JP4890087B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a color filter used in a liquid crystal display device or a solid-state imaging device, a dye-containing color filter, and a method for producing the same.

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

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

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate with a spin coater or a roll coater and dried to form a coating film, and then this coating film is subjected to pattern exposure and development. A color filter is obtained by forming a pixel colored with the above and repeating this operation for each color according to a desired number of hues. As such a pigment dispersion method, an example using a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is known (see, for example, Patent Documents 1 to 5). .

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there are problems such as color unevenness due to the relatively coarse particles of the pigment, and a solid-state imaging device (CCD etc.) Thus, it was not suitable for applications requiring a fine pattern.

In view of the above problems, a technique using a dye instead of a pigment has been proposed (see, for example, Patent Document 6).
JP-A-2-199403 Japanese Patent Laid-Open No. 4-76062 Japanese Patent Laid-Open No. 5-273411 JP-A-6-184482 JP-A-7-140654 JP 2005-99488 A

However, the dye-containing curable composition has new problems such as the following (1) to (3), and further improvement is required. That is,
(1) After preparing the solution of the curable composition, the dye or the complex of the dye and other components gradually precipitates;
(2) Dyes are poorly soluble in alkaline aqueous solutions, or often interact with the same dyes or with other components in the curable composition, so they dissolve between the cured and non-cured parts. The difference in properties (developability) is difficult to obtain, and a good pattern cannot be obtained (deterioration of pattern shape). In addition, the pattern size fluctuates greatly due to a slight difference in exposure amount (decrease in exposure latitude);
(3) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added, and other than the polymerizable compound (monomer), binder, photopolymerization initiator, etc. in the curable composition These components have to be relatively reduced, and the amount of exposure necessary for pattern formation increases (lower sensitivity).

  Also, when forming a film using a curable composition, unlike the case of semiconductor manufacturing applications, the film thickness of 1.5 μm or less is required for the manufacturing applications of color filters for solid-state imaging devices. It is necessary to add a large amount of a dye to the composition, which causes the same problem as described above.

  The present invention has been made in view of the above, and has excellent stability over time after preparation, has good pattern forming properties, and has little pattern line width variation due to variation in exposure amount. It is an object of the present invention to provide a composition, a color filter having excellent hue and resolving power, a good pattern shape and high productivity (high cost performance), and a method for producing the same, and to achieve the object. .

  The present invention has obtained knowledge that a combination of a specific dye and an oxime-based photopolymerization initiator is effective for stability over time after preparation, improvement of a formation pattern, and stabilization. The object is achieved, and the specific means are as follows.

<1> (A) at least two dyes containing either of the following (1) or (2) ; (B) at least one oxime photopolymerization initiator; and (C) at least one radical polymerizable monomer. DOO Ru dye-containing negative curable composition der containing.
(1) two pyrazole azo compound and pyridone azo compound (2) two sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compound) and pyrazole azo compound

< 2 > The dye-containing negative curable composition according to <1 >, wherein at least one of the dyes includes an acidic group.
<3> The dye-containing negative curable composition according to <1> or <2>, wherein the sulfur-containing organic group-substituted phthalocyanine compound (excluding a naphthalocyanine compound) is a compound represented by the following general formula 1. It is a thing.

In General Formula 1, M represents a metal. Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent an atomic group necessary for forming a 6-membered ring containing a carbon atom. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a monovalent substituent, and at least one of the substituents represented by R ^{101 to} R ¹⁰⁴ is an organic group containing a sulfur atom. Represents (sulfur-containing organic group). n1, n2, n3, and n4 each independently represents an integer of 0 to 4.
< 4 > The dye-containing negative curable composition according to any one of <1> to < 3 >, wherein at least two of the dyes contain an acidic group.
< 5 > The mass ratio (B / C) of the total amount of the photopolymerization initiator including the (B) oxime photopolymerization initiator and the total amount of the (C) radical polymerizable monomer is 0.25 or more and 0.75 or less. The dye-containing negative curable composition according to any one of the above items <1> to < 4 >, wherein
< 6 > The content of the (B) oxime photopolymerization initiator is 9% by mass or more based on the total solid content, as described in any one of <1> to < 5 >, The dye-containing negative curable composition.

< 7 > The dye-containing negative curable composition according to < 6 >, wherein the content of the (B) oxime-based photopolymerization initiator is 12% by mass or more based on the total solid content. It is.
< 8 > The dye-containing negative type according to any one of <1> to < 7 >, wherein the content of the (A) dye is 40% by mass or more based on the total solid content. It is a curable composition.
< 9 > The dye-containing negative curable composition according to < 8 >, wherein the content of the dye (A) is 45% by mass to 90% by mass with respect to the total solid content. is there.
< 10 > (D) The dye-containing negative curable composition according to any one of <1> to < 9 >, further comprising an organic solvent.
< 11 > The dye-containing negative curable composition according to any one of <1> to < 10 >, further comprising a photopolymerization initiator other than the oxime photopolymerization initiator. It is.

