TW201416398A - Laminate, color filter comprising the same, method for manufacturing color filter and its application - Google Patents

Abstract

A laminate, a color filter and method for manufacturing the same, and applications of the color filter are provided. A colored layer of the laminate has a high coloring agent concentration. A film surface roughness in a surface of the colored layer is difficult to occur even under high temperature and high humidity conditions. The laminate is formed by forming an oxygen barrier film on a colored layer formed by curing a colored curable composition. The colored curable composition contains a coloring agent, a thermosetting compound and a solvent. Relative to the total solids content of the colored curable composition, the total content of the coloring agent is 50wt% to 90 wt%.

Description

Laminated body and color filter therewith, method of manufacturing the same, and application of color filter

The present invention relates to a laminate, a color filter, a method of producing a color filter, a liquid crystal display device, an organic electroluminescence device, and a solid-state imaging device.

The color filter is an indispensable component in the display of a solid-state imaging element or a liquid crystal display device. In order to form such a color filter, a coloring curable composition has been used (for example, JP-A-2011-248197 and JP-A-2009-251563).

On the other hand, color filters are also required to be thinned.

In order to produce a color resist having excellent spectral characteristics even when a color filter is thinned, it is considered to increase the concentration of the coloring agent in the colored layer. However, as a result of research conducted by the present inventors, it has been found that when the concentration of the coloring agent is increased, when the formed coloring layer is placed under high temperature and high humidity, the film surface roughness of the surface of the colored layer is likely to occur. If the film surface is rough, the element sensitivity and color reproducibility are lowered.

An object of the present invention is to solve the above problems, and an object of the invention is to provide a color filter having a coloring agent having a high concentration of a coloring agent and which is less likely to cause a surface of a colored layer even when placed under high temperature and high humidity. The film surface is rough.

In view of the above, the inventors of the present invention have conducted intensive studies and found that by forming an oxygen blocking film on the colored layer, even if the concentration of the coloring agent is high, the film surface roughness of the surface of the colored layer can be suppressed under high temperature and high humidity. The present invention has been completed.

Specifically, the above problem is solved by the following means <1>, preferably <2> to <13>.

<1> A laminated body in which an oxygen blocking film is formed on a colored layer obtained by curing a colored curable composition, and the colored curable composition contains a coloring agent, a thermosetting compound, and a solvent, and is relatively The total solid content of the coloring curable composition is 50% by mass to 90% by mass based on the total content of the coloring agent.

The layered body according to the above aspect, wherein the coloring agent contains a halogenated indigo dye represented by the following formula (1).

General formula (1)

(In the formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one other of the substituents is a group containing an aromatic group; M represents 2 hydrogens Atom, metal atom, metal oxide or metal halide).

<3> The layered body according to <1>, wherein the thermosetting compound is an epoxy compound.

The layered body according to any one of <1> to <3> wherein the coloring agent further contains a yellow coloring matter.

The layered product according to any one of the above-mentioned items, wherein the total content of the coloring agent is from 6% by mass to 90% by mass based on the total solid content of the colored curable composition.

The layered body according to any one of the above aspects, wherein the colored layer has a thickness of 0.1 μm to 1.0 μm.

The layered body according to any one of <1> to <6> wherein the oxygen blocking film is adjacent to the colored layer.

The laminate according to any one of the above aspects, wherein the oxygen barrier film has a thickness of 10 μm or less.

The laminate according to any one of the above aspects, wherein the oxygen barrier film contains an inorganic material.

<10> A color filter comprising the laminate according to any one of <1> to <9>.

<11> A method for producing a color filter, comprising the steps of: curing a colored curable composition to form a colored layer, wherein the colored curable composition contains a colorant, a thermosetting compound, and a solvent, and is relative to a total solid content of the coloring curable composition, a total content of the coloring agent being 50% by mass to 90% by mass; a step of forming a photoresist layer on the colored layer; and patterning the photoresist layer by exposure and development a step of obtaining a resist pattern; a step of dry etching the colored layer using the resist pattern as an etching mask; and a step of forming an oxygen blocking film on the colored layer after the dry etching.

<12> The method for producing a color filter according to <11>, wherein the oxygen blocking film is formed by sputtering.

<13> A liquid crystal display device, an organic electroluminescence device, or a solid-state imaging device, which has the color filter according to <10> or a color filter as described in <11> or <12> A color filter produced by the manufacturing method.

According to the present invention, it is possible to provide a color filter having a coloring agent having a high concentration of a coloring agent and being difficult to be introduced even under high temperature and high humidity. The film surface of the surface of the colored layer is rough.

10‧‧‧ Solid-state imaging components

11‧‧‧1st colored layer

12‧‧‧1st coloring pattern

13, 100‧‧‧ color filters

14‧‧‧Flat film

15‧‧‧Microlens

20B‧‧‧Blue pixel (3rd color)

20G‧‧‧Green pixels (1st color)

20R‧‧‧Red Picture (2nd color picture)

21‧‧‧Second coloring radiation layer

21A‧‧‧ Location corresponding to the first through hole portion group 121

22‧‧‧2nd coloring pattern

22R‧‧‧ a plurality of second colored pixels provided inside each of the through holes of the second through hole portion group 122

31‧‧‧3rd coloring radiation layer

31A‧‧‧Location corresponding to the second through hole portion group 122

32‧‧‧3rd coloring pattern

41‧‧‧P-well

42‧‧‧Light-receiving components (light diodes)

43‧‧‧ impurity diffusion layer

44‧‧‧Electrode

45‧‧‧Wiring layer

46‧‧‧BPSG membrane

47‧‧‧Insulation film

48‧‧‧P-SiN film

49‧‧‧Flating film layer

51‧‧‧Photoresist layer

51A‧‧‧Resist through hole

52‧‧‧resist pattern (patterned photoresist layer)

60‧‧‧Colored layer

61‧‧‧Oxygen blocking membrane

120‧‧‧through hole group

121‧‧‧1st through hole part group

122‧‧‧2nd through hole part group

FIG. 1 is a schematic cross-sectional view showing a configuration example of a color filter and a solid-state imaging element.

Fig. 2 is a schematic cross-sectional view showing a first colored layer.

3 is a schematic cross-sectional view showing a state in which a photoresist layer is formed on a first colored layer.

4 is a schematic cross-sectional view showing a state in which a resist pattern is formed on the first colored layer.

FIG. 5 is a schematic cross-sectional view showing a state in which a first coloring pattern is formed by providing a through hole group in the first colored layer by etching.

Fig. 6 is a schematic cross-sectional view showing a state in which the resist pattern in Fig. 5 is removed.

FIG. 7 is a schematic cross-sectional view showing a state in which a second colored pattern and a second colored radiation layer are formed.

8 is a schematic cross-sectional view showing a state in which a part of the second coloring radiation layer in FIG. 7 and a second coloring element constituting the second coloring pattern are removed.

FIG. 9 is a schematic cross-sectional view showing a state in which a third colored pattern and a third coloring radiation layer are formed.

FIG. 10 is a schematic cross-sectional view showing a state in which the third coloring radiation layer in FIG. 9 is removed.

Fig. 11 is a schematic cross-sectional view showing an example of a color filter of the present invention.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted formula does not include a substituent, and also includes a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, in the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene oxime. And methacryl oxime.

The term "colored layer" as used in the present invention means a pixel used in a color filter.

The term "dye" as used in the present invention means a dye compound which is soluble in a specific organic solvent. Here, the specific organic solvent is, for example, an organic solvent exemplified in the column of the solvent in which at least the dye and the thermosetting compound are dissolved. Therefore, the dye compound dissolved in the at least one organic solvent corresponds to the dye in the present invention.

Hereinafter, the laminate, the color filter, the method for producing the same, the solid-state imaging device, the liquid crystal display device, and the organic electroluminescence device of the present invention will be described in detail. The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[layered body]

The laminate of the present invention is formed by forming an oxygen barrier film on the colored layer obtained by curing the colored curable composition.

<Coloring hardenable composition>

The colored curable composition used in the present invention contains a coloring agent, a thermosetting compound, and a solvent, and the total content of the coloring agent is 50% by mass to 90% by mass based on the total solid content of the colored curable composition.

<colorant>

The coloring agent is not particularly limited, and for example, a dye containing a dye or a pigment can be used, and an essential dye is particularly preferable. In the present invention, the total amount of the colorant is preferably 60% by mass to 85% by mass, and more preferably 70% by mass to 80% by mass based on the total solid content of the colored curable composition.

(dye)

The dye is not particularly limited, and a dye which has been conventionally used as a color filter can be used. For example, pyrazoloazo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo can be used. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, indigo, benzopyran, indigo Indigo) is a dye such as pyrromethene or methine. In addition, polymers of these dyes can also be used.

Further, in the case of performing water or alkali development, from the viewpoint of completely removing the binder and/or the dye in the unirradiated portion by development, it may be preferable to Use acid dyes and / or their derivatives.

In addition, direct dyes, basic dyes, mordants can also be used usefully. Dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes and/or derivatives of such dyes, and the like.

Further, as the dye, for example, the dye described in the following publication can be used: Japanese specialization Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent No. 2592207, Japanese Patent Laid-Open No. Hei 5-333207, Japanese Patent Laid-Open No. Hei No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115, Japanese Patent Laid-Open No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. This Patent Laid-Open No. 8-302224, Japanese Patent Laid-Open Publication No. 8-73758, Japanese Patent Laid-Open Publication No. 8-179120, Japanese Patent Laid-Open Publication No. 8-151531 and the like.

Among these dyes, an indigo dye having an indigo structure, particularly Halogenated indigo dye. The halogenated indigo dye is a compound having an indigo skeleton and containing one or more halogen atoms as a substituent thereof. In the present invention, it is preferred to have 5 to 15 halogen atoms in one molecule, and more preferably 6 to 14 halogen atoms in one molecule. The halogen atom may, for example, be a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom, a fluorine atom or a bromine atom, more preferably a chlorine atom or a fluorine atom, and further preferably a chlorine atom.

The halogenated indigo dye used in the present invention is usually from 600 nm to 800 A compound having a maximum absorption wavelength in the range of nm, preferably having a maximum absorption wavelength in the range of 630 nm to 750 nm.

The halogenated indigo dye used in the present invention is preferably a compound of the following formula (1) The compound represented.

(In the formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one other of the substituents is a group containing an aromatic group; M represents 2 hydrogens An atom, a metal atom, a metal oxide or a metal halide.)

Here, Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ in the formula (1) represent substituents substituted at 8 positions in the α position of the indigo nucleus, and thus These substituents are also referred to as alpha substituents. Further, similarly, Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ in the formula (1) represent substituents substituted at 8 β positions of the indigo nucleus Therefore, these substituents are also referred to as β-substituents.

Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one other of the substituents is a group containing an aromatic group. It is preferred to have 5 to 15 halogen atoms in one molecule, and more preferably 6 to 14 halogen atoms in one molecule. The halogen atom may, for example, be a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom, a fluorine atom or a bromine atom, more preferably a chlorine atom or a fluorine atom, and further preferably a chlorine atom. The aromatic group in the aromatic group-containing group (preferably the group represented by the following formula (1-2)) is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. The number of the aromatic group-containing groups is preferably from 1 to 11, more preferably from 1 to 10, and more preferably from 2 to 7. Further, Z ¹ to Z ^{16 are} also preferably those in which all of the substituents other than the halogen atom are aromatic group-containing groups.

The substituent is not particularly limited as long as the indigo compound does not lose its function as a dye, and the substituent T described later can be exemplified.

In the formula (1), preferably one to eight of Z ¹ to Z ¹⁶ represent a group represented by the following formula (1-2) or a group represented by the formula (1-4). a group, and at least one of which is a group represented by the formula (1-2), more preferably 2 to 6 of Z ¹ to Z ¹⁶ are a group represented by the formula (1-2) or The group represented by the formula (1-4), and at least one of them is a group represented by the formula (1-2).

General formula (1-2) -XA ¹

(In the formula (1-2), X is an oxygen atom or a sulfur atom, and A ¹ is a phenyl group which may have a substituent or a naphthyl group which may have a substituent.)

(In the formula (1-4), R' represents an alkylene group having 1 to 3 carbon atoms, and R" represents an alkyl group having 1 to 8 carbon atoms. n1 represents an integer of 0 to 4.)

In the formula (1-2), X is an oxygen atom or a sulfur atom, preferably an oxygen atom. When X is an oxygen atom, the maximum absorption wavelength of the obtained indigo compound can be shifted to the short wavelength side.

A ¹ is a phenyl group which may have a substituent or a naphthyl group which may have a substituent, preferably a phenyl group having 1 to 5 substituents or a naphthyl group having 1 to 7 substituents, more preferably having a phenyl group of 1 to 5 substituents.

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

General formula (1-1-2) -X ¹ -A ¹¹

(In the formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ is a phenyl group having 1 to 5 substituents R or a naphthyl group having 1 to 7 substituents R, The substituent R represents a nitro group, COOR ¹ (R ¹ is a group represented by the formula (1-3) or an alkyl group having 1 to 8 carbon atoms), and OR ² (R ² is an alkyl group having 1 to 8 carbon atoms) a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, a group represented by any one of the formulae (4) to (6) or a group selected from the group consisting of the formula (X) group.)

(In the formula (4), R ⁴ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine which may have a substituent A group or an alkylarylamine group which may have a substituent.

In the formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group which may have a substituent or an aryl group which may have a substituent, and when d is 2, R ⁵ An alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent, or a substituted alkylarylamino group .

In the formula (6), R ⁶ and R ⁷ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and may have The alkylsulfonyl group of the substituent, the arylsulfonyl group which may have a substituent. )

-(CH(R ¹¹ )) _n1 -Y ¹ -R ¹² (X)

(In the formula (X), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. n1 represents an integer of 1 to 3. When n1 is 2 or 3, a plurality of R ^{11 's} may be the same or different .Y ¹ represents -O -, - S -, - NR 13 - (R 13 represents a hydrogen atom or an alkyl having 1 to 4), - SO ₂ - or -C (= O) -. R 12 represents A monovalent substituent.)

In the formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, preferably an oxygen atom. When X ¹ is an oxygen atom, the maximum absorption wavelength of the obtained indigo compound can be shifted to the short wavelength side.

A ¹¹ is a phenyl group having 1 to 5 substituents or a naphthyl group having 1 to 7 substituents, more preferably a phenyl group having 1 to 5 substituents.

The number of substituents of the phenyl group is an integer of 1 to 5, and more preferably an integer of 1 to 3 from the viewpoint of the gram extinction coefficient (absorbance per gram), and when the substituent is a halogen atom, the number of substituents is more It is preferably one of the integers from 1 to 5. The number of substituents of the naphthyl group is an integer of 1 to 7, and is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and further preferably 1 or 2, from the viewpoint of the gram absorption coefficient.

The bonding position of the naphthyl group and X ¹ is not particularly limited, and may be any one of the following 1-(1-naphthyl) or 2-(2-naphthyl) groups.

Similarly, the additional substitution is not particularly limited based on the bonding position on the naphthalene ring. For example, in the case where the bonding position of the naphthyl group and X ¹ is 1-position (1-naphthyl group), the substitution position based on the naphthalene ring may be 2, 3, 4, 5, and 6 positions. Any one of the 7-position or the 8-position is preferably 2 or 3, and more preferably 2, in consideration of heat resistance, solvent solubility and the like. Further, in the case where the bonding position of the naphthyl group and X ¹ is a 2-position (2-naphthyl group), the substitution position based on the naphthalene ring may be 1, 3, 4, 5, and 6 positions. Any one of the 7-position or the 8-position is preferably 3 or 6 positions, and more preferably 3 bits in consideration of heat resistance or solvent solubility.

The substituent R of the phenyl or naphthyl group is a nitro group, COOR ¹ (R ¹ is a group represented by the formula (1-3) or an alkyl group having 1 to 8 carbon atoms), and OR ² (R ² is a carbon number) a group of 1 to 8 alkyl groups, a halogen atom, an aryl group, a cyano group, an alkyl group having 1 to 8 carbon atoms, or a group represented by any one of the formulae (4) to (6) or a compound selected from the group consisting of a group in (X).

