KR20170098337A - Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition which is excellent in light shielding property, excellent in dispersibility and formability, and exhibits a sufficiently low relative dielectric constant. The photosensitive coloring composition of the present invention comprises at least a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the colorant (A) 1), a geometric isomer of the compound, a salt of the compound, or an organic black pigment which is a salt of a geometric isomer of the compound, and (B) the dispersant comprises a polymer dispersant having a quaternary ammonium group as a functional group .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coloring composition, a black matrix, a colored spacer, an image display, and a pigment dispersion.

The present invention relates to a photosensitive coloring composition, a black matrix, a coloring spacer, and an image display device. Specifically, the present invention relates to a photosensitive coloring composition excellent in shielding property and plate making property, and a use thereof.

The black matrix for a liquid crystal display element is used to prevent leakage of light from between drive electrodes in a liquid crystal display element. Generally, the black matrix is a pattern of a stripe-shaped or lattice-like light-shielding material formed by photolithography on a transparent substrate such as a glass or plastic sheet paired with a TFT (Thin Film Transistor) element substrate.

In recent years, in order to cope with higher definition and higher luminance of a color liquid crystal display element, a color filter on array system (COA system) in which a color filter is provided on the TFT element substrate side in an active matrix type liquid crystal display, And a black matrix on array system (BOA system) in which only a black matrix is formed on the TFT element substrate side. According to this method, as compared with the case of forming the black matrix on the color filter side, there is no need to provide a margin for alignment with the active element side, so that the aperture ratio can be increased, and as a result, higher luminance can be achieved .

However, in the case of adopting such a structure, it is required that the black matrix has a volume resistivity of not less than a predetermined value and a relative dielectric constant of not more than a certain value so as not to short circuit the electric circuit even if mounted directly on the TFT element.

As such a black matrix, a black matrix using a plurality of organic colored pigments and carbon black as pigments has been proposed (see, for example, Patent Document 1).

A photosensitive composition for a black matrix using an organic black pigment as a pigment is also known. Specifically, a photosensitive composition using aniline black (see, for example, Patent Document 2) or perylene black (see, for example, Patent Document 3) It is known.

On the other hand, bis-oxodihydro-indolylene-benzofuran colorants are known as organic pigments (see, for example, Patent Document 4). In this document, it is described that the pigment is used for forming a red layer, a blue layer and a green layer of a color filter. It is also known that the pigment is also used as an organic black pigment for electrophoretic display (see, for example, Patent Document 5).

[Prior Art Literature]

[Patent Literature]

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

(Patent Document 2) JP-A-8-44049

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

(Patent Document 4) Japanese Published Patent Application No. 2002-528448

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

As a result of intensive investigations by the present inventors, it has been found that the photosensitive composition described in Patent Document 1 has a low shielding 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 .

In addition, the aniline black or perylene black described in Patent Document 2 or 3 is poor in dispersibility and it is necessary to use a large amount of dispersing agent in order to disperse it, there was. Furthermore, it was found that the shielding ratio (optical density) was not sufficient.

In Patent Documents 4 and 5, the use of the bis-oxodihydro-indolylene-benzofuran colorant as a shielding agent for use in an image display device has no description nor description, and was used as a shielding agent for use in an image display device The optical density, and the properties such as dispersibility and plate-making property are unclear.

SUMMARY OF THE INVENTION The present invention has been made in view of the above conventional problems, and an object of the present invention is to provide a photosensitive coloring composition which is excellent in light shielding property, excellent in dispersibility and plate formability, and exhibits a sufficiently low relative dielectric constant.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that an organic black pigment having a specific structure is used as a coloring material in a photosensitive coloring composition and a specific dispersing agent is used, Has reached the invention.

That is, the present invention has the following structures [1] to [17].

[1] A photosensitive coloring composition containing at least a colorant, a dispersant, an alkali-soluble resin, and a photopolymerization initiator, wherein the colorant (A) (B) a polymeric dispersant containing a quaternary ammonium salt group as a functional group, wherein the dispersing agent comprises an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a geometric isomer thereof.

[Chemical Formula 1]

[In the formula (1), R ¹ and R ⁶ independently represent 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 independently represent a hydrogen atom, a halogen atom from all other, 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 , ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR < ¹¹ > bridges; R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[2] In the above general formula (1)

Wherein R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independently of each other a hydrogen atom, a fluorine atom or a chlorine atom, R ³ and R ⁸ independently of one another are 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,? -Naphthyl, SO ₃ H or SO ₃ ^- , 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 R ⁹ And R ⁵ is the same as R ¹⁰ .

[3] The photosensitive coloring composition according to [1] or [2], wherein the polymer dispersant further has a tertiary amine as a functional group.

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

≪ Alkali-soluble resin (c1) >

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting the polybasic acid and / or an anhydride thereof.

≪ Alkali-soluble resin (c2) >

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

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

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

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

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

Purple: Color Index Pigment Violet 23, or 29

Color: Color Index Pigment Orange 43, 64, or 72

[7] The ink composition according to any one of [1] to [3], wherein the content of the organic black pigment (A-1) is 30 to 90% by mass, the content of the organic color pigment (A- , [5] or [6].

[8] The photosensitive colored composition according to any one of [1] to [7], wherein the colorant further comprises (A-3) carbon black.

[9] The ink composition according to any one of [1] to [8], wherein the content of the organic black pigment (A-1) is from 50 to 90 mass%, the content of the carbon black is from 10 to 50 mass% The photosensitive coloring composition according to [8].

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

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

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

[13] A colored spacer formed from the cured product according to [11].

[14] An image display device comprising a black matrix according to [12] or a coloring spacer according to [13].

[15] A pigment dispersion comprising (A) a colorant and (B) a dispersant, wherein the colorant (A) comprises a compound represented by the following general formula (1) (B) a polymer dispersant having a quaternary ammonium salt group as a functional group, wherein the dispersing agent (B) comprises an organic black pigment which is a salt of a geometric isomer.

(2)

Wherein R ¹ and R ⁶ are independently of each other 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 independently represent a hydrogen atom, a halogen atom from all other, 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 , ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ; At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR < ¹¹ > bridges; R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ]

[16] The compound represented by the general formula (1)

^{Wherein, R 2, R 4, R} 5, R 7, R 9 and R ¹⁰ are independently a hydrogen atom, a fluorine atom, or chlorine atom, R ³ and R ⁸ are independently a hydrogen atom, NO ₂ from each other, 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, naphthyl, SO ₃ H or SO ₃ ^- , 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 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.

Since the photosensitive coloring composition of the present invention contains an organic black pigment having a specific structure, the amount of the dispersing agent can be reduced at the time of producing the pigment dispersion, and therefore, the photosensitive coloring composition exhibits excellent plate making characteristics and excellent dispersibility. Therefore, the black matrix formed from the photosensitive coloring composition of the present invention exhibits excellent light shielding properties. The black matrix and the colored spacer of the present invention exhibit a sufficiently low relative dielectric constant so as not to cause a short circuit, a malfunction, or the like even if the black matrix and the colored spacer are formed on the TFT element substrate. The image display device having the black matrix of the present invention has no problems such as TFT failure and hunting of liquid crystal driving, and is excellent in reliability.

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

Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

In the present invention, "(meth) acryl" means "acrylic and / or methacrylic", and "(meth) acrylate" and "(meth) acryloyl"

The term "(co) polymer" means both of a homopolymer (homopolymer) and a copolymer (copolymer), and the term "(co) polymer" Quot; acid " means containing both an acid and an anhydride thereof. In the present invention, "acrylic resin" means a (co) polymer containing (meth) acrylic acid or a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

In the present invention, the term " monomer " refers to a so-called polymer material (polymer), and includes not only the monomer (monomer) but also the dimer, trimer and oligomer.

In the present invention, the term " total solid content " means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.

In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (Gel Permeation Chromatography).

In the present invention, " amine value " means the amine value in terms of effective solid content, unless otherwise stated, and is a value expressed by mass of KOH in terms of the amount of the base group per 1 g of the solid content of the dispersant. The measuring method will be described later. On the other hand, "acid value" means the acid value in terms of effective solid content unless specifically stated, and is calculated by neutralization titration.

In the present specification, the percentages and parts denoted by " mass " have the same meaning as the percentages and parts denoted by " weight ".

[Photosensitive coloring composition]

The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as " photosensitive coloring composition " or " colored resin composition &

(A) Coloring material

(B) Dispersant

(C) an alkali-soluble resin

(D) a photopolymerization initiator

And other additives such as organic solvents and adhesion improvers such as a silane coupling agent, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative and the like, if necessary, , Usually, each compounding component is used in a state dissolved or dispersed in an organic solvent.

<(A) Coloring material>

The colorant (A) used in the present invention includes (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 of a geometric isomer thereof.

(3)

[In the formula (1), R ¹ and R ⁶ independently represent 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 independently represent a hydrogen atom, a halogen atom from all other, 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 , ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;

At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ , Or they may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR &lt; ¹¹ &gt; bridges;

R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an 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 is most stable if necessary.

[Chemical Formula 4]

When the compound represented by the general formula (1) is not anionic, its charge can be converted to any known suitable cation such as a metal, an organic, an inorganic or a metal organic cation, particularly an alkali metal, an alkaline earth metal, , Quaternary ammonium such as primary ammonium, secondary ammonium or trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salt compensated by an organometallic complex. When the geometric isomer of the compound represented by the general formula (1) is not present, it is preferable that the same is the salt.

In terms of the substituents of the formula (1) and their definitions, the shielding ratio tends to be high. This is because it is considered that the following substituents do not absorb and do not affect the color of the pigment.

R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom, or a chlorine atom, more preferably a hydrogen atom.

R ³ and R ⁸ are 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 independently of one another are preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.

Preferably, at least one combination 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 R ⁵ and R ¹⁰ is the same, , 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 .

Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n- octyl group, 1,1,3,3- An ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tosyl group, a norbornyl group, , A norbornyl group, a norbornyl group, a norbornyl group, a 1-adamantyl group or a 2-adamantyl group.

Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, 1-butene-2-yl group, 3-methyl-2-butene-1-yl group, A 1,4-pentadiene-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.

The cycloalkenyl group having 3 to 12 carbon atoms is, for example, a 2-cyclobutene-1-yl group, a 2-cyclopenten-1-yl group, a 2- Cyclohexadien-1-yl group, 1-p-menthene-8-yl group, 4 (10) -tulen-10-yl group, 2-norbornen- En-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphhenyl group.

The alkynyl group having 2 to 12 carbon atoms is, for example, a 1-propyn-3-yl group, a 1-butyne-4-yl group, Pentyne-3-yl group, a 1,3-pentadiyn-5-yl group, a 1-hexyn-6-yl group, 1-octyne-9-yl group, 1-decyne-10-yl group, -Yl group or a 1-dodecyn-12-yl group.

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

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

[Chemical Formula 5]

Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.

The organic black pigment of (A-1) is preferably dispersed in a dispersant or a solvent according to a method described later. When the sulfonic acid derivative of the general formula (2) is present at the time of dispersion, dispersibility and storage stability may be improved.

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

(A-2) The organic colored pigments include various pigments such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments other than (A- Organic pigments can be used. As the structure, various inorganic pigments can be used in addition to organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, and indanthrene pigments. In the present specification, the color of the pigment means the color which is obtained when the pigment is used alone as a coloring material to form a photosensitive coloring composition, unless otherwise specified. In short, for example, a black pigment means a pigment in which the color represented by black when the photosensitive coloring composition is formed by using the pigment alone as a coloring material.

Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. In addition, &quot; C. I. Pigment Red 2 &quot; and the like mean color index (C. I.).