< 12 > The dye-containing negative curable composition according to any one of <1> to < 11 >, further containing a resin.
< 13 > The dye-containing negative curable composition according to any one of <1> to < 12 >, further comprising a surfactant.
< 14 > The < 10 > to < 10 >, wherein the organic solvent (D) is at least one of cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate. It is a dye-containing negative curable composition as described in any one of < 13 >.
< 15 > The dye-containing negative curable composition according to < 14 >, wherein the organic solvent (D) is at least one of propylene glycol monomethyl ether and ethyl 3-ethoxypropionate. .

< 16 > A color filter using the dye-containing negative curable composition according to any one of <1> to < 15 >.
< 17 > A color filter having two or more colored regions on a support,
The color filter according to < 16 >, wherein at least two colors of the colored region include at least one of the following (1) and (2) .
(1) two pyrazole azo compound and pyridone azo compound (2) two sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compound) and pyrazole azo compound

< 18 > A step of coating the dye-containing negative curable composition according to any one of <1> to < 15 > on a support, exposing through a mask, and developing to form a pattern. It is a manufacturing method of a color filter.
The color filter manufacturing method can produce a color filter by forming the step once or a plurality of times to form a one-color or multicolored colored region.

  According to the present invention, a dye-containing negative-type curable composition having reduced insoluble matter precipitation after preparation and excellent stability over time, good pattern forming property, and little variation in pattern line width due to variation in exposure dose. And a color filter having excellent hue and resolution, a good pattern shape and high productivity (high cost performance), and a method for producing the same

  Hereinafter, the dye-containing negative curable composition of the present invention will be described in detail, and a color filter using the dye-containing negative curable composition and a production method thereof will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) includes at least (A) at least two types including any of the following (1) or (2): And (B) at least one oxime photopolymerization initiator (hereinafter sometimes referred to as “initiator according to the present invention”), and (C) at least one radical polymerizable monomer. Preferably, (D) comprises at least one organic solvent, and if necessary, (resin (binder), crosslinking agent, photosensitizer, sensitizer, photoacid generator, surfactant, etc.) E) It can be constructed using other components.
(1) Two types of pyrazole azo compounds and pyridone azo compounds
(2) Sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compounds) and pyrazole azo compounds

(A) Dye The composition of this invention contains at least 2 sort (s) containing either of said (1) or (2) as a dye (an organic solvent soluble dye is included). These dyes are effective in that they are combined with an oxime-based photopolymerization initiator described later to exhibit stability over time after preparation and good pattern formation.

-Heterocyclic azo compounds-
Heterocyclic azo compounds, Ru compound der which heterocyclic azo group (-N = N-) is directly connected.

Specific examples of the heterocyclic ring, pin Razoru, pin chloride emissions (hereinafter, collectively appropriately referred to as "heterocyclic azo compound".) It is.

  Moreover, it is preferable to contain an acid group at any position of the heterocyclic azo compound. Here, the acid group is not particularly limited as long as it is a functional group that can be dissociated with an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, phosphoric acid, and the like. It is done. These acid groups may be a salt of a metal having a valence of 2 or more, and examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron. It is done.

Examples of the heterocyclic azo compound include: 1) a heterocycle directly connected to one bond of an azo group is a pyrazole ring, and a heterocycle is also directly connected to the other bond of the azo group; A compound having an acid group at the position of
2) The heterocycle directly connected to one bond of the azo group is a pyrazole ring, the heterocycle directly connected to the other bond of the azo group is a pyridine ring, and a carboxylic acid and / or at any position in the structure A compound having a sulfonamide,
3) The heterocycle directly connected to one bond of the azo group is a pyrazole ring, the heterocycle directly connected to the other bond of the azo group is a pyrimidine ring, and a carboxylic acid and / or at any position in the structure A compound having a sulfonamide,
Is preferred.

Specific examples of the heterocyclic azo compound (Exemplary compounds A1-1 to A1-12, A1-17 to A1-24, A2-1 to A2-24, A3-1 to A3-24) are shown below. However, the present invention is not limited to these specific examples.

-Sulfur-containing organic group-substituted phthalocyanine compounds-
The sulfur-containing organic group-substituted phthalocyanine compound (excluding the naphthalocyanine compound) is generally a compound represented by the following general formula 1.

General formula 1:

In the general formula 1, M represents a metal, and examples of the metal include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe. and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl metal chlorides such as _2, TiO, metal oxides such as VO, and Si _(OH) include metal hydroxides _2. M is preferably Zn, Pd, Cu, Ni, Co, or VO, more preferably Zn, Cu, Co, or VO, and most preferably Cu.

Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent an atomic group necessary for forming a 6-membered ring containing a carbon atom. The 6-membered ring may be a saturated ring or an unsaturated ring, may be a heterocyclic ring containing a nitrogen atom or the like, and may be unsubstituted or have a substituent. Further, another 5-membered or 6-membered ring may be condensed, and the condensed ring may further have a substituent. Specifically, a benzene ring, a cyclohexane ring, a cyclohexene ring, and a pyridine ring are included.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , and R ¹⁰⁴ each independently represent a monovalent substituent described later. In the present invention, at least one of the substituents represented by a plurality of R ¹⁰¹ to R ^104, an organic group containing a sulfur atom you later (sulfur-containing organic radical).

  n1, n2, n3, and n4 each independently represents an integer of 0 to 4. The sum of the values of n1 to n4 is preferably 1 or more, and more preferably 2 or more.