When a plurality of substituents R are present on a phenyl group or a naphthyl group, a plurality of R groups may be the same or different.

When in the phenyl or naphthyl substituents R ¹ is the case where COOR, COOR ¹ in the group R ¹ represents a substituted alkyl group carbon atoms or the following formula (1-3) 1-8 represented group.

(In the formula (1-3), R ³ represents an alkylene group having 1 to 3 carbon atoms, R ⁴ represents an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 4)

In the case where R ¹ is an alkyl group having 1 to 8 carbon atoms, the alkyl group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of solvent solubility. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. A linear, branched or cyclic alkyl group such as cyclohexyl, n-heptyl, n-octyl or 2-ethylhexyl. The substituent which is present in the alkyl group having 1 to 8 carbon atoms as the case may be an alkoxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group.

The alkoxy group having 1 to 8 carbon atoms which is a substituent of the alkyl group which may be present as the case may be exemplified by a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group or an isobutoxy group. Linear, branched, etc. of a base, a second butoxy group, a third butoxy group, a n-pentyloxy group, a n-hexyloxy group, a cyclohexyloxy group, a n-heptyloxy group, a n-octyloxy group, a 2-ethylhexyloxy group Or a cyclic alkoxy group. Among these groups, an alkoxy group having 1 to 4 carbon atoms is preferred. The halogen atom which is a substituent of the alkyl group which may be present as the case may be a fluorine atom or a chlorine atom. Bromine atom and iodine atom. Among these halogen atoms, a fluorine atom or a chlorine atom is preferred. Examples of the aryl group which is a substituent of the alkyl group which may be present may be phenyl, p-methoxyphenyl, p-tert-butylphenyl or p-chlorophenyl. Among these groups, a phenyl group is preferred. There may be a plurality of such substituents. When there are a plurality of substituents, they may be of the same type or different types, and may be the same or different when they are of the same kind. The number of the substituents of the alkyl group is not particularly limited, but is preferably one to three, and more preferably one or two.

When the substituent R of the phenyl group or the naphthyl group is COOR ¹ and R ¹ is a group represented by the formula (1-3), the formula (for the effect of solubility in the ether solvent) 1-3) R ³ in the group represented by the group is an alkylene group having 1 to 3 carbon atoms.

Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethyl group, an extended propyl group, and an extended isopropyl group. It is preferably an ethyl group and a propyl group.

Further, from the viewpoint of molecular weight, R ⁴ in the group represented by the formula (1-3) is an alkyl group of 1 to 8, more preferably an alkyl group of 1 to 4. The alkyl group having 1 to 8 carbon atoms is exemplified in the column of R ¹ described above. From the viewpoint of molecular weight, n in the group represented by the formula (1-3) is an integer of 1 to 4, preferably an integer of 1 to 3.

On the substituent R is a phenyl or naphthyl group OR ² in the case where, in the R ² OR ² represents an alkyl group having 1 to 8 carbon atoms, the dye in terms of crystallinity, good workability, is preferably It represents an alkyl group having 1 to 3 carbon atoms.

The alkyl group having 1 to 8 carbon atoms represented by R ² may be the same as those described for R ¹ of COOR ¹ as an example of the substituent R, and the preferred range is also the same.

When the substituent R of the phenyl or naphthyl group is a halogen atom, the halogen is The fluorine atom, the chlorine atom, the bromine atom and the iodine atom may be mentioned, and a fluorine atom, a chlorine atom or an iodine atom is preferable. Among them, a chlorine atom or a fluorine atom is preferred because the molecular weight of the dye is small and the gram absorption coefficient is high.

In the case where the substituent R of the phenyl group or the naphthyl group is an aryl group, the aryl group may, for example, be an aryl group such as a phenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group or a p-chlorophenyl group. Among them, a phenyl group is preferred because the molecular weight of the dye becomes small and the gram absorption coefficient becomes high.

When the substituent R of the phenyl group or the naphthyl group is an alkyl group, the alkyl group having 1 to 8 carbon atoms may be the same as those described for R ¹ of COOR ^{1 which} is an example of the substituent R. The range is also the same.

The alkyl group having 1 to 3 carbon atoms is preferred in terms of crystallinity and workability of the dye.

The substituent of the alkyl group which may be present as the case may be a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and more preferably a fluorine atom or a chlorine atom. A plurality of halogen atoms may be present as a substituent of the alkyl group, and may be the same or different when there are a plurality of halogen atoms. The number of the substituents of the alkyl group is not particularly limited, but is preferably one to three.

The case where the substituent R of the phenyl group or the naphthyl group is a group selected from the following general formulae (4) to (6) will be described.

R ⁴ in the formula (4) represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, and a diarylamine group which may have a substituent Or an alkylarylamino group which may have a substituent, preferably a hydrogen atom, an alkyl group having a total carbon number of 1 to 20, an aryl group having a total carbon number of 6 to 20, and a dialkylamine having a total carbon number of 2 to 20. a diarylamine group having a total carbon number of 12 to 20 or an alkylarylamine group having a total carbon number of 7 to 20, and further preferably an alkyl group having a total carbon number of 1 to 20 and a total carbon number of 2 to 20 An alkylamino group, a diarylamine group having a total carbon number of 12 to 20 or an alkylarylamine group having a total carbon number of 7 to 20, particularly preferably a diarylamine group or a total carbon having a total carbon number of 12 to 20 A number of 2 to 20 dialkylamino groups.

The above alkyl moiety and aryl moiety may also have a more substituent, and the substituent is more It is preferably an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, etc., more preferably an alkoxy group, and further preferably a methoxy group or an ethoxy group. Further, a form having no substituent is also preferable.

In the formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group which may have a substituent or an aryl group which may have a substituent, and when d is 2, R ⁵ An alkyl group which may have a substituent, an aryl group which may have a substituent, a dialkylamino group which may have a substituent, a diarylamine group which may have a substituent or an alkylarylamine group which may have a substituent . When d is 2, R ^{5 is} preferably a dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms.

The above alkyl moiety and aryl moiety may further have a substituent, and the substituent The substituent T to be described later may, for example, be an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, more preferably an alkoxy group, and more preferably a methoxy group. Base or ethoxy group. Further, a form having no substituent is also preferable.

In the formula (6), R ⁶ and R ⁷ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, and may have The alkylsulfonyl group of the substituent, the arylsulfonyl group which may have a substituent, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkylcarbonyl group having 2 to 20 carbon atoms , an arylcarbonyl group having 7 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, more preferably an alkylcarbonyl group having 2 to 20 carbon atoms, and a carbon number 7 to 20 arylcarbonyl groups, 1 to 20 carbon alkylsulfonyl groups, and 6 to 20 carbon arylsulfonyl groups.

The above alkyl moiety and aryl moiety may further have a substituent, and the substituent The substituent T to be described later may, for example, be an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, more preferably an alkoxy group, and more preferably a methoxy group. Base or ethoxy group. Further, a form having no substituent is also preferable. Examples of the alkyl group or the like which may have a substituent will be described later.

Preferred examples of the alkyl group which may have a substituent in the above formula are shown. Can have The alkyl group having a substituent may, for example, be methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, ten Hexaalkyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl, phenoxyethyl, benzyl, phenylethyl, N-butylaminosulfonyl Propyl, N-butylaminocarbonylmethyl, N,N-dibutylaminosulfonylpropyl, ethoxyethoxyethyl, 2-chloroethyl, and further preferably: methyl , ethyl, propyl, isopropyl, tert-butyl, phenoxyethyl, benzyl, phenylethyl, N-butylaminosulfonylpropyl, N-butylaminocarbonyl Base, N, N-dibutylaminosulfonylpropyl, ethoxyethoxyethyl, particularly preferably: methyl, ethyl, propyl, tert-butyl, phenoxyethyl , benzyl, phenylethyl, N-butylaminosulfonylpropyl, N-butylaminocarbonylmethyl, N,N-dibutyl Aminosulfonylpropyl, ethoxyethoxyethyl.

The aromatic group which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a base. Examples of such an aryl group include a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 4-butoxycarbonylphenyl group, a 4-N,N-dibutylaminocarbonylphenyl group, and 4- N-butylaminosulfonylphenyl, 4-N,N-dibutylaminosulfonylphenyl, further preferably phenyl, 4-butoxycarbonylphenyl, 4-N, N-dibutylaminocarbonylphenyl, 4-N-butylaminosulfonylphenyl, 4-N,N-dibutylaminosulfonylphenyl, particularly preferably phenyl, 4-butoxycarbonylphenyl, 4-N,N-dibutylaminocarbonylphenyl, 4-N,N-dibutylaminosulfonylphenyl.

Two of the above formula (4) to formula (6) which may have a substituent are shown. A preferred example of an alkylamino group. Such a dialkylamine group may, for example, be N,N-dimethylamino, N,N-dibutylamino, N,N-bis(2-ethylhexyl)amine, N-methyl- N-benzylamino, N,N-bis(2-ethoxyethyl)amino, N,N-bis(2-hydroxyethyl)amino.

Two of the above formula (4) to formula (6) which may have a substituent are shown. A preferred example of an arylamine group. Examples of such a diarylamine group include N,N-diphenylamino group, N,N-bis(4-methoxyphenyl)amino group, and N,N-bis(4-nonylphenyl) group. Amine.

An alkane which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a arylamino group. Examples of such alkylarylamine groups include N-methyl-N-phenylamino group, N-benzyl-N-phenylamino group, and N-methyl-N-(4-methoxyphenyl group). Amino group.

An alkane which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a carbonyl group. Examples of such an alkylcarbonyl group include an ethyl fluorenyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group, and a 2-ethyl group. Oxycarbonylmethylcarbonyl.

The aromatic group which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a carbonyl group. Examples of such an arylcarbonyl group include a benzamidine group, a 4-methoxybenzylidene group, and a 4-ethoxycarbonylbenzylidene group.

An alkane which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a sulfonyl group. Examples of such an alkylsulfonyl group include a methylsulfonyl group, an octylsulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a phenoxypropylsulfonyl group.

The aromatic group which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of a sulfonyl group. Examples of such an arylsulfonyl group include a phenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group.

An alkane which may have a substituent in the above formula (4) to formula (6) is shown A preferred example of the sulfoximine group. Examples of such alkylsulfonylamino groups include methylsulfonylamino, butylsulfonylamino, hydroxypropylsulfonylamino, 2-ethylhexylsulfonylamino, n-octylsulfonylamino , phenoxyethylsulfonylamino, allylsulfonylamino.

a vinyl group having a substituent in the above formula (4) to formula (6) The sulfonamide group may, for example, be a vinylsulfonylamino group or a 1-methylvinylsulfonylamino group.

Arylsulfone which may have a substituent in the above formula (4) to formula (6) The guanamine group may, for example, be a phenylsulfonylamino group, a p-methoxyphenylsulfonylamino group or a p-ethoxycarbonylsulfonylamino group.

Alkylcarbonyl which may have a substituent in the above formula (4) to formula (6) Examples of the amino group include a methylcarbonylamino group, a 2-ethylhexylamino group, a n-heptylcarbonylamino group, an ethoxyethoxymethylcarbonylamino group and the like.

An arylcarbonyl group which may have a substituent in the above formula (4) to formula (6) The base group may, for example, be a benzylamino group, a 2-methoxybenzamide group or a 4-vinylbenzamide group.

An example of the substituent T is shown below.

An alkyl group (preferably a linear, branched or cyclic carbon number of 1 to 24) Alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecane Base, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl (preferably an alkenyl group having 2 to 18 carbon atoms, such as vinyl, allyl, 3 -buten-1-yl), aryl (preferably an aryl group having 6 to 24 carbon atoms, such as phenyl or naphthyl), or a heterocyclic group (preferably a heterocyclic group having 1 to 18 carbon atoms, for example 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazole-1- a decyl group (preferably a decyl group having a carbon number of 3 to 18, such as a trimethyl decyl group, a triethyl decyl group, a tributyl decyl group, a tert-butyl dimethyl decyl group, a third hexyl group) Dimethyl decyl), hydroxy, cyano, nitro, alkoxy (preferably alkoxy having 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butyl) An oxy group, an isopropoxy group, a tert-butoxy group, a dodecyloxy group, and, if it is a cycloalkyloxy group, for example, a cyclopentyloxy group or a cyclohexyloxy group. An aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or a 1-naphthyloxy group) or a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 18 carbon atoms). For example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), decyloxy (preferably a decyloxy group having 1 to 18 carbon atoms, such as trimethyldecyloxy, third Butyl dimethyl decyloxy, diphenylmethyl decyloxy), decyloxy (preferably a decyloxy group having 2 to 24 carbon atoms, For example, ethoxylated, pivaloyloxy, benzhydryloxy, dodecyloxycarbonyl, alkoxycarbonyloxy (preferably alkoxy having 2 to 24 carbon atoms) a carbonyloxy group such as an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and, if it is a cycloalkoxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group a base (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group) or an amine methyloxy group (this is preferably an aminomethyloxy group having 1 to 24 carbon atoms, for example, N,N-dimethylamine methyl methoxy, N-butylamine methyl methoxy, N-phenylamine methyl methoxy, N-ethyl-N-phenylamine methyl methoxy, amine a sulfonyloxy group (preferably an aminesulfonyloxy group having 1 to 24 carbon atoms, such as N,N-diethylaminesulfonyloxy, N-propylaminesulfonyloxy), alkylsulfonyloxy a base (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy) or an arylsulfonyloxy group ( Preferred is an arylsulfonyloxy group having 6 to 24 carbon atoms, for example, a phenylsulfonyloxy group, a fluorenyl group (preferably a fluorenyl group having 1 to 24 carbon atoms, such as a methyl group, an ethyl group, and a third group). Methyl acetamidine (pivaloyl), benzamyl, tetradecylfluorenyl, cyclohexyl), alkoxycarbonyl (preferably alkoxycarbonyl having 2 to 24 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl) , octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably having a carbon number of 7 to 24) An aryloxycarbonyl group, such as a phenoxycarbonyl group, an amine methyl sulfonyl group (preferably an amine carbenyl group having 1 to 24 carbon atoms, such as an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, N -ethyl-N-octylaminecarbamyl, N,N-dibutylaminecarbamyl, N-propylaminecarbamyl, N-phenylaminecarbamyl, N-methyl N-benzene An amine group, an N,N-dicyclohexylamine carbhydryl group, an amine group (preferably an amine group having a carbon number of 24 or less, such as an amine group, a methylamino group, an N,N-dibutylamine) Base, tetradecylamino group, 2-ethylhexylamino group, cyclohexyl Amino), anilino (preferably an anionic group of 6 to 24, such as an anilino group, an N-methylanilino group), a heterocyclic amino group (preferably a heterocyclic amino group of 1 to 18, such as 4-pyridine) Amino), carboguanamine group (preferably 2 to 24 carbonium amine groups, such as acetaminophen, benzhydrylamine, tetradecylguanidino, trimethylethylamine, cyclohexane) Amidino), ureido (preferably a ureido group having a carbon number of 1 to 24, such as a ureido group, an N,N-dimethylureido group, an N-phenylureido group), a quinone imine group (preferably A quinone imine group having a carbon number of 24 or less, such as N-succinimide group, N-phthalimido group, or an alkoxycarbonylamino group (preferably an alkoxy group having 2 to 24 carbon atoms) Carbonylamino group, such as methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group, aryloxycarbonyl group An amine group (preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, such as a phenoxycarbonylamino group) or a sulfonylamino group (preferably a sulfonylamino group having 1 to 24 carbon atoms, such as methylsulfonate) Amidino, sulfonamide, benzenesulfonylamino, hexadecanesulfonylamino, cyclohexylsulfonylamino), aminesulfonylamine (preferably a sulfonamide group of 1 to 24, for example, N,N-dipropylamine sulfonamide, N-ethyl-N-dodecylamamine sulfonamide, azo (preferably An azo group having 1 to 24 carbon atoms, for example, a phenylazo group, a 3-pyrazolylazo group, an alkylthio group (preferably an alkylthio group having 1 to 24 carbon atoms, such as methylthio group, B) Sulfur, octylthio, cyclohexylthio), arylthio (preferably arylthio having 6 to 24 carbon atoms, such as phenylthio), heterocyclic thio (preferably having a carbon number of 1 to 18) a heterocyclic thio group such as a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazoliumthio group, an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 24 carbon atoms) An anthracenyl group such as dodecylsulfinyl), an arylsulfinyl group (preferably an arylsulfinyl group having a carbon number of 6 to 24, such as a phenylsulfinyl group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as methylsulfonyl, Ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexyl Sulfosyl), arylsulfonyl (preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), an aminesulfonyl group (preferably Aminesulfonyl group having a carbon number of 24 or less, such as aminsulfonyl, N,N-dipropylaminesulfonyl, N-ethyl-N-dodecylaminesulfonyl, N-ethyl-N -Phenylamine sulfonyl, N-cyclohexylamine sulfonyl), sulfo, phosphinyl (preferably a fluorenyl group having 1 to 24 carbon atoms, such as phenoxyphosphonium sulfhydryl, octyloxyphosphine) Sulfhydryl, phenylphosphonium fluorenyl), phosphinoyl amine group (preferably a phosphonium amino group having 1 to 24 carbon atoms, such as diethoxyphosphonium amino group, dioctyloxyphosphonium amine group) ).

