TW201520689A - Photosensitive colored composition, black matrix, colored spacer, image display device and pigment dispersion liquid - Google Patents

Abstract

An object of the present invention is to provide a photosensitive colored composition which has an excellent light-blocking property and an excellent dispersibility and plate making property, and shows a sufficiently low relative permittivity. The photosensitive colored composition of the present invention at least comprises (A) a coloring agent, (B) a dispersing agent, (C) a alkali soluble resin and (D) a photopolymerization initiator, wherein the coloring agent (A) contains (A-1) an organic black pigment that is a compound represented by the formula (1), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound, and the dispersing agent (B) contains a polymer dispersing agent having a quaternary ammonium base as a functional group:.

Description

Photosensitive coloring composition, black matrix, colored spacer, image display device, and pigment dispersion

The present invention relates to a photosensitive coloring composition, a black matrix, a colored spacer, and an image display device. In particular, the present invention relates to a photosensitive coloring composition excellent in shielding properties and plate-making properties, and use thereof.

A black matrix for a liquid crystal display element is used to prevent light leakage between self-driving electrodes in a liquid crystal display element. In general, the black matrix is a pattern of a stripe-like or lattice-shaped light-shielding material formed by a photolithography method on a transparent substrate such as a glass or a plastic sheet which is paired with a TFT (Thin Film Transistor) element substrate. Recently, in order to cope with the higher refinement of color liquid crystal display elements. In the active matrix type liquid crystal display, a color filter is disposed on the TFT element substrate side (COA (color filter on array)) or only a black matrix is disposed on the TFT. Black matrix on array (BOA) on the substrate side of the device. According to the above aspect, since it is not necessary to provide a margin for alignment with the active element side as compared with the case where the black matrix is formed on the color filter side, the aperture ratio can be increased, and as a result, high aperture can be achieved. Brightness.

However, in the case of adopting the above configuration, the black matrix is required to have a volume resistivity of a certain value or more or a relative dielectric constant of a certain level or less so that the circuit is not short-circuited even if it is directly mounted on the TFT element. As such a black matrix, it is proposed to have A black matrix of a plurality of organic coloring pigments and carbon black is used in the material (for example, refer to Patent Document 1).

In addition, a photosensitive composition for a black matrix using an organic black pigment as a pigment is known, and specifically, nigrosine (for example, refer to Patent Document 2) or tanning (for example, refer to Patent Document 3) is known. Photosensitive composition. On the other hand, as the organic pigment, a bis-oxodihydro-extended mercapto-benzofuran coloring agent is known (for example, see Patent Document 4). The case where the pigment is used to form a red layer, a blue layer, and a green layer of a color filter is described in this document. Further, this pigment is known to be used as an organic black pigment for an electrophoretic display (see, for example, Patent Document 5).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-75446

Patent Document 2: Japanese Patent Laid-Open No. Hei 8-44049

Patent Document 3: Japanese Patent Laid-Open Publication No. 2006-235153

Patent Document 4: Japanese Patent Laid-Open Publication No. 2002-528448

Patent Document 5: Japanese Patent Laid-Open Publication No. 2012-515240

As a result of intensive studies, the inventors of the present invention have found that the photosensitive composition of Patent Document 1 has a low hiding ratio (optical density) of the organic colored pigment, and it is necessary to increase the film thickness in order to obtain a sufficient optical density. Moreover, it is understood that the aniline black or the black pigmentation described in Patent Document 2 or 3 is inferior in dispersibility, and it is necessary to use a large amount of a dispersant in order to carry out dispersion, and there is a problem in plate-making properties and the like. In addition to this, it is understood that the shielding ratio (optical density) is also insufficient.

Further, in Patent Document 4 or 5, there is no description or teaching regarding the use of a bis-oxodihydro-extended mercapto-benzofuran coloring agent as a masking agent for an image display device, and The optical density, dispersibility, or plate-making properties of the masking agent of the image display device are also unclear. The present invention has been made in view of the above-described conventional circumstances, and an object of the invention is to provide a photosensitive coloring composition which is excellent in light-shielding property and excellent in dispersibility and plate-making property and exhibits a sufficiently low relative dielectric constant.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that by using an organic black pigment having a specific structure as a coloring material in a photosensitive coloring composition and using a specific dispersing agent, the above problems can be solved. The present invention has been completed. That is, the present invention has the following constitutions [1] to [17].

[1] A photosensitive coloring composition comprising at least (A) a colorant, (B) a dispersing agent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, and the above (A) color The material (A-1) is an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt thereof, and the above (B) dispersant contains a polymer dispersant having a quaternary ammonium salt group as a functional group,

[In the formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, a CH ₃ , a CF ₃ , a fluorine atom or a chlorine atom; and R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ^{9 .} And the R ¹⁰ system and all others are independent of each other, and are a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH , SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and selected from R ² and R ³ And R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and at least one of the groups consisting of R ⁹ and R ¹⁰ may be directly bonded to each other, or Bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a carbon number of 2 to 12 Alkenyl group, cycloalkenyl group having 3 to 12 carbon atoms or alkynyl group having 2 to 12 carbon atoms.

[2] The photosensitive coloring composition of [1], wherein, in the above general formula (1), in the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. a fluorine atom or a chlorine atom, and R ³ and R ⁸ are each independently a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , R ¹ is the same as R ⁶ , R ² and R ^{7 is the} same, R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

[3] The photosensitive coloring composition of [1] or [2], wherein the polymer dispersing agent further has a tertiary amine as a functional group.

[4] The photosensitive coloring composition according to any one of [1] to [3] wherein the (C) alkali-soluble resin contains the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2) At least one of them,

<alkali soluble resin (c1)>

By adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group An alkali-soluble resin obtained by reacting an epoxy resin with a polybasic acid and/or an anhydride thereof;

<alkali soluble resin (c2)>

It is obtained by reacting an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin, and further reacting with a polyhydric alcohol, a polybasic acid and/or an anhydride thereof. Alkali soluble resin.

[5] The photosensitive coloring composition according to any one of [1] to [4] wherein the (A) coloring matter further contains (A-2) an organic coloring pigment.

[6] The photosensitive coloring composition of [5], wherein the (A-2) organic coloring pigment contains at least one of the following pigments,

Blue: Chroma Index Pigment Blue 60, or 15:6

Red: Chroma Index Pigment Red 177, 254, or 272

Violet: Chroma Index Pigment Violet 23, or 29

Orange: Chroma Index Pigment Orange 43, 43, or 72.

[7] The photosensitive coloring composition of [5] or [6], wherein the content ratio of the (A-1) organic black pigment is from 30 to 90% by mass based on 100% by mass of the (A) colorant. (A-2) The content ratio of the organic coloring pigment is 10 to 70% by mass.

[A] The photosensitive coloring composition according to any one of [1] to [7] wherein the (A) coloring matter further contains (A-3) carbon black.

[9] The photosensitive coloring composition according to [8], wherein the content ratio of the (A-1) organic black pigment is 50 to 90% by mass based on 100% by mass of the (A) colorant, (A-3) The content of carbon black is 10 to 50% by mass.

[10] The photosensitive coloring composition of any one of [1] to [9], wherein (D) photopolymerization is started The initiator is an oxime ester initiator, and/or a ketoxime initiator.

[11] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [10].

[12] A black matrix formed of a cured product of [11].

[13] A colored spacer formed of a cured product of [11].

[14] An image display device comprising a black matrix of [12] or a color spacer of [13].

[15] A pigment dispersion liquid comprising (A) a colorant and (B) a dispersant, wherein the (A) colorant contains (A-1) a compound represented by the following general formula (1) An organic black pigment whose geometric isomer, a salt thereof, or a salt thereof is a geometrical isomer, and the above (B) dispersant contains a polymer dispersant having a quaternary ammonium salt group as a functional group,

Wherein R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom; R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ And all others are independent of each other, are hydrogen atoms, halogen atoms, R ¹¹ , COOH, COOR ¹¹ , COO ^- , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and selected from R ² and R ³ , R ³ And at least one of the group consisting of R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ may be directly bonded to each other or by An oxygen atom, a sulfur atom, NH or NR ^{11 are} bridged and bonded to each other; R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an alkyl group having 2 to 12 carbon atoms. a group, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.

[16] The pigment dispersion according to [15], wherein, in the above general formula (1), wherein R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, fluorine Atom or a chlorine atom, R ³ and R ⁸ are each independently a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N ( CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , R ¹ is the same as R ⁶ , and R ² is the same as R ⁷ R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

[17] The pigment dispersion according to [15] or [16], wherein the polymer dispersant further has a tertiary amine as a functional group.

The photosensitive coloring composition of the present invention can reduce the amount of the dispersing agent when the pigment dispersion is produced by containing an organic black pigment having a specific structure. Therefore, it exhibits excellent plate-making properties and is excellent in dispersibility. Therefore, the black matrix formed of the photosensitive coloring composition of the present invention exhibits excellent light blocking properties. Moreover, the black matrix and the colored spacer of the present invention are displayed on the TFT element substrate, and are not caused to cause a short circuit. A sufficiently low relative dielectric constant such as a malfunction. The image display device having the black matrix of the present invention has no problems such as TFT failure or disorder of liquid crystal driving, and is excellent in reliability.

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL element.

The embodiments of the present invention are specifically described below, but the present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention. In the present invention, the term "(meth)acrylic group" means "acrylic acid group and/or methacrylic acid group", and "(meth) acrylate" and "(meth) acryl fluorenyl group" The same is true.

The term "(co)polymer" means both a homopolymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydrous) ... acid" means acid. Both with its anhydride. In the present invention, the term "acrylic resin" means a (co)polymer comprising (meth)acrylic acid and a (co)polymer comprising a (meth)acrylate having a carboxyl group.

Further, the term "monomer" in the present invention is a term referring to a polymer substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a narrow monomer. meaning. In the present invention, the "total solid content" means all components other than the solvent contained in the photosensitive coloring composition or the ink described below. The weight average molecular weight in the present invention means a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography). In addition, the "amine value" in the present invention means an amine value in terms of an effective solid content, and is a value expressed by the mass of KOH equivalent to the amount of alkali per gram of the solid content of the dispersant, unless otherwise specified. Further, the measurement method will be described below. On the other hand, the "acid value" is an acid value in terms of an effective solid content, and is calculated by neutralization titration unless otherwise specified.

In addition, in this specification, the percentage or part expressed by "quality" is synonymous with the percentage or part expressed by "weight".

[Photosensitive coloring composition]

The photosensitive coloring composition of the present invention (hereinafter referred to as "photosensitive coloring composition" or "colored resin composition") is contained

(A) colorant

(B) Dispersant

(C) alkali soluble resin

(D) Photopolymerization initiator

Further, as an essential component, if necessary, an organic solvent, a silane coupling agent or the like, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like may be contained. And each of the compounding components is usually used in a state of being dissolved or dispersed in an organic solvent.

<(A) Colorant>

The (A) colorant used in the present invention contains (A-1) an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt thereof .

[In the formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, a CH ₃ , a CF ₃ , a fluorine atom or a chlorine atom; and R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ^{9 .} And the R ¹⁰ system and all others are independent of each other, and are a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH , SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and selected from R ² and R ³ And R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and at least one of the groups consisting of R ⁹ and R ¹⁰ may be directly bonded to each other. Alternatively, they are bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a carbon number of 2 to 2; Alkenyl group 12, cycloalkenyl group having 3 to 12 carbon atoms or alkynyl group having 2 to 12 carbon atoms. The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituent in the structural formula is omitted), and the trans-trans isomer may be the most stable.

In the case where the compound represented by the general formula (1) is anionic, it is preferably any known cation such as a metal, an organic, an inorganic or a metal organic cation, specifically, an alkali metal or an alkaline earth metal. a transition metal, a primary ammonium, a secondary ammonium, a trialkylammonium or the like, a tertiary ammonium such as a tertiary ammonium or a tetraalkylammonium or an organic metal complex to compensate for the charge. Further, in the case where the geometric isomer of the compound represented by the general formula (1) is anionic, the same salt is preferred.

In the substituent of the general formula (1) and the definitions thereof, the tendency of the masking ratio to increase is preferred, and the following is preferred. The reason for this is that the following substituents are considered to have no absorption and do not affect the hue of the pigment. R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently, and are preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom. R ³ and R ⁸ are each independently, preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH _{3 )} (C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently, and are preferably a hydrogen atom, CH ₃ or CF ₃ , and further preferably a hydrogen atom. Preferably, it is selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and at least one of the groups consisting of R ⁵ and R ¹⁰ , more preferably R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ .

The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, t-butyl, 2-methylbutyl, or Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-B Hexyl, decyl, decyl, undecyl or dodecyl.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a arboryl group, and a descending group. base, Base, norcaryl, caryl, Base, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 1,3-butadiene group. -2-yl, 2-penten-1-yl, 3-penten-2-yl, 2- 1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl , hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl 2,4-cyclohexadien-1-yl, 1-pair Alkene-8-yl, 4(10)-terpenal-10-yl, 2-lower Alkene-1-yl, 2,5-lower Dien-1-yl, 7,7-dimethyl-2,4-norpren-3-yl or campphenyl.

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl , 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyne-6-yl, cis-3-methyl-2-pentene-4-yn-1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1 3-hexadiyn-5-yl, 1-octyne-8-yl, 1-decyne-9-yl, 1-decynyl-10-yl or 1-dodecyn-12-yl.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The organic black pigment of the preferred (A-1) is a compound represented by the following general formula (2).

Specific examples of such an organic black pigment include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation). The organic black pigment of (A-1) is preferably used by being dispersed by the following dispersant, solvent or method. Further, when the sulfonic acid derivative of the above general formula (2) is present during dispersion, dispersibility or preservability may be improved.

The photosensitive coloring composition of the present invention may also contain a coloring material other than (A-1) as the (A) coloring material. As the coloring material, a dye can be used, but in terms of heat resistance, light resistance, and the like, a pigment is preferable. In particular, (A-2) an organic coloring pigment and/or (A-3) carbon black can be preferably used. In addition, the organic coloring pigment in the present specification is a powder which is an organic compound used for coloring, and means that it is insoluble in water or oil.

As the (A-2) organic coloring pigment, a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, a black pigment other than (A-1) and (A-3), or the like can be used. Organic pigments of various colors. Further, as the structure, an azo system, a phthalocyanine system, a quinophthalone type, a benzimidazolone type, an isoindolinone type, or a second can be used. In addition to the organic pigments such as the system and the indanthrene, various inorganic pigments and the like can be used. In addition, in the present specification, the color of the pigment means a color which is exhibited when the photosensitive coloring composition is formed by using the pigment as a coloring material, unless otherwise specified. That is, for example, the term "black pigment" means a pigment in which the color exhibited when the photosensitive coloring composition is formed by using the pigment as a coloring material alone becomes black.