The phthalocyanine compound preferably has an acid group at an arbitrary position in the structure. The acid group may be any functional group as long as it is dissociable with respect to an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, and phosphoric acid. .
In addition, these acid groups may be a salt of a metal having a valence of 2 or more. Examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron. Can be mentioned.

As the phthalocyanine compound, any of the following cases is preferable.
1) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is a sulfur-containing organic group. Compound,
2) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is halogen. A compound that is an atom or a sulfur-containing organic group. Furthermore,
3) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is —SR (R is described later) A compound containing an acid group at an arbitrary position of the organic group R,
4) M is Cu, the 6-membered ring formed by Z ¹ , Z ² , Z ³ , and Z ⁴ is a benzene ring and / or a pyridine ring, and at least one of the plurality of R ^{101 to} R ¹⁰⁴ is halogen. Compounds that are atoms or sulfonamide groups are preferred.

  Hereinafter, specific examples (Exemplary Compounds A4-1 to A4-19) of the phthalocyanine compounds will be shown. However, the present invention is not limited to these specific examples.

  In the following specific examples (A5-1 to A5-38), ring A1, ring A2, ring A3, and ring A4 each independently represent a benzene ring or a pyridine ring. In the case of a pyridine ring, there are positional isomers having different N positions depending on the direction of the condensed ring. In addition, isomers having different substitution positions of substituents also exist in each.

-Azomethine compounds-
An azomethine compound refers to a compound having an azomethine group [RaC (Rb) = N-] in the molecule. Here, Ra and Rb represent arbitrary organic groups.

  As the azomethine compound, those containing a heterocycle are preferable. Examples of the heterocyclic ring include those similar to the heterocyclic ring in the above-described heterocyclic azo compound. In these, the heterocyclic ring (nitrogen-containing heterocyclic ring) which contains a nitrogen atom in a ring is preferable.

  In the present invention, those having a structure in which a plurality of the aforementioned heterocycles are condensed are preferable. Among these, a structure in which two heterocycles selected from pyrazole, pyrazoline, imidazole, triazole, and oxazole are condensed is preferable.

  The azomethine compound preferably has an acid group at an arbitrary position in the structure. The acid group is not particularly limited as long as it is a functional group dissociable with an alkaline aqueous solution, and specific examples include sulfonic acid, carboxylic acid, phenolic hydroxyl group, sulfonamide, and phosphoric acid. The acid group may be a salt of a metal having a valence of 2 or more, and examples of the metal include magnesium, calcium, strontium, barium, zinc, aluminum, nickel, copper, cobalt, and iron.

As the azomethine compound, 1) a compound having a condensed structure of pyrazoline and triazole, an aromatic ring substituted on the nitrogen atom of the azomethine group, and an acid group at an arbitrary position in the structure is preferable, Furthermore,
2) A structure in which pyrazoline and 1,2,4-triazole shown below are condensed [from the left side, 7H-pyrazolo [1,5-b] [1,2,4] triazole or 7H-pyrazolo [5,1 -C] [1,2,4] triazole], a compound in which the aromatic ring substituted on the nitrogen atom of the azomethine group is a quinoline skeleton, and has a carboxylic acid and / or a sulfonamide at any position in the structure, Is preferred.

  Hereinafter, specific examples (exemplary compounds A6-1 to A6-28) of azomethine compounds will be shown. However, the present invention is not limited to these specific examples.

-Description of substituents-
The “substituent” in the present specification will be described.
In the present specification, the “substituent” represents an arbitrary group regardless of inorganic or organic, and specifically includes a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxylic acid group, and a sulfonic acid group. , Sulfinic acid group, alkyl group (including linear, branched, and cyclic), alkenyl group (including linear, branched, and cyclic), alkynyl group, aryl group, heterocyclic group, formyl group, or And a group obtained by arbitrarily combining one partial structure selected from the following group (A) and one partial structure selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. It is done.
Group (A): ether group, amino group, thioether group, ketone group, ester group, amide group, urethane group [carbamoyl group -O-CO-N (R)-], urea group [-N (R) -CO -N (R) -], a sulfinyl group [-SO-], a sulfonyl group [-SO ₂ -], a sulfonic acid ester group _[-SO 2 -O-], a sulfonamide group _[-SO 2 -N (R) -], imide group [-CO-N (R) -CO-], sulfonyl amido groups _[-SO 2 -N (R) -CO-], disulfonylimide groups _[-SO 2 -N (R) _{-SO 2-} ]

  R bonded to the nitrogen atom in the group (A) represents any of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

  In the “substituent”, the alkyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, or a norbornyl group. And an adamantyl group. Moreover, you may have a substituent further in the arbitrary positions of these alkyl groups, and all the above-mentioned "substituents" are included in the further substituents including said alkyl group itself. In the case of a cyclic alkyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkenyl group may be linear, branched or cyclic. In the case of a ring, it may be monocyclic or polycyclic. As the alkenyl group, an alkenyl group having 1 to 30 carbon atoms is preferable. Specifically, a vinyl group, an allyl group, a 1-methylvinyl group, a 3-buten-1-yl group, a cyclopentan-2-ene-1 -Yl group, cyclohexane-2-en-1-yl group, cyclohexane-1-en-1-yl group and the like. Further, the alkenyl group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”. In the case of a cyclic alkenyl group, a partial structure selected from the above group (A) may be inserted at any position of the carbon-carbon bond constituting the ring.