In the case where the above substituent is a group which may be substituted, the above may also be Any of the groups is further substituted. Further, in the case of having two or more substituents, the substituents may be the same or different.

The substituent R to a phenyl or naphthyl group is a group represented by the formula (X) The situation is explained.

R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.

N1 represents an integer of 1 to 3, more preferably 1 or 2. In the case where n1 is 2 or 3, a plurality of R ^{11 's} may be the same or different.

Y ¹ represents -O-, -S-, -NR ¹³ -, -SO ₂ - or -C(=O)-, preferably -O-, -SO ₂ - or -C(=O)-, more Good is -O- or -C(=O)-.

R ¹² represents a monovalent substituent, and the substituents may be exemplified by the above-mentioned substituents T, and these substituents T may be further substituted with a substituent T. R ^{12 is} preferably an alkyl group which may have a substituent, a mercapto group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent or an alkylamine group which may have a substituent, and It is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and an alkylamine group having 1 to 12 carbon atoms which may have a substituent.

The mass of the portion of R ¹² per molecule is preferably from 200 to 2,500, more preferably from 250 to 1,500.

R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively.

In the case where the above monovalent group is a group which may be further substituted, It is further substituted by any of the above groups. Further, in the case of having two or more substituents, the substituents may be the same or different.

Next, the general formula (1-4) will be described.

In the formula (1-4), the effect on the solubility of ether and the molecular weight In the surface, R' is an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethyl group, an extended propyl group, and an extended isopropyl group. It is preferably an ethyl group and a propyl group.

In terms of the effect on the solubility of ether and the molecular weight, R" is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 2, an alkyl group having 1 to 8 and a formula (1-3). R ³ in the same meaning is the same, and the preferred range is also the same.

From the viewpoint of the effect of ether solubility and molecular weight, n1 is 0 to 4 An integer, preferably an integer from 1 to 2.

Then, M which is a central portion of the general formula (1) will be described. to In the formula (1), M represents two hydrogen atoms, a metal atom, a metal oxide or a metal halide. In addition, the metal atom may be iron, magnesium, nickel, cobalt, copper, palladium, zinc, Vanadium, titanium, indium, tin, etc. Examples of the metal oxide include titanium oxide, vanadium oxide, and the like. Examples of the metal halide include aluminum chloride, indium chloride, barium chloride, tin (II) chloride, tin (IV) chloride, and barium chloride. Preferably, it is a metal atom, a metal oxide or a metal halide, specifically copper, zinc, cobalt, nickel, iron, vanadium oxide, titanium oxide, indium chloride, tin (II) chloride, more preferably copper, Vanadium oxide and zinc, and preferably zinc or copper, preferably zinc. If the center metal is zinc or copper, heat resistance is high, which is preferable. Further, when the center metal is zinc, the transmittance in the vicinity of 520 nm to 545 nm which is a green wavelength is higher than that in the case of copper, and the brightness can be improved when the color filter is formed, which is particularly preferable. Further, it is particularly preferable because the solvent is highly soluble in a general-purpose solvent such as acetone, methanol or methyl cellosolve, and the solubility in the resin is high and the contrast is high.

The compound represented by the formula (1) is more preferably represented by the following formula (1-1) Said.

(In the general formula (1-1), Z ¹ to Z ¹⁶ each represent a hydrogen atom, a halogen atom, a group represented by the above formula (1-1-2), and a group represented by the above formula (1-3)) In the group represented by the above formula (1-4), one to eight of Z ¹ to Z ¹⁶ represent a group represented by the above formula (1-1-2) or the above formula ( 1-4) at least one of the groups represented by a halogen atom, and at least one of the groups represented by the above formula (1-1-2). M represents 2 hydrogen atoms, metal atoms, metal oxides or Metal halide) Formula (1-1-2), Formula (1-3), Formula (1-4) in the formula (1-1) and the formula described in the above formula (1) (1-1-2), the general formula (1-3), and the general formula (1-4) have the same meanings, and the preferred ranges are also the same. Therefore, Z ¹ to Z ¹⁶ in the general formula (1-1) are preferably in the same range as Z ¹ to Z ¹⁶ of the general formula (1).

M of the formula (1-1) has the same meaning as M in the above formula (1), and the preferred range is also the same.

Examples of Z ¹ to Z ¹⁶ in the general formula (1) and the general formula (1-1) used in the present invention are listed below, but the present invention is not limited to these examples.

The examples of the indigo compounds used in the present invention are listed below, but the present invention is of course not limited to the examples.

The substituents shown in the following formula and the number thereof are shown in the following tables.

Ar in the following table represents the following structure.

In the above formula, Ph is a phenyl group.

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(2,6-Cl ₂ )C ₆ H ₃ S} _y ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _2.88-x {β-(2,6-Cl ₂ )C ₆ H ₃ S} _0.72-y ,H _1.6 Cl _10.8 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x ,(β- NO ₂ ) _0.2 H _0.6 Cl _11.4 ]

. [Zn(C ₃₂ N _8.2 )-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _{3.8 -x} H _0.6 Cl _11.4 ]

. [Zn(C _32.8 N ₈ )-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _{3.8 -x} H _1.2 Cl _11.4 ]

. [Zn(C _32.8 N ₈ )-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _{3.8 -x} H _0.8 Cl _11.4 Br _0.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x ,(β- NH ₂ ) _0.2 H _0.6 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x ,(β- OH) _0.2 H _0.6 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x ,(β- C(CH ₃ ) ₃ ) _0.2 H _0.6 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x H _0.4 Cl _11.8 ]

. [Zn(C ₃₂ N _8.08 )-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _{3.96 -x} H _0.08 Cl _11.88 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x H _0.8 F _11.4 ]

. [ZnPc-α-{(CH ₃ CH(OCH ₃ )C ₂ H ₄ OOC)C ₂ H ₄ S} _0.2 , {α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{ Β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x H _0.6 Cl _11.4 ]

. [ZnPc-{α-(4-SO ₃ C ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-SO ₃ C ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.8-x H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOCH ₃ )C ₆ H ₄ O} _5.7-x H _0.8 Cl _9.5 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _2.28-x H _0.8 Cl _12.92 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _1.14-x H _0.8 Cl _14.06 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₃ O} _y , {β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _2.72-x , {β-(2-OCH ₃ -4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₃ O} _0.68-y H _2.4 Cl _10.2 ]

. [ZnPc-{α-(2-COOC ₂ H ₄ OCH ₃ )C ₁₀ H ₈ -6-O} _x ,{β-(2-COOC ₂ H ₄ OCH ₃ )C ₁₀ H ₈ -6-O} _{3.8 -x} H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(4-CN)C ₆ H ₄ O} _0.96 ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.04-x H _2.88 Cl _9.12 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(2-C ₆ H ₅ )C ₆ H ₄ O} _y ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.42-x , {β-(2-C ₆ H ₅ )C ₆ H ₄ O} _0.38-y H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(2-COOCH ₃ )C ₆ H ₄ S} _y ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.04-x ,{β-(2-COOCH ₃ )C ₆ H ₄ S} _0.76-y H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(4-OCH ₃ )C ₆ H ₄ O} _y , { β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.42-x ,{β-(4-OCH ₃ )C ₆ H ₄ O} _0.38-y H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(2-C(CH ₃ ) ₃ )C ₆ H ₄ O} _y ,{β-(4 -COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _3.42-x , {β-(2-C(CH ₃ ) ₃ )C ₆ H ₄ O} _0.38-y H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-(3-COOC ₂ H ₅ )C ₆ H ₄ O} _y ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _2.66-x , {β-(3-COOC ₂ H ₅ )C ₆ H ₄ O} _1.14-y H _0.8 Cl _11.4 ]

. [ZnPc-{α-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _x ,{α-C ₆ H ₅ O} _y ,{β-(4-COOC ₂ H ₄ OCH ₃ )C ₆ H ₄ O} _1.9-x {β-C ₆ H ₅ O} _0.76-y H _0.8 Br _1.22 Cl _11.32 ]

In the above, Pc represents an indigo nucleus, Zn represents a central metal, and immediately after Pc represents a substituent substituted at the α position, and after substitution with the substituent at the α position, represents a substituent substituted at the β position, Substitution of the substituent at the β position means a substituent which is not dependent on the substitution position. x and y are positive numbers in which the number of substituents is 0 or more.

Since the indigo compound is a mixture having different substitution positions or substitution numbers, it is difficult to describe it uniquely as a structural formula. Further, the number of substitutions shown in the following table is an approximation of the average value of the number of substituents in the mixture, and a few can be obtained.

Method for producing halogenated indigo compound

The method for producing the indigo compound used in the present invention is not particularly limited. Previously known methods can be utilized. A method of cyclizing a phthalonitrile compound and a metal salt in a molten state or an organic solvent is preferred. Hereinafter, a preferred embodiment of the method for producing a indigo compound will be described. However, the invention is not limited to the preferred embodiments described below.

That is, the indigo compound can be produced by the following formula (I) The phthalonitrile compound (1), the phthalonitrile compound (2) represented by the following formula (II), and the phthalonitrile compound represented by the following formula (III) (3) And the phthalonitrile compound (4) represented by the following formula (IV), which is selected from the group consisting of a metal atom, a metal oxide, a metal carbonyl group, a metal halide, and an organic acid metal (also referred to in the present specification) One of the groups consisting of "metal compounds" is subjected to a cyclization reaction.

Further, in the above formulae (I) to (IV), Z ¹ to Z ¹⁶ are defined according to the structure of the desired indigo compound (1). Specifically, in the above formulas (I) to (IV), Z ¹ to Z ¹⁶ are the same as the definitions of Z ¹ to Z ¹⁶ in the above formula (1), and thus the description thereof is omitted.

The cyclization reaction can be carried out by a conventionally known method such as the method described in JP-A-64-45474.

In the above aspect, the cyclization reaction is preferably carried out by combining the phthalonitrile compound of the formula (I) to the formula (IV) with a metal selected from the group consisting of metals, metal oxides, metal carbonyls, metal halides and organic acid metals. One of the groups is reacted in a molten state or in an organic solvent. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal which can be used at this time are as long as the indigo compound obtained after the reaction can be obtained. The central portion (M of the general formula (1)) is not particularly limited. Therefore, a metal such as iron, copper, zinc, vanadium, titanium, indium or tin listed in the item of M in the above formula (1), a metal halide such as a chloride, a bromide or an iodide of the metal, may be mentioned. A metal oxide such as vanadium oxide, titanium oxide or copper oxide; an organic acid metal such as an acetate; a complex compound such as acetylpyruvate; and a metal carbonyl such as carbonyl iron. Specific examples thereof include metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halides such as chlorides, bromides, and iodides of the metal, such as vanadium chloride, titanium chloride, and copper chloride; , zinc chloride, cobalt chloride, nickel chloride, ferric chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, barium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide , indium iodide, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium pentoxide, vanadium trioxide, vanadium oxychloride, vanadium pentoxide, titanium dioxide , iron oxide, ferric oxide, ferroferric oxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt trioxide, cobalt dioxide, cuprous oxide, copper oxide, copper oxide, palladium oxide, Metal oxides such as zinc oxide, cerium oxide and cerium oxide; organic acid metals such as copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate; and complex compounds such as acetylpyruvate and cobalt carbonyl a metal carbonyl group such as an iron carbonyl group or a nickel carbonyl group. Preferably, the metal, the metal oxide and the metal halide are more preferably a metal halide, and more preferably vanadium iodide, copper iodide and zinc iodide, and particularly preferably copper iodide and zinc iodide. The best is zinc iodide. In the case of using zinc iodide, the central metal becomes zinc. Among the metal halides, the iodide is preferably used because it has excellent solubility in a solvent or a resin, and the spectrum of the obtained indigo compound is narrow and can be easily controlled within a range of 640 nm to 750 nm which is a desired wavelength. The use of iodide in the cyclization reaction Although the detailed mechanism of the narrowing of the spectrum at the time of shape is not clear, it is presumed that in the case of using iodide, the iodine remaining in the indigo compound after the reaction has some interaction with the indigo compound, and iodine exists between the layers of the indigo compound. . However, it is not limited to the above mechanism. In order to obtain the same effect as in the case of using a metal iodide in the cyclization reaction, the obtained indigo compound can also be treated with iodine.

Further, in the above aspect, the cyclization reaction may be carried out in the absence of a solvent, but it is preferably carried out using an organic solvent. The organic solvent may be any solvent as long as it has low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit reactivity, and examples thereof include benzene, toluene, and Inactive solvents such as toluene, nitrobenzene, monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; methanol, ethanol, 1- An alcohol such as propanol, 2-propanol, 1-butanol, 1-hexanol, 1-pentanol or 1-octanol; and pyridine, N,N-dimethylformamide, N,N-dimethyl Aprotic polar solvents such as acetamide, N-methyl-2-pyrrolidone, N,N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl hydrazine, and cyclobutyl hydrazine .

Among these solvents, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and 1-octyl alcohol, dichlorobenzene and benzonitrile are more preferably used. These solvents may be used alone or in combination of two or more.

The reaction conditions of the phthalonitrile compound of the formula (I) to the formula (IV) and the metal compound in the above-described aspect are not particularly limited as long as the reaction conditions are carried out, for example, 100 parts by mass based on the organic solvent. The phthalonitrile compound of the above formula (I) to formula (IV) is added in a total amount ranging from 1 part by mass to 500 parts by mass, preferably 10 parts by mass to 350 parts by mass, with respect to the adjacent Phthaquinonitrile compound The metal compound is added in a range of from 4 moles, preferably from 0.8 moles to 2.0 moles, more preferably from 0.8 moles to 1.5 moles. The cyclization is not particularly limited, and it is preferred to carry out the reaction at a reaction temperature of from 30 ° C to 250 ° C, more preferably from 80 ° C to 200 ° C. The reaction time is not particularly limited, but is preferably from 3 hours to 20 hours. Further, after the reaction, filtration, washing, and drying can be carried out in accordance with a conventionally known method for synthesizing a phthalocyanine compound, whereby the phthalocyanine compound usable in the subsequent step can be obtained efficiently and in high purity.

In the above aspect, the phthalonitrile compound of the formula (I) to the formula (IV) as a starting material can be synthesized by a previously known method, and a commercially available product can also be used.

The amount of the dye to be used in the composition used in the present invention is preferably from 1% by mass to 100% by mass, and more preferably from 50% by mass to 100% by mass, based on the coloring agent contained in the composition used in the present invention. More preferably, it is 80% by mass to 100% by mass.

Further, in the coloring agent contained in the composition used in the present invention, the blending amount of the indigo dye (preferably the halogenated indigo dye) is preferably from 55% by mass to 80% by mass, more preferably from 60% by mass to 75% by weight. quality%.