Hereinafter, specific examples of the pigment which can be used in the present invention are indicated by pigment numbers. In addition, the terms "C.I. Pigment Red 2" as exemplified below mean a color index (C.I.). As the red pigment, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53: 1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81: 1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Preferably, CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 are further mentioned, and further preferably CI Pigment Red 177, 209, 224, 254 . Further, in terms of dispersibility or light-shielding property, it is preferred to use C.I. Pigment Red 177, 254, and 272, and when the photosensitive coloring composition of the present invention is cured by ultraviolet rays, For the red pigment, it is preferred to use a lower ultraviolet absorptivity. From this point of view, it is more preferred to use C.I. Pigment Red 254, 272.

As the blue pigment, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 79. Among them, preferred are C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and more preferably C.I. Pigment Blue 15:6. Further, in terms of dispersibility or light-shielding property, CI Pigment Blue 15:6, 16, 60 is preferably used as a blue pigment when the photosensitive coloring composition of the present invention is cured by ultraviolet rays. It is preferred to use a lower ultraviolet absorptivity, and in view of this, it is more preferable to use CI Pigment Blue 60.

As the green pigment, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 is exemplified. Among them, preferred are C.I. Pigment Green 7, 36. As the yellow pigment, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196 199, 200, 202, 203, 204, 205, 206, 207, 208. Among them, preferred are: C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably, C.I. Pigment Yellow 83, 138, 139, 150, 180.

As the orange pigment, CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, preferred are C.I. Pigment Orange 38 and 71. Further, in terms of dispersibility or light-shielding property, CI Pigment Oranges 43, 64, and 72 are preferably used, and when the photosensitive coloring composition of the present invention is cured by ultraviolet rays, it is preferably used as an orange pigment. In order to use a lower ultraviolet absorptivity, it is more preferable to use CI Pigment Orange 64, 72 from this point of view.

As the purple pigment, CI Pigment Violet 1, 1:1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, preferred are C.I. Pigment Violet 19 and 23, and more preferably C.I. Pigment Violet 23. Further, in terms of dispersibility or light-shielding property, CI Pigment Violet 23 and 29 are preferably used, and when the photosensitive coloring composition of the present invention is cured by ultraviolet rays, it is preferably used as a violet pigment. In the case of a lower ultraviolet absorption rate, it is more preferable to use CI Pigment Violet 29.

Among these, it is preferable to contain at least 1 or more of the following pigments.

Blue: Chroma Index Pigment Blue 60, or 15:6

Red: Chroma Index Pigment Red 177, 254, or 272

Violet: Chroma Index Pigment Violet 23 or 29

Orange: Chroma Index Pigment Orange 43, 64 or 72

Furthermore, when combining pigments of different colors, regarding the combination of colors, It is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, or a combination of a blue pigment and an orange pigment and a violet pigment, from the viewpoint of light shielding properties.

Further, a dye may be used instead of the (A-2) organic coloring pigment, and a dye may be used in addition to the (A-2) organic coloring pigment. Examples of the dye which can be used as the coloring material include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone imine dye, a quinoline dye, a nitro dye, a carbonyl dye, and a methine group. Dyes and the like. Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, and CI Direct Yellow 12. CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse blue 165, CI alkaline blue 41, CI alkaline red 18, CI mordant red 7, CI mordant yellow 5, CI mord black 7, and the like.

Examples of the lanthanoid dyes include CI Reduced Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue. 60 and so on. In addition, examples of the phthalocyanine dye include CI reduction blue 5 and the like, and examples of the quinone imine dye include CI basic blue 3 and CI basic blue 9 as a quinoline dye. For example, CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64 may be mentioned, and examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

Further, as the photosensitive coloring composition of the present invention, a black pigment other than (A-1) may be used. The black pigment other than (A-1) may be a single black pigment or may be a mixture of red, green, blue, or the like. Further, the coloring materials can be appropriately selected from inorganic or organic pigments and dyes.

As a coloring material which can be used in combination for preparing a black coloring material, it can be cited as: Victoria Pure blue (42595), auramine O (41000), catilon (catilon) flavin (alkaline 13), rose red 6GCP (45160), rose red B (45170), red OK 70: 100 (50240) , Wool Poppy Red X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), Simlaer Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Symarer Red 4015 (12355), Leonor Red 7B4401 (15850), Fast Gen BlueTGR-L (74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36), etc. (Further, the number in the above () means the color index (CI).

Further, as for other pigments that can be used in combination, examples of the CI number include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, and 148. 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, 61; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI violet pigments 19, 23, 29, 30, 37, 40, 50; CI blue pigments 15, 15: 1, 15: 4, 22, 60, 64; CI Green pigment 7; CI brown pigment 23, 25, 26, and the like.

Further, examples of the black coloring material which can be used alone include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and black.

Further, from the viewpoint of the light blocking ratio and the image characteristics, it is preferred to use (A-3) carbon black as a coloring material other than the (A-1) organic black pigment. Examples of the carbon black include carbon black as follows.

Mitsubishi Chemical Corporation manufactures: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000,# 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B

Made by Degussa: Printex (registered trademark, the same below) 3. Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U , Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot company: Monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark)-8

Made by Columbia Carbon: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVENI020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVENI170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black can also be used by those covered with resin. When carbon black coated with a resin is used, the effect of improving the adhesion to the glass substrate or the volume resistance value can be obtained. As the carbon black coated with the resin, for example, carbon black or the like described in JP-A-H09-71733 can be preferably used.

As the carbon black to be coated by the resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black usually contains Na, or Ca, K, Mg, Al, which is mixed with raw material oil or combustion oil (or gas) at the time of manufacture, reaction stop water or granulated water, and further, furnace materials of the reaction furnace. , Fe, etc. as the ash of the composition. Among them, Na or Ca usually contains several hundred ppm or more, respectively, because if such a large amount is present, it may penetrate into a transparent electrode (ITO) or another electrode and be electrically short-circuited.

As a method of reducing the content of the ash containing Na or Ca, the raw material oil or fuel oil (or gas) and the reaction termination water in the case of producing carbon black can be strictly selected by selecting such a small amount; and the adjustment structure is minimized. The amount of alkaline substance added. As another method, a method of washing carbon black produced by a furnace with water or hydrochloric acid, and dissolving and removing Na or Ca may be mentioned.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide water, a solvent which is hardly soluble in water is added, and carbon black migrates to the solvent side, and is completely separated from water, and is present in carbon black. Most of Na or Ca is dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to less than 100 ppm, although the carbon black manufacturing process in which the raw materials are strictly selected is separately achievable, or the water or acid dissolution method is separately achievable, by using the above two methods in combination, Further, the total amount of Na and Ca can be easily made 100 ppm or less.

Further, the resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. because Since the dispersion diameter (agglomeration diameter) in water becomes small, it becomes possible to coat the fine unit, which is preferable. Further, it is preferably a particle diameter of 40 nm or less and a dibutyl phthalate (DBP) absorption amount of 140 ml/100 g or less. The reason is that when the particle diameter is more than 40 nm and the DBP absorption amount is more than 140 ml/100 g, the dispersibility is excellent when the paste is formed, but the concentration feeling of the coating film is insufficient, and if the film thickness is about 1 to 2 μm, there is The opacity becomes insufficient.

The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, the solvent is mixed with a solvent such as cyclohexanone, toluene or xylene. The resin solution obtained by heating and dissolving is mixed with a suspension containing carbon black and water to separate the carbon black from the water, and then the composition obtained by removing the water and heating and kneading is formed into a sheet shape. a method of drying after pulverization; 2. mixing and stirring the resin solution prepared in the same manner as above, and granulating the carbon black and the resin, and separating the obtained granules, a method of removing residual solvent and water by heating; 3. dissolving a carboxylic acid such as maleic acid or fumaric acid in the solvent exemplified above, adding carbon black, mixing it, drying it, and removing the solvent. After adding a carbon black of a carboxylic acid, adding a resin thereto and performing dry doping; 4. preparing a suspension by rapidly stirring a monomer component containing a reactive group of the resin to be coated with water, and performing polymerization after polymerization Cooling, self After the assembly suspension is obtained containing reactive group of the resin, in which carbon black is added and kneaded, so that reaction with the reactive group of carbon black (carbon black to make grafting), a method for cooling and grinding of the like.

The type of the resin to be subjected to the coating treatment is not particularly limited, and is usually a synthetic resin. In terms of dispersibility and dispersion stability, a resin having a benzene nucleus in a structure is preferable because the resin is The role of the amphoteric surfactant is stronger.

As a specific synthetic resin, a phenol resin, a melamine resin, a xylene resin, a diallyl phthalate resin, a glycerin resin, an epoxy resin, an alkylbenzene resin can be used. Or thermosetting resin; or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polyfluorene, polyparaphenylene terephthalate to benzene A thermoplastic resin such as a diamine, a polyamidimide, a polyimine, a polyamine bismaleimide, a polyether fluorene polyphenyl phthalate, a polyarylate, or a polyether ether ketone. The coating amount of the resin of carbon black is preferably from 1 to 30% by mass based on the total amount of the carbon black and the resin, and if it is less than 1% by mass, only the same as the untreated carbon black is obtained. Dispersion or dispersion stability. On the other hand, when it exceeds 30 mass%, the resin adheres strongly to each other, and becomes agglomerated clot, and does not disperse.

The carbon black obtained by coating with the resin in the above manner can be used as a light-shielding material of a black matrix according to a usual method, and a color filter having the black matrix as a constituent element can be produced by a usual method. When such a carbon black is used, a black matrix having a high light-shielding ratio and a low surface reflectance and a small film thickness can be obtained at low cost. It is presumed that the reason is that the dispersibility or dispersion stability of carbon black is remarkably improved with respect to the resin or solvent constituting the black matrix liquid. Further, it is also presumed that the surface of the carbon black is coated with a resin, and Ca or Na is sealed in the carbon black.

Further, barium sulfate, lead sulfate, titanium oxide, yellow dan, iron oxide, chromium oxide or the like may be used as the pigment.

These various pigments can also be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment may be used in combination, or a blue pigment and a violet pigment may be used in combination.

Among these various pigments, a pigment which is (A-2) an organic coloring pigment can be preferably used in terms of light-shielding properties, and examples thereof include CI Pigment Blue 60, CI Pigment Blue 15:6, and CI Pigment Red 177. , CI Pigment Red 242, CI Pigment Blue 254, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Orange 49, CI Pigment Orange 64, CI Pigment Orange 79. When the (A-2) organic coloring pigment is contained, it is preferred to contain at least one of the above pigments. Further, it is preferred to contain two or more of the above pigments.

Further, as the (A-3) carbon black, it is preferable to coat the carbon black with a resin in terms of volume resistance or dielectric coefficient.

The pigments are preferably dispersed so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the reference of the average particle diameter is the number of pigment particles.

Further, in the present invention, the average particle diameter of the pigment is a value obtained from the particle diameter of the pigment measured by dynamic light scattering (DLS). The particle size measurement is performed on a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if it is a concentration recommended by a measuring device, it is carried out according to the concentration), and is 25 The measurement was carried out at °C.

<(B) Dispersant>

In the photosensitive coloring composition of the present invention, it is important to ensure the stability of the quality, and it is important to finely disperse the (A) coloring material and stabilize the dispersed state, thereby containing (B) a dispersing agent, especially (A-1) From the viewpoint of dispersibility of the organic black pigment, a polymer dispersant having a quaternary ammonium salt group as a functional group is contained.

In terms of dispersion stability, the above polymer dispersant may further have a carboxyl group; a phosphate group; a sulfonic acid group; or such a base; a primary, secondary or tertiary amine group; pyridine, pyrimidine, pyridyl The functional group derived from a nitrogen-containing heterocyclic group or the like. Among them, in terms of dispersing a pigment, a small amount of a dispersing agent can be used for dispersion, and it is particularly preferable to have a primary, secondary or tertiary amine group; pyridine, pyrimidine, pyridyl A polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group.

In the above, (A-1) from the viewpoint of the dispersibility of the organic black pigment, and (A-2) From the viewpoint of dispersibility of the organic coloring pigment and/or (A-3) carbon black, a polymer dispersing agent having a quaternary ammonium salt group and a tertiary amino group as a functional group is preferable.

In addition, examples of the polymer dispersant include an urethane dispersant, an acryl dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and a monomer having an amine group and a giant a dispersant composed of a monomer, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan fatty ester dispersant, An aliphatic modified polyester dispersant or the like.

Specific examples of such a dispersing agent include EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Co., Ltd.), Disparlon (registered trademark, manufactured by Nanben Chemical Co., Ltd.), and SOLSPERS. (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.), and the like.

These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and is usually 100,000 or less, preferably 50,000 or less.

In the above, the (B) dispersant preferably contains a urethane-based polymer dispersant having a functional group and/or an acrylic polymer dispersant, and particularly preferably, in terms of adhesion and linearity. It is an acrylic polymer dispersing agent.

Further, in terms of dispersibility and preservability, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferred.

Examples of the urethane-based and acrylic-based polymer dispersing agents include DISPERBYK 160 to 166, 182 series (all of which are urethane-based), DISPERBYK 2000, 2001, and LPN 21116 (all of which are acrylic) (above). All manufactured by BYK-Chemie).

Specific examples of the preferred chemical structure of the urethane-based polymer dispersant include a polyisocyanate compound and a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule. A compound or a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the same molecule. By treating these with a quaternizing agent such as benzyl chloride, all or a part of the tertiary amine group can be a quaternary ammonium salt group.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5-. Aromatic diisocyanate such as diisocyanate or tolidine diisocyanate; hexamethylene diisocyanate, methyl isocyanate diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Alicyclic diisocyanate; isocyclohexyl diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane or the like alicyclic diisocyanate; benzene Aliphatic diisocyanate having an aromatic ring such as methyl diisocyanate, α,α,α',α'-tetramethylbenzenedimethyl diisocyanate; isocyanate triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanate phenylmethane), tri Triisocyanate such as isocyanate phenyl) thiophosphate; and terpolymers, water An adduct, a polyol adduct of the above, and the like. As the polyisocyanate, a terpolymer of an organic diisocyanate is preferred, and a trimer of toluene diisocyanate and a metapolymer of isophorone diisocyanate are preferred. These may be used alone or in combination of two or more.

Examples of the method for producing the isocyanate terpolymer include the use of a suitable trimerization catalyst, for example, a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like. Isocyanate undergoes partial trimerization of isocyanate groups, borrowing After the trimerization was stopped by the addition of the catalytic agent, the unreacted polyisocyanate was subjected to solvent extraction and removed by thin film distillation to obtain a polyisocyanate containing the intended isocyanurate group.

Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like, and the like. The single terminal hydroxyl group is alkoxylated with an alkyl group having 1 to 25 carbon atoms and a mixture of two or more of these.