As the red pigment,

Among them, preferably CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably CI Pigment Red 177, 209, 224, 254 . Further, it is preferable to use CI Pigment Red 177, 254, and 272 from the viewpoints of dispersibility and light shielding property. When the photosensitive coloring composition of the present invention is cured with ultraviolet rays, a red pigment having a low ultraviolet absorption rate , And from this viewpoint, it is more preferable to use CI Pigment Red 254, 272.

As the blue pigment,

Among them, preferred are CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and more preferably CI Pigment Blue 15: 6. Further, it is preferable to use CI Pigment Blue 15: 6, 16, 60 from the viewpoints of dispersibility and light shielding. When the photosensitive coloring composition of the present invention is cured with ultraviolet rays, the blue pigment has a low ultraviolet absorption It is preferable to use CI Pigment Blue 60 from this viewpoint.

As the green pigment, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, . Among these, CI Pigment Green 7 and CI 36 are preferably used.

As the yellow pigment,

Of these, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185 are preferable, and CI Pigment Yellow 83, 138, have.

As orange (colorant) pigments,

Among these, CI Pigment Orange 38 and 71 are preferred. Further, it is preferable to use CI Pigment Orange 43, 64, 72 from the viewpoints of dispersibility and light-shielding property, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, , And from this viewpoint, it is more preferable to use CI Pigment Orange 64 or 72. [

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, Among them, CI Pigment Violet 19, 23, and more preferably CI Pigment Violet 23 can be mentioned. Further, it is preferable to use CI Pigment Violet 23 or 29 from the viewpoints of dispersibility and light-shielding property, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a low- It is more preferable to use CI Pigment Violet 29 from this point of view.

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

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

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

Purple: Color Index Pigment Violet 23 or 29

Color: Color Index Pigment Orange 43, 64 or 72

When the pigments of different colors are used in combination, the combination of colors is not particularly limited. From the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment, an orange pigment and a purple pigment And combinations thereof.

In place of the organic colored pigment (A-2), a dye may be used, and in addition to the organic colored pigment (A-2), a dye may be used. Examples of the dyes usable as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dyes include CI Exceed Yellow 11, CI Exed Orange 7, CI Exed Red 37, CI Exed Red 180, CI Exed Blue 29, CI Direct Red 28, CI Direct Yellow 83, CI Direct Yellow 12, CI Direct Yellow 12, 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 Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone dyes include CI BAT BLUE 4, CI EXCEPT BLUE 40, CI EXCEPT BLUE 25, CI REACTIVE BLUE 19, CI REACTIVE BLUE 49, CI Disperse Red 60, CI Disperse Blue 56, CI Disperse Blue 60 and the like.

Examples of the phthalocyanine dyes include CI Pad Blue 5, quinoneimine dyes such as CI Basic Blue 3 and CI Basic Blue 9, quinoline dyes such as CI Solvent Yellow 33, CI Exceed Yellow 3, and CI Disperse Yellow 64, and nitro-based dyes such as CI Exceed Yellow 1, CI Exed Orange 3, and CI Disperse Yellow 42.

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

Examples of the usable coloring materials for preparing the black coloring material include Victoria Pure Blue (42595), Oramin O (41000), Kathilon Brillant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170) , Sopranin OK 70: 100 (50240), Eliogluxin X (42080), No.120 / Rionol Yellow 21090, Rionol Yellow GRO 21090, Simulfast Yellow 8GF 21105, Benzidine Yellow Lionol Blue ES (Pigment Blue), Lionidol Blue TG-L (74160), Lionol Blue SM (26150), 4-T4 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like. (The numbers in parentheses indicate color index (CI)).

It is also possible to express the CI number for the further miscible pigments, for example CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI orange pigment 36, 43, 51, 55, 59, 61, CI red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 15, 15, 4, 22, 60, 64, CI green pigment 7, CI 6,22, 227,228,240, CI violet pigment 19,23,29,30,37,40,50, CI blue pigment 15,15: Brown pigments 23, 25, 26, and the like.

Examples of the black color material which can be used alone include acetylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black and perylene black.

Also, carbon black (A-3) as a coloring material other than the organic black pigment (A-1) is preferably used from the viewpoint of light shading ratio and image characteristics. Examples of the carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation:

Manufactured by Degussa Corporation:

Manufactured by Cabot Corporation:

Columbian Carbons Manufacturing:

Carbon black coated with a resin may be used. The use of carbon black coated with a resin has the effect of improving the adhesion to a glass substrate and the volume resistance value. As the carbon black coated with resin, for example, carbon black described in JP-A-09-71733 can be preferably used.

It is preferable that the total content of Na and Ca is 100 ppm or less as the carbon black to be provided for the coating treatment by the resin. The carbon black may be Na, Ca, K, Mg, Al, Fe, or the like mixed in from raw oil, lead oxide (or gas), reaction stop water, granulated water, Is contained in the order of percent. Among them, Na and Ca are generally contained in several hundreds ppm or more, respectively. However, when they are present in a large amount, they penetrate the transparent electrode (ITO) and other electrodes, which may cause electrical short circuit.

As a method for reducing the content of the ash containing Na and Ca, there is a method of selecting as the raw material oil, fuel oil (or gas), and reaction stop water at the time of producing carbon black as possible, The amount of the alkali substance to be added is adjusted as much as possible. As another method, there is a method in which carbon black submitted from a furnace is washed with water or hydrochloric acid to dissolve Na or Ca.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or aqueous hydrogen peroxide and then a soft solvent is added to the water, the carbon black migrates to the solvent side and is completely separated from water, and most Na Ca is dissolved and removed in water or acid. In order to reduce the total amount of Na and Ca to less than 100 ppm, it may be possible to use a raw material in a carbon black manufacturing process alone or in a water or acid dissolving method alone. However, by using both of these methods, the total amount of Na and Ca To 100 ppm or less.

The resin-coated carbon black is preferably an acidic carbon black having a pH of 6 or less. The dispersion diameter (agglomerate diameter) in water becomes small, so that it becomes possible to cover up to the fine unit. It is also preferable that the particle size is 40 nm or less and the amount of dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. If the particle diameter is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility in the case of using a paste is excellent, but the feeling of concentration of the coating film may not be sufficient. This is because there is a possibility of becoming insufficient.

The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the amount of the carbon black and the resin, the resin is mixed with a solvent such as cyclohexanone, toluene or xylene, A suspension obtained by mixing the resin solution with the carbon black and water is mixed and stirred to separate the carbon black and water, and then the water is removed and heated and kneaded. The obtained composition is formed into a sheet, pulverized and dried Way ; 2. A method of granulating carbon black and resin by mixing and stirring the prepared resin solution and suspension in the same manner as above to separate and heat the obtained granular material to remove residual solvent and water; 3. Carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, and the solvent is removed to obtain a carboxylic acid-impregnated carbon black, How to blend; 4. A suspension containing a reactive group-containing monomer component constituting the resin to be coated and water is stirred at a high speed to prepare a suspension. After polymerization and cooling to obtain a reactive group-containing resin from the polymer suspension, carbon black is added thereto, A method of reacting black with a reactive group (grafting carbon black), cooling, and pulverizing can be adopted.

The type of the resin to be coated is not particularly limited, but a synthetic resin is common and a resin having a benzene nucleus in its structure is more preferable as an amphoteric surfactant, so that it is preferable from the viewpoints of dispersibility and dispersion stability.

Specific examples of the synthetic resin include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, grit resin, epoxy resin and alkylbenzene resin, and thermosetting resins such as polystyrene, polycarbonate, polyethylene terephthalate Examples of the thermoplastic resin composition of the present invention include thermoplastic resins such as polybutylene terephthalate, phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylene sulfone, polyarylate, Resin can be used. The covering amount of the resin with respect to the carbon black is preferably from 1 to 30 mass% based on the total amount of the carbon black and the resin, and if the amount is less than 1 mass%, the same dispersibility and dispersion stability as the untreated carbon black . On the other hand, if it is more than 30% by mass, the adhesion between the resins becomes strong, which results in a dendritic mass, which may prevent dispersion.

Carbon black obtained by coating with a resin in this way can be used as a light shielding material of a black matrix according to a conventional method, and a color filter having the black matrix as a component can be produced by a conventional method. When such carbon black is used, a black matrix having a high light-shielding ratio, a low surface reflectance and a thin film thickness can be achieved at low cost. It is presumed that the dispersibility and the dispersion stability of the carbon black are remarkably improved with respect to the resin or solvent constituting the black matrix liquid. It is also presumed that the coating of the carbon black surface with the resin also acts to block Ca or Na in the carbon black.

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, spinach, and chromium oxide may be used.

A plurality of these pigments may be used in combination. For example, to adjust the chromaticity, a green pigment and a yellow pigment may be used together, or a blue pigment and a purple pigment may be used in combination.

Among these various pigments, CI Pigment Blue 60, CI Pigment Blue 15: 6, CI Pigment Red 177, CI Pigment (A-2) 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 colored pigment is included, it preferably contains at least one kind of the above-mentioned pigments, and more preferably contains two or more kinds.

As the carbon black (A-3), resin-coated carbon black is preferably used in terms of volume resistance and permittivity.

These pigments are preferably dispersed and used so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, 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 pigment particle size measured by dynamic light scattering (DLS). The particle diameter measurement is carried out for a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2 mass%, and if there is a recommended concentration by a measuring instrument, the concentration is dependent on the concentration) .

<(B) Dispersant>

In the photosensitive coloring composition of the present invention, since it is important to finely disperse (A) the coloring material and to stabilize the dispersion state thereof, it is important to ensure the stability of the quality. And a polymer dispersant having a quaternary ammonium salt group as a functional group from the viewpoint of dispersibility of the organic black pigment.

The polymer dispersant may further contain a carboxyl group; Phosphate group; Sulfonic acid group; Or a base thereof; A primary, secondary or tertiary amino group; And a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine. Among them, a primary, secondary or tertiary amino group; A polymer dispersant further having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine or pyrazine is preferable from the viewpoint of dispersing the pigment with a small amount of dispersant when dispersing the pigment.

Among these, from the viewpoints of the dispersibility of the organic black pigment (A-1) and the dispersibility of the organic coloring pigment (A-2) and / or the carbon black (A-3), quaternary ammonium salt groups and tertiary amino groups As a functional group is preferable.

Examples of the polymer dispersing agent include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallyl amine dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, An ester-based dispersant, a polyether phosphoric acid-based dispersant, a polyester phosphoric acid-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified polyester-based dispersant.

Specific examples of such dispersants include, but are not limited to, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BICKEMISA), DIPARON (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (Registered trademark) manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Industry Co., Ltd.) and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).

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

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.

Among them, the dispersant (B) preferably contains a urethane-based polymer dispersant and / or an acrylic polymer dispersant having a functional group in view of adhesion and linearity, and particularly preferably contains an acrylic polymer dispersant.

In view of dispersibility and preservability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of the urethane-based and acrylic-based polymer dispersing agents include DISPERBYK 160 to 166 and 182 series (all-urethane type), DISPERBYK 2000, 2001 and LPN21116 (all acrylic type) (all manufactured by Bigmix).

For example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group And a dispersion resin having a weight average molecular weight of 1,000 to 200,000. By treating them with a quaternizing agent such as benzyl chloride, all or a part of the tertiary amino group can be quaternary ammonium salt group.

Examples of the polyisocyanate compound include p-phenylenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene- Alicyclic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, isophorone diisocyanate, 4,4'- Alicyclic diisocyanates such as methylenebis (cyclohexylisocyanate), omega, omega'-diisocyanate dimethylcyclohexane and the like, aromatic rings such as xylylene diisocyanate, alpha, alpha, alpha ', alpha'- tetramethyl xylylene diisocyanate and the like , Lysine ester triisocyanate, 1,6,11-lane &lt; RTI ID = 0.0 &gt; (Isocyanatophenyl) thiophosphate, and the like can be used. Examples of the polyisocyanate compound include polyisocyanates such as polyisocyanate, polyisocyanate, polyisocyanate, polyisocyanate, polyisocyanate, polyisocyanate, Triisocyanates, trimer thereof, water adducts thereof, and polyol adducts thereof. The polyisocyanate is preferably a trimer of an organic diisocyanate, most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used singly or in combination of two or more.