(pigment)

The pigment used in the colorant may be exemplified by various inorganic pigments or organic pigments previously known. Further, the inorganic pigment may be an organic pigment, and in view of preferably having a high transmittance, it is preferred to use a pigment having an average particle diameter as small as possible. The average particle diameter of the pigment is preferably from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm, in view of operability.

The pigment which can be preferably used in the present invention is, for example, the one described in paragraph number 0026 of JP-A-2012-181512, the contents of which are incorporated herein by reference.

Further, examples of the pigment which can be preferably used in the present invention include the following. However, the invention is not limited to the pigments.

Color Index (CI) Pigment Yellow 1, CI Pigment Yellow 2, CI Pigment Yellow 3, CI Pigment Yellow 4, CI Pigment Yellow 5, CI Pigment Yellow 6, CI Pigment Yellow 10, CI Pigment Yellow 11 , CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31 , CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35:1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Yan Huang 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214 Some organic pigments may be used singly or in combination for the purpose of improving color purity.

Regarding the amount of the above pigment in the composition used in the present invention, When it is contained in the colored curable composition, it can be set to 1% by mass to 100% by mass of the colorant. By reducing the amount of the pigment to be blended, the amount of the coloring agent in the coloring curable composition can be further increased, and the effect of the present invention tends to be more effectively exhibited.

(pigment dispersion)

In the case of adjusting the composition constituting the laminate of the present invention, a pigment is used. At the same time, a pigment dispersion can also be produced. From the viewpoint of improving the dispersibility of the pigment, a pigment dispersant may be further added.

The pigment dispersing agent which can be used in the present invention is exemplified by a polymer dispersing agent [Example Such as polyamine-amine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (A (Acrylic copolymer), naphthalenesulfonic acid formalin condensate] and polyoxyalkylene ethyl alkyl phosphate, polyoxyethylene ethylamine, alkanolamine, pigment derivative and the like.

The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure thereof.

The polymer dispersant functions to adsorb on the surface of the pigment to prevent re-agglomeration. Therefore, a terminal modified polymer having a anchor portion to the surface of the pigment, a graft polymer, and a block polymer are preferable. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the surface of the pigment.

The pigment dispersant which can be used in the present invention can also be obtained as a commercially available product, and the specific example can also be described in paragraph number 0050 of JP-A-2012-173635, or Japanese Patent Laid-Open No. 2012-93396 The contents of the paragraph number 0206 of the Gazette are incorporated in the present specification. Further, the dispersing agent described in Paragraph No. 0028 to Paragraph No. 0124 of JP-A-2011-070156 or the dispersing agent described in JP-A-2007-277514 can be preferably used. Incorporated into this specification.

These pigment dispersants may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a pigment derivative in combination with a polymer dispersant.

The content of the pigment dispersant in the composition of the present invention is preferably from 1 part by mass to 80 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the pigment as a colorant. The amount is ~70 parts by mass.

Specifically, in the case of using a polymer dispersant, it is relative to the face. The amount of use of the material is preferably in the range of 5 parts by mass to 100 parts by mass in terms of mass.

In addition, in the case of using a pigment derivative in combination, it is qualitative with respect to the pigment 100. The amount of the pigment derivative to be used is preferably in the range of 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass in terms of mass.

(pigment derivative)

In the case of containing a pigment as a coloring agent, in order to improve the dispersion resin pair The adsorptivity of the pigment preferably further contains a pigment derivative. The term "pigment derivative" means a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimine methyl group. From the viewpoint of dispersibility and dispersion stability, the pigment derivative preferably contains a pigment derivative having an acidic group or a basic group.

For the pigment derivative, for example, Japanese Patent Laid-Open No. 2011-137125 can be used. The contents of the paragraph number 0100 to paragraph number 0119 of the report are incorporated in the present specification.

Pigment derivatives in the composition of the present invention relative to the total mass of the pigment The content is preferably from 1% by mass to 90% by mass, and more preferably from 3% by mass to 80% by mass. The pigment derivative may be used alone or in combination of two or more.

(solvent)

The solvent in the pigment dispersion is not particularly limited as long as it is an organic solvent used in a usual pigment dispersible composition. For example, 1-methoxy-2-propene can be cited. Acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone , such as methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, etc., in order to adjust the melting point or viscosity The dispersibility of the pigment may be used in combination with a plurality of these solvents.

The content of the solvent in the pigment dispersion is appropriately selected depending on the use of the pigment dispersion or the like.

When the pigment dispersion is used for the preparation of a colored curable composition described later, it can contain, in terms of workability, pigment and pigment dispersion with respect to the total mass of the pigment dispersion other than the solvent. The total amount of the agents is 5% by mass to 50% by mass.

(yellow pigment)

As an example of the embodiment of the present invention, a yellow dye can be used by blending a phthalocyanine dye.

The yellow pigment may be a dye or a pigment, or may be a mixture of a dye and a pigment, and is preferably a dye from the viewpoint of obtaining a composition in a uniformly dissolved state without using a dispersant. For example, an azo-based (for example, C.I. solvent yellow 162), a methine-based (C.I. solvent yellow 93) dye, or the like is preferable.

The methine dye is preferably a monomethine dye, more preferably a monomethine dye represented by the following formula (5). When the halogenated indigo dye is combined with the methine dye, the effect of the present invention tends to be more effectively exhibited.

(In the formula (5), R ¹¹ represents an alkyl group or a vinyl group, respectively, and R ¹² represents an aromatic ring group having a substituent, respectively)

R ^{11 is} preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

R ^{12 is} preferably phenyl or naphthyl, and the substituent is preferably alkylsulfonylamino, vinylsulfonylamino, arylsulfonylamino, alkylcarbonylamino, vinylcarbonylamino, aromatic The carbonylamino group is particularly preferably an alkylsulfonylamino group. The alkyl group having 1 to 12 carbon atoms may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

Further, an acid dye and/or a derivative thereof may be preferably used as the colorant. Besides, direct dyes, basic dyes, mordant dyes, acid mord dyes, ice dyes, disperse dyes, oil-soluble dyes, food dyes, and/or derivatives of such dyes, and the like can also be used.

Specific examples of the acid dye are listed below, but are not limited to these specific examples. For example, acid yellow 1, acid yellow 3, acid yellow 7, acid yellow 9, acid yellow 11, acid yellow 17, acid yellow 23, acid yellow 25, acid yellow 29, acid yellow 34, acid yellow 36, acid yellow 38, acid yellow 40, acid yellow 42, acid Yellow 54, Acid Yellow 65, Acid Yellow 72, Acid Yellow 73, Acid Yellow 76, Acid Yellow 79, Acid Yellow 98, Acid Yellow 99, Acid Yellow 111, Acid Yellow 112, Acid Yellow 113, Acid Yellow 114, Acid Yellow 116 Acid Yellow 119, Acid Yellow 123, Acid Yellow 128, Acid Yellow 134, Acid Yellow 135, Acid Yellow 138, Acid Yellow 139, Acid Yellow 140, Acid Yellow 144, Acid Yellow 150, 155, Acid Yellow 157, Acid Yellow 160 Acid Yellow 161, Acid Yellow 163, Acid Yellow 168, Acid Yellow 169, Acid Yellow 172, Acid Yellow 177, Acid Yellow 178, Acid Yellow 179, Acid Yellow 184, Acid Yellow 190, Acid Yellow 193, Acid Yellow 196, Acidic Yellow 197, Acid Yellow 199, Acid Yellow 202, Acid Yellow 203, Acid Yellow 204, Acid Yellow 205, Acid Yellow 207, Acid Yellow 212, Acid Yellow 214, Acid Yellow 220, Acid Yellow 221, Acid Yellow 228, Acid Yellow 230 Acid yellow 232, acid yellow 235, acid yellow 238, acid yellow 240, acid yellow 242, acid yellow 243, acid yellow 251; direct yellow (Direct Yellow) 2, direct yellow 33, direct yellow 34, direct yellow 35, direct Yellow 38, Direct Yellow 39, Direct Yellow 43, Direct Yellow 47, Direct Yellow 50, Direct Yellow 54 Direct yellow 58, direct yellow 68, direct yellow 69, direct yellow 70, direct yellow 71, direct yellow 86, direct yellow 93, direct yellow 94, direct yellow 95, direct yellow 98, direct yellow 102, direct yellow 108, direct yellow 109, Direct Yellow 129, Direct Yellow 136, Direct Yellow 138, Direct Yellow 141; Food Yellow 3; Mordant Yellow 5, mordant yellow 8, mordant yellow 10, mordant yellow 16, mordant yellow 20, Mordant yellow 26, mordant yellow 30, mordant yellow 31, mordant yellow 33, mordant yellow 42, mordant yellow 43, mordant yellow 45, mordant yellow 56, mordant yellow 50, mordant yellow 61, mordant yellow 62, mordant yellow 65; Derivatives of these dyes.

Further, as the pigment, the above pigment can be used.

The blending amount of the yellow pigment in the composition used in the present invention is preferably from 10% by mass to 120% by mass, and more preferably from 25% by mass to 100% by mass, based on 100% by mass of the indigo dye. Good is 50% by mass to 90% by mass.

[thermosetting compound]

The color hardening composition constituting the laminate of the present invention contains at least one kind Thermosetting compound. Here, the thermosetting compound means a film which can be cured by heating, and generally means a compound which is cured by heating at 180 ° C or higher.

The thermosetting compound used in the present invention can be used, for example, to have thermal hardening. A functional group of compounds. The thermosetting functional group is preferably, for example, one having at least one selected from the group consisting of an epoxy group, a methylol group, an alkoxymethyl group, a decyloxymethyl group, an isocyanate group, a vinyl ether group, and a fluorenyl group. The thermosetting compound is more preferably a compound having two or more thermosetting functional groups in one molecule, and more preferably a compound having two or more epoxy groups in one molecule.

Further, the thermosetting compound used in the present invention may be epoxidized. , melamine compound (such as alkoxymethylated melamine compound, decyloxymethylated melamine compound), urea compound (such as alkoxymethylated urea compound, decyloxymethylated urea compound), phenolic compound (e.g., a hydroxymethylated phenol compound, an alkoxymethylated phenol compound or resin, and an alkoxymethyletherified phenol compound), etc., as a preferable example, more preferably an epoxy compound or a melamine compound, and further preferably Epoxy compound.

The thermosetting compound used in the present invention may be a low molecular compound (for example, having a molecular weight of less than 2,000 and further having a molecular weight of less than 1,000) or a polymer compound (for example, having a molecular weight of 1,000 or more and a weight average molecular weight of 1,000 or more in the case of a polymer) . In the present invention, those having a molecular weight of 1,000 or more are preferred, and those having a molecular weight of from 2,000 to 100,000 are more preferred. In the present invention, a compound having two or more epoxy groups in one molecule and having a molecular weight of 1,000 or more is particularly preferable.

<epoxy compound>

When the epoxy compound is a low molecular compound, a compound represented by the following formula (EP1) can be mentioned.

In the formula (EP1), R ^EP1 to R ^EP3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group may have a cyclic structure or may have a substituent. Further, R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Examples of the substituent which the alkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfonic acid group, an alkylsulfonyl group. , an alkylamino group, an alkyl guanamine group, and the like.

Q ^EP represents a single bond or an organic group of n ^EP valence. R ^EP1 ~ R ^EP3 may also bond with Q ^EP to form a ring structure.

n ^EP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. Wherein, in the case where Q ^EP is a single bond, n ^EP is 2.

In the case where Q ^EP is an organic group having an n ^EP valence, a chain or cyclic n ^EP valence saturated hydrocarbon group (preferably having a carbon number of 2 to 20) and an n ^EP valent aromatic ring group are preferred. The above-mentioned structure is a chain or a cyclic saturated hydrocarbon or an aromatic hydrocarbon, and is bonded to an ether group, an ester group, or a guanamine group, in an organic group having a carbon number of 6 to 30) or an n ^EP having the following structure. a divalent linking group such as a sulfonylamino group, an alkylene group (preferably having a carbon number of 1 to 4, more preferably a methylene group), a trivalent linking group such as -N(-) ₂ or a combination of the groups The structure.

Specific examples of the compound having an epoxy structure are exemplified below, but the present invention is not limited to these specific examples.

The epoxy compound used in the present invention is also preferably epoxy on the side chain. A base oligomer or polymer. Examples of such a compound include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an aliphatic epoxy resin.

These compounds can be used as commercially available products, or by side chain conduction to the polymer. Obtained by entering an epoxy group.

For commercial products, for example, bisphenol A type epoxy resin is JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon 860, EPICLON 1050, Epiclon 1051, EPICLON 1055 (above is manufactured by Di Aisheng (DIC) Co., Ltd.); bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above is Japanese epoxy resin) (Stock) manufacturing), Abilon (EPICLON) 830, Abicone (EPICLON) 835 (above is made by Di Aisheng (DIC) (share)), LCE-21, RE-602S (above is Japanese chemical medicine (shares) Manufacture), etc.; phenol novolak type epoxy resin is JER152, JER154, JER157S70, JER157S65 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon (EPICLON) N-740, Epiclon (EPICLON) N -770, Epiclon (EPICLON) N-775 (above produced by Di Aisheng (DIC) Co., Ltd.); cresol novolac type epoxy resin is Epiclon N-660, Abby clone ( EPICLON) N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, Abby EPICLON N-695 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), EOCN-1020 (above manufactured by Nippon Chemical Co., Ltd.), etc.; aliphatic epoxy resin is Adeco resin (ADEKA RESIN) ) EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S (above ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, EPOLEAD PB 4700 (above produced by Daicel Chemical Industry Co., Ltd.), Denacol EX-212L, Dina Kaul ( Denacol) EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (above is Nagase Chemtex) ) Manufacturing) and so on. In addition, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, Adeco resin (ADEKA) RESIN)EP-4011S (above is made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above is Edico ( ADEKA) (manufactured by Japan), JER1031S (manufactured by Nippon Epoxy Co., Ltd.), etc.

In the case of introducing into a polymer side chain for synthesis, the introduction reaction can be carried out, for example, by a tertiary amine such as triethylamine or benzylmethylamine or dodecyltrimethyl chloride. Ammonium, tetramethylammonium chloride, tetraethylammonium chloride and other quaternary ammonium salts, pyridine, triphenylphosphine, etc. as a catalyst, in an organic solvent at a reaction temperature of 50 ° C ~ 150 ° C for several hours ~ a few Ten time response. The introduction amount of the alicyclic epoxy unsaturated compound is preferably such that the acid value of the obtained polymer satisfies 5 KOH. Mg/g~200KOH. The manner of the range of mg/g is controlled. Further, the molecular weight is preferably from 500 to 5,000,000, and more preferably from 1,000 to 500,000, based on the weight average molecular weight.

As the epoxy-unsaturated compound, a glycidyl group such as glycidyl (meth)acrylate or allyl glycidyl ether may be used as the epoxy group, and an unsaturated compound having an alicyclic epoxy group is preferred. Such a compound can be exemplified by the following Compound.

<melamine compound, urea compound, other thermosetting compound>

The thermosetting compound used in the present invention is also preferably the following having N- A compound of a hydroxymethyl group, an N-alkoxymethyl group or an N-methoxymethyl group. Such a compound is usually provided as a melamine compound or a urea compound.

a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-methoxymethyl group The compound is preferably a compound having a partial structure represented by the following formula (CLNM-1) of two or more (more preferably two to eight).

In the formula (CLNM-1), R ^NM1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a pendant oxyalkyl group.

The alkyl group of R ^NM1 in the formula (CLNM-1) is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The cycloalkyl group of R ^NM1 is preferably a cycloalkyl group having 5 to 6 carbon atoms. The ^oxaalkyl group of R ^NM1 is preferably an ^oxaalkyl group having 3 to 6 carbon atoms, and examples thereof include β-side oxypropyl group, β-side oxybutyl group, β-side oxypentyl group, and β. - a pendant oxyhexyl group or the like.

A more preferable aspect of the compound having a partial structure represented by two or more formulas (CLNM-1) is a urea compound represented by the following formula (CLNM-2), and the following formula (CLNM-3) The alkylene urea compound represented by the above formula, the glycoluril compound represented by the following formula (CLNM-4), and the melamine compound represented by the following formula (CLNM-5).