Examples of the polyether diol include a polyether diol, a polyether ester diol, and a mixture of two or more of these. Examples of the polyether diol include those obtained by separately or copolymerizing an alkylene oxide such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, polyoxytetramethylene glycol, polyoxy six. Methylene glycol, polyoxyoctylene glycol, and a mixture of two or more thereof.

The polyether ester diol may be exemplified by reacting a mixture of an ether group-containing diol or another diol with a dicarboxylic acid or an acid anhydride, or reacting an alkylene oxide with a polyester diol. The obtained one is, for example, poly(polyoxytetramethylene) adipate or the like. The polyether diol is preferably a polyethylene glycol, a polypropylene glycol, a polyoxytetramethylene glycol or a compound in which a single terminal hydroxyl group of the compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester diol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or such acid anhydrides. Glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3- Propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2 , 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octane An aliphatic diol such as an alcohol, 2-methyl-1,8-octanediol or 1,9-nonanediol; bishydroxymethylcyclohexane or the like An alicyclic diol; an aromatic diol such as benzenedimethanol or bishydroxyethoxybenzene; an N-alkyl dialkanolamine such as N-methyldiethanolamine; or the like obtained by polycondensation, for example, polyadipate Ethylene diester, polybutylene adipate, polyhexamethylene adipate, polyethylene adipate / propylene glycol, etc.; or using the above glycols or a carbon number of 1 to 25 as a starting point A polylactone diol or a polylactone monol, such as polycaprolactone diol, polymethyl valerolactone, and a mixture of two or more thereof obtained as a starting agent. As the polyester diol, polycaprolactone diol or polycaprolactone having a carbon number of 1 to 25 as a starter is preferred.

Examples of the polycarbonate diol include (1,6-exexhexyl) polycarbonate and (3-methyl-1,5-exopentyl) polycarbonate. Examples of the polyolefin diol include: Polybutadiene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and the like.

These may be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually from 300 to 10,000, preferably from 500 to 6,000, and more preferably from 1,000 to 4,000.

A compound having active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.

The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, may be a hydrogen atom in a functional group such as a hydroxyl group, an amine group or a thiol group. Among them, an amine group is preferred. It is a hydrogen atom of a primary amine group.

The tertiary amino group is not particularly limited, and examples thereof include an amine group having an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring structure, and more specifically, an imidazole ring or a triazole ring.

When such a compound having an active hydrogen and a tertiary amino group in the same molecule is exemplified, N,N-dimethyl-1,3-propanediamine and N,N-diethyl-1 are exemplified. 3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N , N- Diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-di Ethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, and the like.

Further, examples of the nitrogen-containing heterocyclic ring in the case where the tertiary amino group is a nitrogen-containing heterocyclic ring structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, and a carbazole. Ring, benzimidazole ring, benzotriazole ring, benzo Nitrogen-containing five-membered ring such as azole ring, benzothiazole ring, benzothiadiazole ring; pyridine ring, hydrazine Ring, pyrimidine ring, three A nitrogen-containing hetero six-membered ring such as a ring, a quinoline ring, an acridine ring or an isoquinoline ring. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

When the compounds having an imidazole ring and an amine group are specifically exemplified, 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-amino group) are exemplified. Ethyl)imidazole and the like. Further, when a compound having a triazole ring and an amine group is specifically exemplified, 3-amino-1,2,4-triazole and 5-(2-amino-5-chlorophenyl) are exemplified. -3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl- 1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-tri Oxazole and the like. Among them, preferred are N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3 -Amino-1,2,4-triazole.

These may be used alone or in combination of two or more.

A preferred blending ratio of the raw material in the production of the urethane-based polymer dispersant is 10, and the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 is 10 parts by mass based on 100 parts by mass of the polyisocyanate compound. ~200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having active hydrogen and tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by weight. Parts by mass.

The urethane-based polymer dispersant is manufactured based on polyaminocarboxylic acid. A known method for producing an ester resin is carried out. As the solvent at the time of production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone can be usually used; ethyl acetate, butyl acetate, and acetate Esters and the like; hydrocarbons such as benzene, toluene, xylene and hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol and third butanol; chlorides such as dichloromethane and chloroform; tetrahydrofuran An ether such as diethyl ether; an aprotic polar solvent such as dimethylformamide, N-methylpyrrolidone or dimethylhydrazine. These may be used alone or in combination of two or more.

In the above production, a urethanization reaction catalyst can usually be used. Examples of the catalyst include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; irons such as iron acetylate pyruvate and iron chloride; A tertiary amine such as an amine or a triethylethylene diamine. These may be used alone or in combination of two or more.

The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of from 1 to 100 mgKOH/g based on the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a neutralization titration of a basic amine group by an acid to correspond to an acid value and a value expressed in mg of KOH. When the amine value is less than the above range, the dispersibility is lowered, and if it exceeds the above range, the developability is liable to lower.

In the case where the isocyanate group remains in the polymer dispersant in the above reaction, when the isocyanate group is further destroyed by the alcohol or the amine compound, the stability with time of the product becomes high, which is preferable.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor. If it exceeds 200,000, Then, the solubility is lowered, the dispersibility is poor, and the control of the reaction becomes difficult.

As the acrylic polymer dispersant, it is preferred to use an unsaturated group-containing monomer having a functional group (here, a functional group as a functional group as a functional group contained in the polymer dispersant), and A random copolymer, a graft copolymer, or a block copolymer having a functional group-containing unsaturated group-containing monomer. These copolymers can be produced by a known method.

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, and 2-(methyl) propylene oxyethylene. An unsaturated monomer having a carboxyl group such as phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid or an acrylic acid dimer; dimethylaminoethyl (meth)acrylate; Specific examples of the unsaturated monomer having a tertiary amino group and a quaternary ammonium salt group such as diethylaminoethyl methacrylate and such a quaternary compound are mentioned. These may be used alone or in combination of two or more.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Cyclohexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Ester, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinyl pyrrolidone, styrene and its derivatives, α-methyl styrene, N-cyclohexyl N-substituted maleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate, such as imine, N-phenyl maleimide, N-benzyl maleimide Macromonomers such as monomer, polystyrene macromonomer, poly(meth)acrylic acid 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone giant monomer Wait. These may be used alone or in combination of two or more.

The acrylic polymer dispersant is preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group, but in this case, the A block contains the source. The partial structure of the unsaturated group-containing monomer having a functional group may further contain a partial structure derived from the above unsaturated group-containing monomer having no functional group, and may also be in the A block. Any of the states of the copolymerization or block copolymerization contains such. Further, the content of the portion having no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block is composed of a partial structure derived from the above unsaturated group-containing monomer having no functional group, but may have a partial structure derived from two or more kinds of monomers in one B block, and These B blocks may also be contained in any of random copolymerization or block copolymerization.

The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below.

The living polymerization method is an anionic living polymerization method, a cationic living polymerization method, or a radical living polymerization method. The polymerization active material of the anionic living polymerization method is an anion, and is represented, for example, by the following method.

[Chemical 6]

In the above method, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are each an integer of 1 or more.

The polymerization active material in the radical living polymerization method is a radical, and is represented, for example, by the following method.

[Chemistry 7]

In the above method, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , and j and k are each an integer of 1 or more, and R ^a is a hydrogen atom or a monovalent organic group, R ^b is ^a hydrogen atom different from R ^a or a monovalent organic group.

When synthesizing the acrylic polymer dispersant, Japanese Patent Laid-Open No. Hei 9-62002, or P. Lutz, P. Masson et al, polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews et Al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986); Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36,366 ( 1987); Dongcun Min Yan, Sakamoto K., Polymer Proceedings, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); Ada Shozo, Inoue Cheung Ping, Organic A well-known method described in Synthetic Chemistry, 43,300 (1985); DY Sogoh, WR Hertler et al, Macromoleoles, 20, 1473 (1987).

The acrylic polymer dispersing agent usable in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block/B block ratio constituting the copolymer is 1/99 to 80/20. It is preferably 5/95 to 60/40 (mass ratio), and if it is outside this range, it may not have good heat resistance and dispersibility.

Further, the amount of the quaternary ammonium salt group in the AB block copolymer and the BAB block copolymer 1g which can be used in the present invention is usually preferably 0.1 to 10 mmol, and if it is outside the range, it may not be good. Heat resistance and dispersibility.

Further, in such a block copolymer, it is usually contained in the case of an amine group produced in a production process, and its amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10 mgKOH/ It is more than g, more preferably 30 mgKOH/g or more, further preferably 50 mgKOH/g or more, and is preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.

Here, the block copolymers are equal to the amine value in the dispersant, and are expressed by the mass of KOH equivalent to the amount of the base of the solvent removed in the dispersant sample per gram of the base, and are carried out by the following method. Determination.

The dispersant sample was accurately weighed in a 100 mL beaker at 0.5 to 1.5 g, and dissolved in 50 mL of acetic acid. The solution was subjected to neutralization titration using a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titration apparatus equipped with a pH electrode. The bending point of the titration pH curve was set as the end point of the titration, and the amine value was determined by the following formula.

Amine value [mgKOH/g] = (561 × V) / (W × S)

[Where, W represents the amount of the dispersant sample weighed [g], V represents the titer of the end point of the titration [mL], and S represents the solid content concentration [% by mass] of the dispersant sample]

Further, the acid value of the block copolymer depends on the presence or absence of the acidic group which is the basis of the acid value, and generally, the lower one is preferable, and usually it is 10 mgKOH/g or less, and the weight average molecular weight (Mw) ) preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1,000, the dispersion stability tends to be lowered. When the weight average molecular weight exceeds 100,000, the developability and the resolution tend to be lowered.

The specific structure of the polymer dispersing agent having a quaternary ammonium salt group as a functional group is not particularly limited, and from the viewpoint of dispersibility, it is preferably a repeating unit represented by the following formula (i) (below There is a case called "repeating unit (i)").

In the above formula (i), R ³¹ to R ³³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, R ³¹ to R ^{In 33} , two or more of them may be bonded to each other to form a ring structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group and Y ^- is a counter anion.

The number of carbon atoms of the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 1 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. Among them, a methyl group, an ethyl group, a propyl group, and the like are preferable. Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Further, it may be any of a linear chain and a branched chain. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, and preferably 16 or less, more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, a decyl group, and the like. Among them, benzene is preferred. A group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a diethylphenyl group, more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethyl group, a phenyl propyl group, a phenyl butyl group, a phenyl isopropyl group, and the like. Among them, a phenyl group is preferable. The group is a phenylethyl group, a phenyl propyl group, or a phenyl butyl group, more preferably a phenylmethylene group or a phenyl phenyl group.

In the above, from the viewpoint of dispersibility, it is preferred that each of R ³¹ to R ^{33 is} independently an alkyl group or an aralkyl group, and specifically, it is preferred that each of R ³¹ and R ^{33 is} independently a methyl group, or Ethyl, and R ³² is a phenylmethylene group or a phenylethyl group, and further preferably R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethylene group.

Further, when the polymer dispersant has a tertiary amine as a functional group, it is preferably a repeating unit represented by the following formula (ii) from the viewpoint of dispersibility ( Next, there is a case called "repeating unit (ii).

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³⁵ and R ^{36 are} also They can be bonded to each other to form an annular structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

Further, as the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), R ³¹ to R ^{33 which} are the above formula (i) can be preferably used as an example.

Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), R ³¹ to R ^{33 which} are the above formula (i) can be preferably used as an example. Further, as the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), R ³¹ to R ^{33 which} are the above formula (i) can be preferably used as an example.

In these, R ³⁵ and R ³⁶ are each independently an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group.

As R in the above formula (i) of ³¹ ~ R ^33, and R in the above formula (ii) and ³⁶ of ³⁵ in the R alkyl, aralkyl or aryl group may have the substituent include: a halogen atom, an alkoxy group , benzamidine, hydroxyl, and the like.

In the above formulas (i) and (ii), examples of the divalent linking groups X and Z include an alkylene group having 1 to 10 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, and -CONH-R. ⁴³ -yl, -COOR ⁴⁴ -yl [wherein, R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkoxyalkyl group)], Preferred is -COO-R ⁴⁴ - group.

Further, in the above formula (I), as the anion Y ^{-, include: Cl -, Br -, l} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - and the like.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited, and the content ratio of the repeating unit represented by the above formula (i) is expressed by the above formula (ii) from the viewpoint of dispersibility. The total content of the repeating unit is preferably 60% by mole or less, more preferably 50% by mole or less, still more preferably 40% by mole or less, still more preferably 35% by mole or less, and more preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more.

Further, the ratio of the repeating unit represented by the above formula (i) to the total repeating unit of the polymer dispersing agent is not particularly limited, and from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 5 The molar percentage is more than or equal to, more preferably 10% by mole or more, and more preferably 50% by mole or less, more preferably 30% by mole or less, further preferably 20% by mole or less, and particularly preferably 15% by mole. Less than the ear.

Further, the ratio of the repeating unit represented by the above formula (ii) to the total repeating unit of the polymer dispersing agent is not particularly limited, and is preferably 5 mol% or more, and more preferably 10 from the viewpoint of dispersibility. The molar percentage is more than or equal to, more preferably 15% by mole or more, particularly preferably 20% by mole or more, and more preferably 60% by mole or less, more preferably 40% by mole or less, and still more preferably 30% by mole. The ear is below the ear%, and particularly preferably at least 25 mol%.

In addition, from the viewpoint of improving the compatibility with the binder component such as a solvent and improving the dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter referred to as " Repeat the case of unit (iii).

In the above formula (iii), R ⁴⁰ is an exoethyl group or a propyl group, R ⁴¹ is an alkyl group which may have a substituent, and R ⁴² is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

The number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. Among them, a methyl group, an ethyl group, a propyl group, and the like are preferable. Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Further, it may be any of a linear chain and a branched chain. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

In addition, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility of a binder component such as a solvent. Good for 5 or less.

Further, the ratio of the repeating unit represented by the above formula (iii) to the total repeating unit of the polymer dispersing agent is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably It is 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. In the case of the above range, the compatibility with the binder component such as a solvent and the dispersion stability tend to be improved.

In addition, from the viewpoint of improving the compatibility of the dispersant with the binder component such as a solvent and improving the dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter, it is called It is the case of "repeating unit (iv)").

In the above formula (iv), R ³⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ³⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms of the alkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less. More preferably 8 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. Among them, a methyl group, an ethyl group, a propyl group, and the like are preferable. Butyl, pentyl or hexyl, more preferably methyl, ethyl, propyl or butyl. Further, it may be any of a linear chain and a branched chain. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, still more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, a decyl group, and the like. Among them, benzene is preferred. A group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a diethylphenyl group, more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, still more preferably 10 or less. . Specific examples of the aralkyl group include a phenylmethylene group, a phenylethyl group, a phenyl propyl group, a phenyl butyl group, a phenyl isopropyl group, and the like. Among them, a phenyl group is preferable. The group is a phenylethyl group, a phenyl propyl group, or a phenyl butyl group, more preferably a phenylmethylene group or a phenyl phenyl group.

