JP6528475B2 - Photosensitive coloring composition, cured product, coloring spacer, and image display device - Google Patents

Description

  The present invention relates to a photosensitive coloring composition, a cured product, a coloring spacer, and an image display device. More specifically, the present invention relates to a photosensitive coloring composition which has excellent light shielding properties and can suppress impurity elution into a liquid crystal layer to ensure high reliability, and its use.

  A liquid crystal display (LCD) utilizes the property that the alignment of liquid crystal molecules is switched by turning on and off a voltage to the liquid crystal. On the other hand, most of the members constituting the cell of LCD are formed by a method using a photosensitive composition represented by photolithography. The photosensitive composition is expected to be widely applied in the future from the viewpoint of easy formation of a fine structure and easy processing to a large area substrate.

  Recently, in order to cope with further high definition and high brightness of color LCD, in the active matrix LCD, a color filter on array system (COA system) provided with a color filter on the TFT element substrate side and a black matrix A black matrix on array system (BOA system) is proposed in which only the TFT element substrate side is provided. According to this method, the aperture ratio can be increased because it is not necessary to obtain an alignment margin with the active element side as compared to the case where a black matrix is formed on the color filter side, and as a result, high luminance can be achieved. Can be

In addition, with simplification of panel structure and manufacturing process, so-called columnar spacer, colored spacer that integrates photo spacer and black matrix is also used, which is used to keep the distance between two substrates in liquid crystal panel constant. It is done. However, in the case of adopting such a structure, in addition to the shape and compression characteristics required for the ordinary columnar spacer, the colored spacer should have a certain amount or more so as not to cause a short circuit of the electric circuit even if mounted directly on the TFT element. It is required to have a volume resistivity of or a specific dielectric constant less than or equal to
As such a colored spacer, a colored spacer using a plurality of organic coloring pigments as pigments (see, for example, Patent Document 1) and a coloring spacer using an organic black pigment are proposed (see, for example, Patent Document 2) .

Korean Registered Patent No. 10-1266295 Japanese Patent Application Publication No. 2014-529652

In order to prevent leakage of light from between the drive electrodes in the liquid crystal display element, the colored spacer is also required to have a higher light shielding property. As a method of enhancing the light shielding property, a method of using an organic black pigment having high light shielding property, a method of increasing the pigment content ratio in the photosensitive coloring composition, and the like can be mentioned.
As a result of investigations by the present inventors, when a colored spacer is formed using a photosensitive coloring composition containing an organic black pigment having high light shielding property, it can be used as a solvent for forming an alignment film to be an upper layer film of the colored spacer. It has been found that there are many elutions of impurities and the like derived from coloring agents, and there is a problem that the display reliability of the LCD is deteriorated.
Then, this invention is excellent in light-shielding property, and is providing the photosensitive coloring composition which can suppress elution of the impurity to a solvent and can ensure high reliability.

As a result of intensive studies to solve the above problems, the present inventors use a specific organic black pigment as a colorant in a photosensitive coloring composition and use a photopolymerization initiator having a specific skeleton structure. It has been found that the above problems can be solved, and the present invention has been completed.
That is, the present invention has the following configurations [1] to [14].

[1] Photosensitive coloring comprising (a) a colorant, (b) an alkali soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant A composition,
The organic black pigment, wherein the colorant (a) is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer thereof,
The photosensitive coloring composition characterized by the said (c) photoinitiator containing the oxime ester type compound which has a diphenyl sulfide frame represented by following General formula (I).

[In the above general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently of each other are each independently a hydrogen atom, a halogen atom, R ¹¹ COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCN HR 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 , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And 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 , They can also be directly linked to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or carbon It is an alkynyl group of several 2-12. ]

[In the above general formula (I), R ²³ represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ²⁴ represents an alkyl group which may have a substituent.
R ²⁵ represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (I-1), and h represents an integer of 0 to 5.
The benzene ring shown in Formula (I) may further have a substituent. ]

[In the above general formula (I-1), R ^25a represents -O-, -S-, -OCO- or -COO-.
R ^25b represents an alkylene group which may have a substituent.
The alkylene moiety of R ^25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The alkylene moiety of R ²⁵ may be branched side chain and may be cyclohexylene.
R ^25c represents a hydroxyl group or a carboxyl group. ]

[2] The photosensitive coloring composition according to [1], wherein the colorant further comprises an orange pigment and a blue pigment.
[3] The photosensitive coloring composition according to [2], wherein the orange pigment is an orange pigment shown in the following (a-1), and the blue pigment is a blue pigment shown in the following (a-2) .
(A-1) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 72 selected from the group consisting of C.I. I. Pigment blue 60
[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the (a) colorant further contains a purple pigment shown in the following (a-3).
(A-3) C.I. I. Pigment violet 23 and C.I. I. Pigment Violet 29 [5] [1] to [1], wherein the (a) colorant further comprises at least one organic coloring pigment selected from the group shown in the following (a-4): The photosensitive coloring composition in any one of [4].
(A-4)
Blue pigment: C.I. I. Pigment blue 15: 6
Red pigment: C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment red 272