In the formula (CLNM-2), R ^NM1 is the same as R ^NM1 in the formula (CLNM-1), respectively. R ^NM2 represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 6), or a cycloalkyl group (preferably, a carbon number of 5 to 6).

Specific examples of the urea compound represented by the formula (CLNM-2) include N,N-bis(methoxymethyl)urea, N,N-bis(ethoxymethyl)urea, and N,N. - bis(propoxymethyl)urea, N,N-bis(isopropoxymethyl)urea, N,N-bis(butoxymethyl)urea, N,N-di(third butoxide) Methyl)urea, N,N-bis(cyclohexyloxymethyl)urea, N,N-bis(cyclopentyloxymethyl)urea, N,N-bis(adamantyloxymethyl)urea , N, N-di (norbornyloxymethyl) urea, and the like.

In the formula (CLNM-3), R ^NM1 is the same as R ^NM1 in the formula (CLNM-1), respectively. R ^NM3 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 5 to 6), and a pendant oxyalkyl group (preferably, The carbon number is 1 to 6), the alkoxy group (preferably having 1 to 6 carbon atoms) or the pendant oxyalkoxy group (preferably having 1 to 6 carbon atoms).

G represents a single bond, an oxygen atom, a sulfur atom, an alkyl group (preferably a carbon number of 1) ~3) or carbonyl. More specifically, a methylene group, an ethyl group, a propyl group, a 1-methylethyl group, a hydroxymethylene group, a cyanomethylene group, etc. may be mentioned.

Specific examples of the alkylene urea compound represented by the formula (CLNM-3) include, for example, N,N-bis(methoxymethyl)-4,5-di(methoxymethyl)ethylidene. Urea, N, N- Di(ethoxymethyl)-4,5-di(ethoxymethyl)exylethylurea, N,N-bis(propoxymethyl)-4,5-di(propoxymethyl) Ethyl urea, N,N-bis(isopropoxymethyl)-4,5-di(isopropoxymethyl)exylethyl, N,N-di(butoxymethyl) -4,5-bis(butoxymethyl)-extended ethylurea, N,N-bis(t-butoxymethyl)-4,5-di(t-butoxymethyl)-extended ethyl Urea, N,N-bis(cyclohexyloxymethyl)-4,5-di(cyclohexyloxymethyl)-extended ethylurea, N,N-di(cyclopentyloxymethyl)-4, 5-bis(cyclopentyloxymethyl)-extended ethylurea, N,N-di(adamantyloxymethyl)-4,5-di(adamantyloxymethyl)-extended ethylurea, N, N-di(norbornyloxymethyl)-4,5-di(norbornyloxymethyl)-extension ethyl urea and the like.

In the formula (CLNM-4),

R ^NM1 is the same as R ^NM1 in the formula (CLNM-1), respectively.

R ^NM4 represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group, respectively.

The alkyl group of R ^NM4 (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 5 to 6), an alkoxy group (preferably having a carbon number of 1 to 6), more specifically, a methyl group. , ethyl, butyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, butoxy, and the like.

Specific examples of the glycoluril compound represented by the formula (CLNM-4) include, for example, N,N,N,N-tetrakis(methoxymethyl)glycoluril, N,N,N,N-tetra (B Oxymethylmethyl) Urea, N, N, N, N-tetrakis (propoxymethyl) glycoluril, N, N, N, N-tetrakis(isopropoxymethyl) glycoluril, N, N, N, N-four (butoxymethyl) glycoluril, N,N,N,N-tetrakis(t-butoxymethyl)glycoluril, N,N,N,N-tetrakis(cyclohexyloxymethyl)glycoluril , N,N,N,N-tetrakis(cyclopentyloxymethyl)glycoluril, N,N,N,N-tetrakis(adamantyloxymethyl)glycoluril, N,N,N,N-four (norbornyloxymethyl) glycoluril and the like.

In the formula (CLNM-5), R ^NM1 is the same as R ^NM1 in the formula (CLNM-1), respectively. R ^NM5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an atomic group represented by the following formula (CLNM-5'). R ^NM6 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an atomic group represented by the following formula (CLNM-5").

In the general formula (CLNM-5 '), the same as R ^NM1 general formula (CLNM-1) is R ^NM1. In the general formula (CLNM-5 "), the same as R ^NM1 general formula (CLNM-1) in the R ^NM1, R ^NM5 the same as in the general formula (CLNM-5) in the R ^NM5.

R ^NM5 and R ^{NM6 have} an alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 5 to 6), and an aryl group (preferably having a carbon number of 6 to 10). More specifically, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, phenyl, naphthyl and the like.

Examples of the melamine compound represented by the formula (CLNM-5) include N,N,N,N,N,N-hexa(methoxymethyl)melamine, N,N,N,N,N,N- Hexa(ethoxymethyl)melamine, N,N,N,N,N,N-hexa(propyloxymethyl)melamine, N,N,N,N,N,N-hexa(isopropoxy Methyl) melamine, N, N, N, N, N, N-hexa(butoxymethyl) melamine, N, N, N, N, N, N-hexa(t-butoxymethyl) melamine , N,N,N,N,N,N-hexa(cyclohexyloxymethyl)melamine, N,N,N,N,N,N-hexa(cyclopentyloxymethyl)melamine, N,N ,N,N,N,N-hexa (adamantyloxymethyl)melamine, N,N,N,N,N,N-hexa(norbornyloxymethyl)melamine, N,N,N,N ,N,N-hexa(methoxymethyl)acetamide, N,N,N,N,N,N-hexa(ethoxymethyl)acetamide, N,N,N,N ,N,N-hexa(propyloxymethyl)acetamide, N,N,N,N,N,N-hexa(isopropoxymethyl)acetamide, N,N,N, N,N,N-hexa(butoxymethyl)acetamide, N,N,N,N,N,N-hexa(t-butoxymethyl)acetamide, N,N, N,N,N,N-hexa(methoxymethyl)benzoguanamine, N,N,N,N,N,N-hexa(ethoxymethyl)benzamide, N,N ,N,N,N,N-hexa(propyloxymethyl)benzamide N,N,N,N,N,N-hexa(isopropoxymethyl)benzoguanamine, N,N,N,N,N,N-hexa(butoxymethyl)benzoquinone, N , N, N, N, N, N-hexa(t-butoxymethyl)benzamide and the like.

The group represented by R ^NM1 to R ^{NM6 in} the formula (CLNM-1) to the formula (CLNM-5) may further have a substituent. Examples of the substituent which R ^NM1 to R ^NM6 may have include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a cycloalkyl group (preferably having a carbon number of 3 to 20), and an aryl group (preferably a carbon number of 6). ~14), alkoxy group (preferably carbon number 1 to 20), cycloalkoxy group (preferably carbon number 3 to 20), mercapto group (preferably carbon number 2 to 20), decyloxy group ( Preferably, the carbon number is 2 to 20).

Specific examples of the compound having two or more partial structures represented by the above formula (CLNM-1) are exemplified below, but the present invention is not limited to these specific examples. In addition to the compounds shown below, a Nikalac series of compounds manufactured by Sanwa Chemical Co., Ltd., which is not exemplified below, may preferably be used.

<phenol compound>

Examples of the phenol compound include three to five benzene rings in the molecule, and further two or more hydroxymethyl groups or alkoxymethyl groups, and the hydroxymethyl group and the alkoxymethyl group are bonded to each other at least. a phenolic compound formed on either benzene ring or separately bonded to different benzene rings. The alkoxymethyl group bonded to the benzene ring preferably has 6 or less carbon atoms. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, and second butyl are preferred. Oxymethyl group, third butoxymethyl group. Further, it is also preferably, for example, 2-methoxyethoxy and 2-methoxy Alkoxy substituted with alkoxy as -1-propoxy.

The thermosetting compound is more preferably a phenol compound having two or more benzene rings in the molecule, and is preferably a phenol compound containing no nitrogen atom.

The thermosetting compound is preferably a phenol compound having 2 to 8 thermosetting functional groups per molecule, and more preferably having 3 to 6 thermosetting functional groups.

Among these phenol compounds, particularly preferred compounds are listed below. In the formula, L ¹ to L ^{8 each} represent a thermosetting functional group such as an alkoxymethyl group, and may be the same or different, and the thermosetting functional group preferably represents a hydroxymethyl group, a methoxymethyl group or an ethoxy group. base.

A commercially available product may be used as the thermosetting compound, or may be synthesized by a known method. For example, a phenol compound having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group (in the above formula, a compound in which L ¹ to L ⁸ are a hydrogen atom) and formaldehyde under a base catalyst reaction. At this time, in order to prevent resination or gelation, it is preferred to carry out the reaction by setting the reaction temperature to 60 ° C or lower. Specifically, the synthesis can be carried out by the method described in JP-A-H06-282067, JP-A-H07-64285, and the like.

The phenol compound having an alkoxymethyl group can be obtained by reacting a corresponding phenol compound having a hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent resination or gelation, it is preferred to carry out the reaction at a reaction temperature of 100 ° C or lower. Specifically, the synthesis can be carried out by the method described in EP632003A1 or the like. The phenol compound having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable in terms of stability at the time of storage, and the phenol compound having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. good. The phenolic compound having a total of two or more hydroxymethyl groups or alkoxymethyl groups and which is bonded to any one of the benzene rings or separately bonded to different benzene rings may be used alone. Two or more types may be used in combination.

In the present invention, the thermosetting compound may be used singly or in combination of two or more.

The total content of the thermosetting compound in the colored curable composition of the layered product of the present invention varies depending on the material, and is preferably 5% by mass to 40% by mass based on the total solid content (mass) of the colored curable composition. % is more preferably 7 mass% to 35 mass%, and particularly preferably 10 mass% to 30 mass%. In the present invention, by setting the amount of the thermosetting compound, the following effects can be obtained: a cured film excellent in chemical resistance can be obtained.

[solvent]

The colored curable composition constituting the laminate of the present invention contains a solvent (usually an organic solvent) which dissolves at least the dye and the thermosetting compound.

The organic solvent may preferably be exemplified by esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methoxy) Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg 3-oxo) Methyl propyl propionate, ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-B Ethyl oxypropionate, etc.), alkyl 2-oxopropionate (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate )), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methylpropionic acid) Ester, 2-ethoxy-2-methylpropionate etc.), pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxabutyrate, ethyl 2-oxabutyrate, etc.; and as ethers, for example Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, two Ethylene 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.; and as a ketone such as a Base ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; and, for example, toluene, xylene, and the like as an aromatic hydrocarbon.

From the viewpoints of improvement of the coated surface, etc., it is preferable that these solvents are mixed in two or more forms. In this case, a mixed solution composed of two or more selected from the group consisting of the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve is particularly preferable. Acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

In view of the coating property, the content of the solvent in the coloring curable composition is preferably such that the total solid content concentration of the colored curable composition is from 5% by mass to 30% by mass, and further preferably 7 mass%. %~25% by mass, particularly preferably 10% by mass to 20% by mass.

<various additives>

The colored curable composition constituting the laminate of the present invention can be formulated with various additives such as a surfactant, an acid anhydride, a hardener, a hardening catalyst, a filler, and an adhesive, as needed within a range that does not impair the effects of the present invention. Promoter, antioxidant, purple External absorbent, anti-agglomerating agent, etc.

<Surfactant>

From the viewpoint of further improving the coating property, various coloring agents can be added to the colored curable composition constituting the laminate of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, the coloring curable composition constituting the laminate of the present invention further improves the solution characteristics (particularly fluidity) when the coating liquid is prepared by containing a fluorine-based surfactant, so that the uniformity of the coating thickness can be further improved. Or liquid-saving.

In other words, when the film formation is performed using a coating liquid using a coloring curable composition containing a fluorine-based surfactant, the interface surface is coated with the coating liquid to lower the interfacial tension, and the coated surface is coated. The wettability is improved, and the coatability to the coated surface is improved. Therefore, it is effective in the case where a film having a thickness of a few micrometers (μm) is formed with a small amount of liquid, a film having a uniform thickness having a small thickness unevenness can be more preferably formed.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the colored curable composition is also good.

Examples of the fluorine-based surfactant include Megafac F781 (the above is manufactured by DiCai (DIC) Co., Ltd.).

The surfactant may be used alone or in combination of two or more.

The colored curable composition may contain a surfactant or may not contain a surfactant. When the surfactant is contained, the amount of the surfactant added is preferably 0.001% by mass based on the total mass of the colored curable composition. 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass.

In the case where the surfactant is a polymer compound (that is, a resin), the solid content acid value of the polymer compound is set to 80 mgKOH/g or less.

<Acid anhydride>

The colored curable composition constituting the laminate of the present invention may contain an acid anhydride. By containing an acid anhydride, the crosslinkability by thermosetting of a thermosetting compound, especially an epoxy compound can be improved.

Examples of the acid anhydride include phthalic anhydride, an acid anhydride, maleic anhydride, and succinic anhydride. Among them, the acid anhydride is preferably phthalic anhydride in terms of having little influence on the pigment dispersion. Amine compounds are also commonly used as epoxy hardeners, but have the advantage that the pot life is relatively long.

The content of the acid anhydride in the colored curable composition is preferably in the range of 10% by mass to 40% by mass, and more preferably 15% by mass to 30% by mass based on the content of the thermosetting compound (particularly, the epoxy compound). range. When the content of the acid anhydride is 10% by mass or more, the crosslinking density of the thermosetting compound, particularly the epoxide, is improved, and the mechanical strength can be improved. When the content of the acid anhydride is 30% by mass or less, the thermal hardening in the coating film is suppressed. The composition is beneficial to increase the concentration of colored materials.

<hardener>

In the case where an epoxy resin is used as the thermosetting compound, it is preferably Add a hardener. There are many types of hardeners for epoxy resins, and the properties, the usable time, viscosity, hardening temperature, hardening time, heat generation, etc. of the mixture of the resin and the hardener vary greatly depending on the type of hardener used, and therefore must be based on An appropriate hardener is selected for the purpose of use of the hardener, the conditions of use, the working conditions, and the like. The hardening agent is explained in detail in Chapter 5 of "Epoxy Resin (Sheng Sangtang)" edited by Yukihiro. An example of a hardener is shown below.

The hardener which functions as a catalyst has a tertiary amine and a boron trifluoride-amine complex. The hardener which reacts with the functional group of the epoxy resin by stoichiometry includes polyamines, acid anhydrides, etc.; The hardeners are diethylenetriamine and polyamidamine resins, and examples of hardeners which are moderately hardened are diethylaminopropylamine and tris(dimethylaminomethyl)phenol; examples of high temperature hardening are adjacent. Phthalic anhydride, m-phenylenediamine, and the like. Further, in terms of chemical structure classification, examples include diethylenetriamine as an aliphatic polyamine in the amine, m-phenylenediamine as an aromatic polyamine, and tris(dimethylamine) as a tertiary amine. Methyl)phenol; phthalic anhydride as anhydride; polyamine resin; polysulfide resin; boron trifluoride-monoethylamine complex; phenolic resin as initial condensate of synthetic resin; Listed are dicyandiamide and the like.

The hardeners react with the epoxy group by heating to cause polymerization. The crosslink density increases and hardens. In order to achieve the film formation, it is preferable that the binder and the curing agent are as small as possible, and in particular, the curing agent is preferably set to 35 mass% or less, preferably 30 mass% or less, and further preferably the thermosetting compound. Preferably, it is 25 mass% or less.

<hardening catalyst>

In order to achieve a composition having a high concentration of the colorant, in addition to hardening due to the reaction with the hardener, it is effective to harden mainly by the reaction of the epoxy groups with each other. Therefore, it is also possible to use a hardening catalyst without using a hardener. The amount of the curing catalyst to be added is about 1/10 to 1/1000, preferably about 1/20 to 1/500, based on the mass of the epoxy resin having an epoxy equivalent of about 150 to 200. And then it is hard to harden by a slight amount of about 1/30~1/250.

<Method for Preparing Colored Curable Composition>

A preferred method for preparing the colored curable composition constituting the laminate of the present invention will be described. However, the invention is not limited thereto.

