WO2014069314A1

WO2014069314A1 - Laminate and color filter therewith, process for producing same and application of color filter

Info

Publication number: WO2014069314A1
Application number: PCT/JP2013/078762
Authority: WO
Inventors: 俊人空花; 陽祐村上; 賢鮫島
Original assignee: 富士フイルム株式会社
Priority date: 2012-10-31
Filing date: 2013-10-24
Publication date: 2014-05-08
Also published as: JP6088794B2; TW201416398A; TWI630242B; JP2014089408A

Abstract

A laminate provided with a colored layer which has a high colorant concentration and the surface of which is not susceptible to roughening even under high-temperature and high-humidity conditions; a color filter and a process for producing the same; and application of a color filter. This laminate comprises a colored layer and an oxygen barrier film formed thereon, wherein the colored layer is a layer obtained by curing a curable colored composition which comprises a colorant, a thermosetting compound and a solvent and in which the total content of the colorant is 50 to 90 mass% relative to the total amount of the solid constituents of the curable colored composition.

Description

LAMINATE, COLOR FILTER HAVING THE SAME, ITS MANUFACTURING METHOD, AND APPLICATION OF COLOR FILTER

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

The color filter is an indispensable component for a display of a solid-state image sensor or a liquid crystal display device. In order to form such a color filter, a colored curable composition is employed (see, for example, Patent Documents 1 and 2).
On the other hand, the color filter is also required to be thin.

JP 2011-248197 A JP 2009-251563 A

In order to produce a color resist having excellent spectral characteristics even if the color filter is made thin, it is conceivable to increase the concentration of the colorant in the colored layer. However, as a result of studies by the present inventors, it has been found that when the concentration of the colorant is increased, film surface roughness on the surface of the colored layer tends to occur when the formed colored layer is placed under high temperature and high humidity. When film surface roughness occurs, device sensitivity and color reproducibility are reduced.
An object of the present invention is to provide a color filter that solves the above-described problems and is a colored layer having a high concentration of colorant, and is less likely to cause film surface roughness on the surface of the colored layer even under high temperature and high humidity. The purpose is to do.

As a result of intensive studies by the present inventors under such circumstances, by forming an oxygen-blocking film on the colored layer, even if the concentration of the colorant is high, the film surface roughness on the colored layer surface can be reduced under high temperature and high humidity. The inventors have found that it can be suppressed, and have completed the present invention.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <13>.
<1> A colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass relative to the total solid content of the colored curable composition. A laminate in which an oxygen barrier film is formed on a colored layer formed by curing a certain colored curable composition.
<2> The laminate according to <1>, wherein the colorant includes a halogenated phthalocyanine dye represented by the following general formula (1).
General formula (1)

(In the general 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 of the other substituents is aromatic. (M represents a hydrogen atom, a metal atom, a metal oxide, or a metal halide.)
<3> The laminate according to <1> or <2>, wherein the thermosetting compound is an epoxy compound.
<4> The laminate according to any one of <1> to <3>, wherein the colorant further contains a yellow pigment.
<5> The laminate according to any one of <1> to <4>, wherein the total content of the colorant is 60 to 90% by mass with respect to the total solid content of the colored curable composition.
<6> The laminate according to any one of <1> to <5>, wherein the colored layer has a thickness of 0.1 to 1.0 μm.
<7> The laminate according to any one of <1> to <6>, wherein the oxygen blocking film and the colored layer are adjacent to each other.
<8> The laminate according to any one of <1> to <7>, wherein the oxygen blocking film has a thickness of 10 μm or less.
<9> The laminate according to any one of <1> to <8>, wherein the oxygen barrier film includes an inorganic material.
<10> A color filter having the laminate according to any one of <1> to <9>.
<11> A colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass relative to the total solid content of the colored curable composition. A step of curing a colored curable composition to form a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and A method for producing a color filter, comprising: 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 element, or a solid-state imaging device having the color filter according to <10> or the color filter produced by the method for producing a color filter according to <11> or <12>.

According to the present invention, it is possible to provide a color filter that is a colored layer having a high colorant concentration and is less likely to cause film surface roughness on the colored layer surface even under high temperature and high humidity.

It is a schematic sectional drawing which shows the structural example of a color filter and a solid-state image sensor. It is a schematic sectional drawing of a 1st colored layer. It is a schematic sectional drawing which shows the state in which the photoresist layer was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the resist pattern was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the 1st colored pattern was formed by providing a through-hole group in the 1st colored layer by etching. It is a schematic sectional drawing which shows the state from which the resist pattern in FIG. 5 was removed. It is a schematic sectional drawing which shows the state in which the 2nd coloring pattern and the 2nd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 2nd coloring radiation sensitive layer in FIG. 7 and a part of 2nd coloring pixel which comprises a 2nd coloring pattern were removed. It is a schematic sectional drawing which shows the state in which the 3rd coloring pattern and the 3rd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 3rd coloring radiation sensitive layer in FIG. 9 was removed. It is a schematic sectional drawing which shows an example of the color filter of this invention.

Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In addition, in the description of group (atomic group) in this specification, the description which is not describing substitution and non-substitution includes what does not have a substituent and what has 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).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
The “colored layer” in the present invention means a pixel used for a color filter.
The dye in the present invention means a coloring compound that is soluble in a specific organic solvent. Here, the specific organic solvent includes, for example, organic solvents exemplified in the column of a solvent that dissolves at least a dye and a thermosetting compound described later. Therefore, the coloring compound which dissolves in at least one organic solvent corresponds to the dye in the present invention.

Hereinafter, the laminate, the color filter and the manufacturing method thereof, 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 made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[Laminate]
In the laminate of the present invention, an oxygen barrier film is formed on a colored layer obtained by curing a colored curable composition.

<Colored curable composition>
The colored curable composition used in the present invention is a colored curable composition containing a colorant, a thermosetting compound, and a solvent, and the total content of the colorant is the total solid content of the colored curable composition. The content is 50 to 90% by mass.

<Colorant>
The colorant is not particularly limited, and for example, a coloring matter including a dye or a pigment can be used, and it is particularly preferable that the dye is essential. In the present invention, the total amount of the colorant is preferably 60 to 85% by mass and more preferably 70 to 80% by mass with respect to the total solid content of the colored curable composition.
(dye)
There is no restriction | limiting in particular in dye, A well-known dye can be used for color filters conventionally. For example, pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, Phthalocyanine-based, benzopyran-based, indigo-based, pyromethene-based and methine-based dyes can be used. Moreover, you may use the multimer of these dyes.
Moreover, when performing water or alkali image development, an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
Examples of the dye include, for example, JP 2012-181512 A, JP 64-90403 A, JP 64-91102 A, JP 1-94301 A, JP 6-11614 A, Japanese Patent No. 2592207, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115, Japanese Patent Application Laid-Open No. 6-194828, Japanese Patent Application Laid-Open No. No. 249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771. JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP2002-2002 No. 4220, JP-A No. 2002-14221, JP-A No. 2002-14222, JP-A No. 2002-14223, JP-A No. 8-302224, JP-A No. 8-73758, JP-A No. 8-179120 The dyes described in JP-A-8-151531 and the like can be used.

Among these dyes, phthalocyanine dyes having a phthalocyanine structure, particularly halogenated phthalocyanine dyes are particularly preferable. The halogenated phthalocyanine dye refers to a compound having a phthalocyanine skeleton and having one or more halogen atoms as a substituent. In the present invention, 5 to 15 halogen atoms per molecule are preferable, and 6 to 14 halogen atoms are more preferable. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further preferable.
The halogenated phthalocyanine dye used in the present invention is usually a compound having a maximum absorption wavelength in the region of 600 to 800 nm, and preferably having a maximum absorption wavelength in the region of 630 to 750 nm.

The halogenated phthalocyanine dye used in the present invention is preferably a compound represented by the following general formula (1).
General formula (1)

(In the general 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 of the other substituents is aromatic. (M represents a hydrogen atom, a metal atom, a metal oxide, or a metal halide.)

Here, in the general formula (1), Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ represent substituents substituted at eight α positions of the phthalocyanine nucleus. Therefore, these substituents are also referred to as α-position substituents. Similarly, Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ in the general formula (1) are substituents substituted at eight β-positions of the phthalocyanine nucleus. These substituents are also referred to as β-position 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 preferable to have 5 to 15 halogen atoms in one molecule, and more preferable to have 6 to 14 halogen atoms. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. A chlorine atom, a fluorine atom, or a bromine atom is preferable, a chlorine atom or a fluorine atom is more preferable, and a chlorine atom is further preferable. The aromatic group in the group containing an aromatic group (preferably a group represented by the general formula (1-2) described later) is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. The number of groups having an aromatic group is preferably 1 to 11, more preferably 1 to 10, and further preferably 2 to 7 in one molecule. Also preferred is an embodiment in which Z ¹ to Z ¹⁶ are all groups other than halogen atoms having an aromatic group.
The substituent is not particularly defined as long as the phthalocyanine compound does not lose its function as a dye, and examples thereof include substituent T described later.

In the general formula (1), 1 to 8 of Z ¹ to Z ¹⁶ represent a group represented by the following general formula (1-2) or a group represented by the general formula (1-4), And at least one is preferably a group represented by the general formula (1-2), more preferably 2 to 6 of Z ¹ to Z ¹⁶ are represented by the general formula (1-2). Or a group represented by the general formula (1-4), and at least one is a group represented by the general formula (1-2).
Formula (1-2)

(In the general 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. is there.)
General formula (1-4)

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

In general formula (1-2), X represents an oxygen atom or a sulfur atom, and preferably an oxygen atom. When X is an oxygen atom, the maximum absorption wavelength of the obtained phthalocyanine 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, and is a phenyl group having 1 to 5 substituents or 1 to 7 substituents. And a phenyl group having 1 to 5 substituents is more preferable.

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

(In the general formula (1-1-2), X ¹ is an oxygen atom or a sulfur atom, and A ¹¹ has a phenyl group having 1 to 5 substituents R, or 1 to 7 substituents R. The substituent R is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), OR ² (R ² is a naphthyl group) 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 general formulas (4) to (6), or a general formula Represents a group selected from (X).)

(In the general formula (4), R ⁴ is 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, or a substituent. Represents a diarylamino group which may have a substituent or an alkylarylamino group which may have a substituent.
In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ may have an alkyl group which may have a substituent, or may have a substituent. When d is 2, R ⁵ is 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 substituted group; It represents a diarylamino group which may have a group, or an alkylarylamino group which may have a substituent.
In general formula (6), R ⁶ and R ⁷ are each an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, The arylcarbonyl group which may have a substituent, the alkylsulfonyl group which may have a substituent, and the arylsulfonyl group which may have a substituent are represented. )

(In the general 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 are Y ¹ is —O—, —S—, —NR ¹³ — (R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —SO _{2 represents} — or —C (═O) —, and R ¹² represents a monovalent substituent.