Among these, R ^{38 is} preferably an alkyl group or an aralkyl group from the viewpoint of solvent compatibility and dispersion stability, and more preferably a methyl group, an ethyl group or a phenylmethylene group.

Examples of the substituent which the alkyl group in R ³⁸ may have include a halogen atom, an alkoxy group and the like. Further, examples of the substituent which the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group and the like. Further, the chain alkyl group represented by R ³⁸ includes either a linear chain or a branched chain.

Further, the ratio of the repeating unit represented by the above formula (iv) to the total repeating unit of the polymer dispersing agent is preferably 30 mol% or more, and more preferably 40 mol% or more from the viewpoint of dispersibility. Further, it is preferably 50 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less.

The polymer dispersant may also have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (ii), and the repeating unit (iv). Examples of such a repeating unit include a styrene monomer derived from styrene or α-methylstyrene, and a (meth)acrylonium salt monomer such as (meth)acrylonium chloride; a (meth) acrylamide-based monomer such as acrylamide or N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl epoxidized propyl ether; N-methyl acrylonitrile A repeating unit of a monomer such as a phenyl group.

The polymer dispersant preferably contains an A block having a repeating unit (i) and a repeating unit (ii), and has no repeating unit (i) and a repeating unit (ii) from the viewpoint of further improving the dispersibility. a block copolymer of the B block. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. The introduction of the quaternary ammonium salt group into the A block also introduces the tertiary amine group, whereby the dispersing ability of the dispersing agent is unexpectedly improved. Further, the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any of the random copolymerization and the block copolymerization. Further, two or more repeating units (i) and repeating units (ii) may be contained in one A block. In this case, random copolymerization and block copolymerization are carried out in the A block. Either form contains each repeating unit.

Further, the repeating unit (i) and the repeating unit other than the repeating unit (ii) may be contained in the A block. Examples of such a repeating unit include the above-mentioned (meth)acrylate-based monomer. Repeat the unit and so on. Repeat unit (i) and repeat unit other than repeat unit (ii) The content in the A block is preferably from 0 to 50 mol%, more preferably from 0 to 20 mol%, but it is most preferred that the repeating unit is not contained in the A block.

Further, the B block may contain a repeating unit other than the repeating units (iii) and (iv), and examples of such a repeating unit include styrene-based monomers derived from styrene or α-methylstyrene; (Methyl) propylene sulfonium salt monomer such as (meth) acrylonitrile chloride; (meth) acrylamide amine monomer such as (meth) acrylamide or N-methylol acrylamide; vinyl acetate Acrylonitrile; allyl epoxidized propyl ether, butyric acid epoxidized propyl ether; N-methyl propylene fluorenyl A repeating unit of a monomer such as a phenyl group. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably from 0 to 50 mol%, more preferably from 0 to 20 mol%, but most preferably in the B block. This repeat unit is not included.

Further, in terms of improving the dispersion stability, the (B) dispersant is preferably used in combination with the pigment derivative described below.

<(C) alkali soluble resin>

The (C) alkali-soluble resin to be used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include an epoxy (meth)acrylate resin, an acrylic resin, and a carboxyl group-containing resin. An epoxy resin, a carboxyl group-containing urethane resin, a novolac resin, a polyvinyl phenol resin, etc., among them, an epoxy (meth)acrylate resin and an acrylic resin are preferable. These may be used alone or in combination of two or more.

As the alkali-soluble resin used in the present invention, in view of excellent plate-making property, an alkali-soluble resin (c1) and/or an alkali-soluble resin (c2), which is hereinafter referred to as the following, can be preferably used. "Carboxyl group of epoxy (meth) acrylate resin").

<alkali soluble resin (c1)>

By adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group An alkali-soluble resin obtained by reacting an epoxy resin with a polybasic acid and/or an acid anhydride thereof.

<alkali soluble resin (c2)>

It is obtained by reacting an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin, and further reacting with a polyhydric alcohol, a polybasic acid and/or an anhydride thereof. Alkali soluble resin.

For example, "Epikote (registered trademark, the same below) 828", "Epikote 1001", "Epikote 1002", and "Epikote 1001" manufactured by Mitsubishi Chemical Corporation can be preferably used as the epoxy resin to be used as a raw material. Epikote 1004", etc.) An epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, Softening point 76 ° C)), bisphenol F type resin (for example, "Epikote 807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation), by bisphenol F type An epoxy resin obtained by reacting an alcoholic hydroxyl group of an epoxy resin with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type Epoxy resin, biphenyl epoxy propyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenolic novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi Corporation "EP-152", "EP-154" manufactured by Chemical Company, "DEN-438" manufactured by Dow Chemical Co., Ltd., ( , styrene, and p-cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same below) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., and the third ring Oxypropyl propyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), and trisphenol methane epoxy resin (for example, EPPN (registered trademark, the same below) manufactured by Nippon Kayaku Co., Ltd.) -501", "EPN-502", "EPPN-503"), alicyclic epoxy resin ("Celloxide 2021P" manufactured by Daicel Chemical Industry Co., Ltd., "Celloxide (registered trademark, the same below) EHPE") The reaction of cyclopentadiene with phenol makes the phenolic resin epoxy propyl Epoxy resin (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resin represented by the following general formulas (C1) to (C4) Wait. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (C1), and Japan, which is an epoxy resin represented by the following general formula (C2), may be mentioned. "NC-3000" manufactured by Kasei Co., Ltd., "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd., which is an epoxy resin represented by the following general formula (C4).

In the above general formula (C1), a represents an average value and represents a number of 0 to 10. R ¹¹¹ represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Further, each of the plurality of R ¹¹¹ present in one molecule may be the same or different.

In the above general formula (C2), b represents an average value and represents a number of 0 to 10. R ¹²¹ represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Further, each of the plurality of R ¹²¹ present in one molecule may be the same or different.

In the above general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). Among them, one or more adamantane structures are contained in the molecular structure. c represents an integer of 2 or 3.

In the above general formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent. An alkyl group of ~12, or a phenyl group which may have a substituent. * indicates the key combination.

In the above general formula (C4), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ¹⁴³ and R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

In the above, it is preferred to use any one of the general formulas (C1) to (C4). Show epoxy resin.

As the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (A) a monocarboxylic acid such as an alpha-haloalkyl group, an alkoxy group, a halogen, a nitro group, a cyano group, or a monocarboxylic acid such as 2-(meth)acryloxyethyl succinic acid or 2-(methyl) ) propylene methoxyethyl adipate, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl) propylene methoxyethyl hexahydrophthalic acid, 2-( Methyl) propylene oxiranyl ethyl maleic acid, 2-(methyl) propylene methoxy succinic acid, 2-(methyl) propylene methoxy propyl adipic acid, 2-(methyl ) propylene methoxy propyl tetrahydrophthalic acid, 2-(methyl) propylene methoxy propyl phthalic acid, 2-(methyl) propylene methoxy propyl maleic acid, 2- ( Methyl) propylene oxy butyl succinic acid, 2-(methyl) propylene methoxy butyl adipate, 2-(methyl) propylene oxy butyl hydrogen phthalate, 2- ( Methyl)propenyloxybutylphthalic acid, 2-(methyl)propenyloxybutyl maleic acid, ε-caprolactone, β-propiolactone, γ-butyrolactone a lactone such as δ-valerolactone is added to a monomer derived from (meth)acrylic acid, or an acid such as succinic acid (anhydride), phthalic acid (anhydride) or maleic acid (anhydride) ( An anhydride) is added to a monomer obtained from a hydroxyalkyl (meth)acrylate, a pentaerythritol tri(meth)acrylate, or a (meth)acrylic acid dimer.

Among these, (meth)acrylic acid is particularly preferable in terms of sensitivity.

As a method of adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and an epoxy resin may be carried out in the presence of an esterification catalyst at a temperature of 50 to 150 ° C. reaction. As the esterification catalyst used herein, a tertiary amine such as triethylamine, trimethylamine, dimethylbenzylamine or diethylbenzylamine, tetramethylammonium chloride, tetraethylammonium chloride or chlorinated ten can be used. A quaternary ammonium salt such as dialkyltrimethylammonium or the like.

Furthermore, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β- having a carboxyl group The unsaturated monocarboxylic acid ester and the esterification catalyst may be used singly or in combination of two or more.

The amount of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents per 1 equivalent of the epoxy group of the epoxy resin. It is preferably in the range of 0.7 to 1.1 equivalents. If the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is used in a small amount, the amount of the unsaturated group introduced is insufficient, and thus the polybasic acid and/or its anhydride are next. The reaction also becomes insufficient. Also, the case of a large amount of residual epoxy groups is not advantageous. On the other hand, when the amount used is large, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, the tendency of the hardening characteristics to deteriorate was found.

Examples of the polybasic acid and/or its acid anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and pyromellitic acid. Benzotricarboxylic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid And one or more of these acid anhydrides.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, Or such anhydrides. More preferably, it is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

The addition reaction of a polybasic acid and/or an acid anhydride thereof may be carried out by a known method, and may be an epoxy resin with an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. Under the same conditions of the addition reaction, the reaction is continued to obtain a target. The amount of addition of the polybasic acid and/or its anhydride component is preferably such that the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH/g, and more preferably It is in the range of 20 to 140 mgKOH/g. Epoxy (meth) acrylate tree containing carboxyl groups When the acid value of the fat is less than the above range, the alkali developability tends to be insufficient, and if it exceeds the above range, the curing property tends to be inferior.

Further, in the addition reaction of the polybasic acid and/or its acid anhydride, a polyfunctional alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol may be added to form a multi-branched structure.

The carboxyl group-containing epoxy (meth) acrylate resin can usually be obtained by mixing a polybasic acid and/or its anhydride with an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated single having a carboxyl group. After the reactant of the carboxylic acid ester, or mixed with a polybasic acid and/or its anhydride and polyfunctional alcohol in an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group After the reaction, it was obtained by heating. In this case, the order of mixing the polybasic acid and/or its anhydride with the polyfunctional alcohol is not particularly limited. A mixture of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid having a carboxyl group, and a polyfunctional alcohol by heating, a polybasic acid and/or an anhydride thereof Any of the hydroxyl groups present in the reaction is subjected to an addition reaction.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1,000 or more, preferably 1,500 or more, and It is usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less. When the weight average molecular weight is small, the solubility in the developer is high, and if the weight average molecular weight is too large, the solubility in the developer is low.

The carboxyl group-containing epoxy (meth) acrylate resin may be used singly or in combination of two or more kinds of resins.

Further, the (C) alkali-soluble resin used in the present invention may be partially replaced with another binder resin as long as the properties of the present invention are not impaired, as a part of the above-mentioned carboxyl group-containing epoxy (meth) acrylate resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and other binder resins may be used in combination. In this case, it is preferred to use a carboxyl group in the (C) alkali-soluble resin. The ratio of the epoxy (meth) acrylate resin is 50% by mass or more, and particularly 80% by mass or more.

The other binder resin which can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin is not limited as long as the properties of the present invention are not impaired, as long as it is selected from the resins generally used for the photosensitive coloring composition. For example, the adhesive resin described in JP-A-2007-271702, JP-A-2007-316620, JP-A-2007-334290, and the like can be used.

Further, the other binder resins may be used singly or in combination of two or more.

<(D) Photopolymerization initiator>

(D) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. An addition agent such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added as needed.

The photopolymerization initiator may, for example, be a metallocene compound containing a titanocene compound described in each of JP-A-59-152396, and JP-A-61-151197; The hexaarylbiimidazole derivative described in JP-A-2000-56118, and the halomethylation described in JP-A-10-39503 Diazole derivatives, halomethyl--three Free radicals such as N-aryl-α-amino acids such as derivatives and N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters The active agent, the α-aminoalkyl phenone derivative, and the oxime ester derivative described in JP-A-2000-80068, JP-A-2006-36750, and the like.

Specifically, for example, as the titanocene derivative, dicyclopentadienyl titanium dichloride, dicyclopentadienyl biphenyl titanium, and dicyclopentadienyl titanium bis (2, 3, 4,5,6- Pentafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6- Trifluorobenzene-1-yl), dicyclopentadienyl titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4-difluorobenzene-1- , bis(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), bis(methylcyclopentadienyl)titanium (2, 6-Difluorophenyl-1-yl), dicyclopentadienyltitanium (2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl-1-yl) and the like.

Further, examples of the biimidazole derivative include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-. Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl A-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

Halomethylation Examples of oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole and the like.

Also, as a halomethyl--three The derivatives may be exemplified by 2-(4-methoxyphenyl)-4,6-bis(-trichloromethyl)-all three , 2-(4-methoxynaphthyl)-4,6-bis(-trichloromethyl)-all three , 2-(4-ethoxynaphthyl)-4,6-bis(-trichloromethyl)-all three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(-trichloromethyl)-all three Wait.

Further, examples of the α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylamine Phenylpropiophenone, 2-ethylhexyl-1,4-dimethylamine benzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

As a photopolymerization initiator, in particular, in terms of sensitivity or plate-making property, an anthracene derivative (anthracene and ketone oxime compound) is effective, and the use of an alkali-soluble resin containing a phenolic hydroxyl group is equivalent to sensitivity. Since it is disadvantageous, it is especially useful for such an anthracene derivative (an oxime ester and a ketoxime compound) which is excellent in sensitivity.

The oxime-based compound may, for example, be a compound having a structural moiety represented by the following general formula (3), and is preferably an oxime ester-based compound represented by the following general formula (3a).

In the formula (3), R ²² represents an optionally substituted alkanofluorenyl group having 2 to 12 carbon atoms, a heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms, an olefin group having 3 to 25 carbon atoms, and a carbon number of 3 ~8 cycloalkyl fluorenyl group, alkoxycarbonylalkyl fluorenyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl fluorenyl group having 8 to 20 carbon atoms, heteroaryloxycarbonyl alkane having 3 to 20 carbon atoms Base, aminoalkylcarbonyl group having 2 to 10 carbon atoms, arylfluorenyl group having 7 to 20 carbon atoms, heteroarylfluorenyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, or carbon number 7 ~20 aryloxycarbonyl.

In the formula (3a), R ^21a represents a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and a carbon number. Alkoxycarbonylalkyl group of 3 to 20, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylsulfanyl group having 1 to 20 carbon atoms, carbon number 1~ 20 aminoalkyl group, alkane fluorenyl group having 2 to 12 carbon atoms, olefinic group having 3 to 25 carbon atoms, cycloalkyl fluorenyl group having 3 to 8 carbon atoms, aryl fluorenyl group having 7 to 20 carbon atoms, carbon number a heteroaryl group of 1 to 20, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms. R ^21b represents an arbitrary substituent containing an aromatic ring or a hetero aromatic ring.