As a method for producing an isocyanate trimer, there can be mentioned a method of producing a trimer of an isocyanate group by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, The polyisocyanate is subjected to trimerization, quenching is stopped by the addition of a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction or thin-film distillation to obtain an intended isocyanurate group-containing polyisocyanate .

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 glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and compounds in which the terminal hydroxyl groups of these compounds have 1 to 25 , And mixtures of two or more thereof.

Examples of the polyether glycol include polyether diol, polyether ester diol, and mixtures of two or more thereof. Examples of the polyether diol include those obtained by using an alkylene oxide alone or by copolymerization, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, And mixtures of two or more thereof.

Polyetherester diols include those obtained by reacting a mixture with an ether group-containing diol or other glycol with a dicarboxylic acid or anhydride thereof, or by reacting an alkylene oxide with a polyester glycol, for example, poly Oxytetramethylene) adipate, and the like. Polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms is most preferable as the polyether glycol.

Examples of the polyester glycol include dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid and the like) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2 Propylene-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6 Methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5- Aliphatic glycols such as hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, , And bishydroxyethoxybenzene. , N-alkyldialkanolamine such as N-methyldiethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. , Or polylactone diols or polylactone monools obtained by using the diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone, and mixtures of two or more thereof . The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone having an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate diol and poly (3-methyl-1,5-pentylene) carbonate diol. Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, And addition type polyisoprene glycol.

These may be used singly 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 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

Compounds having active hydrogen and tertiary amino groups in the same molecule used in the present invention will be described.

Examples of the hydrogen atom directly bonded to the active hydrogen, that is, the oxygen atom, the nitrogen atom or the sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group. Among them, a hydrogen atom of an amino group, Do.

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

Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl- 1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N , N-dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, , N-dibutyl-1,4-butanediamine, and the like.

Examples of the nitrogen-containing heterocyclic ring when 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 indole ring, a carbazole ring, an indazole ring, A pyridazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an imidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring and a benzothiadiazole ring; , An acridine ring, an isoquinoline ring, and the like. Preferred among these nitrogen-containing heterocyclic rings are imidazole rings or triazole rings.

Specific examples of the compound having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole and 1- (2-aminoethyl) imidazole. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino- 1, 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, -Triazole is preferred.

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

The preferred mixing ratio of the starting materials in the production of the urethane polymer dispersant is 10-200 parts by mass of the compound having a number average molecular weight of 300 to 10,000 and one or two hydroxyl groups in the same molecule per 100 parts by mass of the polyisocyanate compound Preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule in an amount of 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

The production of the urethane-based polymeric dispersant is carried out according to a known method of producing a polyurethane resin. As the solvent in the preparation, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, , Hydrocarbons such as toluene, xylene and hexane, alcohols such as diacetone alcohol, isopropanol, secondary butanol and tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether , Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide, and the like are used. These may be used singly or in combination of two or more.

In the above production, a urethane reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctoate and stannous octoate; iron catalysts such as iron acetylacetonate and ferric chloride; Amines, and tertiary amines such as triethylenediamine. These may be used singly or in combination of two or more.

The introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g as an amine value after the reaction. And more preferably in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing the basic amino group with an acid. When the amine value is lower than the above range, the dispersibility tends to decrease. When the amine value is more than the above range, the developability tends to decrease.

When the isocyanate group remains in the polymer dispersant in the above reaction, further modification of the isocyanate group with an alcohol or an amino compound is preferable because the stability of the product over time is increased.

The weight average molecular weight (Mw) of the urethane type polymeric dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and dispersion stability are inferior. When the molecular weight exceeds 200,000, the solubility is lowered, and when the dispersibility is inferior, it becomes difficult to control the reaction.

Examples of the acrylic polymer dispersant include random copolymers of an unsaturated group-containing monomer having a functional group (the functional group mentioned above as a functional group contained in the polymer dispersant as the functional group described above) and an unsaturated group-containing monomer having no functional group, a graft copolymer, It is preferable to use a block copolymer. These copolymers can be prepared by known methods.

Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- Unsaturated monomers having a carboxyl group such as hydrophthalic acid and dimethacrylic acid, tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternary compounds thereof, unsaturated monomers having a quaternary ammonium salt group As a specific example. These may be used singly 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, isopropyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (Meth) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone , Styrene and its derivatives, N-substituted maleimides such as? -Methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) Rate macro maco Macromonomers such as nomar, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer. These may be used singly or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer comprising an A block having a functional group and a B block having no functional group. In this case, in the A block, in addition to the partial structure derived from an unsaturated group- , And a partial structure derived from an unsaturated group-containing monomer not containing the above-mentioned functional group. These may be contained in the A block in any of the random copolymerization and the block copolymerization. The content of the partial structure not containing a functional group in the A block is usually 80 mass% or less, preferably 50 mass% or less, more preferably 30 mass% or less.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer not containing the above-mentioned functional group. However, one B block may contain a partial structure derived from two or more kinds of monomers. And may be contained in any form of block copolymerization.

The AB or B-A-B block copolymer is prepared, for example, by the living polymerization method shown below.

Examples of the living polymerization method include anion living polymerization method, cationic living polymerization method, and radical living polymerization method. Among them, the anionic living polymerization method is a polymerization activity anion, and is represented by the following scheme, for example.

[Chemical Formula 6]

In the scheme, 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 radical living polymerization method is a polymerization active radical, and is represented by the following scheme, for example.

(7)

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

When this acrylic polymer dispersant is synthesized, it is disclosed in JP-A-9-62002, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. 36, 366 (1987), Higashimura Toshinobu, Mitsuo Sawamoto, Polymer, Journal of Polymer Science, 46, 189 (1989), 17, 977 (1985), 18, 1037 , M. Kuroki, T. Aida, J. Am. Chem. (1987), DY Sogoh, WR Hertler et al., Macromolecules, 20, 1473 (1987), etc. can do.

The acrylic polymer dispersant 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, in particular 5/95 to 60 / 40 (mass ratio). Outside this range, there is a case that good heat resistance and dispersibility can not be combined.

The amount of the quaternary ammonium salt group in 1 g of the AB block copolymer and the BAB block copolymer usable in the present invention is preferably 0.1 to 10 mmol, and if it is outside this range, the heat resistance and dispersibility can be both There is no case.

Such an amino group may be contained in the block copolymer in an amount of usually 1 to 100 mgKOH / g, preferably 10 mgKOH / g or more, more preferably 10 mgKOH / g or more, Preferably not less than 30 mgKOH / g, more preferably not less than 50 mgKOH / g, still more preferably not more than 90 mgKOH / g, even more preferably not more than 80 mgKOH / g, / g.

Here, the amine value of the dispersant such as the block copolymer is represented by the amount of the basic group per 1 g of the solid component excluding the solvent in the dispersant sample and the mass of the equivalent KOH, and is measured by the following method.

0.5 to 1.5 g of the dispersant sample is precisely weighed in a 100 ml beaker and dissolved in 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized with 0.1 mol / l HClO ₄ acetic acid solution. Using the inflection point of the appropriate pH curve as the appropriate end point, the amine value is obtained by the following equation.

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

Wherein W represents a dispersant specimen removal amount (g), V represents an appropriate amount [ml] at an appropriate end point, and S represents a solid content concentration [mass%] of a dispersant sample.

In general, the acid value of the block copolymer is preferably 10 mgKOH / g or less, and the weight average molecular weight (Mw ) Is 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 decrease. When the weight average molecular weight exceeds 100,000, the developability and resolution tend to decrease.

The specific structure of the polymer dispersant having a quaternary ammonium salt group as a functional group is not particularly limited, but from the viewpoint of dispersibility, the polymer dispersant having a quaternary ammonium group as a functional group has a repeating unit represented by the following formula (i) (hereinafter sometimes referred to as " .

[Chemical Formula 8]

In the formula (i), R ³¹ to R ³³ 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 ³¹ to R ³³ Two or more of them may be bonded to each other to form an annular structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter no.

The number of carbon atoms of the alkyl group which may have a substituent in R ³¹ to R ³³ of the formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and 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 and an octyl group. It is preferably a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. It may be either linear or branched. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

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, preferably 16 or less, and 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 and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group, An ethylphenyl group, and 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, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group and a phenylisopropylene group. Of these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenyl Butylene group is preferable, and phenylmethylene group or phenylethylene group is more preferable.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl group or an aralkyl group, specifically, R ³¹ and R ³³ are each independently a methyl group or an ethyl group, and R ³² is phenylmethylene Or a phenylethylene group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

When the polymer dispersant has a tertiary amine as a functional group, it is preferable to have a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as a "repeating unit (ii)") from the viewpoint of dispersibility.

[Chemical Formula 9]

The formula (ii) of, R ³⁵ and R ³⁶ is an aralkyl group which may have an aryl group, or a substituent which may have an alkyl group which may have a hydrogen atom, a substituent, each independently, R ³⁵ and R ³⁶ is They may 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.

Examples of the alkyl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii) include those exemplified as R ³¹ to R ^{33 in the} above formula (i).

Similarly, examples of the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii) include those exemplified as R ³¹ to R ^{33 in the} above formula (i). As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ^{33 in the} above formula (i) can be preferably employed.

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

Examples of the substituent which the alkyl group, aralkyl group or aryl group in R ³¹ to R ^{33 in} the formula (i) and R ³⁵ and R ³⁶ in the formula (ii) may have include a halogen atom, an alkoxy group, a benzoyl group, And the like.

In the formula (i) and (ii), roneun divalent connecting group X and Z, for example having 1 to 10 carbon atoms, alkylene group, arylene group, -CONH-R ⁴³ having a carbon number of 6 to 12-group, -COOR ⁴⁴ - group (provided that R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], and preferably -COO-R ⁴⁴ - is the period.

In the above formula (i), Y ^{- of the} counteranion may be Cl ^- , Br ^- , I ^- , 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, but from the viewpoint of dispersibility, the content of the repeating unit represented by the above formula (i) and the content ratio of the repeating unit represented by the above formula (ii) Is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and still more preferably 5 mol% More preferably 10 mol% or more, still more preferably 20 mol% or more, particularly preferably 30 mol% or more.

The content ratio of the repeating unit represented by the above formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 More preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, particularly preferably 15 mol% or less.

The content ratio of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 15 , More preferably 20 mol% or more, particularly preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and most preferably 25 mol% desirable.

The polymer dispersant may be referred to as a "recurring unit (iii)" hereinafter referred to as "recurring unit (iii)" from the viewpoint of enhancing compatibility with a binder component such as a solvent and improving dispersion stability ).

[Chemical formula 10]

In the formula (iii), R ⁴⁰ is an ethylene group or a propylene 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 of 1 to 20;

The number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ of the formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 10 or less, and 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 and an octyl group. It is preferably a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. It may be either linear or branched. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The n in the formula (iii) is preferably 1 or more, more preferably 2 or more, further preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersion with respect to the binder component such as a solvent Do.

The content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and more preferably 4 mol% , More preferably 30 mol% or less, more preferably 20 mol% or less, and most preferably 10 mol% or less. When the amount is within the above range, compatibility with the binder component such as a solvent tends to be compatible with dispersion stability.