  In the “substituent”, the alkynyl group is an ethynyl group, but may be substituted by a hydrogen atom of the ethynyl group. The substituents herein include all of the above “substituents”.

  In the “substituent”, the aryl group may be either a single ring or a condensed ring as long as it is an aromatic ring, and is preferably an aryl group having 6 to 20 carbon atoms. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. Further, the aryl group may further have a substituent at any position, and examples of the further substituent include all of the above-mentioned “substituents”.

  In the “substituent”, the heterocyclic group has a hetero atom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. It may be a single ring or a condensed ring. For example, tetrahydrofuranyl group, dihydrofuranyl group, dihydrofuranyl group, tetrahydropyranyl group, dihydropyranyl group, oxocanyl group, dioxanyl group, tetrahydrothiophenyl group, dithianyl group, pyrrolidinyl group, pyrrolinyl group, tetrahydropyridinyl Group, piperazinyl group, homopiperazinyl group, piperidinyl group, pyrrolyl group, furyl group, thiophenyl group, benzopyrrolyl group, benzofuryl group, benzothiophenyl group, pyrazolyl group, isoxazolyl group, isothiazolyl group, indazolyl group, benzoisoxazolyl group, Benzoisothiazolyl, imidazolyl, oxazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, pyridyl, quinolinyl, isoquinolinyl, pyrida Nyl group, pyrimidinyl group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, acridinyl group, phenanthridinyl group, phthalazinyl group, carbazolyl group, uracil group, dithiouracil group, carbolinyl group, purinyl group, thiadiazolyl Groups and the like. Further, the heterocyclic group may further have a substituent at any position, and the additional substituent includes all of the above-mentioned “substituents”.

In addition, the above-mentioned “organic group” refers to an “substituent” containing at least a carbon atom.
In the above, the organic group represented by R ^{101 to} R ¹⁰⁴ in the sulfur-containing organic group-substituted phthalocyanine-based compound (excluding the naphthalocyanine-based compound) is a sulfur-containing organic group , and further has a substituent. An alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfonamide group, which may be used, are preferred. Moreover, as an organic group represented by Ra and Rb in the azomethine-based compound, it is preferable that Ra and Rb together form a nitrogen-containing heterocycle.

-Other dyes-
Next, other dyes other than those described above that can be contained in the composition of the present invention will be described.
Further, other dyes (including organic solvent-soluble dyes) that may be contained are not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 The dyes described in JP-A-6-194828 can be used.

  The chemical structure includes azo dyes other than the above, triphenylmethane, anthraquinone, benzylidene, oxonol, phenothiazine, azomethine other than the above, xanthene, phthalocyanine other than the above, benzopyran, indigo And pigments such as anthrapyridone.

  When the resist system is subjected to water or alkali development, at least one of acid dyes and derivatives thereof may be suitably used in that the dye is completely removed by development. In addition, it is also useful to select and use at least one of direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof as appropriate. is there.

  Hereinafter, the acid dye and its derivative will be described. The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group. It is selected in consideration of all required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

  Specific examples and preferred examples of the acid dye include dyes described in JP-A-2005-227722, but the invention is not limited thereto.

When the acid dye is contained as a constituent component of the composition, it may be better to use it as a derivative of the acid dye because it may have insufficient solubility in the organic solvent used for preparation.
As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like can be used. Although it will not specifically limit if it can melt | dissolve in the solution of the prepared composition, The solubility with respect to the organic solvent and the developing solution used at the time of a development process, a light absorbency, interaction with the other component in a composition, light resistance In addition, it is selected in consideration of all necessary performance such as heat resistance.

The salt of said acidic dye and a nitrogen-containing compound is demonstrated. The method of forming a salt with an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.
The nitrogen-containing compound that forms a salt with an acid dye, and the nitrogen-containing compound that forms an amide bond with an acid dye to obtain a sulfonamide of an acid dye are organic solvents or salts used during preparation or development processing of the salt or amide compound. Taking into account all of the solubility in the developer, salt formation, absorbance / color value of the dye, interaction with other components in the dye-containing negative curable composition, heat resistance as a colorant, and light resistance Selected. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, particularly preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

  Hereinafter, specific examples of the nitrogen-containing compound will be given. However, the present invention is not limited to these. In the following compounds, those having no “—NH— group” are not nitrogen-containing compounds forming an amide bond.

  The molar ratio of the nitrogen-containing compound / acid dye in the salt of the acid dye and the nitrogen-containing compound (hereinafter referred to as “n”) will be described. The molar ratio n is a value that determines the molar ratio between the acidic dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acidic dye-amine compound. Specifically, n is a numerical value satisfying 0 <n ≦ 10 among the number of functional groups of an acid in an acid dye for practical use, solubility in an organic solvent or a developer, salt formation, absorbance, dye content It can be selected in consideration of all necessary performances such as interaction with other components in the negative curable composition, light resistance, heat resistance and the like. When selecting only from the viewpoint of absorbance, n is preferably a numerical value satisfying 0 <n ≦ 4.5, more preferably a numerical value satisfying 0 <n ≦ 4, and particularly preferably a numerical value satisfying 0 <n ≦ 3.5. .