In general formula (1-1-2), X ¹ represents 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 phthalocyanine 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, and 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, but from the viewpoint of the gram extinction coefficient (absorbance per gram), an integer of 1 to 3 is more preferable. When the substituent is a halogen atom, The number of substituents is preferably any integer of 1 to 5. The number of substituents of the naphthyl group is an integer of 1 to 7, but is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, from the viewpoint of the gram extinction coefficient. More preferably it is.

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

Similarly, the bonding position of the substituent to the naphthalene ring is not particularly limited. For example, when the bonding position between the naphthyl group and X ¹ is the 1-position (1-naphthyl group), the bonding positions of the substituent to the naphthalene ring are the 2-position, 3-position, 4-position, 5-position, 6-position, However, in view of heat resistance, solvent solubility, etc., the 2nd and 3rd positions are preferable, and the 2nd position is more preferable. When the bonding position between the naphthyl group and X ¹ is the 2-position (2-naphthyl group), the bonding positions of the substituent to the naphthalene ring are the 1-position, 3-position, 4-position, 5-position, 6-position, However, the 3rd and 6th positions are preferable, and the 3rd position is more preferable in consideration of heat resistance and solvent solubility.

The substituent R of the phenyl group or naphthyl group is a nitro group, COOR ¹ (R ¹ is a group represented by the general formula (1-3) or an alkyl group having 1 to 8 carbon atoms), 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 general formulas (4) to (6), or It is a group selected from the formula (X).

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

When the substituent R of the phenyl or naphthyl group is COOR ^1, R ¹ in the COOR ¹ is represented by an alkyl group substituted by 1 carbon atoms which may be 1-8 or the following general formula, (1-3) Represents a group.
General formula (1-3)

(In the general 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). )

When 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, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, and n-pentyl. A linear, branched or cyclic alkyl group such as a group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. Examples of the substituent present in the alkyl group having 1 to 8 carbon atoms include an alkyloxy group having 1 to 8 carbon atoms, a halogen atom or an aryl group.
As the alkyloxy group having 1 to 8 carbon atoms, which may be present as a substituent of the alkyl group, there are methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso- Straight chain such as butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group A branched or cyclic alkyloxy group. Among these, an alkyloxy group having 1 to 4 carbon atoms is preferable. Examples of the halogen atom that is a substituent of the alkyl group that may be present include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable. Examples of the aryl group that is a substituent of the alkyl group that may be present include a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among these, a phenyl group is preferable. A plurality of these substituents may be present. If there are a plurality of these substituents, they may be the same or different, and even if they are the same, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2.

When the substituent R of the phenyl group or naphthyl group is COOR ¹ and R ¹ is a group represented by the general formula (1-3), R ³ in the group represented by the general formula (1-3) is From the viewpoint of the effect on ether solvent solubility, it 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 ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ⁴ in the group represented by the general formula (1-3) is an alkyl group of 1 to 8, more preferably an alkyl group of 1 to 4, from the viewpoint of molecular weight. Examples of the alkyl group having 1 to 8 carbon atoms include those described in the above R ¹ column. N in the group represented by the general formula (1-3) is an integer of 1 to 4, and preferably an integer of 1 to 3, from the viewpoint of molecular weight.

When the substituent R of the phenyl or naphthyl group is OR ^2, R ² in OR ² represents an alkyl group having 1 to 8 carbon atoms, preferably crystalline dye, from the viewpoint of handling of the good, a C1- 3 alkyl groups are shown.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include the same substituents as those described for R ¹ of COOR ¹ , which is an example of the above-described substituent R, and the preferred range is also synonymous. is there.

When the substituent R of the phenyl group or naphthyl group is a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or an iodine atom is preferable. Among them, a chlorine atom and a fluorine atom are preferable because the molecular weight of the dye is reduced and the gram absorption coefficient is increased.

When the substituent R of the phenyl group or naphthyl group is an aryl group, examples of the aryl group include aryl groups such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, and a p-chlorophenyl group. Among them, a phenyl group is preferable because the molecular weight of the dye is reduced and the gram extinction coefficient is increased.

In the case where the substituent R of the phenyl group or naphthyl group is an alkyl group, the alkyl group having 1 to 8 carbon atoms is the same as that described in R ¹ of COOR ¹ as an example of the substituent R. The preferable range is also synonymous.
An alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of the crystallinity and handleability of the dye.
As the substituent of the alkyl group which may be present in some cases, a halogen atom is exemplified, and a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom or a chlorine atom is more preferable. There may be a plurality of halogen atoms as substituents for the alkyl group, and when there are a plurality of halogen atoms, they may be the same or different. The number of substituents on the alkyl group is not particularly limited, but is preferably 1 to 3.

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

R ⁴ in the general 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, or a substituent. A diarylamino group which may have, or an alkylarylamino group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a total carbon atom A dialkylamino group having 2 to 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms in total, or an alkylarylamino group having 7 to 20 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms in total, and 2 to 2 carbon atoms in total. More preferred is a dialkylamino group having 20 carbon atoms, a diarylamino group having 12 to 20 carbon atoms, or an alkylarylamino group having 7 to 20 carbon atoms, and a diarylamino group having 12 to 20 carbon atoms or a total carbon number. Dialkylamino groups to 20 are particularly preferred.
The alkyl moiety and the aryl moiety may further have a substituent, and the substituent is preferably an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group or a halogen atom, and an alkoxy group Are more preferable, and a methoxy group or an ethoxy group is more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In the general formula (5), d represents an integer of 0 to 2, and when d is 0 or 1, R ⁵ is an alkyl group that may have a substituent or an aryl that may have a substituent. And when d is 2, the alkyl group which may have a substituent, the aryl group which may have a substituent, the dialkylamino group which may have a substituent, and the substituent Or a diarylamino group which may be substituted or an alkylarylamino group which may have a substituent. 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 when d is 2.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable.

In general formula (6), R ⁶ and R ⁷ are each 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, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, a carbon number of 6 An aryl group having ˜20, 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, and an arylsulfonyl group having 6 to 20 carbon atoms are preferable. 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, and an arylsulfonyl group having 6 to 20 carbon atoms are more preferable.
The alkyl moiety and the aryl moiety may further have a substituent, and examples of the substituent include a substituent T described later. An alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group. Or a halogen atom etc. are preferable, an alkoxy group is more preferable, and a methoxy group or an ethoxy group is further more preferable. Moreover, the aspect which does not have a substituent is also preferable. Examples of the alkyl group and the like which may have a substituent will be described later.

Preferred examples of the alkyl group that may have a substituent in the above general formula are shown below. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, Hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, ethoxyethoxyethyl group, 2-chloroethyl group can be mentioned, more preferably methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, phenoxyethyl group, benzyl group, Phenylethyl group, N-butyl Examples thereof include aminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group. Particularly preferred are methyl group, ethyl group, propyl group, tert-butyl group, phenoxyethyl. Group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group and ethoxyethoxyethyl group.

Preferred examples of the aryl group which may have a substituent in the general formulas (4) to (6) are shown below. Such aryl groups include phenyl, 2-chlorophenyl, 2-methoxyphenyl, 4-butoxycarbonylphenyl, 4-N, N-dibutylaminocarbonylphenyl, 4-N-butylaminosulfonylphenyl 4-N, N-dibutylaminosulfonylphenyl group, more preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group. 4-N, N-dibutylaminosulfonylphenyl group, particularly preferably phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N, N-dibutylaminosulfonyl group. A phenyl group is mentioned.

Preferred examples of the dialkylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such a dialkylamino group include N, N-dimethylamino group, N, N-dibutylamino group, N, N-di (2-ethylhexyl) amino group, N-methyl-N-benzylamino group, N, N-di (2-ethoxyethyl) amino group, N.I. N-di (2-hydroxyethyl) amino group may be mentioned.

Preferred examples of the diarylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such a diarylamino group include an N, N-diphenylamino group, an N, N-di (4-methoxyphenyl) amino group, and an N, N-di (4-acylphenyl) amino group.

Preferred examples of the alkylarylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylarylamino group include an N-methyl-N-phenylamino group, an N-benzyl-N-phenylamino group, and an N-methyl-N- (4-methoxyphenyl) amino group.

Preferred examples of the alkylcarbonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylcarbonyl group include an acetyl group, a propylcarbonyl group, a heptyl-3-carbonyl group, a 2-ethylhexyloxymethylcarbonyl group, a phenoxymethylcarbonyl group, and a 2-ethylhexyloxycarbonylmethylcarbonyl group.

Preferred examples of the arylcarbonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such arylcarbonyl groups include benzoyl group, 4-methoxybenzoyl group, and 4-ethoxycarbonylbenzoyl group.

Preferred examples of the alkylsulfonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylsulfonyl group include a methanesulfonyl group, an octanesulfonyl group, a dodecylsulfonyl group, a benzylsulfonyl group, and a phenoxypropylsulfonyl group.

Preferred examples of the arylsulfonyl group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an arylsulfonyl group include a phenylsulfonyl group, a 2-methoxyphenylsulfonyl group, and a 4-ethoxycarbonylphenylsulfonyl group.

Preferred examples of the alkylsulfonylamino group which may have a substituent in the general formulas (4) to (6) are shown below. Examples of such an alkylsulfonylamino group include a methylsulfonylamino group, a butylsulfonylamino group, a hydroxypropylsulfonylamino group, a 2-ethylhexylsulfonylamino group, an n-octylsulfonylamino group, a phenoxyethylsulfonylamino group, and an allylsulfonylamino group. Is mentioned.

In the general formulas (4) to (6), examples of the vinylsulfonylamino group which may have a substituent include a vinylsulfonylamino group and a 1-methylvinylsulfonylamino group.

In the general formulas (4) to (6), the arylsulfonylamino group which may have a substituent includes a phenylsulfonylamino group, a p-methoxyphenylsulfonylamino group, a p-ethoxycarbonylsulfonylamino group, and the like. Is mentioned.

In the above general formulas (4) to (6), the alkylcarbonylamino group which may have a substituent is a methylcarbonylamino group, a 2-ethylhexanoylamino group, an n-heptylcarbonylamino group, an ethoxyethoxy group. Examples include a methylcarbonylamino group.

In the general formulas (4) to (6), examples of the arylcarbonylamino group which may have a substituent include a benzoylamino group, a 2-methoxybenzoylamino group, and a 4-vinylbenzoylamino group.