The polymer dispersant is preferably a repeating unit represented by the following formula (iv) (hereinafter referred to as a "repeating unit (iv)") in view of improving compatibility with a binder component such as a solvent of a dispersant and improving dispersion stability ).

(11)

In the 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 formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and is preferably 10 or less , And 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 and an octyl group. It is preferably a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. It may be either linear or branched. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ of the formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, desirable. 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 and an anthracenyl group. Of these, a phenyl group, a methylphenyl group, an ethylphenyl group, An ethylphenyl group, and 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 formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, desirable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group and a phenylisopropylene group. Of these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenyl Butylene group is preferable, and phenylmethylene group or phenylethylene group is more preferable.

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

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

The content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 mol% or more from the viewpoint of dispersibility , More preferably 80 mol% or less, and more preferably 70 mol% or less.

The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii) and the repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic acid salt monomers such as (meth) acrylic acid chloride; (Meth) acrylamide, N-methylol acrylamide, and other (meth) acrylamide monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloylmorpholine.

The polymer dispersant is preferably a block copolymer having an A block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and a repeating unit (ii) Is preferably a copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing a quaternary ammonium group as well as a tertiary amino group in the A block, the dispersing ability of the dispersing agent tends to remarkably improve remarkably. It is more preferable that the B block has the repeating unit (iii), and the B block has the repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. The repeating unit (i) and the repeating unit (ii) may contain two or more kinds of repeating units in each of the A blocks. In this case, the repeating units may be either random copolymerization or block copolymerization .

The repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block. Examples of the repeating unit include repeating units derived from the above-mentioned (meth) acrylate monomer . The content of the repeating units other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol% Most preferably not contained.

The repeating units other than the repeating units (iii) and (iv) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and? -Methylstyrene; (Meth) acrylic acid salt monomers such as (meth) acrylic acid chloride; (Meth) acrylamide, N-methylol acrylamide, and other (meth) acrylamide monomers; Vinyl acetate; Acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; And repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol% Most preferably not contained.

From the viewpoint of improving the dispersion stability, the dispersant (B) is preferably used in combination with the pigment derivative described later.

&Lt; (C) Alkali-soluble resin &gt;

The alkali-soluble resin (C) 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, a carboxyl group-containing epoxy resin, A novolak resin, a polyvinyl phenol resin, and the like. Of these, an epoxy (meth) acrylate resin and an acrylic resin are preferable. These may be used singly or in combination of plural kinds.

As the alkali-soluble resin to be used in the present invention, an excellent alkali-soluble resin (c1) and / or an alkali-soluble resin (c2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth) acrylate resin" It is preferably used from the viewpoint of surname.

&Lt; Alkali-soluble resin (c1) &gt;

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting the polybasic acid and / or an anhydride thereof.

&Lt; Alkali-soluble resin (c2) &gt;

An alkali-soluble resin obtained by adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and further reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.

As the raw material epoxy resin, for example, a bisphenol A type epoxy resin (for example, &quot; Epicote (registered trademark, the same applies hereinafter) 828 &quot;, &quot; Epicote 1001 &quot;, &quot; Epicote 1004 "), epoxy obtained by 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, EP-4001 &quot;, &quot; EP-4002 &quot;, &quot; EP-4004 &quot;, etc.), bisphenol F type resins (for example, "Epikote 807" NER-7406 &quot; (epoxy equivalent: 350, softening point: 66 占 폚) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (For example, Quot; EP-152 &quot;, &quot; EP-154 &quot;, manufactured by Mitsubishi Chemical Corporation), &quot; Cresol novolak type epoxy resin (for example, &quot; EOCN (registered trademark, hereinafter the same) -102S &quot;, manufactured by Nippon Kayaku Co., (For example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenol methane type epoxy resin (for example, "EOCN-1020" (Registered trademark, hereinafter the same) -501, EPN-502 and EPPN-503 manufactured by Kusa Co., Ltd.), alicyclic epoxy resin ("Celloxide 2021P" manufactured by Daicel Chemical Industries, (Registered trademark, hereinafter the same) EHPE), an epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (for example, DIC EXA-7200 manufactured by Nippon Kayaku Co., Ltd., "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) and epoxy resins represented by the following general formulas (C1) to (C4). Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (C2) As the epoxy resin represented by the formula (C4), "ESF-300" manufactured by Shin-Nittsu Chemical Co., Ltd. and the like can be mentioned.

[Chemical Formula 12]

In the general formula (C1), a represents an average value and represents a number of 0 to 10. R ¹¹¹ represents 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. A plurality of R &lt; ¹¹¹ &gt; s present in one molecule may be the same or different.

[Chemical Formula 13]

In the 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, a plurality of R ^{121 s} present in one molecule may be the same or different.

[Chemical Formula 14]

In the general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). However, it includes at least one adamantane structure in the molecular structure. and c represents an integer of 2 or 3.

[Chemical Formula 15]

In the general formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group, a hydrogen atom, An alkyl group having 1 to 12 carbon atoms, or a phenyl group which may have a substituent. * Indicates a combined hand.

[Chemical Formula 16]

In the 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.

Among these, it is preferable to use an epoxy resin represented by any one of the general formulas (C1) to (C4).

Examples of the?,? - unsaturated monocarboxylic acid ester having an?,? -unsaturated monocarboxylic acid or a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl succinic acid, (Meth) acryloyloxypropyl succinic acid, 2 (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxy (Meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid with? -Caprolactone,? -Propiolactone,? -Butyrolactone (anhydrous) phthalic acid, (anhydrous) methacrylic acid, and (meth) acrylic acid are added to monomers which are obtained by adding lactones such as δ-valerolactone, Monomers having an acid (anhydride) added thereto such as maleic acid, and (meth) acrylic acid dimer.

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

As a method for adding an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin, a known technique may be used. For example, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst . Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride Etc. may be used.

Further, the epoxy resin, the?,? -Unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group, and the esterification catalyst may all be used singly or in combination of two or more do.

The amount of the?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, more preferably 0.7 To 1.1 equivalents. If the amount of the?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or carboxyl group is too small, the amount of the unsaturated group introduced is insufficient, and the subsequent reaction with the polybasic acid and / or its anhydride becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, if the amount is large, the?,? - unsaturated monocarboxylic acid or the?,? - unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, the curing properties tend to deteriorate.

Examples of the polybasic acid and / or anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, Hydrofluoric acid, chlorophthalic acid, hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof, and the like.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrous tetrahydrophthalic acid, or biphenyltetracarboxylic acid dianhydride.

The addition reaction of a polybasic acid and / or an anhydride thereof can be carried out by a known method, and an addition reaction of an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group to an epoxy resin and Under the same conditions, the target product can be obtained by continuous reaction. The addition amount of the polybasic acid and / or the anhydride component thereof is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g. &lt; / RTI &gt; When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, the alkaline developability tends to become insufficient. When the acid value exceeds the above range, the curing performance tends to be inferior.

In addition, polyfunctional alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol may be added during the addition reaction of the polybasic acid and / or anhydride thereof to introduce a multibranched structure.

The carboxyl group-containing epoxy (meth) acrylate resin is usually prepared by mixing a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or carboxyl group with a polybasic acid and / Or after mixing a reaction product of an epoxy resin and an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group with a polybasic acid and / or an anhydride thereof and a polyfunctional alcohol, . In this case, the mixing order of the polybasic acid and / or the anhydride thereof and the polyfunctional alcohol is not particularly limited. By heating, polybasic acid and / or polybasic acid can be added to any hydroxyl groups present in a mixture of an epoxy resin and a reaction product of an?,? - unsaturated monocarboxylic acid ester having an?,? - unsaturated monocarboxylic acid or a carboxyl group and a polyfunctional alcohol The anhydride is additionally reacted.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 1,500 or more and usually 10000 or less, 8000 or less, and more preferably 6000 or less. When the weight average molecular weight is small, solubility in a developer is high, and when it is too large, solubility in a developer is low.

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

In the alkali-soluble resin (C) used in the present invention, a part of the above-mentioned carboxyl group-containing epoxy (meth) acrylate resin may be substituted with another binder resin so long as the performance of the present invention is not impaired. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (C) is preferably 50% by mass or more, particularly preferably 80% by mass or more.

As long as the performance of the present invention is not impaired, the other binder resin that can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin is not limited, and may be selected from the resins usually used in the photosensitive coloring composition. For example, binder resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290 and the like can be given.

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

&Lt; (D) Photopolymerization initiator &gt;

(D) The photopolymerization initiator is a component having a function of absorbing light directly to generate a decomposition reaction or a hydrogen withdrawing reaction to generate a polymerization activity radical. If necessary, additives such as polymerization accelerators (chain transfer agents), sensitizing dyes and the like may be added and used.

Examples of the photopolymerization initiator include metallocene compounds containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; Hexaarylbimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl- , N-aryl-? -Amino acid esters and? -Aminoalkylphenone derivatives; Oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, and the like.

Specifically, examples of the titanocene derivative include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6- 1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoropheny-1-yl), dicyclopentadienyl titanium bis (2,4,6- 1-yl), dicyclopentadienyltitanium di (2,6-difluoropheny-1-yl), dicyclopentadienyltitanium di (2,4-difluorophenyl- (Methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di (methylcyclopentadienyl) titanium bis 1-yl), and dicyclopentadienyl titanium [2,6-di-fluoro-3- (pyrro-1-yl) -pheny-1-yl].

Examples of nonimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5- (2'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- Imidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ Vinylidene] -1,3,4-oxadiazole, 2-trichloromethyl-5- [beta - (2 '- (6 "-benzofuryl) 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, and the like.

Examples of halomethyl-s-triazine derived products include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) 4,6-bis (trichloromethyl) -s-triazine, and the like.

Examples of the? -Aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylamino Diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexane Diethylamino-3- (4-diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone.

As the photopolymerization initiator, oxime derivatives (oxime and ketoxime compounds) are particularly effective in view of sensitivity and formability, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, it is disadvantageous in view of sensitivity Oxime derivatives (oxime esters and ketoxime esters) having excellent sensitivity are particularly useful.

Examples of the oxime-based compound include a compound containing a structural moiety represented by the following general formula (3), and an oxime ester-based compound represented by the following general formula (3a).

[Chemical Formula 17]

In the formula (3), R ²² may be substituted or an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, An aryloxy group having 7 to 20 carbon atoms, a heteroaryloxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

[Chemical Formula 18]

In 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, an alkoxycar with 3 to 20 carbon atoms, A phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxy group having 7 to 20 carbon atoms, A carbonyl group, or a cycloalkylalkyl group having 1 to 10 carbon atoms. R ^21b represents an arbitrary substituent including an aromatic ring or a hetero ring.

R ^21a may form a ring together with R ^21b . The linking group may be an alkylene group, a polyethylene group (- (CH = CH) _r -), a polyethynylene group - (C? C) _r -), or a group formed by combining these groups (and r is an integer of 0 to 3).

In formula (3a), R ^22a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms An alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, An arylthio group having 7 to 20 carbon atoms, a heteroarylthio group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

R ^{22 in} general formula (3) and R ^22a in general formula (3a) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a heteroarylalkanoyl group having 3 to 20 carbon atoms, And a cycloalkanoyl group having 1 to 8 carbon atoms.

The R ^21a in the general formula (3a) is preferably an unsubstituted methyl group, an ethyl group, a propyl group or a propyl group substituted with an N-acetyl-N-acetoxyamino group.

Examples of R ^21b in the general formula (3a) include a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, and a phenylsulfide group which may be substituted.

Examples of the substituent in the general formulas (3) and (3a) include an alkyl group, an aryl group, a heterocyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group and an amide group.

Specific examples of the oxime ester compound to be used in the present invention include the compounds exemplified below, but are not limited to these compounds at all.

