-developed with a developer. By the alkali development in this step, the non-cured portion of the positive or negative photosensitive resin composition is developed and removed in accordance with the latent image formed on the photosensitive resin layer by the exposure, and is made of a cured photoresist. A pattern is formed. This pattern functions as a mask when forming a pattern on the colored layer in an etching process described later.

  Development can be performed using a developer, and any developer can be used as long as it can dissolve the exposed portion of the positive photoresist or the unexposed portion of the negative photoresist without adversely affecting the colored layer. Can also be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The alkaline aqueous solution may be an alkaline developer, and those generally marketed have stable performance and good reproducible results. As commercially available products, for example, FHD-5 and CD-2000 manufactured by FUJIFILM Electronics Materials are suitable, but are not limited thereto.

  Processing conditions such as development temperature and development time during development can be appropriately selected depending on the configuration of the image recording material, the type of developer used, and the like.

  In the etching step, the colored layer exposed by alkali development in the pattern forming step is dry-etched to process the colored layer (thermosetting composition) into a pattern. The pattern formed in this step constitutes a color filter or a colored pixel of the color filter.

  Representative examples of the dry etching method include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102. As described in the above publications, there is a method in which a coloring agent is vapor-deposited, a mask resist is applied, and etching is performed after patterning.

In the dry etching of this step, it is possible to perform anisotropic etching using CF-based gas such as oxygen and CF ₄ , CO, CO ₂ gas, etc., and the colored layer is etched according to the pattern of the pattern mask, and rectangular A color pattern (color filter) having excellent properties can be formed.

  After the etching step, the pattern mask, that is, the photosensitive resin layer (photoresist) provided on the colored layer in a pattern shape can be removed using a dedicated stripping solution or solvent. Such removal may be performed after all of the above steps are completed, and after the removal, the second and subsequent color patterns can be produced by repeating the same steps. In addition, when forming the last color pattern, after thermosetting, the excess photocurable composition remaining on the existing color pattern is removed and flattened to produce a pattern of all colors. You may do it.

The color filter produced by the method for producing a color filter of the present invention may be composed of a single color or may be composed of two or more colors.
In the case of being composed of a plurality of colors, a color pattern composed of a plurality of colors can be produced by repeating the above-described pattern formation step, etching step, and other steps as necessary. At this time, since a mask for dry etching treatment is not required when forming a color pattern to be finally formed, an extra thermosetting composition existing on an existing pattern as it is after thermosetting is performed. A multicolor color filter can be formed by removing and flattening.

  In the color filter of the present invention, a composition containing a colorant (preferably a colored layer) is cured with heat, and a colored pattern is formed using dry etching. It is not necessary to add other than additives to guarantee the coating surface condition. Therefore, it can be composed of a colorant and a thermosetting compound and other components as necessary, and the concentration of the colorant is based on the total solid content. Thus, a high concentration of 50% by mass or more can be achieved. When the concentration of the colorant is 50% by mass or more, it is possible to reduce the thickness of the colored layer, that is, the color filter. Specifically, the concentration of the colorant in the colored layer is preferably 50% by mass to less than 100% by mass, more preferably 60% by mass to 90% by mass, and still more preferably 65% by mass to 90% by mass. Furthermore, it is preferably 70% or more and 90% by mass or less, particularly 80% or more and 90% by mass or less, and good curability can be obtained even in such a high concentration range, and thin film formation that cannot be obtained by photolithography is possible. . Moreover, it is possible to form a pattern with good rectangularity without impairing the etching property, and it has excellent solvent resistance, good hue and color density, and is effective for forming a color filter with good spectral characteristics. .