When the colorant is a dye, it is dissolved together with the thermosetting compound in a solvent. In the case where a pigment is contained as a coloring agent, it is usually adjusted in the form of a pigment dispersion as described above.

In particular, when the thermosetting compound is an epoxy compound, it is preferred to add a thermosetting compound and a hardening catalyst or a hardener to the solution of the pigment dispersion or the dye thus obtained, or the binder is already hot. In the case of a curable compound, a curing catalyst or a curing agent is added, and a thermosetting function is imparted thereto, and a solvent is added as needed to prepare a color hardening composition of the present invention.

<Filter Filtering>

The colored curable composition constituting the laminate of the present invention is preferably filtered by a filter in order to remove foreign matter or reduce defects.

The filter used for the filtration of the filter is not particularly limited as long as it is a filter used in filtration applications and the like.

Examples of the material of the above filter may be exemplified by polytetrafluoroethylene. A fluororesin such as (polytetrafluoroethylene, PTFE); a polyamide resin such as nylon-6 or nylon-6,6; a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene or polypropylene (PP). Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the above filter is not particularly limited, and is, for example, 0.01 μm to 20.0. The thickness is about μm, preferably about 0.01 μm to 5 μm, and more preferably about 0.01 μm to 2.0 μm.

By setting the aperture of the filter to the above range, the micro can be effectively removed. Fine particles, which further reduce turbidity.

Here, the pore size of the filter can be referred to the filter maker. Nominal value. Commercially available filters are available, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., and Japan's Entegris Co., Ltd. (formerly Japan's Microris) Ltd.) or a variety of filters available from KITZ Micro Filter Co., Ltd., etc.

In the above filter filtration, two or more types of filters may be used in combination.

For example, the first filter can be used for filtration first, followed by the aperture Filtration is performed by a second filter different from the first filter.

At this time, filtration by the first filter and filtration by the second filter It can be done only once or twice or more.

The second filter can be made of the same material as the first filter described above. Former.

[Coloring layer]

By curing the colored curable composition, a colored layer constituting the laminate of the present invention can be obtained. The method of forming the colored layer will be described later. The colored layer can be preferably used as a coloring layer of a color filter. In particular, it can be preferably used as a coloring curable composition for dry etching.

In the present invention, the thickness of the colored layer is preferably from 0.1 μm to 1.0 μm, more preferably from 0.3 μm to 0.8 μm. In the present invention, since the concentration of the coloring agent in the colored layer can be increased, such thinning can be achieved.

[oxygen barrier film]

The laminate of the present invention has an oxygen barrier film on the colored layer. The oxygen blocking film is formed using an oxygen blocking compound and exhibits high oxygen blocking ability, high transparency, and low light scattering property.

Here, the rough surface of the film refers to a state in which a plurality of aggregates are generated on the surface of the colored layer, whereby a plurality of irregularities are formed on the surface of the colored layer. The factor which causes the film surface roughness on the surface of the colored layer is considered to be caused by the fact that the singlet oxygen decomposes the polymer component (hardened product of the thermosetting compound) in the colored layer, the colorant and the polymer component. Phase separation occurs and the colorants form agglomerates with each other. Further, it is considered that the higher the concentration of the colorant, the smaller the amount of the polymer component in the colored layer is, and therefore the colorants are more likely to form aggregates with each other, and the film surface roughness of the surface of the colored layer is likely to occur. In particular, the inventors of the present application conducted research and found that the solid concentration of the coloring agent in the colored curable composition exceeded In the case of 50% by mass, in the case of more than 60% by mass, film surface roughness is remarkably generated. In particular, it is also known that this tends to be apparently produced under high temperature and high humidity.

The oxygen blocking compound contained in the oxygen blocking film may be any of an inorganic material and an organic material, and is preferably an inorganic material. Specifically, a metal oxide, a metal alkoxy group-containing compound, an organic polymer, or the like can be used. Further, in terms of more excellent oxygen blocking ability, the oxygen blocking film is preferably substantially composed only of the above oxygen blocking compound. The oxygen-only blocking compound is, for example, a content of the oxygen blocking compound in the oxygen blocking film of 99% by mass or more.

Examples of the metal oxide include SiO ₂ , SiN, Al ₂ O ₃ , CaO, Fe ₂ O ₃ , MgO, Ga ₂ O, ZrO ₂ , TiO ₂ , CaF ₂ and the like. The plurality of metal oxide, it is excellent in oxygen barrier properties and transparency viewpoint, preferably SiO _2, SiN, and particularly preferably SiO _2.

The metal alkoxy group-containing compound may, for example, be tetraethoxysilane, tetraethyl orthotitanate, tetramethoxynonane, ethyltriethoxysilane or methyltrimethoxydecane.

Examples of the organic polymer include polyvinyl alcohol (PVA), polyvinylpyrrolidone, polypropylene decylamine, water-soluble polyamide, water-soluble salt of polyacrylic acid, polymerization of polyvinyl ether and maleic anhydride. Cellulose, ethylene oxide polymer, ethyl cellulose, hydroxyethyl cellulose, water-soluble salt of carboxyethyl cellulose, cellulose, arabic gum (Arabic Gum), alkoxyalkylene-containing polymer Or a mixture of two or more of these substances, and among these, from the viewpoint of excellent oxygen barrier properties, polyvinyl alcohol, polyvinylpyrrolidone or polyvinyl alcohol and polyvinylpyrrole are preferred. A mixture of ketones, particularly preferably polyvinyl alcohol.

The polyvinyl alcohol preferably has a weight average molecular weight of from 300 to 2,400, and more preferably from 71 mol% to 100 mol%. Specific examples thereof include PVA-101, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, (all of which are trade names, manufactured by Kuraray Co., Ltd., saponification) The rate is 97%~98%), PVA-203, PVA-204, PVA-205, PVA-210, PVA-220, PBA-224, PVA-217E (all of which are trade names, Kuraray shares limited) The company manufactures, the saponification rate is 87%~88%), PVA-405, PVA-420 (all of which are trade names, manufactured by Kuraray Co., Ltd., saponification rate is 78%~82%), PVA-613 (The above is the trade name, manufactured by Kuraray Co., Ltd., and the saponification rate is 92% to 95%). Further, the last 2 digits × 100 of the 3-digit number after the PVA indicate the degree of polymerization, respectively.

The content of PVA in the mixture of polyvinyl alcohol and polyvinylpyrrolidone is preferably from 25% by mass to 99% by mass, more preferably from 50% by mass to 90% by mass, even more preferably from 50% by mass to 80% by mass. The amount of the polymer added is from 1% by mass to 40% by mass, more preferably from 10% by mass to 35% by mass based on the total of the layer. The content of the polyvinylpyrrolidone is preferably from 1% by mass to 75% by mass, more preferably from 1% by mass to 50% by mass, and even more preferably from 10% by mass to 40% by mass based on the total solid content of the oxygen blocking film. %. By setting the addition amount of the polyvinylpyrrolidone to 1% by mass to 75% by mass based on the total solid content of the oxygen barrier film, the oxygen barrier property can be further improved.

In the present invention, the film thickness of the oxygen barrier film is preferably 10 μm or less. When the film thickness is within the above range, the oxygen blocking film is excellent in sensitivity or flatness, and preferably functions as an oxygen blocking film of the color filter. Oxygen resistance When the film thickness of the film is more than 10 μm, the oxygen permeability of the oxygen barrier film can be suppressed, but the intensity of light passing through the color filter layer is lowered. The film thickness of the oxygen barrier film is preferably 5 μm or less, and more preferably 1 μm or less. The lower limit of the film thickness of the oxygen barrier film is not particularly limited, and is 0.05 μm or more.

The oxygen blocking layer preferably has an oxygen permeability of 200 ml/m ² . Day. Below atm, more preferably 100ml/m ² . Day. Below atm, especially preferably 50ml/m ² . Day. Below atm. The lower limit of the oxygen transmission rate is not particularly limited, but is preferably 0 ml/m ² . Day. Atm. When the oxygen permeability is in the above range, the oxygen blocking layer preferably functions from the viewpoint of the film surface of the colored film being rough.

The method for measuring the oxygen permeability of the oxygen blocking layer can be measured, for example, as follows. The oxygen electrode was a model 3600 manufactured by Orbisphere Laboratories Japan Inc., Japan. The electrode separator is a polyfluoroalkoxy (PFA) 2956A excellent in response speed and sensitivity. A thin film (for example, 1.0 μm) was coated on a thin electrode (for example, 1.0 μm) with a silicone grease (SH111, manufactured by Toray Dow Corning Co., Ltd.), and a film material to be measured was attached thereto, and an oxygen concentration value was measured. Further, it was confirmed that the coating film of the fluorenone oil had no influence on the oxygen permeation rate. Then, the oxygen permeation rate (ml/m2.day.atm) with respect to the oxygen concentration value was converted.

In the case of forming an oxygen barrier film, when the oxygen barrier compound contains an inorganic material, a physical film formation method such as vapor deposition or sputtering, or chemical vapor deposition (CVD) can be used. Membrane method, chemical liquid deposition (CLD), spray method, etc. Various film making methods. In the case where the oxygen blocking compound contains a metal alkoxy group-containing compound or an organic polymer, a roll coater, an air knife coater, a knife coater, a rod coater, a rod can be used. Various coaters such as a coater, a spin coater, and a spray coater.

Hereinafter, preferred embodiments of the laminate of the present invention are listed, but the present invention is not limited to the embodiments.

(First embodiment)

An aspect of forming an oxygen blocking film on the colored layer obtained by curing the colored curable composition, wherein the colored curable composition contains a colorant, a thermosetting compound, and a solvent, and is colored with respect to the colored curable composition. The total solid content and the total content of the colorant are 50% by mass to 90% by mass.

(Second embodiment)

The colorant contains the aspect of the halogenated indigo dye represented by the above formula (1).

(Third embodiment)

The colorant further contains a yellow pigment.

(Fourth embodiment)

The thermosetting compound is in the form of an epoxy compound.

(Fifth Embodiment)

The oxygen blocking membrane contains a state of an inorganic material.

(Sixth embodiment)

The total amount of the colorant relative to the total solid content of the colored curable composition The content is from 60% by mass to 90% by mass.

(Seventh embodiment)

The thickness of the colored layer is from 0.1 μm to 1.0 μm.

(Eighth embodiment)

The oxygen blocking film is adjacent to the colored layer.

(Ninth Embodiment)

The thickness of the oxygen barrier film is 10 μm or less.

(Tenth embodiment)

The aspect of the combination of two or more of the first embodiment to the ninth embodiment is included.

[Color filter and method of manufacturing the same]

An example of the method for producing a color filter of the present invention includes the steps of: forming a coloring layer using the colored curable composition; forming a photoresist layer on the colored layer; and forming a photoresist layer by exposure and development a step of patterning to obtain a resist pattern; a step of dry etching the colored layer using the resist pattern as an etch mask; and a step of forming an oxygen blocking film on the colored layer after dry etching.

In the method for producing a color filter of the present invention, the first colored layer is formed by using the colored curable composition (also referred to as a first coloring curable composition). Here, as described above, the first colored layer is excellent in solvent resistance and alkali resistance developing liquid property. Thereby, it is possible to suppress the possibility of forming a resist pattern (patterned photoresist layer) on the first colored layer as a mask for etching when it is described in detail below, or Formed on the first colored layer by the second color-sensing radiation linear composition In the step of forming the second coloring radiation layer and the step of forming the third coloring radiation layer by the third coloring radiation composition on the first coloring layer, the first coloring layer is dissolved in the second coloring layer The organic solvent in the radiation-sensitive linear composition or the third color-sensitive radiation composition, or the second color-sensitive radiation layer formed by the second color-sensitive radiation composition or the third color-sensitive radiation composition Or a developer used in exposure and development of the third coloring radiation layer, wherein the color component in the first colored layer is eluted into the solvent or the developer; or the second coloring radiation composition or The possibility that the color component in the third coloring radiation composition is mixed into the first colored layer. As a result, generation of discoloration of the color component in the first colored layer or generation of an overlap region in which a plurality of colors overlap each other can be suppressed, so that the performance of the finally obtained color filter can be improved.

In particular, for example, a color filter for a solid-state imaging element having a required thickness of 0.1 μm to 1.0 μm and/or a pixel pattern size (one side of the square pattern) of 2 μm or less (for example, 0.5 μm to 2.0 μm) is prepared. It is effective.

Further, according to the method of manufacturing a color filter of the present invention, it is possible to provide a color filter having a coloring agent having a high concentration of a coloring agent and which is less likely to cause a colored layer surface even when placed under high temperature and high humidity. The film surface is rough.

Here, an example of the solid-state imaging element will be briefly described with reference to FIG. 1 .

As shown in FIG. 1, the solid-state imaging device 10 includes a light receiving element (photodiode) 42, a color filter 13, a planarizing film 14, and a microlens 15 which are provided on a ruthenium substrate. In the present invention, the planarizing film 14 is not necessarily provided. Furthermore, in Figure 1 In order to clarify each part, the ratio of thickness or width of each other is ignored and partially exaggerated.

The support is not particularly limited as long as it is used for the color filter except for the ruthenium substrate, and examples thereof include soda glass, borosilicate glass, and quartz glass used in liquid crystal display elements and the like. A transparent conductive film or a photoelectric conversion element substrate used in a solid-state imaging device or the like, such as an oxide film or tantalum nitride, is attached to the glass. Further, an intermediate layer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.

A P-well 41 is provided on the substrate, and a photodiode 42 is provided on a portion of the surface of the P-well. The photodiode 42 is formed by ion-implanting an N-type impurity such as P or As on a part of the surface of the P well, and then performing heat treatment. Further, in the region of the P well 41 of the germanium substrate which is different from the above portion, the impurity diffusion layer 43 in which the N-type impurity concentration is higher than that of the photodiode 42 is provided. The impurity diffusion layer 43 is formed by ion-implanting an N-type impurity such as P or As, and is subjected to heat treatment to function as a floating diffusion layer, and the floating diffusion layer transfers charges generated by the incident light by the photodiode 42. The wafer 41 may be set to an N-type impurity layer, a photodiode 42 and impurities, except that the wafer 41 is set to a P-type impurity layer, and the photodiode 42 and the impurity diffusion layer 43 are set to an N-type impurity layer. The diffusion layer 43 is set to be a P-type impurity layer.

On the P well 41, the photodiode 42, and the impurity diffusion layer 43, an insulating film 47 of SiO ₂ or SiO ₂ /SiN/SiO ₂ or the like is provided, and the insulating film 47 is provided with polycrystalline germanium, tungsten, tungsten germanium, and aluminum. , electrode 44 of Cu or the like. The electrode 44 functions as a gate of a gate metal oxide semiconductor (MOS) transistor, and functions as a transfer gate for transferring charges generated in the photodiode 42 to the impurity diffusion layer 43. . Further, a wiring layer 45 is formed above the electrode 44. Further above the wiring layer 45, there are a BPSG film 46 and a P-SiN film 48. The interface between the Borophosphosilicate Glass (BPSG) film 46 and the P-SiN film 48 is formed so as to be curved downward above the photodiode 42 and is used to efficiently introduce incident light to The function of the in-layer lens in the photodiode 42. The planarizing film layer 49 is formed on the BPSG film 46 in order to planarize the uneven portions other than the surface of the P-SiN film 48 or the pixel region.

A color filter 13 is formed on the planarization film layer 49. In the following description, the colored film (the so-called integral film) formed on the ruthenium substrate in the undivided region is referred to as a "colored (colored luminescence) layer", and the color formed by patterning the regions is formed. A film (for example, a film patterned in a stripe shape) is referred to as a "coloring pattern". Further, in the colored pattern, a colored pattern (for example, a colored pattern patterned in a square or a rectangular shape) which is an element constituting the color filter 13 is referred to as a "coloring (red, green, blue) pixel" .

The color filter 13 includes a plurality of green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B that are two-dimensionally arranged. Each of the coloring elements 20R, the coloring pixels 20G, and the coloring pixels 20B is formed above the light receiving element 42. The green pixel 20G is formed as a checkerboard pattern, and the blue pixel 20B and the red pixel 20R are formed between the green pixels 20G. Furthermore, in FIG. 1, in order to include the three color pixels for the color filter 13 Incidentally, each of the coloring pixels 20R, the coloring pixels 20G, and the coloring pixels 20B are arranged in a line.