Further, R ^21a may form a ring together with R ^21b , and a linking group thereof may, for example, be an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a polyethylidene group (-(CH=CH) _r - ), a polyacetylene group (-(C≡C) _r -) or a combination of these groups (further, r is an integer from 0 to 3).

In the formula (3a), R ^22a represents each of the optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms, an olefin group having 3 to 25 carbon atoms, and a carbon number of 3 ~8 cycloalkyl fluorenyl group, alkoxycarbonylalkyl fluorenyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl fluorenyl group having 8 to 20 carbon atoms, heteroaryloxycarbonyl alkane having 3 to 20 carbon atoms Alkyl carbonyl group having 2 to 10 carbon atoms, aryl fluorenyl group having 7 to 20 carbon atoms, heteroaryl fluorenyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms or carbon number 7 to 20 Aryloxycarbonyl.

As R ^{22 in the} above general formula (3) and R ^22a in the above general formula (3a), preferred are alkanofluorenyl group having 2 to 12 carbon atoms and heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms. A cycloalkyl fluorenyl group having 3 to 8 carbon atoms.

As R ^21a in the above general formula (3a), preferred are an unsubstituted methyl group, an ethyl group, a propyl group, or a propyl group substituted with an N-ethylindenyl-N-ethoxycarbonylamino group. .

Further, as R ^21b in the above general formula (3a), a oxazolyl group which may be substituted, a 9-oxosulfur which may be substituted may preferably be mentioned. A phenylthio group which may be substituted.

Further, examples of the substituents in the general formulae (3) and (3a) include an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amine group, a decylamino group, and the like. .

Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but are not limited thereto.

[Chemistry 19]

[Chemistry 20]

Further, an oxime ester initiator having a nitro group and a carbazole group is also effective.

The ketone-based compound may, for example, be a compound having a structural moiety represented by the following general formula (4), and preferably an oxime ester-based compound represented by the following general formula (5).

In the above general formula (4), the R ²⁴ system is synonymous with R ²² in the above general formula (3).

In the above general formula (5), R ^23a represents each of a phenyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and carbon. Alkoxycarbonylalkyl group of 3 to 20, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylsulfanyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms a heteroarylsulfanyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an olefin group having 3 to 25 carbon atoms, and a cycloalkane group having 3 to 8 carbon atoms. , an aromatic fluorenyl group having 7 to 20 carbon atoms, a heteroaryl fluorenyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a carbon number of 1 to 10 a cycloalkylalkyl group.

R ^23b represents an arbitrary substituent containing an aromatic ring or a hetero aromatic ring.

Further, R ^23a may form a ring together with R ^23b , and a linking group thereof may, for example, be an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a polyethylidene group (-(CH=CH) _r - ), a polyacetylene group (-(C≡C) _r -) or a combination of these groups (further, r is an integer from 0 to 3).

In the general formula (5), R ^24a represents each of the optionally substituted alkanofluorenyl groups having 2 to 12 carbon atoms, an olefinic group having 3 to 25 carbon atoms, a cycloalkylidene group having 4 to 8 carbon atoms, and a carbon number of 7~ 20 benzylidene group, heterocyclic fluorenyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, Or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

As R ^{24 in the} above general formula (4) and R ^24a in the above general formula (5), preferred are alkanofluorenyl group having 2 to 12 carbon atoms and heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms. And a cycloalkyl fluorenyl group having 3 to 8 carbon atoms and an aromatic fluorenyl group having 7 to 20 carbon atoms.

The R ^23a in the above general formula (5) is preferably an unsubstituted ethyl group, a propyl group, a butyl group or an ethyl or propyl group substituted by a methoxycarbonyl group.

Further, as R ^23b in the above general formula (5), a oxazolyl group which may be substituted and a phenylthio group which may be substituted are preferable.

Further, examples of the substituent in the above general formulas (4) and (5) include an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amine group, a decylamino group, and the like. .

Specific examples of the ketoxime ester-based compound suitable for the present invention include the compounds exemplified below, but are not limited thereto.

[Chem. 24]

The oxime and the ketone oxime ester compound are each a compound known per se, and are, for example, one of a series of compounds described in JP-A-2000-80068 or JP-A-2006-36750. In the present invention, the (D) photopolymerization initiator is preferably a oxime ester initiator and/or a ketoxime initiator.

The photopolymerization initiator may be used singly or in combination of two or more.

The proportion of the photopolymerization initiator in the photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass, preferably 0.5 to 10% by mass based on the total solid content. When the ratio of the photopolymerization initiator is too large, the developability tends to be lowered. On the other hand, if the amount is too small, the shape and step of the preferred colored cured product cannot be formed.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methyl hydrazine, 2-ethyl hydrazine, 2-third Anthracene derivatives such as butyl hydrazine and 1-chloroindole; benzophenone, mischoketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl bis a benzophenone derivative such as benzophenone, 2-chlorobenzophenone, 4-bromobenzophenone or 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(different Propyl phenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4'-methylthienyl)-2- Acetophenone derivatives such as phenyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl) ketone; 9-oxosulfur 2-ethyl 9-oxosulfur 2-isopropyl-9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur Derivatives; benzoic acid derivatives such as p-dimethylaminobenzoic acid ethyl ester, p-diethylaminobenzoic acid ethyl ester; 9-phenyl acridine, 9-(p-methoxyphenyl)fluorene Acridine derivatives such as pyridine; 9,10-dimethylbenzophenone Ethyl Derivatives; anthrone derivatives such as benzofluorenone and the like.

Among these photopolymerization initiators, an oxime ester derivative (an oxime ester compound) is particularly preferable in terms of sensitivity.

Among the oxime ester derivatives, a photopolymerization initiator having a diphenyl sulfide skeleton is preferred from the viewpoint of solvent resistance, and for example, those represented by the following general formula (5-1) can be used.

Here, R ^23a and R ^24a are synonymous with the above general formula (5).

R ^25a and R ^25b each independently represent R ^25c , OR ^25c , CN, OH or a halogen atom, f represents an integer of 0 to 5, and g represents an integer of 0 to 4.

R ^25c represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the substituent represented by R ^25c may be further substituted by a halogen atom, and the alkyl moiety of the substituent represented by R ^25c may also be -O-, -S-, -COO-, -OCO- or - NR ^25d - Cut 1~5 times. R ^25d represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl moiety of the substituent represented by R ^25c may be a branched side chain, and may also be a cyclopentyl group or a cyclohexyl group.

R ²⁶ represents OH, COOH or a group represented by the following general formula (5-2), and h represents an integer of 0 to 5.

In the formula (5-2), R ^26a represents -O-, -S-, -OCO- or -COO-.

R ^26b represents an alkylene group having 1 to 20 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, or an extended alkyl group having 7 to 30 carbon atoms.

The alkyl group of the substituent represented by R ^26b may also be cleaved 1 - 5 times by -O-, -S-, -COO- or -OCO-. The alkyl moiety of the substituent represented by R ^26b may be a branched side chain or a cyclohexyl group.

R ^26c represents OH or COOH, and i represents an integer of 1 to 3.

* indicates the key combination.

The photopolymerization initiator may be used singly or in combination of two or more.

The photopolymerization initiator may be formulated with a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source for the purpose of improving the sensitivity of the induction. Examples of the sensitizing dyes include those described in JP-A-4-221958 and JP-A-4-219756. A coumarin dye having a heterocyclic ring described in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. The 3-keto coumarin compound described in Japanese Laid-Open Patent Publication No. Hei 6-19240, and the Japanese Patent Laid-Open No. Sho. 155292, Japanese Patent Publication No. Sho 45-37377, Japanese Patent Laid-Open No. Sho 48-84183, Japanese Patent Laid-Open No. Sho 52-112681, Japanese Patent Laid-Open No. Sho 58-15503, Japanese Patent Laid-Open No. 60-88005 Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. Hei 5-170761, Japanese Patent Laid-Open No. 5-210240, Japan A dye having a dialkylamino benzene skeleton described in JP-A-4-288818 or the like.

Among these sensitizing dyes, an amine group-containing sensitizing dye is preferred, and a compound having an amine group and a phenyl group in the same molecule is more preferred. More preferably, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, a benzophenone compound such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone or 3,4-diaminobenzophenone; 2-(pair two Methylaminophenyl)benzo Oxazole, 2-(p-diethylaminophenyl) benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo Azole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Azole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-( p-Diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (pair Diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylamino) A compound containing a p-dialkylaminophenyl group such as a phenyl)pyrimidine or the like. The best one is 4,4'-dialkylaminobenzophenone.

The sensitizing dye may be used singly or in combination of two or more.

As the polymerization accelerator, for example, an aromatic amine such as p-dimethylaminobenzoic acid ethyl ester or 2-dimethylaminoethyl benzoate, an aliphatic amine such as n-butylamine or N-methyldiethanolamine, or the like can be used. a mercapto compound or the like. One type of the polymerization accelerator may be used alone or two or more types may be used in combination.

<Photopolymerizable monomer>

In the photosensitive coloring composition of the present invention, it is preferred to further contain a photopolymerizable monomer (photopolymerizable compound) in terms of sensitivity and the like.

The photopolymerizable monomer used in the present invention may be a compound having at least one ethylenically unsaturated group in the molecule (hereinafter referred to as "ethylenic monomer"). Specific examples thereof include (meth)acrylic acid, alkyl (meth)acrylate, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond, and a monoester of a polyhydric or monohydric alcohol. Wait.

In the present invention, it is preferred to use a polyfunctional ethylenic monomer having, in particular, two or more ethylenically unsaturated groups in one molecule.

Examples of such a polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; and an aliphatic polyhydroxy compound; A polyvalent hydroxy compound such as an aromatic polyhydroxy compound, an ester obtained by esterification reaction with an unsaturated carboxylic acid or a polyvalent carboxylic acid, or the like.

Examples of the ester of the above aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. An acrylate of an aliphatic polyhydroxy compound such as an ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or glyceryl acrylate, The acrylate of the exemplified compound is replaced by a methacrylate of methacrylate, the imiconate of the iconate is replaced by the butyrate of the butenoate or the maleate. Maleic acid ester and the like.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl. Aromatic polyhydroxyl groups such as acrylate and pyrogallol triacrylate Acrylates and methacrylates of the compounds.

The ester obtained by the esterification reaction of a polyvalent carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, and specific examples thereof include acrylic acid, phthalic acid, and And condensate of ethylene glycol; condensate of acrylic acid, maleic acid, and diethylene glycol; condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensation of acrylic acid, adipic acid, butanediol and glycerin Things and so on.

In addition to the above, examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate, or a polyisocyanate compound and a polyol and a hydroxyl group-containing (methyl group). a (meth)acrylic acid urethane obtained by reacting an acrylate; an epoxy acrylate such as an addition reaction of a polyvalent epoxy compound with a hydroxy (meth) acrylate or (meth) acrylate; An acrylamide such as ethyl bis acrylamide; an allyl ester such as diallyl phthalate; a vinyl group-containing compound such as divinyl phthalate or the like is useful.

Examples of the (meth)acrylic acid amides include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, and U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Xierongshe Chemical Co., Ltd.) ), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Co., Ltd.).

These may be used alone or in combination of two or more.

<Other compounding ingredients of photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, an adhesion improving agent such as an organic solvent or a decane coupling agent, a coating property improving agent, a development improving agent, or the like may be appropriately added in addition to the above components. Ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, and the like.

(1) Organic solvents

The photosensitive coloring composition of the present invention usually has (A) a color material, (B) a dispersing agent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and optionally a photopolymerizable monomer, Various other materials are used in a state of being dissolved or dispersed in an organic solvent.

As the organic solvent, those having a boiling point of from 100 to 300 ° C are preferably selected. More preferably, it is a solvent having a boiling point of 120 to 280 °C.

As such an organic solvent, the following are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-third dibutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3 - ethylene glycol monoalkyl ethers such as methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether Glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Ester, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate Diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid 3-methyl-3 -methoxybutyl ester a glycol dialkyl acetate such as ethylene glycol diacetate, 1,3-butylene glycol diacetate or 1,6-hexanol diacetate; An alkyl acetate such as cyclohexanol acetate; an ether such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether or dihexyl ether. Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexyl Ketones such as ketone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl decyl ketone, methoxy methyl pentanone; ethanol, propanol, butanol, hexanol, ring a monohydric or polyhydric alcohol such as hexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol; n-pentane An aliphatic hydrocarbon such as n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene or dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, Alicyclic hydrocarbons such as bicyclohexane; benzene, toluene, dimethyl , aromatic hydrocarbons such as cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, C Ethyl acetate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate , 3-ethoxypropionic acid ethyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester a chain or cyclic ester such as γ-butyrolactone; an alkoxycarboxylic acid such as 3-methoxypropionic acid or 3-ethoxypropionic acid; Halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; and the like.

As a solvent which is commercially available as described above, examples thereof include mineral spirits, APSOL #2, Apco #18 Solvent, Apco thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl cellosolve ("cellosolve" is a registered trademark, the same below), Ethyl cellosolve, Ethyl cellosolve acetate, Methyl cellosolve acetate, Diglyme (all trade names).

These organic solvents may be used singly or in combination of two or more.

In the case of forming a pixel or a black matrix of a color filter by photolithography, it is preferable to select a boiling point of 100 to 200 ° C as an organic solvent (pressure 1013.25 [hPa]. Hereinafter, the boiling points are all the same) The scope of the. More preferably, it has a boiling point of 120 to 170 °C.

Among the above organic solvents, the balance between coatability and surface tension is good, and the solubility of the constituent components in the composition is relatively high, and diol alkyl ether acetates are preferred.

Further, the glycol alkyl ether acetates may be used singly, but other organic solvents may be used in combination. As the organic solvent to be used in combination, a diol monoalkyl ether is particularly preferable. Among them, in particular, the solubility of the constituent components in the composition is preferably propylene glycol monomethyl ether. Further, the diol monoalkyl ether has a high polarity, and if the amount is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained afterwards tends to decrease, and the storage stability tends to decrease. The ratio of the diol monoalkyl ether is preferably from 5% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass.

Further, an organic solvent having a boiling point of 150 ° C or higher is used in combination (hereinafter referred to as The case of "high boiling point solvent" is also preferred. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being rapidly dried and destroyed. In other words, for example, there is an effect of preventing the occurrence of foreign matter defects caused by precipitation or solidification of the color material or the like in the tip end of the slit nozzle. In terms of such a higher effect, among the above various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred. ester.

The content ratio of the high boiling point solvent in the organic solvent is preferably from 3% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, even more preferably from 5% by mass to 30% by mass. When the amount of the high-boiling solvent is too small, for example, there is a possibility that a color material at the tip end of the slit nozzle is precipitated or solidified to cause foreign matter defects, and if the amount is too large, the drying time of the composition becomes slow, and the following black color is caused. Concerns about poor touch of the vacuum drying process in the matrix manufacturing step, or traces of pre-baked pores.