The color filter of the present invention has a spectral characteristic equal to or higher than that of a color filter obtained by a photolithography method, and is formed into a thin film. In order to reduce the film thickness, it is necessary to increase the solid content concentration in the film obtained by the photolithographic method. However, when the solid content other than the colorant is decreased, depending on the photolithographic method, curing failure or alkali development accompanying this may occur. Since the disappearance of the pattern (flow in the development and rinsing steps) occurs, there is a limit to the concentration of the colorant, and in particular, pattern formation was almost impossible in the range where the concentration was 65% by mass or more. In the present invention, since the heat-cured film is subjected to dry etching to form a pattern, an essential monomer (photopolymerizable compound) or photopolymerization initiator is not required in the photolithography method, and the thermosetting composition is colored. Since it can be composed of a colorant and a thermosetting resin, the concentration of the colorant can be 50% by mass or more as described above.
The concentration of the colorant is desired to be 100% as in the vapor deposition method, and the film thickness is also desired to be a thin film as in the vapor deposition method, but device contamination and adhesion may be a problem. In addition, the method of applying a thermosetting composition with a high colorant concentration and thermosetting to form a thin film is thicker than the vapor deposition method in which a thermosetting resin is added, but alkali developability is not required. Therefore, it is possible to prepare a composition containing a colorant at a higher concentration than allowed by the photolithography method.

  Further, the high molecular weight dye according to the present invention can be cured even if the crosslinking site is a part, and unlike the monomer dye having a weight average molecular weight of less than 5,000, the entangled structure by the network formation between polymers. The effect of improving the solvent resistance is also obtained, and a cured film having good curability can be formed even at a higher dye concentration, specifically, a dye concentration of 80% or more. In addition, the dye density | concentration here represents the density | concentration with respect to the total solid of the monomer component which comprises high molecular weight dye.

  The color filter produced by the method for producing a color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. It is. For example, it can be used as a color filter disposed between a light receiving portion of each pixel constituting the CCD and a microlens for collecting light.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

Example 1
-Preparation of thermosetting composition 1 containing green colorant-
The following composition was mixed to prepare a colorant-containing thermosetting composition 1.
-Acid Green 25 ... 115 parts (weight average molecular weight = 622.59)
-High molecular weight dye (yellow dye) according to the present invention 40 parts (Exemplary compound (14) described above; weight average molecular weight 20,000)
Resin: 25 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) 19.6 parts ・ Curing catalyst (1B2PZ, manufactured by Shikoku Chemicals Co., Ltd.) 0.4 parts

  A silicon wafer substrate having an undercoat layer obtained by applying and curing “CT-2000L” manufactured by FUJIFILM Electronics Materials Co., Ltd. is prepared, and the coloring obtained as described above on the undercoat layer of the silicon wafer substrate. After coating the agent-containing thermosetting composition 1 so as to form a coating film having a film thickness of 0.5 μm with a spin coater, heat treatment is performed at 100 ° C. for 2 minutes on a hot plate, and the coating film is dried. A colored layer for forming a green pattern was provided. Subsequently, heating was performed at 215 ° C. for 5 minutes using a hot plate to thermally cure the colored layer. The layer thickness after thermosetting was 0.5 μm.

  Next, a silicon wafer substrate having an undercoat layer as described above is prepared separately from the above, and FHi-3950 (manufactured by Fuji Film Electronics Materials; positive photoresist) is formed on the undercoat layer with a film thickness of about 1 After coating with a spin coater to a thickness of 5 μm to form a resist layer, this was heat-treated at 100 ° C. for 2 minutes and dried. Thus, an image recording material was produced.

Thereafter, pattern exposure was performed from above the resist layer using an i-line stepper at an exposure amount of 350 mJ / cm ² . Next, the image recording material after pattern exposure is developed for 1 minute using an alkali developer FHD-5 (manufactured by Fujifilm Electronics Materials) to form a 1.5 μm × 1.5 μm size grid. Then, a mask portion where the resist layer remains and a non-mask portion where the photoresist is dissolved to expose the colored layer were formed.