Examples of the substituent T are shown below.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having a carbon number of 2 to 18 alkenyl groups such as vinyl group, allyl group, 3-buten-1-yl group), aryl groups (preferably aryl groups having 6 to 24 carbon atoms such as phenyl group, naphthyl group), heterocyclic ring Group (preferably a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2- Limidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 18 carbon atoms, for example, trimethylsilyl Group, triethylsilyl group, tributylsilyl group, tert-butyldimethylsilyl group, tert-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 24 carbon atoms, , Methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group) An aryloxy group (preferably having 6 to 2 carbon atoms) Aryloxy groups such as phenoxy group and 1-naphthoxy group, and heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 18 carbon atoms such as 1-phenyltetrazole-5-oxy group, 2- Tetrahydropyranyloxy group), silyloxy group (preferably a silyloxy group having 1 to 18 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably carbon number) An acyloxy group having 2 to 24, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, ethoxycarbonyloxy Tert-butoki In the case of a sicarbonyloxy group or a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, phenoxy Carbonyloxy group), carbamoyloxy group (preferably a carbamoyloxy group having 1 to 24 carbon atoms such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N- Ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyl group) Oxy group), alkyl A sulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably having a carbon number of 6 to 24) An arylsulfonyloxy group such as a phenylsulfonyloxy group, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexayl group, Noyl group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2,6-di-ter -Butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl group), carbamoyl group (preferably carbamoyl having 1 to 24 carbon atoms) Groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN -Phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 24 or less carbon atoms, for example, amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group) Group, 2-ethylhexylamino group, cyclohexyl Silamino group), anilino group (preferably 6 to 24 anilino group such as anilino group, N-methylanilino group), heterocyclic amino group (preferably 1 to 18 heterocyclic amino group such as 4-pyridylamino) Group), a carbonamide group (preferably a carbonamide group having 2 to 24 carbon atoms, such as an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a ureido having 1 to 24 carbon atoms Group, for example, ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide group, N-phthalimide group), Alkoxycarbonylamino group (preferably an alkoxycarbonyl group having 2 to 24 carbon atoms) Group, for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having 7 to 24 carbon atoms) An aryloxycarbonylamino group such as a phenoxycarbonylamino group, a sulfonamide group (preferably a sulfonamide group having 1 to 24 carbon atoms, such as a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, hexadecane Sulfonamido group, cyclohexanesulfonamido group), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N Ethyl-N-dodecylsulfamoylamino group), azo group (preferably an azo group having 1 to 24 carbon atoms, for example, phenylazo group, 3-pyrazolylazo group), alkylthio group (preferably having 1 to 24 carbon atoms). Alkylthio group, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably arylthio group having 6 to 24 carbon atoms, for example, phenylthio group), heterocyclic thio group (preferably having carbon number) 1 to 18 heterocyclic thio groups such as 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably alkylsulfinyl group having 1 to 24 carbon atoms) For example, dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 2 carbon atoms) 4 arylsulfinyl groups such as phenylsulfinyl group, alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 24 carbon atoms such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropyl Sulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, for example, phenylsulfonyl group, 1-naphthylsulfonyl group) Group), a sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, such as a sulfamoyl group, an N, N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-ethyl group). Ru-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably phosphonyl group having 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, Phenylphosphonyl group) and a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group).

When the above-described substituent is a substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

The case where the substituent R of the phenyl group or naphthyl group is a group represented by the general formula (X) will be described.

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 more preferably a hydrogen atom.
n1 represents an integer of 1 to 3, more preferably 1 or 2. When n1 is 2 or 3, the plurality of R ¹¹ may be the same or different.
Y ¹ represents —O—, —S—, —NR ¹³ —, —SO ₂ —, or —C (═O) —, and represents —O—, —SO ₂ —, or —C (═O). -Is preferred, and -O- or -C (= O)-is more preferred.
R ¹² represents a monovalent substituent, and examples of the substituent include the above-described substituent T. The substituent T may be further substituted with the substituent T. R ¹² is preferably an alkyl group which may have a substituent, an acyl group which may have a substituent, a sulfonyl group which may have a substituent, an alkoxy group which may have a substituent, Or an alkylamino group which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 12 carbon atoms which may have a substituent. And an alkylamino group having 1 to 12 carbon atoms which may have a substituent.
The mass of the R ¹² portion per molecule is preferably 200 to 2500, and more preferably 250 to 1500.
R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

Next, general formula (1-4) will be described.
In the general formula (1-4), R ′ is an alkylene group having 1 to 3 carbon atoms from the viewpoint of ether solubility and molecular weight. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, an ethylene group, an n-propylene group, and an iso-propylene group. Preferably, they are an ethylene group and a propylene group.
R ″ is an alkyl group having 1 to 8 carbon atoms, and preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoint of ether solubility and molecular weight. It is synonymous with R ³ in 1-3), and the preferred range is also synonymous.
n1 is an integer of 0 to 4, more preferably an integer of 1 to 2, from the viewpoint of ether solubility and molecular weight.

Next, M, which is the central part of the general formula (1), will be described. In the general formula (1), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. Examples of the metal atom include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal atom, a metal oxide or a metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper. Vanadyl and zinc, more preferably zinc and copper, and most preferably zinc. It is preferable that the central metal is zinc or copper because of high heat resistance. Further, it is particularly preferable that the central metal is zinc because the transmittance in the vicinity of 520 nm to 545 nm, which is a green wavelength, is higher than that of copper, and the luminance can be improved when a color filter is formed. Further, it is particularly preferable because it has high solvent solubility in general-purpose solvents such as acetone, methanol, and methyl cellosolve, and has high solubility in resins and high contrast.

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

(In the general formula (1-1), Z ¹ to Z ¹⁶ are each a hydrogen atom, a halogen atom, a group represented by the general formula (1-1-2), or a general formula (1-3). Or a group represented by the above general formula (1-4), and 1 to 8 of Z ¹ to Z ¹⁶ are represented by the above general formula (1-1-2). Or at least one is a halogen atom and at least one is a group represented by the general formula (1-1-2) M represents two hydrogen atoms, metal atoms, metal oxides or metal halides.)

The general formula (1-1-2), the general formula (1-3), and the general formula (1-4) in the general formula (1-1) are represented by the general formula (1-1) described in the general formula (1). -2), synonymous with general formula (1-3) and general formula (1-4), and a preferred range is also synonymous. Therefore, Z ¹ to Z ¹⁶ in the general formula (1-1) are more preferably in the same range as Z ¹ to Z ^{16 in} the general formula (1).
M in the general formula (1-1) has the same meaning as M in the general formula (1), and a preferred range is also the same.

Examples of Z ¹ to Z ¹⁶ in the general formula (1) and general formula (1-1) used in the present invention will be given below, but the present invention is not limited thereto.

Although the example of the phthalocyanine compound used by this invention is given to the following, it cannot be overemphasized that this invention is not limited to these.
The following table shows the substituents represented by the following general formula and their numbers.

Ar in the following table represents the following structure.

In the above formula, Ph is a phenyl group.

In the above, Pc represents a phthalocyanine nucleus, Zn represents a central metal, represents a substituent substituted at the α-position immediately after Pc, and a substituent substituted at the β-position after the substituent substituted at the α-position Represents a substituent that does not depend on the substitution position after the substituent that is substituted at the β-position. x and y are positive numbers whose number of substituents is an integer of 0 or more.

Since the phthalocyanine compound becomes a mixture having different substitution positions and substitution numbers, it is difficult to uniquely describe it as a structural formula. Further, the number of substitutions shown in the following table is a value obtained by approximating the average value of the number of substituents in the mixture, and may be a small number.

Method for Producing Halogenated Phthalocyanine Compound The method for producing the phthalocyanine compound used in the present invention is not particularly limited, and a conventionally known method can be used. A method of cyclizing a phthalonitrile compound and a metal salt in a molten state or an organic solvent is particularly preferable. Hereinafter, preferred embodiments of the method for producing a phthalocyanine compound will be described. However, the present invention is not limited to the following preferred embodiments.
That is, the following formula (I):

A phthalonitrile compound (1) represented by the following formula (II):

A phthalonitrile compound (2) represented by the following formula (III):

And a phthalonitrile compound (3) represented by the following formula (IV):

A phthalonitrile compound (4) represented by the formula: from the group consisting of metal atoms, metal oxides, metal carbonyls, metal halides and organic acid metals (also collectively referred to as “metal compounds” in this specification). A phthalocyanine compound can be produced by cyclization reaction with one selected.
In the above formulas (I) to (IV), Z ¹ to Z ¹⁶ are defined by the structure of the desired phthalocyanine 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), respectively, and thus description thereof is omitted here. To do.

The cyclization reaction can be synthesized by a conventionally known method such as the method described in JP-A No. 64-45474.
In the above embodiment, the cyclization reaction is carried out by melting one kind selected from the group consisting of the phthalonitrile compounds of formulas (I) to (IV) and a metal, a metal oxide, a metal carbonyl, a metal halide and an organic acid metal in a molten state or organic It is preferable to react in a solvent. The metal, metal oxide, metal carbonyl, metal halide, and organic acid metal that can be used at this time are those corresponding to the central portion of the phthalocyanine compound obtained after the reaction (M in the general formula (1)). If there is, it is not particularly limited. Therefore, metals such as iron, copper, zinc, vanadium, titanium, indium, and tin listed in the item M in the general formula (1), metal halide compounds such as chloride, bromide, and iodide of the metal, Examples thereof include metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetate, complex compounds such as acetylacetonate, and metal carbonyls such as carbonyl iron. Specifically, metals such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; metal halides such as chloride, bromide, and iodide of the metal, such as vanadium chloride, titanium chloride, and chloride. Copper, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, copper iodide, zinc iodide, cobalt iodide, indium iodide, iodide Aluminum, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide; vanadium monoxide, vanadium trioxide, vanadium tetroxide, vanadium pentoxide, titanium dioxide, iron monoxide, three Iron dioxide, triiron tetroxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt dioxide Metal oxides such as cobalt dioxide, cuprous oxide, cuprous oxide, cupric oxide, copper trioxide, barium oxide, zinc oxide, germanium monoxide, and germanium dioxide; copper acetate, zinc acetate, cobalt acetate, copper benzoate And organic acid metals such as zinc benzoate; and complex compounds such as acetylacetonate and metal carbonyls such as cobalt carbonyl, iron carbonyl and nickel carbonyl. Of these, metals, metal oxides and metal halides are preferable, metal halides are more preferable, vanadium iodide, copper iodide and zinc iodide are more preferable, and iodine is particularly preferable. Copper iodide and zinc iodide, most preferably zinc iodide. When zinc iodide is used, the central metal is zinc. Among metal halides, it is preferable to use iodide because it has excellent solubility in solvents and resins, and the spectrum of the resulting phthalocyanine compound is sharp and easily fits within the desired wavelength range of 640 to 750 nm. is there. The detailed mechanism of sharpening the spectrum when using iodide during the cyclization reaction is unknown, but when iodide is used, the iodine remaining in the phthalocyanine compound after the reaction may not interact with the phthalocyanine compound. It is presumed that iodine is present between the layers of the phthalocyanine compound due to the action. However, the mechanism is not limited to the above mechanism. In order to obtain the same effect as when metal iodide is used for the cyclization reaction, the obtained phthalocyanine compound may be treated with iodine.