Further, the high boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, may not additionally contain a high boiling point solvent having a boiling point of 150 ° C or higher. .

Preferred examples of the high-boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, and dipropylene glycol methyl ether acetate. 3-butanediol diacetate, 1,6-hexanol diacetate, triacetin, and the like.

(2) Adhesion improver

In the photosensitive coloring composition of the present invention, in order to improve the adhesion to the substrate, an adhesion improving agent may be contained. The adhesion improving agent is preferably a decane coupling agent or a phosphate group-containing compound.

As the type of the decane coupling agent, one of the epoxy group, the (meth)acrylic acid group, and the amine group may be used alone or in combination of two or more kinds thereof.

Preferred examples of the decane coupling agent include (meth)acryl oxime such as 3-methacryloxypropylmethyldimethoxydecane or 3-methylpropoxypropyltrimethoxydecane. Oxydecanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldi Epoxy decanes such as ethoxy decane, 3-glycidoxypropyl triethoxy decane; ureido decanes such as 3-ureidopropyltriethoxy decane; 3-isocyanatepropyltriethyl Isocyanate decanes such as oxoxane are particularly preferred as decane coupling agents for epoxy decanes.

The phosphate group-containing compound is preferably a (meth)acrylonitrile group-containing phosphate, and is preferably represented by the following general formula (g1), (g2) or (g3).

In the above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, and l and l' are integers of 1 to 10, and m is 1, 2 or 3.

These phosphate group-containing compounds may be used alone or in combination of two or more.

(3) Surfactant

In the photosensitive coloring composition of the present invention, a surfactant may be contained in order to improve coatability.

As the surfactant, for example, an anionic, a cationic, a nonionic or an amphoteric surfactant can be used. Among them, a nonionic surfactant is preferably used in that it is less likely to adversely affect various properties, and a fluorine-based or lanthanide-based surfactant has an effect on coatability.

Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by NEOS Corporation), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie Co., Ltd.), and KP340 (for example). Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone), DS-401 (manufactured by Daikin), L-77 (Unicar, Japan) Made by the company), FC4430 (manufactured by Sumitomo 3M).

Further, one type of the surfactant may be used, or two or more types may be used in any combination and in any ratio.

(4) Pigment derivatives

In the photosensitive coloring composition of the present invention, a pigment derivative may be contained as a dispersing aid in order to improve dispersibility and storage stability.

Examples of the pigment derivative include an azo type, a phthalocyanine type, a quinophthalone type, a benzimidazolone type, a quinoline yellow type, an isoindolinone type, and two. Department, lanthanide, indanthrene, lanthanide, Perynone, diketopyrrolopyrrole, two A derivative such as a phthalocyanine or a quinoline yellow is preferred.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonylamino group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and a decylamino group. Wait It is preferably a sulfonic acid group, which is bonded to the pigment skeleton directly or via an alkyl group, an aryl group or a heterocyclic group. Further, the substituents may be subjected to plural substitution in one pigment skeleton.

Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinoline yellow, a sulfonic acid derivative of hydrazine, a sulfonic acid derivative of quinacridone, and a diketopyrrole. Pyrrole sulfonic acid derivative, two Sulfonic acid derivatives and the like. These may be used alone or in combination of two or more.

(5) Photoacid generator

The photoacid generator is a compound which generates an acid by ultraviolet rays, and the crosslinking reaction proceeds by, for example, the presence of a crosslinking agent such as a melamine compound by the action of an acid generated during exposure. Among such photoacid generators, those having a solubility in a solvent, particularly a solvent used in a photosensitive coloring composition, are preferable, and examples thereof include diphenyl hydrazine and xylyl hydrazine. Phenyl (p-anisyl) anthracene, bis(m-nitrophenyl)anthracene, bis(p-butylphenyl)anthracene, bis(p-chlorophenyl)anthracene, bis(n-dodecyl)anthracene, a diaryl fluorene such as p-isobutylphenyl (p-tolyl) fluorene, p-isopropylphenyl (p-tolyl) fluorene, or a triaryl sulfonium chloride such as triphenylphosphonium, bromide or fluoroboron Salt, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis(pentafluorophenyl)borate, etc., or diphenyl benzamidine methyl fluorene (n-butyl) triphenylboronic acid An organic boron lanthanum complex such as a salt or 2-methyl-4,6-bis-trichloromethyl three 2-(4-methoxyphenyl)-4,6-bis-trichloromethyl three Wait three Compounds and the like, but are not limited thereto.

(6) Crosslinker

Further, a crosslinking agent may be further added to the photosensitive coloring composition of the present invention, and for example, a melamine or a guanamine-based compound may be used. As such a crosslinking agent, for example, the following A compound of the melamine or guanamine type represented by the general formula (6).

In the formula (6), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or a carbon number 6 to 12 aryl group, and when R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ And one of R ⁶⁶ and R ⁶⁷ , and in the case where R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a -CH ₂ OR ⁶⁸ group, and the remainder R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent hydrogen or a —CH ₂ OR ⁶⁸ group. Here, R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and a substituent such as an alkyl group, an alkoxy group or a halogen atom may be bonded to the phenyl group. Or naphthyl. The alkyl group and the alkoxy group may each have a carbon number of about 1 to 6. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

The melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1) includes hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine , pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.

In the case of the formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents -CH ₂ OR ⁶⁸ group, the remaining R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of each other represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents a hydrogen atom or an alkyl group .

Further, the compound corresponding to the general formula (6), that is, the compound of the general formula (6) wherein R ⁶¹ is an aryl group, includes tetramethylol benzoguanamine and tetramethoxymethylbenzene. Indoleamine, trimethoxymethylbenzamide, tetraethoxymethylbenzamide, and the like.

Further, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are listed below.

2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl) ) all hydrogen-1,3,5-three 2-ketone (commonly known as N-ethyl dimethylol III) Ketone) or its dimethyl ether, dimethyloltrimethylene urea or its dimethyl ether, 3,5-bis(hydroxymethyl)perhydro-1,3,5- two 4-ketone (commonly known as dimethylol urea) or its dimethyl ether, tetramethylol glyoxydialkyl urea or its tetramethyl ether body.

In addition, these crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is preferably from 0.1 to 15% by mass, particularly preferably from 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(7) mercapto compounds

Further, in order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.

As the kind of the mercapto compound, 2-mercaptobenzothiazole and 2-mercaptobenzoene are exemplified. Azole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-mercaptopropionate, butanediol bis-mercapto glycolate, ethylene glycol Bis-glycolate, trimethylolpropane tridecyl glycolate, butanediol bis-mercaptopropionate, trimethylolpropane tridecyl propionate, trimethylolpropane tridecyl glycolate, pentaerythritol Mercaptopropionate, pentaerythritol tetradecyl glycolate, trishydroxyethyltrimethylpropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1, 4-bis(3-mercaptobutyloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate) ), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3, 5-tris(3-mercaptobutoxyethyl)-1,3,5-three a heterocyclic fluorenyl compound or an aliphatic polyfunctional fluorenyl compound such as 2,4,6(1H,3H,5H)-trione or the like. These may be used alone or in combination of two or more.

<Component blending amount in photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, the content of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more based on the total solid content of the photosensitive coloring composition. It is 50% by mass or less. If the content of the (A) color material is too small, sufficient optical density (OD) may not be obtained, and conversely, if the content of the (A) color material is too large, sufficient image formation property may not be obtained. . In addition, the content ratio of the (A-1) organic black pigment in an amount of 100% by mass of the (A) color material is usually 10% by mass or more, preferably 30% by mass or more, and usually 100% by mass or less. If the content ratio of the (A-1) organic black pigment in the (A) color material is too small, sufficient optical density (OD) may not be obtained.

In the photosensitive coloring composition of the present invention, the (A-2) organic coloring pigment may be contained together with the (A-1) organic black pigment in the (A) coloring material. In this case, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 90 quality The amount is preferably not more than 80% by mass, more preferably not more than 60% by mass. In addition, the content ratio of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass. The following is more preferably 70% by mass or less. If the content of the (A-2) organic coloring pigment is too large, sufficient optical density may not be obtained. In addition, the content ratio of the (A-1) organic black pigment in 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 900 parts by mass or less. It is preferably 800 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 200 parts by mass or less.

In the photosensitive coloring composition of the present invention, (A-3) carbon black may be contained together with the (A-1) organic black pigment in the (A) color material. In this case, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) color material is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably It is 90% by mass or less. In addition, the content ratio of (A-3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. If the content of (A-3) carbon black is too large, the volume resistance value may decrease or the relative dielectric constant may become large. In addition, the content ratio of the (A-1) organic black pigment in 100 parts by mass of the (A-3) carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2,000 parts by mass or less. Preferably, it is 1000 parts by mass or less.

Further, in the photosensitive coloring composition of the present invention, the (A-2) organic coloring pigment and the (A-3) carbon black are contained together with the (A-1) organic black pigment in the (A) coloring material. The situation. In this case, the content ratio of the (A-1) organic black pigment to 100% by mass of the (A) color material is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably It is 70% by mass or less. Further, the content ratio of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably It is 50% by mass or less. Further, the content ratio of (A-3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. In this case, the content ratio of the (A-1) organic black pigment to 100 parts by mass of the (A-2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800% by mass. The amount is preferably below 700 parts by weight. In addition, the content ratio of the (A-1) organic black pigment to 100 parts by mass of the (A-3) carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1,000 parts by mass or less. It is preferably 900 parts by mass or less.

The content of the dispersant in the solid content of the photosensitive coloring composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less, and preferably 30% by mass or less. It is 20% by mass or less, and particularly preferably 15% by mass or less. In addition, the content of the (B) dispersant based on 100% by mass of the (A) color material is usually 5% by mass or more, particularly preferably 10% by mass or more, and usually 50% by mass or less, and particularly preferably 30% by mass or less. . When the content of the (B) dispersant is too small, sufficient dispersibility may not be obtained. When the content of the (B) dispersant is too large, the ratio of other components may be relatively decreased, and the sensitivity and plate-making property may be lowered.

The content of the (C) alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, and usually 85% by mass or less, and preferably 85% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. 80% by mass or less. When the content of the (C) alkali-soluble resin is remarkably small, the solubility of the unexposed portion to the developer is lowered, and the development failure is liable to occur. On the other hand, when the content of the (C) alkali-soluble resin is too large, the permeability of the developer to the exposed portion tends to be high, and the sharpness or adhesion of the pixel may be lowered.

The content of the (D) photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. Further, it is preferably 1% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less. When the content of the (D) photopolymerization initiator is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed portion to the developer is lowered, and development failure is likely to occur.

When a polymerization accelerator is used together with the (D) photopolymerization initiator, the content of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the photosensitive coloring composition of the present invention, and usually The polymerization accelerator is preferably used in an amount of 10% by mass or less, preferably 5% by mass or less, based on 100 parts by mass of the (D) photopolymerization initiator, and is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by weight. The proportion of the mass is used.

When the ratio of the photopolymerization initiator component composed of the (D) photopolymerization initiator and the polymerization accelerator is remarkably low, there is a case where the sensitivity to the exposure light is lowered, and if it is significantly higher, Further, there is a case where the solubility of the unexposed portion to the developer is lowered to cause poor development.

In addition, the ratio of the sensitizing dye to the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15%, based on the total solid content of the photosensitive coloring composition. The mass% or less is further preferably 10% by mass or less.

When the photopolymerizable monomer is used, the content thereof is usually 30% by mass or less, preferably 20% by mass or less based on the total solid content in the photosensitive coloring composition. When the content of the photopolymerizable monomer is too large, the permeability of the developer to the exposed portion becomes high, and it becomes difficult to obtain a good image. In addition, the lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more.

When the adhesion improving agent is used, the content thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% based on the total solid content in the photosensitive coloring composition. quality%. If the content of the adhesion improver is less than the above range, In the case where the effect of improving the adhesion is not sufficiently obtained, if the amount is more than the above range, the sensitivity may be lowered or the residue may remain as a defect after development.

Further, in the case of using a surfactant, the content thereof is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01%, based on the total solid content in the photosensitive coloring composition. 0.5% by mass, preferably 0.03 to 0.3% by mass. When the content of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be exhibited. When the content is more than the above range, the smoothness and uniformity of the coating film are not revealed, and other characteristics are obtained. There are also cases of deterioration.

In addition, the photosensitive coloring composition of the present invention is prepared by using the above organic solvent, and the solid content thereof is usually 5 to 50% by mass, preferably 10 to 30% by mass.

<Physical properties of photosensitive coloring composition>

The photosensitive coloring composition of the present invention can be preferably used for the formation of a black matrix. From this viewpoint, it is preferably black, and the film thickness of the coating film is preferably 1.0 per 1 μm. the above.

<Method for Producing Photosensitive Coloring Composition>

The photosensitive coloring composition of the present invention (hereinafter referred to as "resist") is produced according to a conventional method.

Usually, the (A) color material is preferably subjected to dispersion treatment using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like in advance. Since the (A) color material is finely divided by the dispersion treatment, the coating properties of the resist are improved.

The dispersion treatment is preferably used in combination with (A) color materials, organic solvents, and (B) The dispersing agent and (C) one or a part of the alkali-soluble resin are carried out in a system (hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment are referred to as "ink" or "pigment dispersion" The situation). In particular, when a polymer dispersant is used as the (B) dispersant, the obtained ink and the resist are suppressed in viscosity over time (excellent dispersion stability), which is preferable.

As described above, in the step of producing a resist, it is preferred to produce a pigment dispersion liquid containing at least (A) a color material, an organic solvent, and (B) a dispersant. As the coloring material (A), the organic solvent, and the (B) dispersing agent which can be used for the pigment dispersion liquid, those which can be used as a photosensitive coloring composition can be preferably used.

In addition, when the liquid containing all the components blended in the colored resin composition is subjected to dispersion treatment, there is a possibility that the highly reactive component is modified due to heat generated during the dispersion treatment. Therefore, it is preferred to carry out a dispersion treatment in a system containing a polymer dispersant.

When the (A) color material is dispersed by a sand mill, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm can be preferably used. The conditions of the dispersion treatment are usually in the range of from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time and the reasonable time vary depending on the composition of the liquid and the size of the dispersion processing apparatus, and are appropriately adjusted. The standard of dispersion is to control the gloss of the ink in such a manner that the 20 degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the gloss of the resist is low, the dispersion treatment is insufficient, and the pigment (color material) particles remaining in confusion are often left, and the developability, the adhesion, the resolution, and the like are insufficient. . Further, when the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is broken to generate a large amount of ultrafine particles, and thus the dispersion stability tends to be impaired.

Further, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.

Then, the ink obtained by the above dispersion treatment is mixed with the above-mentioned other components contained in the resist to prepare a uniform solution. In the step of producing the resist, fine dirt is often mixed into the liquid, and therefore the obtained resist is preferably subjected to filtration treatment by a filter or the like.