Next, the image recording material on which the mask portion and the non-mask portion are formed is subjected to a dry etching process using a mixed gas of CF ₄ / O ₂ / Ar = 2/2/1, and the non-mask portion of the colored layer. Was etched to form a mask-like pattern in the colored layer. Thereafter, the remaining resist layer was peeled off using MS-230 (manufactured by FUJIFILM Electromaterials Co., Ltd.), and a color filter in which a good green pattern with a rectangular pattern having a lattice pattern size of 1.5 μm was formed was produced. .
Note that the dry etching process was performed by an emission spectroscopic analysis method, and the etching was set to end when the colored layer of the non-mask portion was just etched.

(Comparative Example 1)
In Example 1, a color filter was produced in the same manner as in Example 1 except that the green colorant-containing thermosetting composition 1 was replaced with the green colorant-containing thermosetting composition 2 having the following composition. did.

-Preparation of green colorant-containing thermosetting composition 2-
The following composition was mixed to prepare a colorant-containing thermosetting composition 2.
-Acid Green 25 ... 115 parts (weight average molecular weight = 622.59)
-Acid Yellow 42 ... 40 parts (weight average molecular weight = 714.73)
Resin: 25 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) ・ ・ ・ 19.6 parts ・ Curing catalyst (1B2PZ, manufactured by Shikoku Chemicals Co., Ltd.) ・ ・ ・ 0.4 parts

(Example 2)
In Example 1, the green colorant-containing thermosetting composition 1 is replaced with a red colorant-containing thermosetting composition 3 having the following composition, and after dry etching, the resist layer using MS-230 is prepared. A color filter was produced in the same manner as in Example 1 except that the remaining resist was removed so as to be polished while performing the planarization treatment of the colored layer by CMP (Chemical Mechanical Polishing) technique instead of peeling.

-Preparation of thermosetting composition 3 containing red colorant-
The following composition was mixed to prepare a colorant-containing thermosetting composition 3.
-Acid Red 8 ... 80 parts (weight average molecular weight = 480.43)
-High molecular weight dye (red dye) according to the present invention 20 parts (Exemplary compound (4) described above; weight average molecular weight 10,000)
Resin: 10 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (Epolide GT401, manufactured by Daicel Corporation) 5 parts ・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) 9.6 parts ・ Curing catalyst (IM-1000, Corporation) Japan Energy) ... 0.3 part ・ Curing catalyst (1B2PZ, Shikoku Kasei Co., Ltd.) ... 0.1 part

(Examples 3 to 4)
In “Preparation of Red Colorant-Containing Thermosetting Composition 3” in Example 2, the weight average molecular weight of the high molecular weight dye (red dye) according to the present invention in the composition is 10,000 to 30,000 (implementation) A color filter was produced in the same manner as in Example 2 except that the colorant-containing thermosetting compositions 4 and 5 were prepared in the same manner as in Example 3) and 50,000 (Example 4).

(Comparative Example 2)
In Example 2, a color filter was produced in the same manner as in Example 2, except that the red colorant-containing thermosetting composition 3 was replaced with the green colorant-containing thermosetting composition 6 having the following composition. did.

-Preparation of red colorant-containing thermosetting composition 6-
The following composition was mixed to prepare a colorant-containing thermosetting composition 6.
-Acid Red 8 ... 80 parts (weight average molecular weight = 480.43)
-Acid Yellow42 ... 20 parts (weight average molecular weight = 714.73)
Resin: 10 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (Epolide GT401, manufactured by Daicel Corporation) 5 parts ・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) 9.6 parts ・ Curing catalyst (IM-1000, Corporation) Japan Energy) ... 0.3 part ・ Curing catalyst (1B2PZ, Shikoku Kasei Co., Ltd.) ... 0.1 part

(Example 5)
In Example 1, the green colorant-containing thermosetting composition 1 was replaced with a yellow colorant-containing thermosetting composition 7 having the following composition, the thermosetting was changed from 215 ° C. to 225 ° C., and dry Example 1 except that after the etching process, instead of removing the resist layer using MS-230, the remaining resist was removed so as to be polished while performing the planarization process of the colored layer by CMP (Chemical Mechanical Polishing) technique. A color filter was produced in the same manner as described above.