[Chemical Formula 19]

[Chemical Formula 20]

Oxime ester initiation system having a carbazole group having a nitro group is also effective.

Examples of the ketoxime compound include a compound containing a structural moiety represented by the following general formula (4), and an oxime ester-based compound represented by the following general formula (5).

[Chemical Formula 21]

In the general formula (4), R ²⁴ has the same meaning as R ²² in the general formula (3).

[Chemical Formula 22]

In the general formula (5), R ^23a represents an optionally substituted phenyl group, 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, an alkoxy group having 3 to 20 carbon atoms A carbonylalkyl group, a phenoxycarbonylalkyl group having a carbon number of 8 to 20, an alkylthioalkyl group having a carbon number of 2 to 20, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having a carbon number of 1 to 20, an aminoalkyl group having a carbon number of 1 to 20, An alkenyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an arylthio group having 7 to 20 carbon atoms, a heteroarylmono group having 1 to 20 carbon atoms, An alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms.

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

R ^23a may form a ring together with R ^23b . The linking group may be an alkylene group, a polyethylene group (- (CH = CH) _r -) having 1 to 10 carbon atoms which may have a substituent, (- (C≡C) _r -), or a group formed by combining these groups (and r is an integer of 0 to 3).

In the general formula (5), R ^24a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms , A heteroaryloxy group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

Wherein in the formula (4) R ²⁴ and the roneun formula R ^24a according to (5), preferably a heteroaryl alkanoyl group, having a carbon number of 3 having a carbon number of 2 - 12 alkanoyl groups, having from 1 to 20 A cycloalkanoyl group having 8 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.

As R ^23a in the general formula (5), an ethyl group or a propyl group preferably substituted with an unsubstituted ethyl group, propyl group, butyl group, or methoxycarbonyl group can be exemplified.

Examples of R ^23b in the general formula (5) include a substituted or unsubstituted carbazoyl group or an optionally substituted phenylsulfide group.

Examples of the substituent in the general formulas (4) and (5) include an alkyl group, an aryl group, a heterocyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group and an amide group.

Specific examples of the ketoxime ester compound preferred for the present invention include the compounds exemplified below, but are not limited to these compounds at all.

(23)

&Lt; EMI ID =

These oxime and ketoxime ester compounds are known compounds themselves and are a kind of a series of compounds described, for example, in JP-A-2000-80068 and JP-A-2006-36750. In the present invention, it is preferable that the photopolymerization initiator (D) is an oxime ester initiator and / or a ketoxime ester initiator.

These photopolymerization initiators 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 generally 0.4 to 15 mass%, preferably 0.5 to 10 mass%, based on the total solid content. When the proportion of the photo-polymerization initiator is excessively larger than this range, the developability tends to decrease. On the other hand, when the proportion is too small, the shape and step of the desired colored cured product may not be formed.

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; Anthraquinone derivatives such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; Hydroxy-2-methylphenylacetophenone, 1-hydroxy-2-methylphenyl acetophenone, 1-hydroxycyclohexyl phenyl ketone, Ethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) , And 1,1,1-trichloromethyl- (p-butylphenyl) ketone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di Thioxanthone derivatives such as isopropyl thioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; And anthrone derivatives such as benzanthrone.

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

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

(25)

Here, R ^23a and R ^24a have the same meanings as in the 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. A - R a hydrogen atom of the substituent represented by ^25c is, and may be further substituted with a halogen atom, the alkylene portion of the substituent represented by R ^25c is -O-, -S-, -COO-, -OCO- or -NR ^25d Or may be interrupted one to five 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 have a branched side chain, or may be cyclopentyl or cyclohexyl.

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;

(26)

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 arylene group having 6 to 30 carbon atoms, or an arylenealkylene group having 7 to 30 carbon atoms.

The alkylene moiety of the substituent represented by R ^26b may be interrupted one to five times by -O-, -S-, -COO- or -OCO-. The alkylene moiety of the substituent represented by R ^26b may have a branch side chain or may be cyclohexylene.

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

* Indicates a combined hand.

One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The photopolymerization initiator may be compounded with a sensitizing dye and a polymerization promoter depending on the wavelength of the image exposure light source for the purpose of increasing the sensitivity of sensitivity as needed. Examples of the sensitizing dye include xanthene dye described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335 A coumarin dye having the heterocycle described above, a 3-ketocoumarin compound described in JP-A Nos. 3-239703 and 5-289335, a pyrromethene dye described in JP-A No. 6-19240 JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 Japanese Patent Application Laid-Open No. 58-15503, Japanese Laid-Open Patent Publication No. 60-88005, Japanese Laid-Open Patent Application No. 59-56403, Japanese Laid-Open Patent Application No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088 JP-A-5-107761, JP-A-5-210240, JP-A- A dye having a dialkylaminobenzene skeleton described in JP-A No. 4-288818, and the like.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, Benzophenone compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; Benzooxazole, 2- (p-dimethylaminophenyl) benzooxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 2- Sol, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis Diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p- dimethylaminophenyl) quinoline, (P-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, and other p-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

The sensitizing dyes may also be used singly or in combination of two or more species.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, mercapto compounds described later, and the like do. The polymerization promoters may be used singly or in combination of two or more kinds.

&Lt; Photopolymerizable monomer &gt;

In the photosensitive coloring composition of the present invention, it is preferable to further include a photopolymerizable monomer (photopolymerizable compound) from the viewpoint of sensitivity and the like.

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

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

Examples of such polyfunctional ethylenic monomers include, for example, esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; An ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; Aliphatic polyhydroxy compounds, and aromatic polyhydroxy compounds, and esters obtained by esterification reaction of an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, Examples of the aliphatic polyhydroxy compound such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate include acrylic acid Esters, methacrylic acid esters obtained by changing the acrylate of these exemplified compounds to methacrylate, itaconic acid esters similarly modified with itaconate, maleic acid esters modified with crotonate, maleic acid esters modified with maleic acid Back There.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include aromatic polyesters such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinodiacrylate, resorcine dimethacrylate and pyrogallol triacrylate; Acrylic acid esters and methacrylic acid esters of hydroxy compounds, and the like.

The ester obtained by the esterification reaction of the polybasic carboxylic acid and the unsaturated carboxylic acid with the polyhydric hydroxy compound is not necessarily a single substance. Representative examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol, acrylic acid, maleic acid , Condensates of diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.

Examples of the polyfunctional ethylenic monomer used in the present invention include urethane (meth) acrylate obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylic acid ester or polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) Acrylates; Epoxy acrylates such as polyaddition epoxy compounds and addition reactants of hydroxy (meth) acrylate or (meth) acrylic acid; Acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; And vinyl group-containing compounds such as divinyl phthalate.

U-2PPA, U-6LPA, U-6LPA, and U-6LPA are examples of the urethane (meth) acrylates. UA-510H, UF-8001G (manufactured by Kyowa Chemical Industry Co., Ltd.), UV-1700B, UA- UV-7600B, UV-7605B, UV-7630B and UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

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

&Lt; Other compounding components of photosensitive coloring composition &gt;

The photosensitive coloring composition of the present invention may suitably contain, in addition to the components described above, adhesion improvers such as organic solvents and silane coupling agents, coating improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants and pigment derivatives .

(1) Organic solvents

The photosensitive coloring composition of the present invention is a photosensitive coloring composition which is usually prepared by mixing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, It is used in a state dissolved or dispersed in a solvent.

As the organic solvent, it is preferable to select one having a boiling point in the range of 100 to 300 占 폚. And more preferably a solvent having a boiling point of 120 to 280 ° C.

Such organic solvents include, for example, the following.

Ethylene glycol monoethyl 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- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether ;

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, propylene glycol monobutyl ether But are not limited to, 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 mono Glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate and 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate and 1,6-hexanediol acetate;

Alkyl acetates such as cyclohexanol acetate;

Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether;

Examples of the solvent include acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, Ketones such as ketone, methyl nonyl ketone, methoxymethyl pentanone;

But are not limited to, monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, Ryu;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane;

Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene and cumene;

Ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, methyl isobutyrate, ethyl isobutyrate, ethyl propionate, propyl propionate, isobutyl butyrate, methyl isobutyrate, Ethyl propionate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Chain or cyclic esters such as butyl methoxypropionate and? -Butyrolactone;

Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

Halogenated hydrocarbons such as butyl chloride and amyl chloride;

Ether ketones such as methoxymethylpentanone;

Nitriles such as acetonitrile, benzonitrile, and the like.

Examples of commercially available solvents include Mineral Spray, Barthol # 2, Acco # 18 Solvent, Afucosiner, SoCal Solvent No.1 and No.2, Solvesso # 150, Shell TS28 Solvent, Carbitol, Ethylcellosolve acetate, methylcellosolve acetate, diglyme (all trade names), and the like may be used as the carrier. The term &quot; cellosolve &quot; .

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

When a pixel or a black matrix of a color filter is formed by a photolithography method, the organic solvent is selected to have a boiling point in the range of 100 to 200 DEG C (under the pressure of 1013.25 [hPa], all the same with respect to the boiling point) . More preferably a boiling point of 120 to 170 占 폚.

Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Especially preferred as the organic solvent to be used in combination are glycol monoalkyl ethers. Among them, propylene glycol monomethyl ether is particularly preferable from the solubility of the constituent components in the composition. The glycol monoalkyl ether has a high polarity. When the amount of the glycol monoalkyl ether to be added is too large, the pigment tends to aggregate, and the storage stability tends to be lowered, for example, the viscosity of the resulting colored resin composition tends to be lowered. Is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150 캜 or more (hereinafter sometimes referred to as a &quot; high boiling point solvent &quot;). When such a high boiling point solvent is used in combination, the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being broken by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of high effect.

The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. If the amount of the high-boiling point solvent is too small, for example, the coloring material precipitates and solidifies at the tip of the slit nozzle to cause foreign matter defects. If the amount is too large, the drying temperature of the composition is slowed, It may cause problems such as tack in the reduced-pressure drying process and pin marks on the pre-baking.

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. In this case, a high boiling point solvent having a boiling point of 150 ° C or more may not be separately contained.

As preferred high boiling point solvents, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate , 1,6-hexanediol diacetate, triacetin, and the like.

(2) Adhesion improving agent

The photosensitive coloring composition of the present invention may contain an adhesion-improving agent for improving the adhesion with the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.

Examples of the silane coupling agent include various epoxy compounds, (meth) acrylic compounds, amino compounds, and the like, or a mixture of two or more thereof.

As preferred silane coupling agents there may be mentioned, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Epoxy silanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, 3-ureidopropyl Ureido silanes such as triethoxy silane, and isocyanate silanes such as 3-isocyanate propyl triethoxy silane. Particularly preferred are silane coupling agents of epoxysilanes.

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

(27)

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

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

(3) Surfactants

The photosensitive coloring composition of the present invention may contain a surfactant for improving the coatability.

As the surfactant, various kinds of surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant in view of a low possibility of adversely affecting the properties, and in particular, a fluorine-based or silicone-based surfactant is effective in terms of application.

Examples of such a surfactant include TSF4460 (manufactured by Zitoshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325 and BYK- (Manufactured by DIC), SH7PA (manufactured by Toray Silicone Co., Ltd.), DS-401 (manufactured by DICKINSU), and L-77 (manufactured by Nippon Unicar Co., Ltd.), F-470, F-475, F- , FC4430 (manufactured by Sumitomo 3M Co., Ltd.), and the like.

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

(4) Pigment derivatives

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

Examples of the pigment derivative include azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, quinophthalone pigments, isoindolinone pigments, dioxazine pigments, anthraquinone pigments, indanthrene pigments, perylene pigments, perinone pigments, A thiophene, a thiophene, a thiophene, a thiophene, a thiophene, a thiophene, and a thiophene.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group and the like directly to the pigment skeleton or an alkyl group, an aryl group, , And preferably a sulfonic acid group. These substituents may be substituted by plural substituents on one pigment skeleton.

Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfonic acid derivative . These may be used singly or in combination of two or more.

(5)

The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and by the action of an acid generated upon exposure, a cross-linking agent such as a melamine compound is allowed to advance the cross-linking reaction. Of these photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a photosensitive coloring composition, are preferred, and examples thereof include diphenyl iodonium, ditolyl iodonium, phenyl (p- anisyl) iodonium Iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p Diaryl iodonium such as iodonium iodide, p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium, such as triphenylsulfonium chloride, bromide, or boronate, hexafluorophosphate salt (Pentafluorophenyl) borate salts and the like, sulfonium organic boron complexes such as diphenylphenazylsulfonium (n-butyl) triphenylborate and the like, or 2-fluorobenzenesulfonium salts such as 2 - methyl-4,6-bist trichloromethyl triazine, And triazine compounds such as 2- (4-methoxyphenyl) -4,6-bistricloromethyltriazine, but are not limited thereto.

(6) Crosslinking agent

In the photosensitive coloring composition of the present invention, a crosslinking agent may be further added, and for example, a melamine or guanamine-based compound may be used. Examples of the crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (6).

(28)

In the formula (6), R ⁶¹ represents an -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ represents -NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ and one of R ^67, and R ⁶¹ in this case, an aryl group having 6 to 12, R ^62, R ^63, either R ⁶⁴ and R ⁶⁵ represents a group _{^{-CH 2 OR 68, R 62,}} R 63, R 64, R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or a -CH ₂ OR ⁶⁸ group, wherein 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 the phenyl group or the naphthyl group may have a substituent such as an alkyl group, an alkoxy group or a halogen atom. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, particularly a methyl group.

Examples of the melamine compound corresponding to the general formula (6), that is, the compound represented by the general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl Melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.

[Chemical Formula 29]

When one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ in the formula (6-1) is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is -CH ₂ OR ^And the remaining of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a -CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or an alkyl group.

In addition, a guanamine compound corresponding to the formula (6), that is, a compound wherein R ⁶¹ in the formula (6) is aryl includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo Guanamine, tetraethoxymethylbenzoguanamine, and the like.

A crosslinking agent having a methylol group or a methylol alkyl ether group may also be used. An example is given below.

(Hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl- -1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis (hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (also known as dimethyloluron) or a dimethyl ether thereof, tetramethylolglyoxaldiurene or tetramethyl ether thereof.

These crosslinking agents may be used singly or in combination of two or more kinds. The amount when the crosslinking agent is 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 compound

A mercapto compound may also be added as a polymerization promoter and in order to improve adhesion to a substrate.

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol Butadiene bis-thioglycolate, trimethylolpropane tris-thioglycolate, trimethylolpropane tris-thiopropionate, trimethylolpropane tristy- thioglycolate, , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tris thiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyl (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tri (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutylate), butanediol bis (3-mercaptoisobutyl Triethylolpropane tris (3-mercaptoisobutylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 1H, 3H, 5H) -trione, and the like, and the like. These may be used alone or in combination of two or more.

&Lt; Amount of component in photosensitive coloring composition &gt;

In the photosensitive coloring composition of the present invention, the content of the colorant (A) is usually 10% by mass or more, preferably 20% by mass or more, and usually 50% by mass or less based on the total solid content in the photosensitive coloring composition. If the content of the coloring material (A) is too small, a sufficient optical density (OD) may not be obtained. On the other hand, if the content of the coloring material (A) is too large, sufficient image forming properties may not be obtained. The content ratio of (A-1) the organic black pigment to (A) 100 mass% of the coloring material is usually 10 mass% or more, preferably 30 mass% or more, and usually 100 mass% or less. If the content of the organic black pigment (A-1) in the coloring material (A) is too small, a sufficient optical density (OD) may not be obtained.

In the photosensitive coloring composition of the present invention, the (A-1) organic black pigment and the (A-2) organic colored pigment may be contained in the (A) At this time, the content of the organic black pigment (A-1) relative to 100 mass% of the (A) coloring material is usually 10 mass% or more, preferably 20 mass% or more, more preferably 30 mass% % Or less, preferably 80 mass% or less, and more preferably 60 mass% or less. The content ratio of (A-2) the organic colored pigment is usually 10 mass% or more, preferably 20 mass% or more, more preferably 40 mass% or more, and usually 90 mass% or less, preferably 80 mass % Or less, more preferably 70 mass% or less. (A-2) If the content of the organic colored pigment is too large, a sufficient optical density may not be obtained. The content ratio of (A-1) the organic black pigment to 100 parts by mass of the organic colored pigment (A-2) is usually not less than 15 parts by mass, preferably not less than 20 parts by mass, and usually not more than 900 parts by mass, 800 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 200 parts by mass or less.

The photosensitive coloring composition of the present invention may contain (A-3) carbon black together with the organic black pigment (A-1) in the colorant (A) The content of the organic black pigment (A-1) relative to 100 mass% of the (A) coloring material is usually 50 mass% or more, preferably 60 mass% or more, and usually 95 mass% or less, preferably 90 mass% Or less. The content ratio of (A-3) carbon black is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less. (A-3) If the content of carbon black is too large, the volume resistivity may decrease or the relative dielectric constant may increase. The content ratio of (A-1) the organic black pigment to 100 parts by mass of (A-3) carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more and usually 2000 parts by mass or less, Parts by mass or less.

The photosensitive coloring composition of the present invention may contain (A-2) an organic colored pigment and (A-3) carbon black together with the (A-1) organic black pigment in the colorant (A). The content of the organic black pigment (A-1) relative to 100 mass% of the (A) coloring material is usually 10 mass% or more, preferably 20 mass% or more, and usually 80 mass% or less, preferably 70 mass% Or less. The content ratio of (A-2) the organic colored pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less. The content ratio of (A-3) carbon black is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less. In this case, the content ratio of (A-1) the organic black pigment to 100 parts by mass of the organic colored pigment (A-2) is usually not less than 15 parts by mass, preferably not less than 20 parts by mass, usually not more than 800 parts by mass, Is not more than 700 parts by mass. The content ratio of the organic black pigment (A-1) relative to 100 parts by mass of (A-3) carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more and usually 1000 parts by mass or less, Parts by mass or less.

The content of the dispersant (B) 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% , And particularly preferably 15 mass% or less. The content of the dispersant (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and usually 50% by mass or less, particularly preferably 30% by mass or less, based on 100% by mass of the colorant (A). If the content of the dispersant (B) is too small, sufficient dispersibility may not be obtained. If the content of the dispersant is too large, the proportion of other components may be decreased, and the plate formability may be deteriorated.

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

The content of the (D) photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and usually 15% by mass or less based on the total solid content of the photosensitive coloring composition of the present invention , Preferably not more than 10 mass%. If the content of the photopolymerization initiator (D) is too small, the sensitivity may be lowered. On the contrary, if the content is too high, the solubility of the unexposed portion in the developer is lowered.

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

If the compounding ratio of the photopolymerization initiator (D) photopolymerization initiator and the polymerization accelerator is too low, the sensitivity to exposure light may be lowered. On the contrary, if the proportion is too high, The solubility is lowered, which may cause defective development.

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

When a photopolymerizable monomer is used, its content is usually 30 mass% or less, preferably 20 mass% or less, based on the total solid content of the photosensitive coloring composition. If the content of the photopolymerizable monomer is too large, permeation of the developer into the exposed portion increases, and it becomes difficult to obtain a good image in some cases. The lower limit of the content of the photopolymerizable monomer is generally 1% by mass or more, and preferably 5% by mass or more.

When the adhesion improver is used, the content thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass, based on the total solid content in the photosensitive coloring composition. If the content of the adhesion-promoting agent is less than the above-mentioned range, the effect of improving the adhesion can not be sufficiently obtained. If the content is too large, the sensitivity may decrease or the residue may remain after development.

When a surfactant is used, the content thereof is usually from 0.001 to 10% by mass, preferably from 0.005 to 1% by mass, more preferably from 0.01 to 0.5% by mass, and most preferably from 0.005 to 1% by mass based on the total solid content in the photosensitive coloring composition 0.03 to 0.3% by mass. If the content of the surfactant is less than the above range, there is a possibility that the smoothness and uniformity of the coated film can not be exhibited. If the content is too large, the smoothness and uniformity of the coated film can not be exhibited and other properties may deteriorate.

In addition, the photosensitive coloring composition of the present invention is adjusted to have a solid content concentration of usually 5 to 50% by mass, preferably 10 to 30% by mass, using the above-described organic solvent.

&Lt; Physical Properties of Photosensitive Coloring Composition &gt;

The photosensitive coloring composition of the present invention can be preferably used for forming a black matrix. From this viewpoint, it is preferable that the photosensitive coloring composition exhibits black color, and the optical density (OD) per 1 m of the film thickness of the coating film is preferably 1.0 or more.

&Lt; Method for producing photosensitive coloring composition &gt;

The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as &quot; resist &quot;) is prepared by a conventional method.

Usually, the colorant (A) is preferably subjected to dispersion treatment in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant (A) is made into fine particles by the dispersion treatment, the coating property of the resist is improved.

The dispersion treatment is preferably carried out in a system in which a part or all of (A) a colorant, an organic solvent, (B) a dispersant and (C) an alkali-soluble resin are used in combination (hereinafter, And a composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). Particularly, when a polymer dispersant (B) is used as a dispersant, it is preferable to suppress the increase in viscosity of the resulting ink and resist over time (dispersion stability is excellent).

Thus, in the step of producing a resist, it is preferable to prepare a pigment dispersion containing at least (A) a coloring material, an organic solvent, and (B) a dispersing agent. As the coloring material (A), the organic solvent, and the dispersing agent (B) which can be used for the pigment dispersion, those described as being usable in the photosensitive coloring composition can be preferably employed.

Further, when a dispersion containing the entire components to be mixed with the colored resin composition is subjected to dispersion treatment, there is a possibility that the highly reactive component is denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out a dispersion treatment in a system including a polymeric dispersant.

When dispersing the coloring material (A) in a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are usually 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time differs depending on the composition of the liquid and the size of the dispersion treatment apparatus. It is a goal of dispersion to control the gloss of the ink so that the 20-degree mirror surface gloss (JIS Z8741) of the resist is in the range of 50 to 300. If the gloss of the resist is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, and resolution. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment tends to be broken and the dispersion stability tends to be rather deteriorated because many ultrafine particles are produced.

The dispersion particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 占 퐉 and is measured by a dynamic light scattering method or the like.

Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a homogeneous solution. In the process of producing a resist, fine dust is often mixed in a liquid, and therefore, the obtained resist is preferably subjected to filtration treatment with a filter or the like.

[Cured goods]

By curing the photosensitive coloring composition of the present invention, a cured product can be obtained. The cured product obtained by curing the photosensitive coloring 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 with reference to its production method.

(1)

The support for forming the black matrix is not particularly limited as long as it has a suitable strength. A transparent substrate is mainly used. As the material, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate, , Thermosetting resin sheets such as epoxy resin, unsaturated polyester resin and poly (meth) acrylic resin, and various glasses. Of these, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, may be formed on the TFT array.

The support may be subjected to a corona discharge treatment, an ozone treatment, a silane coupling agent, a thin film formation treatment of various resins such as a urethane resin, etc., if necessary, in order to improve surface physical properties such as adhesiveness.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film formation treatment of various resins is carried out, the film thickness is usually in the range of 0.01 to 10 mu m, preferably 0.05 to 5 mu m.