  In addition, the dye essential to the present invention and / or other dyes may have at least one addition-polymerizable ethylenically unsaturated double bond in the structure. The organic solvent-soluble dye may be bonded to the resin.

  The concentration of the dye in the total solid component in the dye-containing negative curable composition varies depending on the type of the dye, but is usually 0.5 to 97% by mass, preferably 40 to 95% by mass, and 45 to 90%. Mass% is particularly preferred.

(B) Oxime-based photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one oxime-based photopolymerization initiator (initiator according to the present invention). This oxime-based photopolymerization initiator can be polymerized and cured together with a radically polymerizable monomer described later when the dye-containing negative curable composition is constituted as a negative type.

  Examples of the oxime photopolymerization initiator include, for example, JP 2000-80068, JP 2001-233842, WO 2005-080337, JP 2001-235858, JP 2002-519732, Examples thereof include compounds described in Table 2004-534797, WO 2004-050653, and the like. However, it is not limited to these.

  Specific examples of the oxime photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl)- Butane-1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methyl) A preferred example is benzoyl) -9H-carbazol-3-yl] ethanone.

  Among the above, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is particularly preferred.

  The oxime photopolymerization initiator has the following isomers (A) and (B) in terms of the compound structure, but may be used as a mixture of isomers or only one isomer.

In (A) and (B), R ¹ and R ² represent the above-mentioned “substituent”, and R ³ represents the organic group. However, R ¹ and R ² do not represent hydrogen atoms at the same time.

  In the present invention, two or more oxime photopolymerization initiators may be mixed and used at an arbitrary mass ratio.

Next, other photopolymerization initiators that can be used in combination with the oxime photopolymerization initiator will be described.
The other photopolymerization initiator is not particularly limited as long as it can cause a monomer having a polymerizable group to undergo a polymerization reaction, but is preferably selected from the viewpoint of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. .

  As other photopolymerization initiators, (tri) halomethyltriazine compounds, α-aminoketone compounds, and acylphosphine (oxide) compounds are suitable.

  Examples of the (tri) halomethyltriazine compounds include, for example, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281, and JP-A-53-133428 as halomethyl-s-triazine compounds. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound described in the above, Can be mentioned.

Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1) Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho 2-yl) -4,6-bis - trichloromethyl -s- triazine, 2- (5-methoxy - naphth-1-yl)
-4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine,

2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminopheny ] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o- Chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition to the above, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical Co., Ltd. may be mentioned. .

  Examples of the α-aminoketone compound include Irgacure series (for example, Irgacure 907 and Irgacure 369) manufactured by Ciba Specialty Chemicals, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. It is done.

  Although it does not specifically limit as said acylphosphine (oxide) type compound, Irgacure 819, Darocur 4265, Darocur TPO, etc. by Ciba Specialty Chemicals are mentioned.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators can be used in the dye-containing negative curable composition of the present invention. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Examples include benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.

  Specifically, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, And cyclopentadiene-benzene-iron complex and salts thereof.

Examples of the active halogen compound which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-
And trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, and the like. .

  Further, T series manufactured by PANCHIM is also effective, and examples thereof include T-OMS, T-BMP, TR, and TB. The Irgacure series manufactured by Ciba Specialty Chemicals is also effective, and examples thereof include Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 261, Darocur 1173, and the like.

  Besides these, 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethyl Amino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxy) Phenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl Dazoriru dimer, 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, etc. are used also useful.

  A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators. Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p -Methylstyryl ketone, benzophenone, p- (di Chiruamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, and benzanthrone, etc., benzothiazole compounds described in JP-B-51-48516, etc., Tinuvin 1130, the 400, and the like

  The oxime photopolymerization initiator or / and other photopolymerization initiator essential for the present invention includes at least one addition-polymerizable ethylenically unsaturated double bond, a perfluoroalkyl structure, or siloxane in the structure. It may have a group having at least one surface active function such as a structure. These initiators may be bonded to the resin.

The total amount of the photopolymerization initiator in the dye-containing negative curable composition is usually 5% by mass or more based on the total solid content of the composition. Furthermore, 9 mass% or more is preferable with respect to the total solid content, and it is more preferable that it is 12 mass% or more. Moreover, the upper limit of this total amount is 40 mass% normally, Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less.
Of the total amount, from the viewpoint of the effect of the present invention, the content of the initiator (oxime photopolymerization initiator) according to the present invention is preferably 100 to 20% by mass, and more preferably 100 to 30% by mass.

  In the dye-containing negative curable composition, the mass ratio (B / B) of the total amount of the photopolymerization initiator (B) including the oxime-based photopolymerization initiator and the total amount of the (C) radical polymerizable monomer described later is used. C) is usually 0.1 or more and 1 or less, preferably 0.25 or more and 0.75 or less, and more preferably 0.3 or more and 0.70 or less. When the mass ratio (B / C) is within the above range, the polymerization reaction can be performed satisfactorily and the polymerization rate increases, but the molecular weight does not decrease and the film strength does not decrease.