The planarizing film 14 is formed to cover the upper surface of the color filter 13, and planarizes the surface of the color filter.

The microlens 15 is a condensing lens that is disposed such that the convex surface faces upward, and is disposed above the planarizing film 14 (a color filter when the planarizing film is not provided) and above the light receiving element 42. Each of the microlenses 15 efficiently guides light from the subject to the respective light receiving elements 42.

Next, a method of manufacturing a color filter according to an embodiment of the present invention will be described.

In the method of manufacturing a color filter according to the embodiment of the present invention, first, as shown in the schematic cross-sectional view of FIG. 2, the first colored layer 11 is formed by the first colored curable composition (step (A)). . Here, the first coloring curable composition is the coloring curable composition described above.

The formation of the first colored layer 11 can be formed by applying a colored curable composition to a support by a coating method such as spin coating, slit coating, or spray coating, and applying Dry to form a colored layer.

The thickness of the first colored layer 11 is preferably in the range of 0.3 μm to 1.0 μm, more preferably in the range of 0.35 μm to 0.8 μm, and still more preferably in the range of 0.35 μm to 0.7 μm.

In the case where the first colored curable composition contains a thermosetting compound, it is preferred that the first colored layer 11 is heated and cured by a heating means such as a hot plate or an oven. The heating temperature is preferably from 120 ° C to 250 ° C, more preferably 160 ° C ~ 230 ° C. The heating time varies depending on the heating mechanism. When heating on a hot plate, it is usually about 3 minutes to 30 minutes. When heating in an oven, it is usually about 30 minutes to 90 minutes.

Then, patterning is performed by dry etching so that the through-hole group is formed in the first colored layer 11 (step (B)). Thereby, the first coloring pattern is formed. According to this method, the first colored layer is formed by the coloring sensitizing radiation composition, and the through hole group is provided by exposure and development of the first colored layer, whereby the desired shape can be more reliably set. Through-hole group. The reason for this is that a coloring radiation-releasing composition having a coloring agent content of 50% by mass or more based on the total solid content of the colored curable composition can be added to the composition to contribute to the developing ability. There is limited room for it, so it is difficult to achieve reliable patterning.

The first coloring pattern may be a coloring pattern provided as a first color on the support, and may be, for example, a second color or a third color after the support having the existing pattern. Set the color pattern.

The dry etching can be performed on the first colored layer 11 using the patterned photoresist layer as a mask using an etching gas. For example, as shown in the schematic cross-sectional view of FIG. 3, the photoresist layer 51 is first formed on the first colored layer 11.

Specifically, a positive or negative radiation sensitive composition is applied (preferably coated) to the colored layer and dried to form a photoresist layer. Regarding the formation of the photoresist layer 51, it is preferable to further perform a prebaking treatment. In particular, the formation process of the photoresist is preferably a form in which heat treatment (Post Exposure Bake (PEB)) after exposure and heat treatment (post-baking treatment) after development are performed.

For the photoresist, for example, a positive type radiation sensitive composition can be used. The positive type radiation sensitive composition can be used as a positive type suitable for inducing ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays. A positive resist composition for photoresist. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is obtained by decomposing a quinonediazide group by light irradiation at a wavelength of 500 nm or less to produce a carboxyl group, and as a result, the alkali-insoluble state changes to Alkali soluble. Since this positive type resist is excellent in resolving power, it is used to manufacture an integrated circuit such as an integrated circuit (IC) or a large scale integrated circuit (LSI). The quinonediazide compound may be a naphthoquinonediazide compound.

The thickness of the photoresist layer 51 is preferably from 0.1 μm to 3 μm, more preferably from 0.2 μm to 2.5 μm, still more preferably from 0.3 μm to 2 μm. Further, the application of the photoresist layer 51 can be preferably carried out by using the coating method of the first colored layer 11 described above.

Then, as shown in the schematic cross-sectional view of FIG. 4, the resist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with the resist through-hole group 51A.

The formation of the resist pattern 52 is not particularly limited, and the technique of the conventionally known photolithography can be appropriately optimized. A resist through-hole group 51A is provided in the photoresist layer 51 by exposure and development, whereby the etch used in the subsequent etching is used. The resist pattern 52 of the mask is provided on the first colored layer 11.

The exposure of the photoresist layer 51 can be performed by using a predetermined mask pattern, by g-ray, h-ray, i-ray, etc., preferably an i-ray alignment type or a negative type radiation-sensitive composition. Implement exposure. After the exposure, development processing is performed by the developer to thereby remove the photoresist in accordance with the region where the colored pattern is to be formed.

The developer can be used as long as it does not affect the first colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. For example, a combination of various organic solvents can be used. Or an alkaline aqueous solution. The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like. Further, when an alkaline aqueous solution is used as the developing solution, the cleaning treatment is usually performed by water after development.

Then, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the through-hole group group 120 is formed in the first colored layer 11. Thereby, the 1st coloring pattern 12 is formed. Here, the through hole group 120 has the first through hole portion group 121 and the second through hole portion group 122.

The through hole group 120 is provided in the first colored layer 11 in a checkerboard shape. Therefore, the first coloring map in which the through hole group 120 is provided in the first colored layer 11 The case 12 has a plurality of square-shaped first colored pixels in a checkerboard shape.

Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. Sho 59-46628, Japanese Patent Laid-Open No. Sho 58-9108, Japanese Patent Laid-Open No. Sho 58-2809, Japan The method described in Japanese Laid-Open Patent Publication No. Sho 57-148706, and the like.

From the viewpoint of forming the pattern cross section closer to a rectangular shape or further reducing the damage to the support, the dry etching is preferably carried out in the following manner.

It is preferable to include a first-stage etching, a second-stage etching, and an over-etching. The first-stage etching uses a mixed gas of a fluorine-based gas and oxygen (O ₂ ), and is etched until the support is not exposed. The (secondary) etching is performed by etching the first stage after the first stage of etching, using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until the support is exposed. The over-etching is performed after the support is exposed. Hereinafter, a specific method of dry etching, etching in the first stage, etching in the second stage, and over etching will be described.

Dry etching is performed by previously obtaining etching conditions by the following method.

(1) The etching rate (nm/min) of the etching in the first stage and the etching rate (nm/min) in the etching in the second stage were respectively calculated.

(2) Calculate the time required for etching in the etching of the first stage and the time required to etch the required thickness in the etching of the second stage.

(3) The first-stage etching is performed in accordance with the etching time calculated in the above (2).

(4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the etching time may be determined by an end point detection, and the second etching may be performed in accordance with the determined etching time.

(5) The overetching time is calculated with respect to the total time of the above (3) and (4), and over etching is performed.

The mixed gas used in the first step of the etching step preferably contains a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the film to be processed into a rectangular shape. Further, the etching step of the first step can be prevented from being damaged by the support so as to be etched to a region where the support is not exposed.

Further, from the viewpoint of avoiding damage of the support, the etching step and the over-etching step in the second step are preferably performed by etching a mixed gas of a fluorine-based gas and oxygen in the etching step of the first step until the support is performed. After the area where the body is not exposed, the etching treatment is performed using a mixed gas of nitrogen gas and oxygen gas.

It is important to determine the ratio of the etching amount in the etching step in the first step to the etching amount in the etching step in the second step, without impairing the rectangularity of the etching treatment in the etching step of the first step. Further, the ratio of the latter in the total etching amount (the total of the etching amount in the etching step in the first step and the etching amount in the etching step in the second step) is preferably in a range of more than 0% and not more than 50%. More preferably 10% to 20%. The amount of etching refers to the residual film thickness of the film to be etched.

Further, the etching preferably includes an overetching treatment. The overetching process is preferably The overetch ratio is set to proceed. Further, the overetch ratio is preferably calculated based on the etching processing time performed first. The overetching ratio can be arbitrarily set, and is preferably 30% or less, more preferably 5% to 25%, of the etching treatment time in the etching step in terms of the etching resistance of the photoresist and the rectangularity of the etching pattern. , especially good for 10% to 15%.

Then, as shown in the schematic cross-sectional view of Fig. 6, the resist remaining after the etching The agent pattern (ie, the etch mask) 52 is removed. The removal of the resist pattern 52 preferably includes the steps of: applying a stripping liquid or a solvent to the resist pattern 52, adjusting the state in which the resist pattern 52 can be removed; and using the cleaning water to pattern the resist 52 steps to remove.

The stripping solution or solvent is applied to the resist pattern 52 to be adjusted to remove the anti-resistance The step of the state of the etchant pattern 52 is, for example, a step of applying a peeling liquid or a solvent to at least the resist pattern 52, and stagnation for a predetermined period of time to perform immersion development. The time for stopping the stripping solution or the solvent is not particularly limited, and is preferably from several tens of seconds to several minutes.

In addition, the step of removing the resist pattern 52 using the washing water can be listed, for example. A step of ejecting the cleaning water to the resist pattern 52 from the spray or spray type spray nozzle to remove the resist pattern 52. Pure water can be preferably used for the washing water. Further, the injection nozzle may be an injection nozzle that includes the entire support body in the injection range thereof, or an injection nozzle that is a movable injection nozzle and whose movable range includes the entire support body. When the ejection nozzle is movable, the cleaning water can be more effectively removed by spraying the cleaning water twice or more from the center of the support to the end of the support in the step of removing the resist pattern 52. Agent pattern 52.

The stripping solution usually contains an organic solvent, and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether or an acetal-based compound, 5) a ketone or an aldehyde-based compound, and 6) an ester-based compound, and 7) A polyol compound, 8) a carboxylic acid or an anhydride thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The stripper preferably contains a nitrogen-containing compound, more preferably an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine or the like is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-甲. Pyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrolidone N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as acyclic nitrogen-containing compound. At least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine, and further preferably contains a single Ethanolamine and N-methyl-2-pyrrolidone.

When the removal is performed by the stripping solution, it is formed in the first coloring map. The resist pattern 52 in the case 12 may be removed, and when a deposit as an etching product adheres to the side wall of the first coloring pattern 12, the deposit may not be completely removed. The deposit means that the etching product adheres to the side wall of the colored layer.

The stripping solution is desirably the following solution: 100 parts by mass relative to the stripping solution, The content of the acyclic nitrogen-containing compound is from 9 parts by mass to 11 parts by mass, and the content of the cyclic nitrogen-containing compound is from 65 parts by mass to 70 parts by mass based on 100 parts by mass of the peeling liquid. Further, the peeling liquid is preferably one obtained by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

Then, as shown in the schematic cross-sectional view of Fig. 7, the second coloring radiation is emitted. The linear composition is embedded in the inside of each of the through holes of the first through hole portion group 121 and the second through hole portion group 122, and forms a plurality of second colored pixels in the first colored layer (that is, in the first In the first colored pattern 12) in which the through-hole group 120 is formed in the colored layer 11, the second color-sensing radiation layer 21 is laminated by the second color-sensing radiation linear composition (step (C)). Thereby, the second coloring pattern 22 having a plurality of second colored pixels is formed in the through hole group 120 of the first colored layer 11. Here, the second colored pixel is a quadrangular pixel. The formation of the second coloring radiation layer 21 can be performed in the same manner as the method of forming the first coloring layer 11 described above.

Here, the thickness of the second coloring-sensitive radiation layer 21 is preferably 0.3 μm. a range of 1 μm, more preferably in the range of 0.35 μm to 0.8 μm, and further preferably 0.35 μm A range of ~0.7 μm.

Then, the second color-sensing radiation layer 21 is exposed and developed at a position 21A corresponding to the first through-hole portion group 121 provided in the first colored layer 11 of the second coloring radiation layer 21, The plurality of second colored pixels 22R provided in the respective through holes of the second through hole portion group 122 are removed (step (D)) (see a schematic cross-sectional view of FIG. 8).

Then, as shown in the schematic cross-sectional view of FIG. 9, the third colored radiation-radiating composition is embedded in the inside of each of the through holes of the second through-hole portion group 122, and a plurality of third colored pixels are formed. The third colored layer is formed on the first colored layer (that is, the first colored pattern 12 in which the second colored pattern 22 is formed in the first through-hole portion group 121). The linear layer 31 is radiated (step (E)). Thereby, the third coloring pattern 32 having a plurality of third colored pixels is formed in the second through hole portion group 122 of the first colored layer 11. Here, the third colored pixel is a quadrilateral pixel. The formation of the third coloring radiation layer 31 can be performed in the same manner as the method of forming the first coloring layer 11 described above.

The thickness of the third coloring radiation layer 31 herein is preferably in the range of 0.3 μm to 1 μm, more preferably in the range of 0.35 μm to 0.8 μm, and still more preferably in the range of 0.35 μm to 0.7 μm.

Then, the third coloring radiation layer 31 is exposed and developed at a position 31A corresponding to the second through hole portion group 122 provided in the first colored layer 11, thereby removing the third coloring radiation layer. 31. Thus, as shown in the schematic cross-sectional view of FIG. 10, the first coloring pattern 12, the second coloring pattern 22, and the third coloring are produced. The coloring layer 60 of the pattern 32 (step (F)).

In the method of manufacturing the color filter of the present invention, as shown in FIG. The oxygen blocking film 61 is formed on the colored layer 60, and the color filter 100 in which the oxygen blocking film 61 is formed on the colored layer 60 can be manufactured.

The second colored radiation linear composition and the third colored radiation linearity The compositions each contain a colorant. The coloring agent may similarly exemplify the coloring agent of the coloring curable composition, and it is preferable that one of the second coloring element and the third coloring element is a red transmitting portion and the other is a blue transmitting portion.

Coloring contained in the colored curable composition for forming the red transmissive portion The agent is preferably one or more selected from the group consisting of: Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17:1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, and CI Pigment Red 1, Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81:2, CI Pigment Red 81:3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144 , CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172 , CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190 , CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224 , CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Yan Red 255, C.I. Pigment Red 264, C.I. Pigment Red 270, C.I. Pigment Red 272, C.I. Pigment Red 279.

The coloring agent contained in the colored curable composition for forming the blue transmissive portion is preferably one or more selected from the group consisting of: Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42 and CI Pigment Blue (1), Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15 : 2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, C.I. Pigment Blue 80.

The second coloring radiation composition and the third coloring radiation linear composition The content of the colorant in the total solid content of the composition is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. Further, the content of the colorant with respect to the total solid content of the composition is usually 90% by mass or less, preferably 80% by mass or less.

In addition, the second coloring sensitizing radiation composition and the third coloring sensation radiation Preferably, the sexual compositions are each a negative radiation sensitive composition. The negative-type radiation-sensitive linear composition can use negative-inductance radiation that induces ultraviolet rays (g-rays, h-rays, and i-rays), far-ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays. Composition. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

Specifically, the negative-type radiation sensitive composition preferably contains photopolymerization Examples of the composition of the initiator, the polymerization component (polymerizable compound), and the binder resin (alkali-soluble resin), etc., are described in paragraph number [0017] to paragraph number [0064] of JP-A-2005-326453. Recorder. In the negative-type radiation-sensitive linear composition, the photopolymerization initiator initiates a polymerization reaction of the polymerizable compound by irradiation with radiation, and as a result, it changes from an alkali-soluble state to an alkali-insoluble property.

The second coloring-sensing radiation layer 21 and the third coloring-sensing radiation layer 31 The exposure can be performed by using g-rays, h-rays, i-rays, or the like, preferably by using i-rays.

In addition, the development performed after exposure is usually performed by using a developing solution. Shadow processing is carried out.

The developer may be the same as the developer described above for exposure and development of the photoresist layer 51.

Further, when an alkaline aqueous solution is used as the developer, the cleaning treatment is usually carried out using water after development.

From the viewpoint of image resolution, the length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (in the case where the pixel is a rectangle) means the length of the short side, and the pixel In the case of a square, it means that the length of one side is preferably 0.5 μm to 1.7 μm, more preferably 0.6 μm to 1.5 μm.