In the above embodiment, the cyclization reaction can be performed in the absence of a solvent, but it is preferably performed using an organic solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material, and preferably exhibits no reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o -Inert solvents such as chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol, 1-hexanol, 1-pentanol, 1-octanol; and pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, Triethylamine, tri n- butylamine, dimethyl sulfoxide, aprotic polar solvents such as sulfolane.
Of these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene and benzonitrile are preferably used, and more preferably 1-octanol, dichlorobenzene and benzonitrile are used. These solvents may be used alone or in combination of two or more.

The reaction conditions for the phthalonitrile compound of formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds. On the other hand, the total amount of the phthalonitrile compounds of the above formulas (I) to (IV) is 1 to 500 parts by weight, preferably 10 to 350 parts by weight, and the metal compound is used with respect to 4 moles of the phthalonitrile compound. , Preferably 0.8 to 2.0 mol, more preferably 0.8 to 1.5 mol. The cyclization is not particularly limited, but the reaction is preferably performed at a reaction temperature of 30 to 250 ° C., more preferably 80 to 200 ° C. The reaction time is not particularly limited, but is preferably 3 to 20 hours. After the reaction, a phthalocyanine compound that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

In the above embodiment, the starting phthalonitrile compounds of formulas (I) to (IV) can be synthesized by a conventionally known method, or commercially available products can also be used.

The amount of the dye described above in the composition used in the present invention is preferably 1 to 100% by mass, more preferably 50 to 100% by mass of the colorant contained in the composition used in the present invention, It is particularly preferably 80 to 100% by mass.
Further, among the colorants contained in the composition used in the present invention, the blending amount of the phthalocyanine dye (preferably a halogenated phthalocyanine dye) is preferably 55 to 80% by mass, and preferably 60 to 75% by mass. It is more preferable.

(Pigment)
Examples of the pigment used for the colorant include conventionally known various inorganic pigments or organic pigments. In addition, it is preferable to use a pigment having an average particle diameter as small as possible considering that high transmittance is preferable regardless of whether it is an inorganic pigment or an organic pigment. Considering handling properties, the average particle size of the pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.
Examples of pigments that can be preferably used in the present invention include those described in paragraph No. 0026 of JP2012-181512A, the contents of which are incorporated herein.
Moreover, the following can be mentioned as a pigment which can be preferably used in this invention. However, the present invention is not limited to these.
C. I.

Pigment Yellow

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

The amount of the pigment described above in the composition used in the present invention may be 1 to 100% by mass of the colorant when included in the colored curable composition. By reducing the blending amount of the pigment, the blending amount of the colorant in the colored curable composition can be further increased, and the effects of the present invention tend to be exhibited more effectively.

(Pigment dispersion)
When a pigment is used for adjusting the composition constituting the laminate of the present invention, it may be a pigment dispersion. From the viewpoint of improving the dispersibility of the pigment, a pigment dispersant may be further added.
Examples of the pigment dispersant that can be used in the present invention include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meta ) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, 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 from the structure thereof.
The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting adsorption of the polymer dispersant by modifying the pigment surface.
The pigment dispersant that can be used in the present invention is also available as a commercial product. Specific examples thereof include those described in paragraph No. 0050 of JP2012-173635A and JP2012-93396A. Those described in paragraph number 0206 of the publication are used, and the contents thereof are incorporated in the present specification. In addition, a dispersant described in paragraphs 0028 to 0124 of JP2011-070156A and a dispersant described in JP2007-277514A are also preferably used, and the contents thereof are incorporated herein.
These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

The content of the pigment dispersant in the composition of the present invention is preferably 1 to 80 parts by mass and more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment as the colorant.
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts by mass in terms of mass with respect to 100 parts by mass of the pigment.
When the pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 to 30 parts by mass, preferably in the range of 3 to 20 parts by mass, with respect to 100 parts by mass of the pigment. Is more preferable.

(Pigment derivative)
When a pigment is contained as a colorant, it is preferable to further contain a pigment derivative in order to increase the adsorptivity of the dispersion resin to the pigment. The pigment derivative is a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
As the pigment derivative, for example, those described in JP-A-2011-137125, paragraphs 0100 to 0119 are used, the contents of which are incorporated herein.
The content of the pigment derivative in the composition of the present invention is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, based on the total mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

(solvent)
The solvent in the pigment dispersion is not particularly limited as long as it is an organic solvent used in general pigment dispersible compositions. For example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol , 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene, and the like, and a plurality of these may be used in combination to adjust the melting point, viscosity, and pigment dispersibility. Is also possible.

The content of the solvent in the pigment dispersion is appropriately selected according to the use of the pigment dispersion.
When the pigment dispersion is used for the preparation of a colored curable composition to be described later, from the viewpoint of handleability, the sum of the pigment and the pigment dispersant is 5 to 5 based on the total mass excluding the solvent of the pigment dispersion. It can contain so that it may become 50 mass%.

(Yellow pigment)
As an example of an embodiment of the present invention, the use of a phthalocyanine dye mixed with a yellow pigment is exemplified.
The yellow pigment may be a dye, a pigment, or a mixed system of a dye and a pigment, but a dye is preferred from the viewpoint of obtaining a uniformly dissolved composition without using a dispersant. For example, an azo dye (for example, CI solvent yellow 162), a methine dye (CI solvent yellow 93) dye, or the like is preferable.
As the methine dye, a monomethine dye is preferable, and a monomethine dye represented by the following general formula (5) is more preferable. When a halogenated phthalocyanine dye and a methine dye are combined, the effects of the present invention tend to be more effectively exhibited.

(In General Formula (5), R ¹¹ represents an alkyl group or a vinyl group, and R ¹² represents an aromatic ring group having a substituent.)
R ¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
R ¹² is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, a vinylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group, a vinylcarbonylamino group, or an arylcarbonylamino group. An alkylsulfonylamino group is preferred. The alkyl group having 1 to 12 carbon atoms may have an unsaturated bond, and examples of such a substituent include an allylsulfonylamino group.

In addition, as a colorant, an acid dye and / or a derivative thereof may be suitably used. In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. For example, acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

Direct Yellow

2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141; Food Yellow 3;

Modern Yellow

5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65; and these dyes And derivatives thereof.

Further, as the pigment, the above-described pigments can be used.

The blending amount of the above-described yellow pigment in the composition used in the present invention is preferably 10 to 120% by mass, more preferably 25 to 100% by mass with respect to 100% by mass of the phthalocyanine dye, It is particularly preferable that the content be ˜90% by mass.

[Thermosetting compound]
The colored curable composition constituting the laminate of the present invention contains at least one thermosetting compound. Here, the thermosetting compound refers to a compound that can be cured by heating, and generally refers to a compound that is cured by heating at 180 ° C. or higher.
As the thermosetting compound used in the present invention, for example, a compound having a thermosetting functional group can be used. As the thermosetting functional group, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, an isocyanate group, a vinyl ether group, and a mercapto group are preferable. As the thermosetting compound, those having two or more thermosetting functional groups in one molecule are more preferable, and compounds having two or more epoxy groups in one molecule are more preferable.
The thermosetting compound used in the present invention includes epoxy compounds, melamine compounds (for example, alkoxymethylated, acyloxymethylated melamine compounds), urea compounds (for example, alkoxymethylated, acyloxymethylated urea compounds), phenol compounds ( For example, preferred examples include hydroxymethylated or alkoxymethylated phenol compounds or resins, and alkoxymethyl etherified phenol compounds), epoxy compounds and melamine compounds are more preferred, and epoxy compounds are more preferred.

The thermosetting compound used in the present invention may be a low molecular compound (for example, a molecular weight of less than 2000, and further a molecular weight of less than 1000), or a high molecular compound (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). In the present invention, those having a molecular weight of 1000 or more are preferred, and those having a molecular weight of 2000 to 100,000 are more preferred. In the present invention, a compound having 2 or more epoxy groups in one molecule and a molecular weight of 1000 or more is particularly preferable.

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

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and has a substituent. May be. R ^EP1 and R ^EP2 and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. Examples of the substituent that 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 alkylsulfone group, an alkylsulfonyl group, and an alkylamino group. Groups, alkylamide groups, and the like.
^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 ~ R ^EP3 combines with Q ^EP may form a ring structure.
^nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.

When ^QEP is an ^nEP- valent organic group, a linear or cyclic ^nEP- valent saturated hydrocarbon group (preferably having 2 to 20 carbon atoms), ^nEP- valent aromatic ring group (preferably having 6 to 30 carbon atoms) ), Or a linear or cyclic saturated hydrocarbon or aromatic hydrocarbon such as an ether group, an ester group, an amide group, a sulfonamide group, an alkylene group (preferably having 1 to 4 carbon atoms, more preferably a methylene group), etc. A divalent linking group, a trivalent linking group such as —N (—) _2, or an n ^EP valent organic group having a structure in which a combination thereof is linked is preferable.

Specific examples of the compound having an epoxy structure are illustrated below, but the present invention is not limited thereto.

The epoxy compound used in the present invention is also preferably an oligomer or polymer having an epoxy group in the side chain. Examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins and the like.
These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.

As a commercial product, for example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc., and bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835. (Above DIC Corporation), LCE-21, RE-602S (above, Japan) YER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N- 775 (manufactured by DIC Corporation), etc., and cresol novolak type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N- 690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and ADEKA RESIN EP as an aliphatic epoxy resin 4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Chemical Industries, Ltd.) Manufactured), Denacor EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

In the case of synthesizing by introducing into a polymer side chain, for example, the introduction reaction includes tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, pyridine, The reaction can be carried out in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours using triphenylphosphine as a catalyst. The amount of the alicyclic epoxy unsaturated compound introduced is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH · mg / g. The molecular weight is preferably in the range of 500 to 5000000, more preferably 1000 to 500000 on a weight average.
As the epoxy unsaturated compound, those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but preferred are unsaturated compounds having an alicyclic epoxy group. Examples of such compounds include the following compounds.

<Melamine compounds, urea compounds, other thermosetting compounds>
As the thermosetting compound used in the present invention, compounds having the following N-hydroxymethyl group, N-alkoxymethyl group, or N-acyloxymethyl group are also preferable. Such a compound is usually provided as a melamine compound or a urea compound.

The compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group has two or more (more preferably 2 to 8) partial structures represented by the following general formula (CLNM-1). ) Is preferred.