-Preparation of thermosetting composition 7 containing yellow colorant-
The following composition was mixed to prepare a colorant-containing thermosetting composition 7.
High molecular weight dye (yellow dye) according to the present invention: 100 parts (Exemplary compound (1) described above; weight average molecular weight 6,000)
Resin: 10 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (Epolide GT401, manufactured by Daicel Corporation) 5 parts ・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) 9.6 parts ・ Curing catalyst (IM-1000, Corporation) Japan Energy) ... 0.3 part ・ Curing catalyst (1B2PZ, Shikoku Kasei Co., Ltd.) ... 0.1 part

(Comparative Example 3)
In Example 5, a color filter was produced in the same manner as in Example 5 except that the red colorant-containing thermosetting composition 7 was replaced with a yellow colorant-containing thermosetting composition 8 having the following composition. did.

-Preparation of thermosetting composition 8 containing yellow colorant-
The following composition was mixed to prepare a colorant-containing thermosetting composition 8.
-Acid Yellow42 ... 100 parts (weight average molecular weight = 714.73)
Resin: 10 parts [Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight 30,000)]
・ Epoxy resin (Epolide GT401, manufactured by Daicel Corporation) 5 parts ・ Epoxy resin (EHPE-3150, manufactured by Daicel Corporation) 9.6 parts ・ Curing catalyst (IM-1000, Corporation) Japan Energy) ... 0.3 part ・ Curing catalyst (1B2PZ, Shikoku Kasei Co., Ltd.) ... 0.1 part

(Evaluation)
-1. Solvent resistance
Each of the colorant-containing thermosetting compositions was applied and heat-treated (at 215 ° C. for 5 minutes) in the same manner as above except that the silicon wafer used in each Example and each Comparative Example was replaced with a glass substrate. The colored layer was dipped in cyclohexanone for 1 minute, taken out, and subjected to spectral comparison of the colored layer before and after immersion with MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and used as an index for evaluating solvent resistance. The degree of curing of the colored layer can be estimated from the solvent resistance, that is, the change in the spectrum. The evaluation results are shown in Table 1 below.

-2. Adhesion
About the obtained color filter, the abrasion resistance by CMP (Chemical Mechanical Polishing) technique was evaluated according to the following evaluation criteria about the adhesiveness with the silicon wafer substrate (specifically undercoat layer) of a green pattern. The evaluation results are shown in Table 1 below.
〔Evaluation criteria〕
○: No peeling was observed.
Δ: Peeling was observed in the range of less than 20%.
X: Peeling was observed in the range of 20% or more.

As shown in Table 1, in the examples, there was no spectral change, excellent spectral characteristics, no color mixing, good adhesion to the substrate (specifically, the undercoat layer), and no pattern peeling due to CMP. . Moreover, the pattern rectangularity of the color filter was also good.
On the other hand, in all of the comparative examples not using a dye having a molecular weight of 5,000 or more, dissolution of the dye in the resist layer was visually confirmed, and the transmittance at 400 to 500 nm after immersion in cyclohexanone was increased (solvent resistance The spectral properties were not maintained, and the curability was insufficient. Moreover, the adhesion to the substrate (specifically, the undercoat layer) was also poor.

Claims (4)

  A thermosetting composition containing a dye having a weight average molecular weight of 5,000 or more.   A color filter comprising the thermosetting composition according to claim 1.   An image recording material having a photosensitive resin layer on the thermosetting composition according to claim 1.   A step of forming a pattern on at least the photosensitive resin layer of an image recording material having a photosensitive resin layer on the thermosetting composition according to claim 1, and dry etching the image recording material on which the pattern is formed And a step of forming a colored pattern on the thermosetting composition by performing a treatment.