In the present invention, among the above, two kinds of pyrazole azo compounds and pyridone azo compounds, or two kinds ( dyes) of sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compounds) and pyrazole azo compounds are used. It is a combination with an oxime photopolymerization initiator.

  It is preferable to further add a thermal polymerization inhibitor together with the above photopolymerization initiator. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

(C) Radical polymerizable monomer The dye-containing negative curable composition of the present invention contains at least one radical polymerizable monomer. As the radical polymerizable monomer, a compound having at least one addition-polymerizable ethylenically unsaturated double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable.

  Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and then (meth) acrylated after adding ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof described in JP-B-52-30490 Can do. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  In addition to the above, radically polymerizable monomers containing carboxyl groups such as the following general formulas (V-1) and (V-2) can also be suitably used. In general formulas (V-1) and (V-2), when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X, and W.

In the said general formula (V-1), n is 0-14 and m is 1-8. In the said general formula (V-2), W is R or X synonymous with general formula (V-1), and 3 or more W is R among six W. p is 0-14 and q is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.
Of the radical polymerizable monomers represented by the general formulas (V-1) and (V-2), the following specific examples (Exemplary Compounds M-1 to M-12) are specifically preferred. Exemplified compounds M-2, M-3, and M-5 are preferred.

  The content of the radically polymerizable monomer in the dye-containing negative curable composition is preferably 20% by mass or more and preferably 30% by mass or more in terms of solid content in the total solid content of the composition. More preferably, it is most preferable to contain 35% by mass or more.

(D) Organic solvent In preparing the dye-containing negative curable composition of the present invention, generally an organic solvent (also simply referred to as “solvent” in the present specification) can be used. The solvent is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but particularly considering the solubility, coating property, and safety of the dye and the alkali-soluble binder. Are preferably selected.

  Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

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

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

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

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbi Tall acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

  Among the above, in terms of solubility of each component and viscosity after preparation, one or more selected from cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl 3-ethoxypropionate An embodiment constituted by one or more of propylene glycol monomethyl ether and ethyl 3-ethoxypropionate is further selected from the viewpoints of liquid aging stability and coating properties. More preferred.

(E) Other components-Resin (binder)-
The dye-containing negative curable composition of the present invention may further use a resin (binder). The resin can be appropriately selected from known resins regardless of whether it is alkali-soluble or alkali-insoluble.

  As the resin, an alkali-soluble resin (hereinafter referred to as an alkali-soluble binder) is preferable. Hereinafter, the alkali-soluble binder will be described.

The alkali-soluble binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol and the like are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  In addition, the hydrophilic monomer includes a tetrahydrofurfuryl group, a phosphoric acid site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group and its salt, a morpholinoethyl group, and the like. A monomer or the like is also useful.

  In addition, from the viewpoint of improving the crosslinking efficiency, a polymer having a polymerizable group in the side chain and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Hereinafter, examples of the polymer containing these polymerizable groups are shown, but the polymer is not limited thereto as long as it contains an alkali-soluble group such as a COOH group, an OH group, and an ammonium group and an unsaturated bond between carbon atoms.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.

  As the compound having reactivity with the OH group, a compound having an acid anhydride, an isocyanate group, and an acryloyl group can be used in addition to the epoxy ring. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd.); Biscote R-264, KS resist 106 (both made by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both made by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Yu) CB Co., Ltd.).

  When the resin (binder) is contained, the content of the resin in the dye-containing negative curable composition is usually 0.5 to 90% by mass with respect to the total solid content of the composition.

~ Surfactant ~
The composition of the present invention may further use a surfactant. The surfactant can be selected from known surfactants according to the purpose and the like.
Preferred surfactants are polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkyl allyl ethers such as ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-366 (manufactured by Troy Chemical Co., Ltd.), etc. Siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co.) and acrylic or methacrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.).
The surfactant is any one of fluorine and / or silicon surfactants (fluorine surfactants and silicon surfactants, surfactants containing both fluorine atoms and silicon atoms), or It is preferable to contain 2 or more types.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63- No. 34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A 2002-277862, US Pat. No. 5,405,720 , No. 5,360,692, No. 5,529,881, No. 5,296,330, No. 5,543,098, No. 5,576,143, No. 5,294,511, No. 5,824,451. The following commercially available surfactants can also be used as they are.

Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine-based surfactant or silicon-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).
Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy Copolymer) of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group. Coalescence And the like.
These surfactants may be added alone or in some combination.

  When the surfactant is contained, the content of the surfactant in the dye-containing negative curable composition is preferably 0.0001 to 5% by mass with respect to the total mass of the composition, 0.001 to 1 The mass% is more preferable.

~ Crosslinking agent ~
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and acyloxymethyl. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from the group A phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with Of these, polyfunctional epoxy resins are preferred.

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

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

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

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

  Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

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

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

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

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

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

  Examples of the skeletal compound in the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

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

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

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

  In the present invention, it is not always necessary to contain a crosslinking agent. When a crosslinking agent is contained, the total content of the crosslinking agents (a) to (c) in the dye-containing negative curable composition varies depending on the material, but is based on the total solid content (mass) of the composition. 1 to 70% by mass is preferable, and 5 to 50% by mass is more preferable.