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

In general formula (CLNM-1), the alkyl group represented by R ^NM1 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 oxoalkyl group of R ^NM1 is preferably an oxoalkyl group having 3 to 6 carbon atoms, and examples thereof include a β-oxopropyl group, a β-oxobutyl group, a β-oxopentyl group, and a β-oxohexyl group. it can.

As a more preferable embodiment of the compound having two or more partial structures represented by the general formula (CLNM-1), a urea compound represented by the following general formula (CLNM-2), a compound represented by the following general formula (CLNM-3) An alkylene urea compound represented by the following general formula (CLNM-4), and a melamine compound represented by the following general formula (CLNM-5).

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

Specific examples of the urea compound represented by the general formula (CLNM-2) include, for example, N, N-di (methoxymethyl) urea, N, N-di (ethoxymethyl) urea, N, N-di (propoxy). Methyl) urea, N, N-di (isopropoxymethyl) urea, N, N-di (butoxymethyl) urea, N, N-di (t-butoxymethyl) urea, N, N-di (cyclohexyloxymethyl) Examples include urea, N, N-di (cyclopentyloxymethyl) urea, N, N-di (adamantyloxymethyl) urea, N, N-di (norbornyloxymethyl) urea and the like.

In formula (CLNM-3), R ^NM1 respectively, in formula (CLNM-1), is the same as R ^NM1. R ^NM3 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 5 to 6 carbon atoms), an oxoalkyl group (having 1 to 6 carbon atoms). 6), an alkoxy group (preferably having 1 to 6 carbon atoms) or an oxoalkoxy group (preferably having 1 to 6 carbon atoms).
G represents a single bond, an oxygen atom, a sulfur atom, an alkylene group (preferably having 1 to 3 carbon atoms) or a carbonyl group. More specific examples include a methylene group, an ethylene group, a propylene group, a 1-methylethylene group, a hydroxymethylene group, a cyanomethylene group, and the like.

Specific examples of the alkylene urea compound represented by the general formula (CLNM-3) include, for example, N, N-di (methoxymethyl) -4,5-di (methoxymethyl) ethylene urea, N, N-di ( Ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneurea, N, N-di (propoxymethyl) -4,5-di (propoxymethyl) ethyleneurea, N, N-di (isopropoxymethyl) -4 , 5-Di (isopropoxymethyl) ethyleneurea, N, N-di (butoxymethyl) -4,5-di (butoxymethyl) ethyleneurea, N, N-di (t-butoxymethyl) -4,5- Di (t-butoxymethyl) ethyleneurea, N, N-di (cyclohexyloxymethyl) -4,5-di (cyclohexyloxymethyl) ethyleneurea, N, N-di (cyclo Nthyloxymethyl) -4,5-di (cyclopentyloxymethyl) ethylene urea, N, N-di (adamantyloxymethyl) -4,5-di (adamantyloxymethyl) ethylene urea, N, N-di (nor And bornyloxymethyl) -4,5-di (norbornyloxymethyl) ethyleneurea.

In the general formula (CLNM-4),
R ^NM1 respectively, in formula (CLNM-1), is the same as R ^NM1.
R ^NM4 represents a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group or an alkoxy group, respectively.

R ^NM4 alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 5 to 6 carbon atoms), alkoxy group (preferably having 1 to 6 carbon atoms), more specifically, methyl group, Examples include an ethyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a methoxy group, an ethoxy group, and a butoxy group.

Specific examples of the glycoluril compound represented by the general formula (CLNM-4) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) ) Glycoluril, N, N, N, N-tetra (propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (butoxymethyl) Glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, N, N, N, N-tetra (cyclohexyloxymethyl) glycoluril, N, N, N, N-tetra (cyclopentyloxy) Methyl) glycoluril, N, N, N, N-tetra (adamantyloxymethyl) glycoluril, N, N, N, N- Tiger (norbornyloxymethyl) glycoluril, and the like.

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

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

Alkyl group R ^NM5 and R ^NM6 (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably 5 to 6 carbon atoms), aryl group (preferably 6 to 10 carbon atoms), and more specifically, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a naphthyl group.

Examples of the melamine compound represented by the general 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 (propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) 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 (cyclohexyl) Oxymethyl) 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 ( Rubornyloxymethyl) melamine, N, N, N, N, N, N-hexa (methoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (isopropoxymethyl) acetoguanamine, N, N, N, N, N, N -Hexa (butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) acetoguanamine, N, N, N, N, N, N-hexa (methoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (ethoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (propoxymethyl) benzoguanamine, N, N, N, N, N, N Hexa (isopropoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (butoxymethyl) benzoguanamine, N, N, N, N, N, N-hexa (t-butoxymethyl) benzoguanamine, etc. Can be mentioned.

The groups represented by R ^NM1 to R ^NM6 in the general formulas (CLNM-1) to (CLNM-5) may further have a substituent. Examples of the substituent that R ^NM1 to R ^NM6 may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 20 carbon atoms), cycloalkoxy group (preferably 3 to 20 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably carbon atoms) 2 to 20).
Specific examples of the compound having two or more partial structures represented by the general formula (CLNM-1) are illustrated below, but the present invention is not limited thereto. In addition to the compounds shown below, compounds from Sanwa Chemical Co., Ltd. and Nicarac series which are not exemplified below can also be preferably used.

<Phenol compound>
The phenol compound contains 3 to 5 benzene rings in the molecule, and further has two or more hydroxymethyl groups or alkoxymethyl groups. Mention may be made of phenolic compounds which are concentrated or distributed and bonded. As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, sec-butoxymethyl group, and t-butoxymethyl group are preferable. Furthermore, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propoxy group are also preferable.
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 3 to 6 thermosetting functional groups.

Among these phenol compounds, particularly preferable ones are listed below. In the formula, L ¹ to L ⁸ represent a thermosetting functional group such as an alkoxymethyl group, which may be the same or different, and the thermosetting functional group is preferably a hydroxymethyl group, a methoxymethyl group or An ethoxymethyl group is shown.

As the thermosetting compound, a commercially available one can be used, or it can be synthesized by a known method. For example, a phenol compound having a hydroxymethyl group is obtained by reacting a corresponding phenol compound having no hydroxymethyl group (a compound in which L ¹ to L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. be able to. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

A phenol compound having an alkoxymethyl group can be obtained by reacting a corresponding phenol compound having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like. A phenol compound having a hydroxymethyl group or an alkoxymethyl group synthesized in this manner is preferable from the viewpoint of stability during storage, but a phenol compound having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. Such a phenol compound having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

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

The total content of the thermosetting compound in the colored curable composition constituting the laminate of the present invention varies depending on the material, but is 5 to 40 with respect to the total solid content (mass) of the colored curable composition. % By mass is preferable, 7 to 35% by mass is more preferable, and 10 to 30% by mass is particularly preferable. In this invention, the effect that the cured film excellent in chemical-resistance can be obtained by setting it as the compounding quantity of such a thermosetting compound is acquired.

[solvent]
The colored curable composition which comprises the laminated body of this invention contains the solvent (usually organic solvent) which melt | dissolves a dye and a thermosetting compound at least.
Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As well 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, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc., and aromatic hydrocarbons such as, for example, Preferred examples include ruene and xylene.

These solvents are preferably mixed in two or more types from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the solvent in the colored curable composition is preferably such that the total solid concentration of the colored curable composition is 5 to 30% by mass, and 7 to 25% by mass from the viewpoint of applicability. More preferred is 10 to 20% by mass.

<Various additives>
The colored curable composition constituting the laminate of the present invention is, as necessary, various additives such as surfactants, acid anhydrides, curing agents, curing catalysts, as long as the effects of the present invention are not impaired. A filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.

<Surfactant>
Various surfactants may be added to the colored curable composition constituting the laminate of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the colored curable composition constituting the laminate of the present invention contains a fluorine-based surfactant, liquid properties (particularly, fluidity) when prepared as a coating liquid are further improved. The uniformity of coating thickness and liquid-saving property can be further improved.
That is, in the case of forming a film using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

Examples of the fluorosurfactant include MegaFuck F781 (manufactured by DIC Corporation).

Only one type of surfactant may be used, or two or more types may be combined.

The colored curable composition may or may not contain a surfactant, but when it is contained, the addition amount of the surfactant is 0.001% by mass relative to the total mass of the colored curable composition. The content is preferably -2.0% by mass, more preferably 0.005% -1.0% by mass.

In addition, when the surfactant is a polymer compound (that is, a resin), the solid content acid value of the polymer compound is 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, it is possible to improve the crosslinkability of the thermosetting compound, particularly the epoxy compound, by thermosetting.

Examples of the acid anhydride include phthalic acid anhydride, nadic acid anhydride, maleic acid anhydride, and succinic acid anhydride. Among these, phthalic anhydride is preferable because the acid anhydride has little influence on pigment dispersion. An amine compound is generally used as an epoxy curing agent, but has advantages such as a relatively long pot life.

The content of the acid anhydride in the colored curable composition is preferably in the range of 10 to 40% by mass, and in the range of 15 to 30% by mass with respect to the content of the thermosetting compound (particularly the epoxy compound). More preferred. When the content of the acid anhydride is 10% by mass or more, the crosslinking density of the thermosetting compound, particularly epoxy, can be improved, and the mechanical strength can be increased. Curing components are suppressed, which is advantageous for increasing the concentration of the coloring material.

<Curing agent>
When using an epoxy resin as the thermosetting compound, it is preferable to add a curing agent. There are many types of curing agents for epoxy resins, and the properties, the pot life of the mixture of resin and curing agent, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like. The curing agent is explained in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are shown below.

Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, for amines, diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.

These curing agents react with an epoxy group by heating and polymerize to increase the crosslinking density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. In particular, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting compound. It is preferable that

<Curing catalyst>
In order to realize a composition having a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with a curing agent. For this reason, a curing catalyst can be used without using a curing agent. The addition amount of the curing catalyst is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably about 1/30, based on the weight of the epoxy resin having an epoxy equivalent of about 150 to 200. It can be cured with a small amount of about 1/250.

<Preparation method of colored curable composition>
The preferable preparation method of the colored curable composition which comprises the laminated body of this invention is demonstrated. However, the present invention is not limited to this.

If the colorant is a dye, dissolve it in a solvent together with the thermosetting compound. When a pigment is included as a colorant, it is usually blended after preparing as a pigment dispersion as described above.

In particular, when the thermosetting compound is an epoxy compound, a thermosetting compound and a curing catalyst or a curing agent are added to the pigment dispersion or dye solution thus obtained, or the binder is already thermosetting. In the case of a compound, it is preferable to prepare the colored curable composition in the present invention by adding a curing catalyst or a curing agent to impart a thermosetting function, and adding a solvent as necessary.