(2) Black Matrix

In order to form the black matrix of the present invention by the above-described photosensitive coloring composition of the present invention, the photosensitive coloring composition of the present invention is applied onto a transparent substrate and dried. Then, a photomask is placed on the photosensitive coloring composition, A black matrix is formed by image exposure, development, and thermosetting or photo-curing, if necessary, through a photomask.

Further, the black matrix of the present invention is effective for forming on the TFT element substrate, but its configuration is not particularly limited in the respective methods of COA and BOA, and various configurations can be dealt with.

(3) Formation of black matrix

(3-1) Application of Photosensitive Coloring Composition

The application of the photosensitive coloring composition for black matrix onto the transparent substrate can be carried out by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like. Among them, the die coating method is preferable from the viewpoint of synthesis, in that the application amount of coating liquid is greatly reduced, and there is no influence of mist or the like attached by the spin coating method and the generation of foreign matter is suppressed.

When the thickness of the coating film is excessively large, pattern development becomes difficult and the gap adjustment in the liquid crystal cell formation step becomes difficult. When the coating thickness is too thin, it is difficult to increase the pigment concentration, and desired color development becomes impossible . The thickness of the coated film is preferably in the range of 0.2 to 10 mu m, more preferably in the range of 0.5 to 6 mu m, and more preferably in the range of 1 to 4 mu m, as the film thickness after drying.

(3-2) Drying of Coating Film

 Drying of the coated film after application of the photosensitive coloring composition 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 generally selected within the range of from 40 to 200 캜 for 15 seconds to 5 minutes, preferably from 50 to 130 캜 for 30 seconds to 50 minutes, depending on the kind of the solvent component and the performance of the dryer to be used. 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, the alkali-soluble resin (C) may be decomposed and thermal polymerization may occur to cause defective development. The drying process of the coated film may be a reduced pressure drying method in which the drying is performed in the decompression chamber without raising the temperature.

(3-3) Exposure

The image exposure is performed by overlapping a negative mask pattern on a coating film of the photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. At this time, if necessary, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed to light, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen. The light source used for the image exposure is not particularly limited. Examples of the light source include a lamp light source such as 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 laser light source such as an excimer laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser. An optical filter may be used when light of a specific wavelength is used for irradiation.

(3-4) phenomenon

The black matrix according to the present invention is a black matrix in which an image is formed on a substrate by applying an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after subjecting the coating film of the photosensitive coloring composition to image exposure by the light source . The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate Mono-di- or triethanolamine, mono- di- or trimethylamine, mono- di- or triethylamine, mono-di- or triethanolamine, mono-di- or triethanolamine, Or organic alkaline compounds such as diisopropylamine, n-butylamine, mono- di- or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline and the like. These alkaline compounds may be a mixture of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters, alkyl Anionic surfactants such as benzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts, amphoteric surfactants such as alkyl betaines and amino acids.

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

The developing conditions are not particularly limited, and the developing temperature is usually in the range of 10 to 50 占 폚, preferably 15 to 45 占 폚, particularly preferably 20 to 40 占 폚. The developing method includes an immersion developing method, a spray developing method, A developing method, an ultrasonic developing method, or the like.

(3-5) Thermal curing treatment

The substrate after development is subjected to a heat curing treatment or a light curing treatment, preferably a heat curing treatment. The heat curing treatment conditions at this time are selected in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.

The line width of the black matrix thus formed is usually from 3 to 50 mu m, preferably from 4 to 30 mu m, and the height is usually from 0.5 to 5 mu m, preferably from 1 to 4 mu m. The volume resistivity is not less than 1 × 10 ¹³ Ω · cm, preferably not less than 1 × 10 ¹⁴ Ω · cm, and the relative dielectric constant is not more than 6, preferably not more than 5, and usually not less than 2.

The optical density (OD) per 1 mu m of 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 a method described later.

[Coloring Spacer]

The photosensitive coloring composition of this embodiment may be used as a resist for a colored spacer in addition to a black matrix. When the spacer is used for a TFT-type LCD, the TFT as a switching element may malfunction due to the light incident on the TFT, and the coloring spacer is used for preventing this. For example, Japanese Unexamined Patent Application Publication No. 8-234212 The spacer is made light-shielding. The coloring spacer can be formed in the same manner as the above-described black matrix except that a mask for a coloring spacer is used.

[Image display device]

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

[Liquid crystal display device]

The liquid crystal display device of the present invention is manufactured by using the black matrix of the present invention described above and is not particularly limited such as the formation order of the color pixel or the black matrix and the formation position thereof.

For example, a black matrix of the present invention is formed on a TFT element substrate, red, green, and blue pixels are formed, and if necessary, an overcoat layer is formed. Then, ITO, IZO And is used as a part of parts such as a color display and a liquid crystal display device. In some applications such as a planar alignment type driving method (IPS mode), a transparent electrode may not be formed.

In a liquid crystal display device, a liquid crystal cell is usually formed by forming an alignment film on a color filter, spraying a spacer on the alignment film, or forming a photo-spacer and then bonding the film to a counter substrate to form a liquid crystal cell, And the liquid crystal is injected into the liquid crystal layer and connected to the counter electrode. As the alignment film, a resin film such as polyimide is preferable. The orientation film is usually formed by a gravure printing method and / or a flexo printing method, and the thickness of the alignment film is several tens nm. After curing treatment of the alignment film by thermo-firing, it is surface-treated by irradiation with ultraviolet rays or treatment with rubbing cloth, and is processed into a surface state in which the inclination of the liquid crystal can be adjusted.

If the black matrix of the present invention is used, the order of formation of the color pixel or the black matrix and the forming position are not particularly limited.

As the spacer, a material having a size corresponding to a gap (gap) with the counter substrate is used, and it is preferable that the spacer is usually 2 to 8 mu m. A photo-spacer PS of a transparent resin film may be formed on the color filter substrate by a photolithography method, and this may be utilized instead of a spacer.

The bonding gap with the counter substrate differs depending on the use of the liquid crystal display, and is usually selected in the range of 2 to 8 mu m. After bonding with the counter substrate, the portion other than the liquid crystal injection hole is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating to seal the periphery of the liquid crystal cell.

The liquid crystal cell sealed in its periphery is cut in panel units and then decompressed in a vacuum chamber. After the liquid crystal injection port is immersed in the liquid crystal, the inside of the chamber is leaked to inject liquid crystal into the liquid crystal cell. The degree of vacuum in the liquid crystal cell is usually 1 × 10 ^-2 to 1 × 10 ^-7 Pa, but preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. It is preferable to warm the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 DEG C, more preferably 50 to 90 DEG C. The heating and holding at the time of the decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is sealed with a UV curable resin which hardens the liquid crystal injection port, thereby completing a liquid crystal display (panel).

There is no particular limitation on the type of the liquid crystal, and conventionally known liquid crystals such as an aromatic system, an aliphatic system, and a polycyclic compound may be used, such as a lyotropic liquid crystal or a thermotropic liquid crystal. Nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known as the thermotropic liquid crystal, but any of them may be used.

[Organic EL display]

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

In the case of manufacturing an organic EL display using the black matrix of the present invention, for example, as shown in Fig. 1, a pattern formed by a colored resin composition (i.e., a pixel 20, And a black matrix (not shown) formed between the adjacent pixels 20) are formed on the color filter, and an organic light emitting element (not shown) is formed on the color filter through the organic protective layer 30 and the inorganic oxide film 40 500) are stacked, the organic EL device 100 can be manufactured. At least one of the pixel 20 and the black matrix is manufactured using the photosensitive coloring composition of the present invention. A method of laminating the organic light emitting element 500 includes a method in which 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 ), A method in which an organic light emitting material 500 formed on a separate substrate is bonded onto the inorganic oxide film 40, and the like. The organic EL device 100 manufactured in this manner can be used to form the organic EL display by the method described in, for example, &quot; Organic EL Display &quot; (OMO, published on Aug. 20, 2004, Shizuo Tokido, Adachi Chihaya, Murata Hideyuki) An organic EL display can be manufactured.

The black matrix of the present invention is also applicable to an organic EL display of passive driving type and an organic EL display of active driving type.

Example

Next, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

The components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

&Lt; (A-1) Organic black pigment &gt;

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

(30)

&Lt; Organic black pigment: perylene black &gt;

Manufactured by BASF, Lumogen (R) Black FK4281

&Lt; Organic black pigment: aniline black &gt;

Paliotol (registered trademark) Black L0080 manufactured by BASF Corporation

<Alkali-soluble resin-I>

And 145 parts by mass of propylene glycol monomethyl ether acetate were stirred while substituting with nitrogen, and the temperature was raised to 120 占 폚. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2'-azobis- 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and further stirring was continued at 90 ° C for 2 hours. Subsequently, 0.7 parts by mass of trisdimethylaminomethylphenol 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 占 폚 for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C for 3.5 hours. The alkali-soluble resin-I thus obtained 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" (weight average molecular weight Mw = 5000 to 6000, acid value = about 60 mg-KOH / g) manufactured by Nippon Kayaku Co.,

<Alkali-soluble resin-III>

(31)

50 g of the epoxy compound having the above structure (epoxy equivalent 247), 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine and 0.05 g of para-methoxyphenol were placed in a flask equipped with a thermometer, And the mixture was reacted at 90 DEG C with stirring until the acid value became 5 mgKOH / g or less. The reaction required 12 hours, and an epoxy acrylate solution was obtained.

, 25 parts by mass of the above epoxy acrylate solution, and 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA) and 2.8 parts by mass of tetrahydrophthalic anhydride (THPA) The mixture was placed in a flask equipped with a cooling tube, and slowly heated to 105 DEG C with stirring to react.

When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a resin having a solid content of 50% by mass. The carboxyl group-containing epoxy resin having an acid value of 131 mgKOH / g and a weight average molecular weight (Mw) of 4000 in terms of polystyrene measured by GPC Acrylate resin (c1).

<Alkali-soluble resin-IV>

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

<Dispersant-I>

DISPERBYK-LPN21116 &quot; (an acrylic block AB block made of A block having a quaternary ammonium salt group and a tertiary amino group in the side chain and a B block having no quaternary ammonium salt group and no amino group, 70 mg KOH / g. Acid value is not more than 1 mgKOH / g.)

The content of the repeating units represented by the following formulas (1a), (2a) and (3a) in the total repeating units of the dispersant-I was 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

(32)

<Dispersant-II>

DISPERBYK-2000 &quot; (an A block having a quaternary ammonium salt group in the side chain and an acrylic A-B block copolymer comprising a B block having no quaternary ammonium salt group)

<Dispersant-III>

EFKA-4300 "(an acrylic polymer dispersant having a tertiary amino group and a butyl group in the side chain and not having a quaternary ammonium salt group in the side chain) manufactured by EFKA.

<Pigment Derivative>

&Quot; Solsperse 12000 &quot; manufactured by Lubrizol Corporation

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxybutanol

&Lt; Photopolymerization initiator-I &gt;

(33)

Compound 1 (0.98 g, 5 mmol) and methylene chloride (17 ml) were added to a 50 ml three-necked flask under a nitrogen atmosphere. After cooling to 3 캜, o-toluoyl chloride (0.77 g, 5 mmol) was added dropwise. In this, 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 methylene chloride (8 ml) was added. Next, anhydrous glutaric acid (0.68 g, 6 mmol) was added over 30 minutes and then 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 added little by little to ice water (400 ml). Sodium chloride (80 g) was added to the aqueous layer and extracted five times with methylene chloride (50 ml). The organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and then the solvent was distilled off using this separator to obtain Compound 2 (2.13 g, crude yield: 100%). This was used in the next reaction without purification.

(34)

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

The organic layer was washed successively with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and then the solvent was distilled off using this separator to obtain Compound 3 (1.72 g, crude yield 78%). This was used in the next reaction without purification.