~ Various additives ~
In the dye-containing negative curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, Transition metal complexes and the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; vinyltrimethoxysilane Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane Adhesion promoters such as 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6 -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

  In the dye-containing negative curable composition of the present invention, a transition metal complex having a maximum molar extinction coefficient ε in the visible light region smaller than the molar extinction coefficient ε of the dye can be used. This transition metal complex is a negative curable composition containing a dye, in which a negative, neutral or positive monodentate or multidentate ligand is coordinated around a transition metal atom or transition metal ion. And it is effective in improving the light resistance of a color filter using the same.

  A transition metal complex having a maximum molar extinction coefficient ε in the visible light region (380 to 780 nm) of 0 or more and 8000 or less is preferable in terms of color sharpness. Further, as the transition metal complex, the maximum value of the molar extinction coefficient ε in the above wavelength range is preferably 0 or more and 6000 or less, and more preferably 0 or more and 3000 or less.

  Examples of transition metals constituting transition metal atoms and transition metal ions of transition metal complexes include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), yttel Um (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), Platinum (Pt), Gold (Au), Etc.

  Preferred examples of the transition metal complex include those in which the transition metal belongs to the first series (that is, the fourth period of the long periodic table; the same applies hereinafter), that is, scandium (Sc), titanium (Ti), vanadium (V), chromium Examples include (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). Of these, Mn, Fe, Co, Ni, and Cu are preferable.

As the ligand of the transition metal complex, the ligand alone preferably has a maximum molar extinction coefficient ε in the visible light region of 0 or more and 3000 or less, and the maximum value of ε is 0 or more and 2000 or less. Is more preferable, and the maximum value of ε is particularly preferably 0 or more and 1000 or less.
In addition, the molecular weight of one ligand in the transition metal complex is preferably 20 or more and less than 300 in terms of light resistance and alkali developability.

Further, when the alkali solubility of the uncured part is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The dye-containing negative curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs), solid-state imaging devices (eg, CCDs, CMOSs, etc.), electroluminescent color filters, etc. Also, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, a color filter is produced using the above-described dye-containing negative curable composition of the present invention. Specifically, the radiation-sensitive composition layer is formed by coating the dye-containing negative curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like. Is exposed through a predetermined mask pattern and developed with a developer to form a negative colored pattern (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.
By repeating the image forming step (and the curing step if necessary) as many times as desired, a color filter having a desired hue can be produced.
As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferable.

  The color filter of the present invention uses the above-described dye-containing negative curable composition of the present invention, and preferably has two or more colored regions (for example, red (R), green (G ) And blue (B) (colored regions of three colors) are provided in a desired pattern shape (for example, a stripe shape, a lattice shape, a delta array shape, etc.). The color filter of the present invention can be most suitably produced by the method for producing a color filter of the present invention.

In the case where two or more colored regions are provided on the support, a dye-containing negative curable composition containing at least two of the following (1) or (2) at least two colors of the colored region constituting the color filter The aspect currently formed using the thing is preferable.
(1) two pyrazole azo compound and pyridone azo compound (2) two sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compound) and pyrazole azo compound
Before SL (1) are as described above in regard to details, a preferred embodiment of the compound (2).

Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing negative curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As an organic solvent here, the above-mentioned organic solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

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

  The color filter of the present invention can be used for a liquid crystal display element (LCD) or a solid-state imaging element (for example, CCD, CMOS, etc.), and is particularly suitable for a high-resolution CCD element, CMOS, etc. exceeding 1 million pixels. is there. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

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

(Examples 1-6, Reference Examples 7-10 , Comparative Examples 1-5)
1) Preparation of resist solution A compound having the following composition was mixed and dissolved to prepare a resist solution.
Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA)
-Ethyl lactate ... 36.67 parts-Resin (binder) ... 30.51 parts [41% PGMEA of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/20/20) solution〕
Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol): 0.0061 part ・ Fluorosurfactant: 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator: 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator), manufactured by Midori Chemical Co., Ltd.)

2) Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes or more. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm. After application, the resist solution is heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Obtained.

3) Preparation of dye-containing negative curable composition The components shown in Table 1 below (the amounts are as shown in Table 1) are dissolved in the organic solvent shown in Table 1 below, and the dye-containing negative type of the present invention is used. Curable compositions N-1 to N-15 were prepared.

4) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable compositions N-1 to N-15 obtained in 3) were each filtered using a filter. After filtration, the dye-containing negative curable compositions N-1 to N-15 are each 0.8 μm in film thickness on each undercoat layer of the separate undercoat-coated silicon wafer substrate obtained in 2) above. In this way, the coating was applied using a spin coater, and the coated film was heat-treated (prebaked) at 100 ° C. for 120 seconds.

  Next, using the i-line reduction projection exposure apparatus, the coating amount obtained above was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm while changing the exposure amount by 100 mJ. After irradiation, the film was developed using a developer of 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) at 23 ° C. for 60 seconds. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a colored filter film (color filter). The formation of the image was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

5) Evaluation With respect to the dye-containing negative curable compositions N-1 to N-15 and color filters obtained in the above-described Examples , Reference Examples and Comparative Examples, the line width variation rate due to the change in the exposure amount by the method described below. And the number of coating defects increased over time. The evaluation results are shown in Table 1 below.