<Filter filtration>
The colored curable composition constituting the laminate of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of the material of the filter include: a fluororesin such as PTFE (polytetrafluoroethylene); a polyamide resin such as nylon-6 and nylon-6, 6; a polyolefin resin such as polyethylene and polypropylene (PP) (high density, Including ultra high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore size of the filter within the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .

In the filter filtration, two or more filters may be used in combination.
For example, the filtration can be performed first using a first filter and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or may be performed twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

[Colored layer]
It can be set as the colored layer which comprises the laminated body of this invention by hardening the colored curable composition mentioned above. A method for forming the colored layer will be described later. This colored layer can be preferably used as a colored layer of a color filter. In particular, it can be preferably used as a colored curable composition for dry etching.
In the present invention, the thickness of the colored layer is preferably 0.1 to 1.0 μm, and more preferably 0.3 to 0.8 μm. In this invention, since the density | concentration of the coloring agent in a colored layer can be raised, such a film thinning is attained.

[Oxygen barrier film]
The laminate of the present invention has an oxygen barrier film on the above-described colored layer. This oxygen blocking film is formed using an oxygen blocking compound and exhibits high oxygen blocking ability, high transparency, and low light scattering.
Here, the film surface roughness means a state in which a large number of aggregates are generated on the surface of the colored layer, so that a large number of irregularities are formed on the surface of the colored layer. The cause of film surface roughness on the surface of the colored layer is that singlet oxygen decomposes the polymer component (cured product of the thermosetting compound) in the colored layer, causing color separation from the polymer component and coloration. It is thought that this occurs when the agents form aggregates. And since the quantity of the polymer component in a colored layer decreases, so that the density | concentration of a coloring agent is high, colorants will form an aggregate more easily and it will be thought that the film surface roughness on the surface of a colored layer becomes easy to generate | occur | produce. In particular, the inventors of the present application have examined that when the solid content concentration of the colorant in the colored curable composition exceeds 50% by mass, and further exceeds 60% by mass, the film surface is significantly roughened. I found. It was also found that this tendency is particularly likely to occur under high temperature and high humidity.
The oxygen barrier compound contained in the oxygen barrier film may be either an inorganic material or an organic material, and an inorganic material is preferred. Specifically, a metal oxide, a metal alkoxy group-containing compound, an organic polymer, or the like can be used. In addition, it is preferable that an oxygen interruption | blocking film | membrane is substantially comprised only with the said oxygen interruption | blocking compound from the point which is excellent by oxygen interruption | blocking ability. The term “substantially oxygen-blocking compound only” means, for example, that the content of the oxygen-blocking compound in the oxygen-blocking film is 99% by mass or more.

As the metal _{_{oxide, SiO 2, SiN, Al 2}} O 3, CaO, Fe 2 O 3, MgO, Ga 2 O, ZrO 2, TiO 2, etc. CaF ₂ and the like. Among these, from the viewpoint of excellent oxygen barrier properties and transparency, SiO ₂ and SiN are preferable, and SiO ₂ is particularly preferable.

Examples of the metal alkoxy group-containing compound include tetraethoxysilane, tetraethyl orthotitanate, tetramethoxysilane, ethyltriethoxysilane, and methyltrimethoxysilane.

Organic polymers include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, polymers of polyvinyl ether and maleic anhydride, ethylene oxide polymers, ethyl cellulose, hydroxyethyl cellulose , Celluloses such as water-soluble salts of carboxyethyl cellulose, gum arabic, alkoxysilane-containing polymers and the like, and mixtures of two or more thereof. Among these, from the viewpoint of excellent oxygen barrier properties, polyvinyl alcohol, Polyvinyl pyrrolidone or a mixture of polyvinyl alcohol and polyvinyl pyrrolidone is preferred, and polyvinyl alcohol is particularly preferred.

The polyvinyl alcohol preferably has a weight average molecular weight of 300 to 2400 and is preferably hydrolyzed 71 to 100 mol%. Specifically, PVA-101, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124 (all trade names, manufactured by Kuraray Co., Ltd., saponification rate 97 to 98%) ), PVA-203, PVA-204, PVA-205, PVA-210, PVA-220, PBA-224, PVA-217E (saponification rate 87-88%), PVA-405, PVA-420, (same as above) Saponification rate 78 to 82%) and PVA-613 (saponification rate 92 to 95%). In addition, the last two digits × 100 of the three-digit numbers after PVA indicate the degree of polymerization.

The content of PVA in the mixture of polyvinyl alcohol and polyvinyl pyrrolidone is preferably 25 to 99% by mass, more preferably 50 to 90% by mass, and particularly preferably 50 to 80% by mass. The amount of these polymers added is 1 to 40% by mass, more preferably 10 to 35% by mass, based on the entire layer. The content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably 10 to 40% by mass, based on the total solid content of the oxygen barrier film. By adding polyvinylpyrrolidone in an amount of 1 to 75% by mass based on the total solid content of the oxygen barrier film, the oxygen barrier property can be improved.

In the present invention, the thickness of the oxygen blocking film is preferably 10 μm or less. When the film thickness is in the above range, the oxygen blocking film is excellent in sensitivity and flatness of the formed color pixel and functions suitably as an oxygen blocking film for the color filter. When the thickness of the oxygen blocking film exceeds 10 μm, the oxygen permeability of the oxygen blocking film can be suppressed, but the intensity of light passing through the color filter layer may be reduced. The film thickness of the oxygen barrier film is more preferably 5 μm or less, and further preferably 1 μm or less. The lower limit of the thickness of the oxygen blocking film is not particularly defined, but is 0.05 μm or more.

The oxygen barrier layer preferably has an oxygen permeability of 200 ml / m ² · day · atm or less, more preferably 100 ml / m ² · day · atm or less, and 50 ml / m ² · day · atm or less. It is particularly preferred. The lower limit of the oxygen transmission rate is not particularly limited, but 0 ml / m ² · day · atm is preferable. When the oxygen permeability is in the above range, it functions suitably from the viewpoint of roughening the surface of the colored film.

As a method for measuring the oxygen permeability of the oxygen blocking layer, for example, it can be measured as follows. Orbis Fair Laboratories Japan Inc. model 3600 is used as the oxygen electrode. As the electrode diaphragm, polyfluoroalkoxy (PFA) 2956A having excellent response speed and sensitivity is used. Silicone grease (SH111, manufactured by Toray Dow Corning Co., Ltd.) is applied thinly (for example, 1.0 μm) to the electrode diaphragm, and a thin film material to be measured is applied thereon, and the oxygen concentration value is measured. It has been confirmed that the coating film of silicone grease does not affect the oxygen transmission rate. Next, the oxygen transmission rate (ml / m ² · day · atm) with respect to the oxygen concentration value is converted.

As the method for forming the oxygen blocking film, when the oxygen blocking compound is made of an inorganic material, a physical film forming method such as vapor deposition and sputtering, a chemical film forming method such as CVD, a wet process such as CLD and spraying method, etc. Various film forming methods such as a film method can be used. When the oxygen-blocking compound is composed of a metal alkoxy group-containing compound or an organic polymer, various coaters such as a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a spin coater, and a spray coater can be used.

Although preferable embodiment of the laminated body of this invention is given to the following, this invention is not limited to these.
(First embodiment)
A colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass relative to the total solid content of the colored curable composition An embodiment in which an oxygen barrier film is formed on a colored layer formed by curing a product.
(Second Embodiment)
The aspect in which a coloring agent contains the halogenated phthalocyanine dye represented by the said General formula (1).
(Third embodiment)
A mode in which the colorant further contains a yellow pigment.
(Fourth embodiment)
An embodiment in which the thermosetting compound is an epoxy compound.
(Fifth embodiment)
The aspect in which an oxygen barrier film contains an inorganic material.
(Sixth embodiment)
An embodiment in which the total content of the colorants is 60 to 90% by mass with respect to the total solid content of the colored curable composition.
(Seventh embodiment)
An embodiment in which the thickness of the colored layer is 0.1 to 1.0 μm.
(Eighth embodiment)
A mode in which the oxygen barrier film and the colored layer are adjacent to each other.
(Ninth embodiment)
A mode in which the thickness of the oxygen barrier film is 10 μm or less.
(Tenth embodiment)
A form comprising a combination of two or more of the first to ninth embodiments.

[Color filter and manufacturing method thereof]
As an example of the method for producing the color filter of the present invention, a step of forming a colored layer using the above-described colored curable composition, a step of forming a photoresist layer on the colored layer, a photoresist by exposure and development A step of patterning the layer to obtain 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 dry etching.

The manufacturing method of the color filter of this invention forms a 1st colored layer using the colored curable composition (it is also mentioned 1st colored curable composition) mentioned above. Here, as described above, the first colored layer is excellent in solvent resistance and alkali developer resistance. As a result, a developer used when forming a resist pattern (patterned photoresist layer) as an etching mask on the first colored layer, which will be described in detail later, or a second on the first colored layer. In the step of forming the second colored radiation-sensitive layer with the colored radiation-sensitive composition and the step of forming the third colored radiation-sensitive layer with the third colored radiation-sensitive composition on the first colored layer, The first colored layer exposes the organic solvent in the second or third colored radiation-sensitive composition or the second or third colored radiation-sensitive layer formed by the second or third colored radiation-sensitive composition; The color component in the first colored layer is dissolved in the developer used for development, and the color component in the second or third colored radiation-sensitive composition may be dissolved in the solvent or developer. Mixed in 1 colored layer Etc. can be suppressed Ruosore. As a result, it is possible to suppress the occurrence of color fading in the first colored layer and the occurrence of overlapping regions in which a plurality of colors overlap each other, so that the performance of the finally obtained color filter can be improved.
In particular, for example, a solid-state imaging device that is required to have a minute size such that the thickness is 0.1 to 1.0 μm and / or the pixel pattern size (one side in a square pattern) is 2 μm or less (for example, 0.5 to 2.0 μm) It is effective in producing a color filter for use.
In addition, according to the method for producing a color filter of the present invention, it is possible to provide a color filter that is a colored layer having a high concentration of a colorant and that hardly causes film surface roughness on the surface of the colored layer even under high temperature and high humidity. it can.

Here, the solid-state imaging device will be briefly described with reference to FIG. 1 as an example.
As shown in FIG. 1, the solid-state imaging device 10 includes a light receiving element (photodiode) 42 provided on a silicon substrate, a color filter 13, a planarizing film 14, a microlens 15, and the like. In the present invention, the planarizing film 14 is not necessarily provided. In FIG. 1, in order to clarify each part, the ratios of the thicknesses and widths are disregarded and some of them are exaggerated.