[hardened material]

The cured product can be obtained by curing the photosensitive coloring composition of the present invention. A cured product obtained by hardening the photosensitive colored composition can be preferably used as a black matrix or a colored spacer.

[black matrix]

Next, the black matrix using the photosensitive coloring composition of the present invention will be described in accordance with the production method thereof.

(1) Support

The material for forming the black matrix is not particularly limited as long as it has appropriate strength. The transparent substrate is mainly used, and examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, and polymethyl methacrylate. A thermosetting resin sheet such as a thermoplastic resin such as polyfluorene, an epoxy resin, an unsaturated polyester resin, or a poly(meth)acrylic resin, or various glasses. Among them, from the viewpoint of heat resistance, glass or a heat resistant resin is preferred. Further, a case where a transparent electrode such as ITO or IZO is formed on the surface of the substrate may be formed. In addition to the transparent substrate, it can also be formed on the TFT array.

Support body, in order to improve the surface properties such as adhesion, can also be improved A film forming treatment of various resins such as a corona discharge treatment, an ozone treatment, a decane coupling agent, or a urethane-based resin.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Further, in the case of performing film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black matrix

The black matrix of the present invention is formed from the photosensitive coloring composition of the present invention, and the photosensitive coloring composition of the present invention is applied onto a transparent substrate and dried, and then a photomask is placed on the photosensitive coloring composition. The reticle is subjected to image exposure, development, and, if necessary, thermal hardening or photohardening, thereby forming a black matrix.

Further, the black matrix of the present invention is preferably formed on the TFT element substrate, but the configuration thereof is not particularly limited in each of the COA and BOA modes, and can be configured in accordance with various configurations.

(3) Formation of black matrix (3-1) Coating of photosensitive coloring composition

The application of the photosensitive coloring composition for the black matrix to the transparent substrate can be carried out by a spin coating method, a wire bar coating method, a shower coating method, a die coating method, a roll coating method, a spray coating method, or the like. In the meantime, it is preferable to reduce the amount of the coating liquid used by the die coating method, and it is not affected by the mist or the like adhered by the spin coating method, and it is preferable from the viewpoint of suppressing the generation of foreign matter.

When the thickness of the coating film is too thick, pattern development becomes difficult, and the gap adjustment in the liquid crystal unitization step becomes difficult. If it is too thin, it becomes difficult to increase the pigment concentration, and the desired color becomes Unable to show the situation. Thickness of the film, as a dry The film thickness after drying is preferably in the range of usually 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, still more preferably in the range of 1 to 4 μm.

(3-2) Drying of the coating film

The drying of the coating film after the photosensitive coloring composition is applied to the substrate is preferably carried out by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected at a temperature of 40 to 200 ° C in the range of 15 seconds to 5 minutes, preferably at a temperature of 50 to 130 ° C, depending on the type of the solvent component and the performance of the dryer to be used. Choose from 30 seconds to 3 minutes.

The higher the drying temperature, the higher the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the (C) alkali-soluble resin is decomposed to cause thermal polymerization to cause development failure. Further, the drying step of the coating film may be a vacuum drying method in which drying is performed in a decompression chamber without increasing the temperature.

(3-3) exposure

The image exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating the light source of ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent a decrease in the sensitivity of the photopolymerizable layer caused by oxygen, it is also possible to form an oxygen shielding layer such as a polyvinyl alcohol layer on the photopolymerizable coating film, followed by exposure. The light source used for the above image exposure is not particularly limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, and the like; or an argon ion laser , YAG laser, excimer laser, nitrogen laser, xenon-cadmium laser, semiconductor laser and other laser sources. Irradiation specific When a light of a wavelength is used, an optical filter can also be utilized.

(3-4) Development

The black matrix of the present invention can be image-exposed by the coating film based on the photosensitive coloring composition by the above-mentioned light source, and then formed on the substrate by using an organic solvent or an aqueous solution containing a surfactant and a basic compound. Produced by video. The aqueous solution may further contain an organic solvent, a buffer, a binder, a dye or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, and sodium phosphate. An inorganic basic compound such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium hydroxide; or mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or tri- An organic basic compound such as ethylamine, mono or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethylenediamine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline or the like. These basic compounds may also be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic interfacial activity such as nonionic surfactants; alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates An amphoteric surfactant such as an alkyl betaine or an amino acid.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl sirolius, butyl siroli, phenyl racelus, propylene glycol, and diacetone alcohol. The organic solvent may be used singly or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C, of which 15 to 45 ° C, particularly preferably 20 to 40 ° C, and the development method can be impregnated. Any of a developing method, a jet developing method, a brush developing method, and an ultrasonic developing method.

(3-5) Thermal hardening treatment

The substrate after development is subjected to a heat hardening treatment or a photohardening treatment, preferably a heat hardening treatment. In the thermal hardening treatment conditions at this time, the temperature is selected in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is selected within the range of 5 to 60 minutes.

The black matrix formed in the above manner has a line width of usually 3 to 50 μm, preferably 4 to 30 μm, and a height of usually 0.5 to 5 μm, preferably 1 to 4 μm. Also, the volume resistivity is 1 × 10 ¹³ Ω. Above cm, preferably 1 × 10 ¹⁴ Ω. Above cm, the relative dielectric constant is 6 or less, preferably 5 or less, and usually 2 or more.

Further, the optical density (OD) per 1 μm of the thickness is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 4.0 or less. Here, the optical density (OD) is a value measured by the following method.

[Coloring spacer]

In addition to the black matrix, the photosensitive coloring composition of the present embodiment may be used as a resist for a coloring spacer. When a spacer is used for a TFT type LCD, there is a case where a TFT as a switching element malfunctions due to light incident on the TFT, and a colored spacer is used to prevent the above, for example, Japanese Patent Laid-Open No. Hei 8-234212 The case of the spacer is described as a light-shielding property. The colored spacers may be formed by the same method as the above-described black matrix, in addition to the mask for the colored spacers.

[Image display device]

The image display device of the present invention is not particularly limited as long as it is a device for displaying an image or an image, and examples thereof include a liquid crystal display device or an organic EL (Electro Luminescence) display.

[Liquid Crystal Display Device]

The liquid crystal display device of the present invention is produced by using the black matrix of the present invention described above, and the order in which the color pixels or the black matrix are formed or the formation position is not particularly limited.

For example, a black matrix of the present invention is provided on a TFT element substrate to form red, green, and blue pixels, and a protective layer is formed as needed, and then a transparent electrode such as ITO or IZO is formed on the image as a color display. Part of the parts such as liquid crystal display devices. Further, in some applications such as a planar alignment type driving method (IPS mode), a transparent electrode is not formed.

In a liquid crystal display device, an alignment film is usually formed on a color filter, and a spacer or a photosensitive spacer is formed on the alignment film, and then bonded to the opposite substrate to form a liquid crystal cell, and the liquid crystal cell is formed. The liquid crystal is injected and the wiring is completed on the opposite electrode. As the alignment film, a resin film such as polyimide or the like is preferable. The formation of the alignment film is usually performed by a gravure printing method and/or a quick-drying printing method, and the thickness of the alignment film is set to several tens of nm. After the hardening treatment of the alignment film by thermal calcination, the surface treatment is performed by irradiation with ultraviolet rays or treatment with a rubbing cloth, and processed into a surface state in which the slope of the liquid crystal can be adjusted.

The formation order or formation position of the color pixel or the black matrix is not particularly limited as long as the black matrix of the present invention is used.

As the spacer, a size corresponding to the gap of the counter substrate can be used, and usually 2 to 8 μm is preferable. A photosensitive spacer (PS) of a transparent resin film may be formed on the color filter substrate by photolithography, and may be used in place of the spacer.

The gap to be bonded to the counter substrate differs depending on the use of the liquid crystal display device, and is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed by a sealing material such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.

After the liquid crystal cell sealed in the periphery is cut into panel units, the pressure is reduced in the vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. The degree of pressure reduction in the liquid crystal cell is usually from 1 × 10 ^-2 to 1 × 10 ^-7 Pa, but preferably from 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, it is preferred to heat the liquid crystal cell at a reduced pressure, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The heating at the time of pressure reduction is usually set to a range of 10 to 60 minutes, and thereafter immersed in a liquid crystal. A liquid crystal cell in which a liquid crystal is injected is injected, and a liquid crystal injection port is sealed with a cured UV curing resin, thereby completing a liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be any known liquid crystal such as an aromatic system, an aliphatic system or a polycyclic compound, and is any one of a lyotropic liquid crystal and a thermotropic liquid crystal. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, or the like is known, but any of them may be used.

[Organic EL Display]

The organic EL display of the present invention can be produced using the black matrix of the present invention.

When an organic EL display is produced by using the black matrix of the present invention, for example, as shown in FIG. 1, a pattern formed of a colored resin composition is first formed on the transparent supporting substrate 10 (that is, provided on the pixel 20, and a color filter formed by a black matrix (not shown) between the adjacent pixels 20, and the organic light-emitting body 500 is laminated on the color filter via the organic protective layer 30 and the inorganic oxide film 40. The organic EL element 100 can be fabricated. Furthermore, At least one of the pixel 20 and the black matrix is produced using the photosensitive coloring composition of the present invention. As a method of laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. The method or the method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40, or the like. The organic EL device 100 produced in the above manner can be used, for example, by the method described in "Organic EL Display" (Ohm Corporation, issued on August 20, 2004, at the time of Jingshi, Anda Chiba, and Murata Yuki). Production of organic EL displays.

Furthermore, the black matrix of the present invention can be applied to an organic EL display of a passive driving type, and can also be applied to an organic EL display of an active driving type.

[Examples]

Hereinafter, the present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples, and the present invention is not limited to the following examples as long as the scope of the present invention is not exceeded.

The constituent components of the photosensitive coloring composition used in the following examples and comparative examples are as follows.

<(A-1) Organic Black Pigment>

Manufactured by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Organic Black Pigment: Dark Black>

Manufactured by BASF, Lumogen (registered trademark) Black FK4281

<Organic Black Pigment: Aniline Black>

Manufactured by BASF, Paliotol (registered trademark) Black L0080

<alkali soluble resin-I>

To 145 parts by mass of propylene glycol monomethyl ether acetate, the mixture was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of a monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a cyclodecane skeleton were added dropwise thereto, and a dropwise addition was carried out for 3 hours. 2.47 parts by mass of 2,2'-azo-2-methylbutyronitrile, and further stirring was continued at 90 ° C for 2 hours. Then, the inside of the reaction vessel was replaced with air, and 0.7 parts by mass of tris-dimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C for 3.5 hours. The alkali-soluble resin-I obtained in the above manner had a weight average molecular weight Mw of about 8400 and an acid value of 80 mgKOH/g as measured by GPC.

<alkali soluble resin-II>

"ZCR-1664H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw=5000~6000, acid value=about 60mg-KOH/g)

<alkali soluble resin-III>

[化31]

50 g of the epoxy compound (epoxy equivalent 247) having the above structure, 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine, and 0.05 g of p-methoxyphenol were placed in a thermometer and a mixer. In the flask of the cooling tube, the reaction was carried out at 90 ° C while stirring until the acid value became 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the above epoxy acrylate solution, 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.8 parts by mass of tetrahydrophthalic anhydride (THPA). The flask was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the mixture was gradually heated to 105 ° C while stirring to carry out a reaction.

When the resin solution was made transparent, it was diluted with methoxybutyl acetate, and the solid content was 50% by mass to obtain a weight average molecular weight of 131 mg KOH/g and polystyrene equivalent by GPC. (Mw) 4000 carboxyl group-containing epoxy acrylate resin (c1).

<alkali soluble resin-IV>

"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (MW=6500, acid value = 98 mg-KOH/g)

<dispersant-I>

"DISPERBYK-LPN21116" manufactured by BYK-Chemie Co., Ltd. (A block composed of A block having a quaternary ammonium salt group and a tertiary amino group in a side chain, and a B block having no quaternary ammonium salt group and amine group) AB block copolymer. The amine value is 70 mgKOH/g. The acid value is 1 mgKOH/g or less).

The content ratio of the repeating unit of the following formulas (1a), (2a), and (3a) to all the repeating units of the dispersing agent-I was 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

<Dispersant-II>

"DISPERBYK-2000" manufactured by BYK-Chemie Co., Ltd. (A block of A-blocks having a quaternary ammonium salt group in a side chain and an A-B block copolymer composed of a B block having no quaternary ammonium salt group)

<Dispersant-III>

"EFKA-4300" manufactured by EFKA Co., Ltd. (acrylic polymer dispersant having a tertiary amino group and a butyl group in the side chain. The side chain does not have a quaternary ammonium salt group).

<Pigment Derivative>

"Solsperse12000" manufactured by Lubrizol

<solvent-I>

PGMEA: propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxybutanol

<Photopolymerization initiator-I>

Compound 1 (0.98 g, 5 mmol) and dichloromethane (17 mL) were added to a 50 mL three-neck flask under a nitrogen atmosphere. After cooling to 3 ° C, o-toluene chloride (0.77 g, 5 mmol) was added dropwise. Thereto, aluminum chloride (0.67 g, 5 mmol) was slowly added over 1 hour. After completion of the addition, the mixture was further stirred at 3 ° C for 2 hours, and dichloromethane (8 mL) was added. Then, after adding glutaric anhydride (0.68 g, 6 mmol) over 30 minutes, aluminum chloride (1.90 g, 14 mmol) was added over 30 minutes.

After completion of the addition, the mixture was further stirred at 3 ° C for 2 hours, and the reaction solution was slowly poured into ice water (400 mL). Sodium chloride (80 g) was added to the aqueous layer, and extraction was carried out five times with dichloromethane (50 mL). The organic layer was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound 2 (2.13 g, crude yield 100%). It was not refined and used for the next reaction.

Under a nitrogen atmosphere, Compound 2 (2.13 g, 5 mmol), methanol (22 mL) and concentrated sulfuric acid (5 mg) were added to a 50 mL three-neck flask, and the mixture was heated under reflux for 3 hours. After cooling, the solvent was concentrated, water (10 mL) and ethyl acetate (30 mL).

The organic layer was washed successively with a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound 3 (1.72 g, crude yield 78%). It was not refined and used for the next reaction.

Compound 3 (1.00 g, 2.26 mmol) and dichloromethane (10 mL) were added to a 50 mL three-neck flask under a nitrogen atmosphere, and the mixture was cooled to 10 °C. A 1N solution of hydrogen chloride in diethyl ether (4.68 mL) was added. Then, amyl nitrite (0.36 g, 3.04 mmol) was added, and the mixture was reacted at 10 ° C for 4 hours. After adding water (10 mL), it was washed successively with a saturated aqueous sodium hydrogencarbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering with anhydrous magnesium sulfate, the solvent was evaporated to give a pale yellow solid (0.88 g). This was re-refined with toluene (3.5 mL) to give Compound 4 (0.45 g, yield 42%).