(35)

Compound 3 (1.00 g, 2.26 mmol) and methylene chloride (10 ml) were placed in a 50 ml three-necked flask under a nitrogen atmosphere and cooled to 10 占 폚. To this was added a 1N solution of hydrogen chloride in diethyl ether (4.68 mL). Next, amyl nitrite (0.36 g, 3.04 mmol) was added and reacted at 10 ° C for 4 hours. Water (10 ml) was added, and the mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and then the solvent was distilled off using this separator to obtain a light yellow solid (0.88 g). This was subjected to recrystallization purification with toluene (3.5 ml) to obtain Compound 4 (0.45 g, yield 42%).

(36)

Compound 4 (3.50 g, 7.44 mmol) and methylene chloride (35 ml) were placed in a 50 ml three-necked flask under a nitrogen atmosphere and cooled to 4 캜. To this was added triethylamine (1.50 g, 14.9 mmol). Then, acetyl chloride (0.70 g, 8.93 mmol) was added, and the reaction was continued for 1 hour. A saturated aqueous solution of sodium hydrogencarbonate (10 ml) was added, and the organic layer was separated. The organic layer was further washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution successively, and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and then the solvent was distilled off using this separator to obtain an oily oily product (3.65 g). This was purified by column chromatography (ethyl acetate / hexane = 1/1) to obtain Compound 5 (3.12 g, yield 82%, photopolymerization initiator-I). The chemical shift of Compound 5 is shown below.

&Lt; Photopolymerization initiator-II &gt;

(37)

&Lt; Photopolymerizable monomer-I &gt;

DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

&Lt; Photopolymerizable monomer-II &gt;

DPHA-40H: urethane acrylate manufactured by Nippon Kayaku Co., Ltd.

<Additive-I>

KAYAMER PM-21 (methacryloyl group-containing phosphate), manufactured by Nippon Kayaku Co.,

<Surfactant-I>

Megapack F-559 manufactured by DIC Corporation

<Preparation of Pigment Dispersions-1 to 7>

The pigments, dispersant, dispersion assisting agent, alkali-soluble resin, and solvent described in Table 1 were mixed in a mass ratio as shown in Table 1. This solution was dispersed by a paint shaker at 25 to 45 캜 for 3 hours. As the beads, zirconia beads of 0.5 mm phi were used and a mass of 2.5 times the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare Pigment Dispersion 1-7.

Here, when the perylene black was dispersed under the same conditions as the pigment dispersion-1, the viscosity of the perylene black increased greatly. Therefore, in order to disperse these pigments, it is necessary to increase the amount of the dispersing agent to a large extent, such as the pigment dispersion-6.

<Coated Carbon Black Dispersion>

Carbon black was produced by a conventional oil furnace method. However, ethylene bottom oil having a small amount of Na, Ca and S was used as the raw material flow path, and coke oven gas was used for combustion. As the reaction stoppage water, pure water treated with an ion exchange resin was used. 540 g of the obtained carbon black was mixed with 14500 g of pure water using a homomixer at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. The slurry was transferred to a container equipped with a screw type stirrer, and 600 g of toluene in which 60 g of an epoxy resin "Epicoat 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in small amounts while mixing at about 1,000 rpm. At about 15 minutes, the carbon black dispersed in the water migrated toward the total amount of toluene and became a granule of about 1 mm.

Subsequently, the water was removed with a 60-mesh wire net, and the resultant was put in a vacuum drier and dried at 70 DEG 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 Bigkema) as a dispersing agent and 4.5 parts by mass of Solsperse 12000 (manufactured by Lubrizol Corporation) as a pigment derivative were added to obtain a solid content concentration of 25% by mass Propylene glycol monomethyl ether acetate (PGMEA) was added.

This was sufficiently stirred by an agitator, and premixing was carried out. Next, dispersion treatment was carried out by a paint shaker for 6 hours in the range of 25 to 45 占 폚. As the beads, zirconia beads of 0.5 mm phi were used and the same mass as the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter.

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

Using the prepared pigment dispersions and coated carbon black dispersions, each component was added so that the ratio of the solid components to the solid components was the mixing ratios shown in Table 2, and PGMEA was further added thereto so as to have a solid content of 17 mass%, followed by stirring and dissolution. To prepare a coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid content was 40 mass%, and in Comparative Example 3, the pigment concentration in the solid content was 30 mass%. In all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer was 3, the photopolymerization initiator was added in an amount of 4 mass% in the solid content, 0.5 mass% And 0.1% by mass of the surfactant. Using the obtained photosensitive coloring composition, evaluation was carried out by the following method.

[Measurement of optical density (OD) per 1 mu m]

The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater to a final film thickness of 2 탆, dried under reduced pressure for 1 minute, and then dried with a hot plate at 100 캜 for 90 seconds. And then heated at 230 占 폚 for 30 minutes to obtain a resist coating substrate (substrate-1). The optical density (OD) of the obtained substrate was measured by a transmission densitometer Gretax Macbeth D200-II, and the film thickness was measured by VertScan (R) 2.0, a noncontact surface / layer cross sectional shape measuring system manufactured by Ryoka Corporation. Table 3 shows the optical density (OD) per 1 mu m of the film thickness.

[Measurement of relative dielectric constant]

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

[Characteristics of plate making]

And dried by a hot plate in the same manner as in the substrate-1. This sample was subjected to image exposure (illuminance: 30 mW / cm 2, exposure dose: 20 mJ / cm 2) through a negative-type mask having a straight line pattern with an opening of 20 μm. At this time, the distance between the sample and the mask was 200 mu m. Thereafter, spraying was carried out at a temperature of 25 캜 using a developer having a KOH concentration of 0.05% by mass. The development time was 1.5 times the dissolution time of the unexposed portion. Table 3 shows the results of line width of the obtained line pattern. However, when the resists of Comparative Examples 1 and 2 were used, no pattern was obtained even when developed 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 colored composition of the present invention had a high OD and a high shielding property when the same pigment concentration was used. In Comparative Examples 1 and 2, no line-shaped pattern was obtained even after developing for 10 minutes. This is because Comparative Examples 1 and 2 contain perylene black as a pigment, but it is necessary to use a large amount of a dispersing agent when dispersing the perylene black, which is considered to have adversely affected plate making characteristics. The larger the value of the line width, the higher the sensitivity, but it was found that the combination of (A-1) the organic black pigment and (A-2) the organic colored pigment can increase the sensitivity without significantly lowering the OD, And 5, respectively.

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

[Evaluation of dispersibility]

<Preparation of Pigment Dispersions-8 to 11>

The pigments, dispersants, dispersion aids, alkali-soluble resins, and solvents described in Table 4 were mixed in the mass ratios shown in Table 4. This solution was dispersed by a paint shaker at 25 to 45 캜 for 3 hours. As the beads, zirconia beads of 0.5 mm phi were used and a mass of 2.5 times the dispersion was added. After dispersion was completed, the beads and the dispersion were separated by a filter to prepare Pigment Dispersion-8 to 11.

[Example 9 and Comparative Examples 5 to 7]

Using the pigment dispersion prepared above, each component was added so that the proportion thereof in the solid content was as shown in Table 5, and PGMEA was further added so as to have a solid content of 17 mass%, followed by stirring and dissolution to prepare a photosensitive coloring composition .

The viscosity of each of the photosensitive coloring compositions thus obtained was measured by an RC80L type viscometer (measuring conditions: 23 ° C, 50 rpm) manufactured by Toray Industries, Inc. The results are shown in Table 5.

In general, in order to disperse an organic pigment in a photosensitive coloring composition, a basic polymer dispersing system having a quaternary ammonium salt group and a basic polymer dispersing system having no quaternary ammonium salt group are treated equivalently and are known to exhibit equivalent dispersibility. Actually, in Comparative Examples 6 and 7 shown in Table 5, the viscosity of the photosensitive coloring composition is not significantly different even when the dispersant I or the dispersant III is used as the perylene black as the organic black pigment.

(A-1) By using a polymeric dispersant (dispersant I) having a quaternary ammonium salt group as a functional group, it was found that, in the photosensitive coloring composition containing the organic black pigment, (A-1) the organic black pigment was uniformly dispersed, as compared with the case of using a polymer dispersant (dispersant III) having no quaternary ammonium salt group as a functional group.

Table 6 shows the values of the viscosities measured in the same manner as in Example 9 for the photosensitive colored compositions of Examples 1 to 8.

(A-1) organic black pigment and (A-2) an organic coloring pigment in combination as well as Examples 1 and 2 using the (A-1) organic black pigment alone as a pigment as shown in Table 6 Example 6, (A-1) an organic black pigment, (A-2) an organic colored pigment and (A-1) an organic black pigment in Examples 3 to 5 and 8, A-3) In all of Example 7 in which carbon black was used in combination, the viscosity was equivalent to that of Examples 1 and 2, and the pigment was uniformly dispersed even in any of the photosensitive coloring compositions.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Japanese Patent Application 2013-198425) filed on September 25, 2013, the content of which is incorporated herein by reference.

10: transparent support substrate
20: pixel
30: Organic protective layer
40: inorganic oxide film
50: Transparent anode
51: Hole injection layer
52: hole transport layer
53: light emitting layer
54: electron injection layer
55: cathode
100: Organic EL device
500: organic luminescent material

Claims (20)

(A) a colorant, and (B) a dispersant,
Wherein the colorant (A) comprises (A-1) an organic black pigment which is a compound represented by the following general formula (2) and a sulfonic acid derivative represented by the following general formula (2)
Wherein the dispersant (B) comprises a polymer dispersant having a quaternary ammonium salt group and a tertiary amine as a functional group.
[Chemical Formula 1]

The method according to claim 1,
A pigment dispersion wherein the colorant (A) further comprises (A-2) an organic coloring pigment. The method according to claim 1,
A pigment dispersion wherein the colorant (A) further contains (A-3) carbon black. The method according to claim 1,
Wherein the polymer dispersant is an acrylic block copolymer of AB or BAB, wherein the polymer dispersant is composed of an A block having the quaternary ammonium salt group and the tertiary amine, and a B block having no quaternary ammonium salt group and the tertiary amine. 5. The method of claim 4,
Wherein the amount of the quaternary ammonium salt group in 1 g of the copolymer is 0.1 to 10 mmol. 5. The method of claim 4,
Wherein the copolymer has an amine value of 1 to 100 mgKOH / g. The method according to claim 6,
Wherein the copolymer has an amine value of 30 mgKOH / g or more. The method according to claim 1,
A pigment dispersion further containing an organic solvent. 9. The method of claim 8,
Wherein the organic solvent has an organic solvent having a boiling point of 100 to 200 DEG C under a pressure of 1013.25 [hPa]. 9. The method of claim 8,
Wherein the organic solvent contains propylene glycol monomethyl ether acetate. The method according to claim 1,
Further comprising (C) an alkali-soluble resin. The method according to claim 1,
Pigment dispersion for the preparation of photosensitive colored compositions. 12. A photosensitive coloring composition comprising at least the pigment dispersion according to any one of claims 1 to 12 and (D) a photopolymerization initiator. 14. The method of claim 13,
(A) the coloring material content is 20 mass% or more based on the total solid content in the photosensitive coloring composition. 14. The method of claim 13,
(D) the photopolymerization initiator is an oxime ester initiator, a ketoxime ester initiator, or an oxime ester initiator and a ketoxime ester initiator. 14. The method of claim 13,
A photosensitive coloring composition for forming a colored spacer. A cured product obtained by curing the photosensitive colored composition according to claim 13. A black matrix formed from the cured product according to claim 17. A colored spacer formed from the cured product according to claim 17. An image display device comprising a black matrix or a colored spacer formed from the cured product according to claim 17.

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