The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. 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 silicon substrate, and a photodiode 42 is provided on a part of the surface of the P well. The photodiode 42 is formed by performing heat treatment after ion-implanting N-type impurities such as P and As into a part of the surface of the P-well. In addition, an impurity diffusion layer 43 having an N-type impurity concentration higher than that of the photodiode 42 is provided in a region different from the above portion on the surface of the P well 41 of the silicon substrate. The impurity diffusion layer 43 is formed by ion implantation of N-type impurities such as P and As and then performing heat treatment, and the role of the floating diffusion layer that transfers charges generated when the photodiode 42 receives incident light. Fulfill. In addition to the well 41 being a P-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 being an N-type impurity layer, the well 41 is an N-type impurity layer and the photodiode 42 and the impurity diffusion layer 43 being a P-type impurity layer. You can also

An insulating film 47 such as SiO ₂ or SiO ₂ / SiN / SiO ₂ is provided on the P well 41, the photodiode 42, and the impurity diffusion layer 43. On the insulating film 47, poly-Si, tungsten, An electrode 44 made of tungsten silicide, Al, Cu or the like is provided. The electrode 44 serves as the gate of the gate MOS transistor, and can serve 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. Above the wiring layer 45, a BPSG film 46 and a P-SiN film 48 are provided. The interface between the BPSG film 46 and the P-SiN film 48 is formed so as to be curved downward above the photodiode 42, and serves as an in-layer lens for efficiently guiding incident light to the photodiode 42. Fulfill. On the BPSG film 46, a planarizing film layer 49 is formed for the purpose of planarizing the surface of the P-SiN film 48 or uneven portions other than the pixel region.

The color filter 13 is formed on the planarizing film layer 49. In the following description, a colored film (so-called solid film) formed on a silicon substrate without dividing the region is referred to as a “colored (colored radiation sensitive) layer”, and is formed by dividing the region into a pattern. A colored film (for example, a film patterned in a stripe shape) is referred to as a “colored pattern”. In addition, among the colored patterns, a colored pattern that is an element constituting the color filter 13 (for example, a colored pattern patterned into a square or a rectangle) is referred to as a “colored (red, green, blue) pixel”.

The color filter 13 includes a plurality of two-dimensionally arranged green pixels (first color pixels) 20G, red pixels (second color pixels) 20R, and blue pixels (third color pixels) 20B. Each of the

colored pixels

20R, 20G, and 20B is formed above the light receiving element 42. The green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G. In FIG. 1, in order to explain that the color filter 13 is composed of pixels of three colors, the

colored pixels

20R, 20G, and 20B are displayed in a line.

The planarization film 14 is formed so as to cover the upper surface of the color filter 13 and planarizes the color filter surface.

The microlens 15 is a condensing lens arranged with the convex surface facing upward, and is provided above the planarizing film 14 (or a color filter when no planarizing film is provided) and above the light receiving element 42. Each microlens 15 efficiently guides light from the subject to each light receiving element 42.

Next, the manufacturing method of the color filter which concerns on embodiment of this invention is demonstrated.
In the method for producing 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 from the first colored curable composition (step (a)). . Here, the first colored curable composition is the above-described colored curable composition.

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

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

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

Next, patterning is performed by dry etching so that a group of through holes is formed in the first colored layer 11 (step (A)). Thereby, a first colored pattern is formed. According to this technique, a through-hole having a desired shape is formed as compared with the case where a first colored layer is formed from a colored radiation-sensitive composition and the first colored layer is exposed and developed to provide a group of through-holes. A group can be provided more reliably. This is because, in a colored radiation-sensitive composition in which the content of the colorant with respect to the total solid content of the colored curable composition is 50% by mass or more, there is room for adding a component that contributes to developability to the composition. This is because reliable patterning becomes difficult due to the limitation.

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

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

Specifically, a positive or negative radiation-sensitive composition is applied (preferably applied) on the colored layer and dried to form a photoresist layer. In forming the photoresist layer 51, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. As this positive type radiation sensitive composition, positive type photo sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition suitable for resist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. Examples of the quinonediazide compound include a naphthoquinonediazide compound.

The thickness of the photoresist layer 51 is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm. The application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11 described above.

Next, as shown in the schematic cross-sectional view of FIG. 4, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist through-hole group 51A.
The formation of the resist pattern 52 is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing the resist through hole group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.

The exposure of the photoresist layer 51 is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. be able to. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the first colored layer containing the colorant. A combination of these organic solvents or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

Next, as shown in the schematic cross-sectional view of FIG. 5, patterning is performed by dry etching so that the through hole group 120 is formed in the first colored layer 11 using the resist pattern 52 as an etching mask. Thereby, the 1st coloring pattern 12 is formed. Here, the through-hole group 120 has a first through-hole part group 121 and a second through-hole part group 122.
The through-hole group 120 is provided in a checkered pattern in the first colored layer 11. Therefore, the 1st coloring pattern 12 by which the through-hole group 120 is provided in the 1st coloring layer 11 has a some square-shaped 1st coloring pixel in checkered form.

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 JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. There is a method described in this publication.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching, and the first stage etching, the second stage etching, and the overetching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first stage etching is performed according to the etching time calculated in (2) above. (4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.

The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
The second etching step and the over-etching step are performed in the first etching step after etching to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount refers to the remaining film thickness of the film to be etched.

Further, the etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

Next, as shown in the schematic cross-sectional view of FIG. 6, the resist pattern (that is, etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water. Is preferred.

As a step of applying a stripping solution or solvent on the resist pattern 52 to make the resist pattern 52 removable, for example, a stripping solution or solvent is applied on at least the resist pattern 52, and the paddle is stagnated for a predetermined time. A step of developing can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

Examples of the step of removing the resist pattern 52 using cleaning water include a step of removing the resist pattern 52 by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle. it can. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern 52 is more effectively moved by spraying the cleaning water by moving from the support center to the support end twice or more during the step of removing the resist pattern 52. Can be removed.

The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains 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 include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine. Preferably, they are monoethanolamine, diethanolamine, and triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.

When removing with the stripping solution, it is sufficient that the resist pattern 52 formed on the first colored pattern 12 is removed, and a deposit as an etching product adheres to the side wall of the first colored pattern 12 However, the deposit may not be completely removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

Next, as shown in the schematic cross-sectional view of FIG. 7, the second colored radiation-sensitive composition is embedded in each through-hole in the first through-hole portion group 121 and the second through-hole portion group 122 to obtain a plurality of The second colored radiation-sensitive composition is formed on the first colored layer (that is, the first colored pattern 12 in which the through-hole group 120 is formed in the first colored layer 11) so that the second colored pixel is formed. The second colored radiation-sensitive layer 21 is laminated (step (c)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the through-hole group 120 of the 1st coloring layer 11 is formed. Here, the second colored pixel is a square pixel. The second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
Here, the thickness of the second colored radiation-sensitive layer 21 is preferably in the range of 0.3 to 1 μm, more preferably in the range of 0.35 to 0.8 μm, and more preferably in the range of 0.35 to 0.7 μm. preferable.

Then, the second colored radiation-sensitive 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 colored radiation-sensitive layer 21. Then, the plurality of second colored pixels 22R provided inside each through hole of the second through hole portion group 122 are removed (step (D)) (see the schematic sectional view of FIG. 8).

Next, as shown in the schematic cross-sectional view of FIG. 9, a third colored radiation-sensitive composition is embedded in each through hole in the second through hole portion group 122 to form a plurality of third colored pixels. As described above, the third coloring radiation sensitive composition is used for the third coloring on the first coloring layer (that is, the first coloring pattern 12 in which the second coloring pattern 22 is formed in the first through-hole portion group 121). The radiation sensitive layer 31 is formed (process (e)). Thereby, the third colored 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 square pixel. The third colored radiation-sensitive layer 31 can be formed in the same manner as the method for forming the first colored layer 11 described above.
The thickness of the third colored radiation-sensitive layer 31 here is preferably in the range of 0.3 to 1 μm, more preferably in the range of 0.35 to 0.8 μm, and more preferably in the range of 0.35 to 0.7 μm. preferable.

Then, the third colored radiation-sensitive 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 of the third colored radiation-sensitive layer 31. As shown in the schematic cross-sectional view of FIG. 10, the colored layer 60 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured (process (capacitor). )).

In the color filter manufacturing method of the present invention, as shown in FIG. 11, the color filter 100 in which the oxygen blocking film 61 is formed on the colored layer 60 by forming the oxygen blocking film 61 described above on the colored layer 60. Can be manufactured.

The second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant. As the colorant, those of the above-described colored curable composition can be mentioned in the same manner, but it is preferable that one of the second colored pixel and the third colored pixel is a red transmissive part and the other is a blue transmissive part. .
The colorant contained in the colored curable composition for forming the red transmission part is C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, And C.I. I.

Pigment Red

1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 Species It is preferable that.
The colorant contained in the colored curable composition for forming the blue transmission part is C.I. I.

Pigment Violet

1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is preferable.

In each of the second colored radiation-sensitive composition and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

Also, it is preferable that a negative radiation sensitive composition is used for each of the second colored radiation sensitive composition and the third colored radiation sensitive composition. As this negative type radiation sensitive composition, there is a negative type feeling sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A radiation composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.

Specifically, as the negative radiation sensitive composition, a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) is preferable. Examples described in paragraph Nos. [0017] to [0064] of JP-A-2005-326453. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

The exposure with respect to the 2nd colored radiation sensitive layer 21 and the 3rd colored radiation sensitive layer 31 can be performed by exposing with g line | wire, h line | wire, i line | wire, etc., Preferably i line | wire.
The development performed after exposure is usually performed by developing with a developer.
Examples of the developer include the same developers as those already described in the exposure and development of the photoresist layer 51.
When an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development.

The length of one side of the first colored pixel, the second colored pixel, and the third colored pixel (the length of the short side when the pixel is a rectangle, and the length of one side when the pixel is a square) is From the viewpoint of image resolution, 0.5 to 1.7 μm is preferable, and 0.6 to 1.5 μm is more preferable.

According to the method for producing a color filter of the present invention described above, a color filter having a high colorant concentration, which is less likely to cause film surface roughness on the color layer surface even under high temperature and high humidity, is provided. be able to.
Moreover, according to the manufacturing method of the color filter of this invention, since a 1st colored layer, especially a 1st colored pixel is formed with the colored curable composition with the high density | concentration of the coloring agent of this invention, 1st coloring The thickness of the pixel can be extremely reduced (for example, 0.7 μm or less). Thereby, a color filter in which crosstalk (mixture of light) is suppressed can be manufactured.
Moreover, the 1st colored pixel formed with the colored curable composition mentioned above becomes what was excellent in solvent resistance and alkali developing solution resistance. Therefore, it is possible to reduce the occurrence of overlap regions overlapping with colors in 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 suitably used for a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). Moreover, it can use suitably also for image display devices, such as electronic paper and organic electroluminescence. In particular, the color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD and a CMOS.

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 provided with such a color filter can display a high-quality image having a good display image color tone and excellent display characteristics.