Compound 4 (3.50 g, 7.44 mmol) and dichloromethane (35 mL) were added to a 50 mL three-neck flask under a nitrogen atmosphere, and cooled to 4 °C. Triethylamine (1.50 g, 14.9 mmol) was added thereto. Then, after adding ethyl hydrazine chloride (0.70 g, 8.93 mmol), it was directly reacted for 1 hour. After adding a saturated aqueous sodium hydrogencarbonate solution (10 mL), the organic layer was separated, and washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering with anhydrous magnesium sulfate, the solvent was evaporated to give a yellow oil (3.65 g). This was purified by column chromatography (ethyl acetate / hexane: 1 / 1) to give Compound 5 (3.12 g, yield 82%, photopolymerization initiator-I). The chemical shift of Compound 5 is shown below.

¹ H-NMR δ [ppm] (CDCl ₃ ) 1.49 (t, 3H), 2.29 (s, 3H), 2.36 (s, 3H), 2.73 (t, 2H), 3.14 (t, 2H), 3.60 (s) , 3H), 4.43 (q, 2H), 7.3~r7.5 (m, 6H), 8.06 (dd, 1H), 8.29 (dd, 1H), 8.59 (d, 1H), 8.83 (dd, 1H)

<Photopolymerization initiator-II>

<Photopolymerizable monomer-I>

DPHA: manufactured by Nippon Chemical Co., Ltd. Dipentaerythritol hexaacrylate

<Photopolymerizable monomer II>

DPHA-40H: Nippon Chemical Co., Ltd. Manufacture of urethane acrylate

<Additive-I>

Manufactured by Nippon Chemical Co., Ltd., KAYAMER PM-21 (phosphate containing methacryl oxime)

<Surfactant-I>

DIC (share) manufacturing MEGAFAC F-559

<Preparation of Pigment Dispersion-1~7>

The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent described in Table 1 were mixed so as to have the mass ratios shown in Table 1. The solution was subjected to dispersion treatment for 3 hours in a range of 25 to 45 ° C by a paint shaker. As a bead, use 0.5mm The zirconia beads were added to the mass of 2.5 times the dispersion. After the completion of the dispersion, the beads were separated from the dispersion by a filter to prepare a pigment dispersion-1 to 7.

Here, when the blackening was carried out under the same conditions as those of the pigment dispersion-1, the viscosity of the blackening was greatly increased. Therefore, in the dispersion of the pigments, it is necessary to greatly increase the amount of the dispersant as in the case of the pigment dispersion liquid-6.

<coated carbon black dispersion>

Carbon black is produced by a conventional oil furnace method. Among them, as the raw material oil, an ethylene base oil having a small Na, Ca, and S component is used, and a gas coke oven is used for the combustion. Further, as the reaction termination water, pure water treated with an ion exchange resin was used. Using a homomixer, 540 g of the obtained carbon black and 14500 g of pure water were stirred at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. The slurry was transferred to a vessel equipped with a screw-type mixer, and 600 g of toluene dissolved in 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was added little by little while mixing at about 1,000 rpm. Within about 15 minutes, all of the carbon black dispersed in the water was moved to the toluene side to become a pellet of about 1 mm.

Then, water was removed using a 60 mesh wire mesh, placed in a vacuum dryer, and dried at 70 ° C for 7 hours to completely remove toluene and water.

To 90 parts by mass of the obtained coated carbon black, 20 parts by mass of DISPERBYK-167 (manufactured by BYK-Chemie Co., Ltd.) as a dispersing agent, and 4.5 parts by mass of Solsperse 12000 (manufactured by Lubrizol Co., Ltd.) as a pigment derivative were added, and the solid concentration was determined. Propylene glycol monomethyl ether acetate (PGMEA) was added in a form of 25% by mass.

The mixture was sufficiently stirred by a stirrer to carry out premixing. Then, dispersion treatment was carried out for 6 hours in the range of 25 to 45 ° C by means of a paint shaker. As beads, use 0.5mm The zirconia beads are added in the same mass as the dispersion. After the completion of the dispersion, the beads were separated from the dispersion by a filter to prepare.

[Examples 1 to 8 and Comparative Examples 1 to 4]

By using the pigment dispersion liquid and the coated carbon black dispersion liquid prepared above, each component is added so that the ratio in the solid content becomes the compounding ratio of Table 2, and the solid content is 17 mass. PGMEA was added in an amount of %, stirred and dissolved to prepare a photosensitive coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid portion was 40% by mass, and in Comparative Example 3, the pigment concentration in the solid portion was 30% by mass. Further, in all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer is set to 3, and the photopolymerization initiator is made into a solid portion. 4% by mass, the additive was set to 0.5% by mass, and the surfactant was set to 0.1% by mass. The photosensitive coloring composition obtained was evaluated by the following method.

[Measurement of optical density (OD) per 1 μm]

The prepared photosensitive coloring composition was applied onto a glass substrate so as to have a final film thickness of 2 μm by a spin coater, dried under reduced pressure for 1 minute, and dried at 100 ° C for 90 seconds using a hot plate. A resist coated substrate (substrate-1) was obtained by heating at 230 ° C for 30 minutes. The optical density (OD) of the obtained substrate was measured by a penetrating densitometer Gretag Macbeth D200-II, and the non-contact surface layer cross-sectional shape measuring system VertScan(R) manufactured by Rhombus Systems was used. The film thickness was measured in 2.0. The optical density (OD) per 1 μm of the film thickness is shown in Table 3.

[Measurement of Relative Dielectric Coefficient]

In the method of producing the substrate-1, a substrate (substrate-2) was produced in the same manner except that a glass substrate having a chromium deposited film was used instead of the glass substrate. The chromium film of the sample was used as a main electrode, and a gold counter electrode was formed on the resist coating film by a vapor deposition method. Also, use "LCR meter 4284A" manufactured by HP (now Agilent), for 1 kHz. The relative dielectric constant at 1 V was measured. The results are shown in Table 3.

[plate making characteristics]

Drying using a hot plate was carried out in the same manner as in the substrate-1. The sample was subjected to image exposure (illuminance: 30 mW/cm ² , exposure amount: 20 mJ/cm ² ) through a negative-type mask having a linear pattern having an opening of 20 μm using a high-pressure mercury lamp. At this time, the distance between the sample and the mask was set to 200 μm. Thereafter, spray development was carried out using a developer having a KOH concentration of 0.05% by mass at a temperature of 25 °C. The development time was set to 1.5 times the dissolution time of the unexposed portion. The results of the line widths of the obtained line patterns are shown in Table 3. However, in the case of using the resists of Comparative Examples 1 and 2, the pattern could not be obtained even after development for 10 minutes.

From the comparison between Example 1 and Comparative Examples 1, 2 and 4, it was confirmed that the substrate obtained from the photosensitive coloring composition of the present invention has a higher OD and a higher shielding property when the pigment concentration is the same. Further, in Comparative Examples 1 and 2, even if development was performed for 10 minutes, a linear pattern could not be obtained. The reason for this is considered to be that the comparative examples 1 and 2 contain a black pigment as a pigment, but it is necessary to use a large amount of a dispersant when dispersing the black, which adversely affects the plate-making property. Further, it was confirmed from Examples 4 and 5 that the larger the value of the line width is, the higher the sensitivity is. However, by using the organic black pigment (A-1) and the (A-2) organic coloring pigment in combination, the OD can be prevented from being greatly lowered. And improve the sensitivity.

In Comparative Example 3, it was found that the pigment was coated only with carbon black and showed a higher OD, but the relative dielectric constant became higher. It is confirmed from Examples 6 and 7 that by using the (A-1) organic black pigment and (A-3) carbon black used in the present invention in combination, the OD is high and the relative dielectric constant can be kept low.

[Dispersion evaluation] <Preparation of Pigment Dispersion -8~11>

The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent described in Table 4 were mixed so as to have the mass ratios shown in Table 4. The solution was subjected to dispersion treatment for 3 hours in a range of 25 to 45 ° C by a paint shaker. As beads, use 0.5mm The zirconia beads were added to the mass of 2.5 times the dispersion. After the completion of the dispersion, the beads were separated from the dispersion by a filter to prepare a pigment dispersion liquid -8-11.

[Example 9 and Comparative Examples 5 to 7]

By using the above-prepared pigment dispersion liquid, each component was added so that the ratio of the solid content became the blending ratio of Table 5, and PGMEA was added so that the solid content became 17% by mass, and the mixture was stirred and dissolved to prepare photosensitive coloring. Composition.

In addition, the viscosity of each of the obtained photosensitive coloring compositions was measured by an RC80L type viscometer (measurement conditions: 23 ° C, 50 rpm) manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 5.

In general, it is known that in order to disperse an organic pigment in a photosensitive coloring composition, an alkaline polymer dispersing agent having a quaternary ammonium salt group or an alkali polymer dispersing agent having no quaternary ammonium salt group is known. , all equally used, and showing the same dispersion. In fact, in Comparative Examples 6 and 7 of Table 5, the black pigment belonging to the organic black pigment, whether in the case of using the dispersant I or in the case of using the dispersant III, on the viscosity of the photosensitive coloring composition There is no significant difference.

Surprisingly, from the comparison of Example 9 of Table 5 with Comparative Example 5, the photosensitive coloring composition containing the (A-1) organic black pigment is as follows, that is, without using a quaternary ammonium salt group. In the case of the polymer-based polymer dispersant (dispersant III), the viscosity of the photosensitive coloring composition is half by using a polymer dispersant (dispersant I) having a quaternary ammonium salt group as a functional group. Left and right, and (A-1) organic black pigment is uniformly dispersed.

Further, Table 6 shows the values of the viscosity obtained by measuring the photosensitive coloring compositions of Examples 1 to 8 by the same method as in Example 9.

As shown in Table 6, in Examples 1 and 2 in which (A-1) an organic black pigment was used as a pigment alone, the (A-1) organic black pigment and (A-2) organic coloring pigment were used in combination. 3~5 and 8, using (A-1) organic black pigment and (A-3) carbon black in Example 6, using (A-1) organic black pigment and (A-2) organic coloring pigment and (A- 3) In any of Examples 7 of carbon black, the viscosity is the same as that of Examples 1 and 2, and any of the photosensitive coloring compositions is uniformly dispersed as a pigment.

The present invention has been described in detail with reference to the preferred embodiments thereof. The present application is based on Japanese Patent Application No. 2013-198425, filed on

Claims (17)

A photosensitive coloring composition containing at least (A) a color material, (B) a dispersing agent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) color material contains (A) -1) an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt thereof, and the above-mentioned (B) dispersant contains a quaternary ammonium salt a polymer dispersant as a functional group, [In the formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, a CH ₃ , a CF ₃ , a fluorine atom or a chlorine atom; and R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ^{9 .} And the R ¹⁰ system and all others are independent of each other, and are a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH , SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and selected from R ² and R ³ And R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and at least one of the groups consisting of R ⁹ and R ¹⁰ may be directly bonded to each other. Alternatively, they are bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a carbon number of 2 to 2; Alkenyl group 12, cycloalkenyl group having 3 to 12 carbon atoms or alkynyl group having 2 to 12 carbon atoms. The photosensitive coloring composition of the first aspect of the invention, wherein in the above general formula (1), in the formula, R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom. a fluorine atom or a chlorine atom, and R ³ and R ⁸ are each independently a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , R ¹ is the same as R ⁶ , R ² and R ^{7 is the} same, R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ . The photosensitive coloring composition of the first or second aspect of the invention, wherein the polymer dispersing agent further has a tertiary amine as a functional group. The photosensitive coloring composition according to any one of the items 1 to 3, wherein the (C) alkali-soluble resin contains at least at least the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2) Any of the <alkali-soluble resin (c1)> is added to the epoxy resin by an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and further with a polybasic acid and/or An alkali-soluble resin obtained by reacting an anhydride thereof; <alkali-soluble resin (c2)> is added to an epoxy by making an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group An alkali-soluble resin obtained by reacting a resin with a polyhydric alcohol and a polybasic acid and/or an anhydride thereof. The photosensitive coloring composition of any one of Claims 1 to 4, wherein the (A) color material further contains (A-2) an organic coloring pigment. The photosensitive coloring composition of the fifth aspect of the invention, wherein the (A-2) organic coloring pigment contains at least one of the following pigments, Blue: Chroma Index Pigment Blue 60, or 15:6 Red: Chroma Index Pigment Red 177, 254, or 272 Violet: Chroma Index Pigment Violet 23, or 29 Orange: Chroma Index Pigment Orange 43, 64, or 72 . The photosensitive coloring composition of the fifth or sixth aspect of the invention, wherein the content ratio of the (A-1) organic black pigment is from 30 to 90% by mass based on 100% by mass of the (A) color material, ( A-2) The content of the organic coloring pigment is from 10 to 70% by mass. The photosensitive coloring composition according to any one of the items 1 to 7 wherein the (A) color material further contains (A-3) carbon black. The photosensitive coloring composition of the eighth aspect of the invention, wherein the content ratio of the (A-1) organic black pigment is 50 to 90% by mass based on 100% by mass of the (A) color material, (A- 3) The content of carbon black is 10 to 50% by mass. The photosensitive coloring composition according to any one of claims 1 to 9, wherein the (D) photopolymerization initiator is an oxime ester initiator and/or a ketoxime initiator. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 10. A black matrix formed of a cured product of claim 11 of the patent application. A colored spacer formed of a cured product of claim 11 of the patent application. An image display device comprising the black matrix of claim 12 or the colored spacer of claim 13 of the patent application. A pigment dispersion liquid containing (A) a color material and (B) a dispersant, wherein the (A) color material contains (A-1) a compound represented by the following general formula (1), and its geometric isomerism An organic black pigment of a salt of a substance, a salt thereof or a geometric isomer thereof, and the above (B) dispersant contains a polymer dispersant having a quaternary ammonium salt group as a functional group, [In the formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, a CH ₃ , a CF ₃ , a fluorine atom or a chlorine atom; and R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ^{9 .} And the R ¹⁰ system and all others are independent of each other, and are a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH , SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; and selected from R ² and R ³ And R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and at least one of the groups consisting of R ⁹ and R ¹⁰ may be directly bonded to each other. Alternatively, they are bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ ; R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a carbon number of 2 to 2; Alkenyl group 12, cycloalkenyl group having 3 to 12 carbon atoms or alkynyl group having 2 to 12 carbon atoms. The pigment dispersion according to claim 15 wherein, in the above general formula (1), wherein R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a fluorine atom. Atom or a chlorine atom, R ³ and R ⁸ are each independently a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N ( CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , R ¹ is the same as R ⁶ , and R ² is the same as R ⁷ R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ . The pigment dispersion according to claim 15 or 16, wherein the polymer dispersant further has a tertiary amine as a functional group.