According to the method for producing a color filter of the present invention described above, it is possible to provide a color filter having a coloring agent having a high concentration of a coloring agent and being hard to cause even when placed under high temperature and high humidity. The film surface of the surface of the colored layer is rough.

Further, according to the method for producing a color filter of the present invention, the first colored layer, particularly the first colored pixel, is formed of the color-curable composition having a high concentration of the coloring agent of the present invention, so that the first coloring can be performed. The thickness of the pixels is extremely thin (for example, 0.7 μm or less). Thereby, a color filter in which crosstalk (crosstalk of light) is suppressed can be manufactured.

In addition, the first coloring element formed by the coloring curable composition is excellent in solvent resistance and alkali resistance developing liquid property. Therefore, it is possible to reduce the occurrence of overlapping regions overlapping with the colors of other colored layers and other colored patterns, and as a result, a high-performance color filter can be manufactured.

The color filter of the present invention can be preferably used as a liquid crystal display device (Liquid Crystal Display (LCD) or solid-state imaging device (for example, Charge-coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS), etc.). Further, it can also be preferably used in an image display element such as an electronic paper or an organic electroluminescence. In particular, the color filter of the present invention can be preferably used as a solid-state imaging element such as a CCD or a CMOS.

Further, the color filter of the present invention is also suitable as a color filter for a liquid crystal display device. A liquid crystal display device including such a color filter can display an image in which a high-quality image having a good color tone and excellent display characteristics is displayed.

The definition of the display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association (share), issued in 1990)", "Display elements (Ibuki Shunzhang, Industrial Book) (shares), issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (Edited by Uchida Ryoko, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Color filter of the present invention for color film transistor (Thin Film Transistor, TFT) liquid crystal display device is useful. The liquid crystal display device of the color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a transverse electric field driving method such as In-Plane Switching (IPS) or a pixel such as MVA. Expanded liquid crystal display device such as split mode, Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (Optically Compensated Splay, OCS), Fringe Field Switching (FFS), and Reflective Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention is also available in a bright and high-definition color-filter on Array (COA) mode.

In the coloring layer formed by the COA method, in order to electrically connect the indium tin oxide (ITO) electrode disposed on the colored layer and the terminal of the driving substrate below the coloring layer, the length of one side must be 1 μm. It is preferable to set the size of the via (or the length of one side) to 5 μm or less in a rectangular through hole of about 15 μm or a via of a U-shaped recess. According to the invention, a conduction path of 5 μm or less can also be formed. These image display methods are described, for example, in "Electroluminescence (EL), Plasma Display Panel (PDP), LCD Display - Technology and Market Trends - (Toray Research Center Survey) The research department, issued in 2001), 43 pages, etc.

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display element composed of these well-known members. For these components, for example, it is described in "94 The market for liquid crystal display materials and chemistry (Mitanda Kentaro, CMC (share), issued in 1994)", "The current status and future prospects of the liquid crystal-related market in 2003 (volume) (Former Liangji, Fuji Chimera) Research Institute), issued in 2003).

About the backlight, it is described in the "Information Display Society Conference Summary (SID) Meeting Digest) 1380 (2005) (A. Konno et al.) or "Monthly Display, December 2005 issue, 18 pages to 24 pages (Island Kang Yu)", "Monthly display, December 2005 issue, 25 to 30 pages (Yamamu Longming) and so on.

If the color filter of the present invention is used in a liquid crystal display device, The high-contrast can be realized when the three-wavelength tube of the previously known cold cathode tube is combined, and the red, green, and blue light-emitting diode (LED) light source (RGB-LED) can be provided as a backlight. A liquid crystal display device having high brightness and high color reproducibility with good color reproducibility.

Example

The invention is more specifically illustrated by the following examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are the quality standards.

<Synthesis Example 1 - Synthesis of Dye A>

(Synthesis of Intermediate A)

Tetrachlorophthalonitrile (15.0 g, 56.4 mmol), HO-C ₆ H ₄ -COOC ₂ H ₄ OCH ₃ (12.65 g, 56.4 mmol), and 75.0 g of acetonitrile were placed in a flask, and a magnetic stirrer (magnetic) was used. After stirring for 30 minutes until the internal temperature was stable at 40 ° C, potassium carbonate (8.58 g, 62.1 mmol) was added and reacted for about 3 hours. The solution obtained by suction filtration after cooling was concentrated under reduced pressure at 40 ° C for 1 hour, and the solvent was distilled off. Further, it was vacuum dried at 110 ° C overnight to obtain about 23.0 g (89.9%) of Intermediate A.

(Synthesis of Dye A)

Intermediate A (2.13 g, 4.7 mmol) and benzonitrile 2.35 were placed in the flask. After stirring for about 1 hour under a nitrogen flow (10 mL/min) using a magnetic stirrer until the internal temperature was stabilized at 150 ° C, 0.43 g (1.3 mmol) of zinc iodide was added and reacted for about 35 hours. After cooling, 30 mL of methanol was added, and the mixture was stirred at room temperature using a magnetic stirrer to prepare a crystallization solution. The crystallization solution was decanted, and the remaining residue was purified by silica gel column chromatography (chloroform / methanol). 20 mL of methanol was added to the obtained purified product, and the mixture was stirred under heating at 60 ° C for 1 hour using a magnetic stirrer. After cooling, suction filtration was carried out, and 20 mL of methanol was added to the obtained crystal, and the mixture was heated and stirred at 60 ° C for 1 hour using a magnetic stirrer. After cooling, suction filtration was carried out, and the obtained crystals were air-dried at 40 ° C overnight to obtain about 1.95 g (88.2%) of dye A.

<Synthesis Example 2 - Synthesis of Other Dyes>

The dye B~ dye E was synthesized in accordance with the above Synthesis Example 1.

<Preparation of Pigment Dispersion>

Use zirconia beads with a diameter of 0.3mm, using a bead mill (with decompression The organization's high-pressure disperser NANO-3000-10 (made by Japan BEE Co., Ltd.) will be adjusted The mixed solution containing the following compounds was mixed and dispersed for 3 hours to prepare a pigment dispersion liquid. The type of the pigment is set as described in the following table, and the blending amount of each component is blended so that the composition ratio of the finally obtained colored curable composition is a ratio described in the following table.

. Pigments (pigments shown in the table below)

. derivative

. Dispersant

. Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Other indigo dyes were synthesized in accordance with the above Synthesis Example 1.

<Preparation of Colored Curable Composition>

Each component was mixed so as to have the composition described in the following table, and the mixture was stirred to prepare a colored curable composition.

. Dye (colorant)

. Yellow pigment (colorant)

. Thermosetting compound

. Solvent...the final solid content concentration is 15% by mass

Halogenated indigo dye A:

Halogenated Indigo Dye B:

Halogenated Indigo Dye C:

Halogenated indigo dye D:

Non-halogenated indigo dye E:

<Other colorants>

Yellow pigment A (azo pigment (pigment)): P.Y150

Yellow pigment B (methine methyl pigment (azo methine pigment) (dye)): (Synthesis example will be described later)

<derivative>

<dispersant>

In the above, a is 2.0, b is 4.0, an acid value is 10 mgKOH/g, and Mw is 20,000.

Further, a and b in the dispersant A respectively indicate the number of partial structures indicated in the parentheses, and satisfy a+b=6.

<thermosetting compound>

Thermosetting compound A: Epoxy compound: EHPE3150 (manufactured by Daicel Chemical Industries, Ltd., molecular weight = 2234)

Thermosetting compound B: melamine compound: Nikalac MW-30M (manufactured by Sanwa Chemical Co., Ltd.)

<Surfactant>

Surfactant: F-781 (manufactured by Di Aisheng (DIC) Co., Ltd., fluorine-based surfactant)

<Synthesis of methine dye B>

The methine-based dye B was synthesized in the following scheme.

(Synthesis of Intermediate A)

A mixed solution of 100 parts by weight of the above-mentioned compound (A) (synthesized by the method described in JP 0571959A2) and 390 ml of pyridine was cooled to 5 ° C, and 87 parts by weight of octylsulfonate chloride was added dropwise at a reaction temperature of 25 ° C or lower. After the reaction mixture was stirred at room temperature for 2 hours, 2 L of a 4N aqueous hydrochloric acid solution was added, and the mixture was stirred at room temperature and then filtered. The crystals collected by washing with 500 ml of methanol were washed and dried, whereby Intermediate 153 g (yield: 91%) was obtained.

¹ H-NMR CDCl ₃ δ 0.8 (t, 3H) 1.0-1.4 (m, 19), 1.6 (m, 2H) 3.2 (t, 2H) 5.6 (s, 1H) 7.3 (d, 2H) 7.9 (d, 2H) 10.2 (s, 1H) 12.9 (s, 1H)

(Synthesis of methine dye B)

68 g of ethyl orthoformate was added to a suspension solution of 110 g of Intermediate A and 650 ml of acetic acid at room temperature, and the reaction mixture was stirred at 80 ° C for 3 hours. 1.1 L of methanol was added to the reaction solution, and after cooling, it was filtered and washed with methanol to obtain a methine group. Pigment B 96 g (yield 88%).

¹ H-NMR CDCl ₃ δ 0.8 (t, 6H) 1.2-2.0 (m, 41H) 3.3 (t, 4H) 7.3 (d, 4H), 7.6 (br, 2H) 7.8 (d, 4H) 8.4 (s, 1H) The following composition was evaluated.

<Production of Film Surface Roughness Evaluation Substrate>

The composition was applied onto a 7.5 cm × 7.5 cm glass substrate by a spin coater so as to be a coating film having a film thickness of 0.5 μm, and then dried by heating at 100 ° C for 2 minutes using a hot plate, followed by 200 Heating was carried out for 5 minutes at ° C, and the coating film was cured to form a colored layer.

<Formation of oxygen blocking film>

In Example 1 to Example 3 and Comparative Example 2, SiO ₂ or SiN was sputtered on the produced glass substrate by a sputtering apparatus (SRV-4300 manufactured by Shinko Seiki Co., Ltd.), and the film thickness was formed on the colored layer. A 0.1 μm oxygen blocking membrane. Further, in Example 4 and Example 5, a polyvinyl alcohol (weight average molecular weight: 2000) aqueous solution or a polyvinyl base was applied to each of the produced glass substrates by using a spin coater (1H-D7 manufactured by Sanken Co., Ltd.). An aqueous solution of pyrrolidone (weight average molecular weight: 1800) was formed on the colored layer to form an oxygen barrier film having a film thickness of 1.0 μm. The results are shown in Table 1. Further, in Table 1, the inorganic material A represents SiO ₂ , the inorganic material B represents SiN, the organic material A represents polyvinyl alcohol, and the organic material B represents polyvinylpyrrolidone. In Comparative Example 1, none of them is formed. Oxygen blocks the membrane.

<High temperature and high humidity test>

Use high acceleration life test device (made by Espec) The manufactured EHS-221) was subjected to a high-temperature and high-humidity test for 168 hours under conditions of a temperature of 85 ° C and a humidity of 85% on a glass substrate on which an oxygen barrier film was formed.

<Film roughness evaluation>

The glass substrate on which the oxygen barrier film was formed after the high-temperature and high-humidity test was visually evaluated for agglomerated foreign matter under the condition of 200-fold reflection using an optical microscope (MX-50 manufactured by Olympus Co., Ltd.). The results are shown in the table below. 3 to 5 were evaluated as practically problem-free according to the following criteria.

- Evaluation criteria -

5: No condensed foreign matter was produced at all.

4: A very small amount of condensed foreign matter is generated (5 or more and less than 25 in 5 fields of view).

3: A small amount of condensed foreign matter is generated (more than 25 in less than 5 fields of view).

2: A plurality of agglomerated foreign matter was generated (100 or more and less than 500 in 5 fields of view).

1: Condensed foreign matter is apparent (more than 500 in 5 fields of view).

It is clear from the above table that it is thermosetting for the use of a coloring agent. The coloring layer formed of the colored curable composition having a total solid content of the colored curable composition and a total amount of the coloring agent of 50% by mass to 90% by mass is formed on the colored layer. The laminate of the oxygen barrier film (Examples 1 to 10) can suppress film surface roughness.

Further, it is found that in Examples 1 to 10, there is an excellent spectroscopic Sex, and has good light resistance.

On the other hand, it was found that the laminate of the oxygen barrier film was not formed (Comparative Example 1). The result of rough film surface is not good. In addition, when the total content of the coloring agent is less than 50% (Comparative Example 2) with respect to the total solid content of the coloring curable composition, the film surface roughness is suppressed, but the coloring agent is suppressed. The concentration is low, so filming cannot be achieved.

10‧‧‧ Solid-state imaging components

13‧‧‧Color filters

14‧‧‧Flat film

15‧‧‧Microlens

20B‧‧‧Blue pixel (3rd color)

20G‧‧‧Green pixels (1st color)

20R‧‧‧Red Picture (2nd color picture)

41‧‧‧P-well

42‧‧‧Light-receiving components (light diodes)

43‧‧‧ impurity diffusion layer

44‧‧‧Electrode

45‧‧‧Wiring layer

46‧‧‧BPSG membrane

47‧‧‧Insulation film

48‧‧‧P-SiN film

49‧‧‧Flating film layer

Claims (18)

A laminated body in which a layered body of an oxygen blocking film is formed on a colored layer obtained by curing a colored curable composition, and the colored curable composition contains a coloring agent, a thermosetting compound, and a solvent, and The total solid content of the coloring curable composition is 50% by mass to 90% by mass based on the total content of the coloring agent. The laminate according to the first aspect of the invention, wherein the colorant contains a halogenated indigo dye represented by the following formula (1), (In the formula (1), Z ¹ to Z ¹⁶ are each a hydrogen atom or a substituent, at least one of the substituents is a halogen atom, and at least one other of the substituents is a group containing an aromatic group; M represents 2 hydrogens Atom, metal atom, metal oxide or metal halide). The laminate according to claim 1 or 2, wherein the thermosetting compound is an epoxy compound. The laminate according to claim 1 or 2, wherein the coloring agent further contains a yellow pigment. The laminated body according to the above aspect of the invention, wherein the total content of the coloring agent is 60% by mass to 90% by mass based on the total solid content of the colored curable composition. The laminate according to claim 1 or 2, wherein the colored layer has a thickness of 0.1 μm to 1.0 μm. The laminate according to claim 1 or 2, wherein the oxygen barrier film is adjacent to the colored layer. The laminate according to the first or second aspect of the invention, wherein the oxygen barrier film has a thickness of 10 μm or less. The laminate according to claim 1 or 2, wherein the oxygen barrier film contains an inorganic material. The laminate according to the first or second aspect of the invention, wherein the thermosetting compound is an epoxy compound, and the coloring agent further contains a yellow pigment. The laminated body according to the above aspect of the invention, wherein the coloring agent further contains a yellow coloring matter, and the total content of the coloring agent is 60% by mass based on the total solid content of the colored curable composition. ~90% by mass. The laminated body according to the first or second aspect of the invention, wherein the thickness of the oxygen blocking film is 10 μm or less, and the thickness of the colored layer is 0.1 μm to 1.0 μm. A color filter comprising the laminate as described in claim 1 body. A method for producing a color filter, comprising: a step of curing a colored curable composition to form a colored layer, wherein the colored curable composition contains a colorant, a thermosetting compound, and a solvent, and is composed of the coloring hardenability composition a total solid content of the material, a total content of the colorant of 50% by mass to 90% by mass; a step of forming a photoresist layer on the colored layer; and patterning the photoresist layer by exposure and development to obtain a resist a step of patterning; a step of dry etching the colored layer using the resist pattern as an etch mask; and a step of forming an oxygen blocking film on the colored layer after the dry etching. The method of producing a color filter according to claim 14, wherein the oxygen blocking film is formed by sputtering. A liquid crystal display device comprising the color filter according to claim 13 or the color filter manufactured by the method for producing a color filter according to claim 14 or 15 Light film. An organic electroluminescence device comprising the color filter of claim 13 or the method for producing a color filter according to claim 14 or 15 Color filter. A solid-state photographic element comprising the color filter of claim 13 or by the method of claim 14 or 15 A color filter produced by a method of manufacturing a color filter.