For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be 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”.

The color filter of the present invention is useful for a color TFT type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.
The colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less, but by using the present invention, It is also possible to form a conduction path of 5 μm or less. These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

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 guarantee 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 known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Synthesis Example 1 Synthesis of Dye A>
(Synthesis of Intermediate A)
A flask was charged with 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, and a magnetic stirrer. After stirring for 30 minutes until the internal temperature was stabilized at 40 ° C., potassium carbonate (8.58 g, 62.1 mmol) was added and allowed to react for about 3 hours. After cooling, the solution obtained by suction filtration was concentrated under reduced pressure at 40 ° C. for 1 hour, and the solvent was distilled off. Furthermore, it vacuum-dried at 110 degreeC overnight, and about 23.0 g (89.9%) of intermediate body A was obtained.

(Synthesis of Dye A)
Intermediate A (2.13 g, 4.7 mmol) and 2.35 mL of benzonitrile were added to the flask, and about 1 hour until the internal temperature was stabilized at 150 ° C. using a magnetic stirrer under a nitrogen stream (10 mL / min). After stirring, 0.43 g (1.3 mmol) of zinc iodide was added and allowed to react for about 35 hours. 30 mL of methanol was added after cooling, and it was set as the crystallization solution by stirring at room temperature using a magnetic stirrer. 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 purified product obtained, and the mixture was heated and stirred at 60 ° C. for 1 hour using a magnetic stirrer. After cooling, suction filtration was performed, 20 mL of methanol was added to the obtained crystals, 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 resulting crystals were air-dried overnight at 40 ° C. to obtain about 1.95 g (88.2%) of dye A.

<Synthesis Example 2-Synthesis of other dyes>
Dye B to Dye E were synthesized according to Synthesis Example 1 above.

<Preparation of pigment dispersion>
The mixed liquid containing the following compound was mixed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)). Dispersed to prepare a pigment dispersion. The types of pigments are those described in the following table, and the blending amounts of the respective components are blended so that the composition ratio in the finally obtained colored curable composition is the ratio described in the following table.
・ Pigments (Pigments shown in the table below)
・ Derivatives ・ Dispersants ・ Solvent: Propylene glycol monomethyl ether acetate (PGMEA)
According to Synthesis Example 1, another phthalocyanine dye was synthesized.

<Preparation of colored curable composition>
Each component was mixed so that it might become a composition of the following table | surface, and it stirred and prepared the colored curable composition.
・ Dyes (colorants)
・ Yellow pigment (colorant)
・ Thermosetting compound ・ Solvent: The amount that the final solid content concentration becomes 15 mass%

Halogenated phthalocyanine dye A:

Halogenated phthalocyanine dye B:

Halogenated phthalocyanine dye C:

Halogenated phthalocyanine dye D:

Non-halogenated phthalocyanine dye E:

<Other colorants>
Yellow dye A (azo dye (pigment)): P.I. Y150
Yellow pigment B (methine pigment (azomethine pigment) (dye)): (Synthesis examples will be described later.)

In the above, a is 2.0, b is 4.0, acid value is 10 mgKOH / g, and Mw20000.
Further, a and b in the dispersant A each represent the number of partial structures represented in parentheses and satisfy a + b = 6.

<Thermosetting compound>
Thermosetting compound A: Epoxy compound: EHPE3150 (Daicel Chemical Industries, Ltd. molecular weight = 2234)
Thermosetting compound B: Melamine compound: Nicalac MW-30M (manufactured by Sanwa Chemical Co., Ltd.)
<Surfactant>
Surfactant: F-781 (Fluorosurfactant manufactured by DIC Corporation)

<Synthesis of methine dye B>
Methine dye B was synthesized according to the following scheme.

(Synthesis of Intermediate A)
A mixed solution of 100 parts by weight of the above compound (A) (synthesized by the method described in EP 0571959A2) and 390 ml of pyridine was cooled to 5 ° C., and 87 parts by weight of octanesulfonyl chloride was added dropwise at a reaction temperature of 25 ° C. or less. The reaction mixture was stirred at room temperature for 2 hours, 2 L of 4N aqueous hydrochloric acid solution was added, and the mixture was stirred at room temperature and collected by filtration. The crystals collected by filtration were washed with 500 ml of methanol and dried to obtain 153 g of intermediate A (yield 91%).
¹ H-NMR CDCl ₃ δ0.8 (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)
To a suspension of 110 g of Intermediate A and 650 ml of acetic acid, 68 g of ethyl orthoformate was added at room temperature, and the reaction solution was allowed to stir at 80 ° C. for 3 hours. Methanol 1.1L was added to the reaction liquid, and after cooling, it was filtered and washed with methanol to obtain 96 g (yield 88%) of methine dye B.
¹ H-NMR CDCl ₃ δ0.8 (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 evaluation was performed about the obtained composition.

<Production of film surface roughness evaluation substrate>
After applying the above composition to a 0.5 μm-thick coating film on a 7.5 cm × 7.5 cm glass substrate with a spin coater, heating at 100 ° C. for 2 minutes using a hot plate It dried and then heated at 200 ° C. for 5 minutes to cure the coating film to form a colored layer.

<Formation of oxygen barrier film>
In Examples 1 to 3 and Comparative Example 2, the produced glass substrate was sputtered with SiO ₂ or SiN using a sputtering apparatus (SRV-4300 manufactured by Shinko Seiki Co., Ltd.) to form an oxygen blocking film with a thickness of 0.1 μm. Formed on the colored layer. Further, in Example 4 and Example 5, the produced glass substrate was subjected to an aqueous solution of polyvinyl alcohol (weight average molecular weight: 2000) or polyvinyl pyrrolidone (weight average molecular weight: 1800) using a spin coater (1H-D7 manufactured by Mikasa). Each aqueous solution was applied to form an oxygen barrier film having a thickness of 1.0 μm on the colored layer. The results are shown in Table 1. In Table 1, inorganic material A is SiO ₂ , inorganic material B is SiN, organic material A is polyvinyl alcohol, and organic material B is polyvinyl pyrrolidone. In Comparative Example 1, no oxygen blocking film is formed. It was.

<High temperature and high humidity test>
The glass substrate on which the oxygen barrier film was formed 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% using a high acceleration life test apparatus (EHS-221 manufactured by Espec Corp.).

<Roughness evaluation of film surface>
The glass substrate on which the oxygen barrier film after the high-temperature and high-humidity test was formed was visually evaluated for aggregated foreign substances using an optical microscope (MX-50 manufactured by Olympus Corporation) under the condition of reflection 200 times. The results are shown in the table below. Based on the following criteria, 3 to 5 are evaluated as having no practical problem.
-Evaluation criteria-
5: There is no occurrence of aggregated foreign matters.
4: An extremely small number of aggregated foreign matters (5 or more and less than 25 in 5 visual field regions) was generated.
3: A small number of aggregated foreign substances (25 or more and less than 100 in 5 fields of view) occurred.
2: A large number of aggregated foreign matters (100 or more and less than 500 in 5 fields of view) were generated.
1: Agglomerated foreign matter was remarkably generated (500 or more in 5 fields of view).

As is apparent from the above table, a colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass relative to the total solid content of the colored curable composition. In the colored layer formed using the product, it was found that the laminates (Examples 1 to 10) in which the oxygen blocking film was formed on the colored layer had suppressed film surface roughness.
In addition, Examples 1 to 10 were found to have excellent spectral characteristics and good light resistance.
On the other hand, it was found that the laminate (Comparative Example 1) in which the oxygen barrier film was not formed did not have a good film surface roughness. In addition, when the oxygen barrier film is formed but the total content of the colorants is less than 50% with respect to the total solid content of the colored curable composition (Comparative Example 2), film surface roughness is suppressed. However, since the concentration of the colorant is low, it cannot be thinned.

DESCRIPTION OF SYMBOLS 10 Solid-state image sensor 11 1st colored layer 12 1st colored pattern 13,100 Color filter 14 Flattening film 15 Microlens 20G Green pixel (1st color pixel)
20R red pixel (second color pixel)
20B Blue pixel (third color pixel)
21 2nd coloring radiation sensitive layer 21A The position corresponding to the 1st through-hole part group 121 22 2nd coloring pattern 22R The some 2nd coloring pixel 31 provided in the inside of each through-hole of the 2nd through-hole part group 122 Third colored radiation-sensitive layer 31A Position corresponding to second through-hole portion group 32 Third colored pattern 41 P well 42 Light receiving element (photodiode)
43 Impurity diffusion layer 44 Electrode 45 Wiring layer 46 BPSG film 47 Insulating film 48 P-SiN film 49 Planarizing film layer 51 Photoresist layer 51A Resist through hole 52 Resist pattern (patterned photoresist layer)
60 colored layer 61 oxygen blocking film 120 through-hole group 121 first through-hole part group 122 second through-hole part group

Claims

A colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass with respect to the total solid content of the colored curable composition. The laminated body in which the oxygen barrier film was formed on the colored layer formed by hardening an adhesive composition.
The laminate according to claim 1, wherein the colorant contains a halogenated phthalocyanine dye represented by the following general formula (1).
General formula (1)

(In the general 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 of the other substituents is aromatic. (M represents a hydrogen atom, a metal atom, a metal oxide, or a metal halide.)
The laminate according to claim 1 or 2, wherein the thermosetting compound is an epoxy compound.
The laminate according to any one of claims 1 to 3, wherein the colorant further contains a yellow pigment.
The laminate according to any one of claims 1 to 4, wherein the total content of the colorant is 60 to 90% by mass with respect to the total solid content of the colored curable composition.
The laminate according to any one of claims 1 to 5, wherein the colored layer has a thickness of 0.1 to 1.0 µm.
The laminate according to any one of claims 1 to 6, wherein the oxygen blocking film and the colored layer are adjacent to each other.
The laminate according to any one of claims 1 to 7, wherein the oxygen barrier film has a thickness of 10 袖 m or less.
The laminate according to any one of claims 1 to 8, wherein the oxygen barrier film includes an inorganic material.
A color filter having the laminate according to any one of claims 1 to 9.
A colored curable composition comprising a colorant, a thermosetting compound and a solvent, wherein the total content of the colorant is 50 to 90% by mass with respect to the total solid content of the colored curable composition. A step of curing the adhesive composition to form a colored layer, a step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and the resist pattern A method for producing a color filter, comprising: a step of dry-etching the colored layer using an etching mask; and a step of forming an oxygen blocking film on the colored layer after the dry etching.
The method for producing a color filter according to claim 11, wherein the oxygen blocking film is formed by sputtering.
A liquid crystal display device, an organic electroluminescence element, or a solid-state imaging device having the color filter according to claim 10 or the color filter produced by the method for producing a color filter according to claim 11 or 12.