-1. Evaluation of line width variation rate due to exposure change-
In a 2 μm width pattern, the exposure amount at which the dot-space width is 1: 1 is the appropriate exposure amount (sensitivity), and the line width variation rate when the exposure amount is increased or decreased by 100 mJ from this appropriate exposure amount is as follows. Calculated from the formula. In addition, “||” in the following formula represents an absolute value.
Line width fluctuation rate (%) =
| (Line width at 100 mJ deviation from appropriate exposure amount ^* ) − (Line width at appropriate exposure amount) | / (Line width at appropriate exposure amount) × 100
* Here, out of the line widths when increased or decreased by 100 mJ from the appropriate exposure amount, the one that is more deviated from the line width at the appropriate exposure amount was used. The smaller the value of the line width variation rate, the better the performance.

-2. Evaluation of increase in coating defects over time-
The dye-containing negative curable compositions N-1 to N-15 immediately after the preparation in 3) are applied onto the undercoat layer of the silicon wafer substrate with an undercoat layer obtained in 2) in the same manner as described above. did. And this coating film was observed with the optical microscope, the number of the hole-like and radial coating defects was counted, and the sum total of the number of defects seen in one 6 inch silicon wafer was calculated. Next, after storing the dye-containing negative curable compositions N-1 to N-15 at 25 ° C. for 2 weeks, the total number of coating and coating defects was determined in the same manner as described above. Subsequently, the number of coating defects increased over time was calculated from the following formula and used as an index for evaluating the temporal stability of the dye-containing negative curable composition. The stability over time indicates that the smaller the value of the increase number, the better.
Increased number of coating defects over time =
(Number of coating defects after 2 weeks)-(Number of coating defects immediately after preparation)

Details of each component in Table 1 are shown below.
(A) Dye The column of the name of an Example shows the number of the exemplary compound of the dye mentioned above.
Dyes H-1 to H-4 of Comparative Examples
H-1: Varifast Yellow 1101
-H-2: C.I. I. Acid Red 249
・ H-3: Variefast Blue 2620
H-4: C.I. I. Acid Red 80
(B) Photopolymerization initiator B-1: Irgacure OXE01 (manufactured by Ciba Specialty Chemicals; initiator according to the present invention)
B-2: CGI-242 (manufactured by Ciba Specialty Chemicals; initiator according to the present invention)
B-3: Irgacure 369 (manufactured by Ciba Specialty Chemicals; α-aminoketone photopolymerization initiator)
B-4: TAZ-107 (manufactured by Midori Chemical Co .; trihalomethyltriazine photopolymerization initiator)
B-5: Irgacure 819 (manufactured by Ciba Specialty Chemicals; acylphosphine photopolymerization initiator)
B-6: 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (C) radical polymerizable monomer C-1: radical A 3: 7 mixture of the exemplified compound (M-2) and dipentaerythritol hexaacrylate described above as a polymerizable monomer (D) Organic solvent D-1: cyclohexanone D-2: ethyl lactate D-3: propylene glycol monomethyl ether Acetate (PGMEA)
D-4: Propylene glycol monomethyl ether D-5: Ethyl 3-ethoxypropionate (E) Other components * Resin (binder)
E-1: benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30000)
* Surfactant F-1: Fluorosurfactant F-475 (Dainippon Ink Chemical Co., Ltd.)

  As shown in Table 1, in the examples, the increase in coating defects with time was small, the line width variation rate of the formed pattern was small, and the pattern forming property was excellent. On the other hand, in the comparative example, the increase in coating defects with time was remarkable, the line width variation rate of the formed pattern was large, and the pattern formability was inferior.

Claims (5)

(A) contains at least two dyes containing either of the following (1) or (2), (B) at least one oxime photopolymerization initiator, and (C) at least one radical polymerizable monomer A dye-containing negative curable composition.
(1) Two types of pyrazole azo compounds and pyridone azo compounds
(2) Sulfur-containing organic group-substituted phthalocyanine compounds (excluding naphthalocyanine compounds) and pyrazole azo compounds The dye-containing negative curable composition according to claim 1, wherein at least one of the dyes is a compound containing an acidic group. The dye-containing negative curable composition according to claim 1 or 2, wherein the sulfur-containing organic group-substituted phthalocyanine compound (excluding a naphthalocyanine compound) is a compound represented by the following general formula 1.

In General Formula 1, M represents a metal. Z ¹ , Z ² , Z ³ And Z ⁴ Each independently represents a group of atoms necessary to form a 6-membered ring containing carbon atoms. R ¹⁰¹ , R ¹⁰² , R ¹⁰³ And R ¹⁰⁴ Each independently represents a monovalent substituent, R ¹⁰¹ ~ R ¹⁰⁴ At least one of the substituents represented by (1) represents an organic group containing a sulfur atom (a sulfur-containing organic group). n1, n2, n3, and n4 each independently represents an integer of 0 to 4.   The color filter which uses the dye-containing negative curable composition of any one of Claims 1-3.   The manufacturing method of a color filter including the process of apply | coating the dye-containing negative curable composition of any one of Claims 1-3 on a support body, exposing through a mask, developing, and forming a pattern.