[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the (a) colorant further contains carbon black.
[7] The photosensitive coloring according to any one of [1] to [6], wherein the content of the (a) coloring agent is 10% by mass or more based on the total solid content in the photosensitive coloring composition. Composition.
[8] The photosensitive coloring according to any one of [1] to [7], wherein the content ratio of the (a) coloring agent is 50% by mass or less based on the total solid content in the photosensitive coloring composition. Composition.
[9] The photosensitive coloring composition according to any one of [1] to [8], wherein the optical density per 1 μm of the film thickness of the cured coating is 1.0 or more.
[10] The photosensitive coloring composition according to any one of [1] to [9], which is used to form a colored spacer.

[11] The photosensitive coloring composition according to [10], which is used to collectively form colored spacers having different heights by photolithography.
[12] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [11].
[13] A colored spacer formed from the cured product according to [12].
[14] An image display device comprising the colored spacer according to [13].

  The photosensitive coloring composition of the present invention is excellent in the light shielding property, and can suppress the elution of impurities into the solvent to ensure high reliability. In addition, a cured product and a colored spacer which are excellent in light shielding property and highly reliable can be provided, and further, an image display device provided with such a colored spacer can be provided.

Hereinafter, the embodiments of the present invention will be specifically described. However, 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) acrylic” means “acrylic and / or methacrylic”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

  "(Co) polymer" is meant to include both a homopolymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride) ... acid" Is meant to include both the acid and its anhydride. In the present invention, the term "acrylic resin" means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing (meth) acrylic acid ester having a carboxyl group.

Further, in the present invention, the term "monomer" is a term opposite to the so-called high molecular substance (polymer), and in addition to the narrowly defined monomer (monomer), it also includes dimers, trimers, oligomers, etc. It is.
In the present invention, the term "total solids" means all components other than the solvent contained in the photosensitive coloring composition or in the ink described later.
In the present invention, the "weight average molecular weight" refers to a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, “amine value” means an amine value in terms of effective solid content, unless otherwise noted, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. It is. The measuring method will be described later. On the other hand, "acid value" means an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

  Moreover, in the present specification, percentages and parts represented by "mass" are synonymous with percentages and parts represented by "weight".

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compound (e) Solvent (f) A dispersant is contained as an essential component, and if necessary, a silane cup is further added It contains other compounding components such as adhesion improvers such as ring agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc. Usually, each compounded component is It is used in a state of being dissolved or dispersed in a solvent.

<(A) Colorant>
The (a) colorant used in the present invention is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or an organic black pigment which is a salt of the geometric isomer (hereinafter referred to as “general formula ( It may be abbreviated as "organic black pigment" represented by 1). Thus, it is considered that low dielectric constant and high light blocking ratio can be realized by containing a specific organic black pigment.

In formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently of each other are each independently a hydrogen atom, a halogen atom, R ¹¹ COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCN HR 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 , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And 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 , They can also be directly linked to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or carbon It is an alkynyl group of several 2-12.

  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 probably the most stable. .

  When the compound represented by the general formula (1) is anionic, the charge thereof may be any known suitable cation such as metal, organic, inorganic or metal organic cation, specifically alkali metal, alkaline earth metal It is preferred that the salt be a salt compensated by a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as trialkyl ammonium, a quaternary ammonium such as tetra alkyl ammonium or an organometallic complex. Moreover, when the geometric isomer of the compound represented by General formula (1) is anionic, it is preferable that it is the same salt.

In the substituents of the general formula (1) and their definitions, the following is preferable since the shielding ratio tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ³ and R ⁸ are preferably, independently of one another, hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, 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, beta-naphthyl, SO ₃ H or SO ₃ ^- and is, more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ independently of each other 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 identical, more preferably R ¹ is identical to R ⁶ , R ² is identical to R ⁷ , R ³ is identical to R ⁸ , R ⁴ is identical to R ⁹ , and R ⁵ is R ¹⁰ and It is the same.

  The alkyl group having 1 to 12 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl A nonyl group, a decyl group, an undecyl group or a dodecyl group.

  The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, thudyl group, norbornyl group, bornyl group, norcalyl group A caryl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group or a 2-adamantyl group.

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

  The cycloalkenyl group having a carbon number of 3 to 12 is, for example, 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2 , 4-Cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -tugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -Yl group, 7,7-dimethyl-2,4-norcaradiene-3-yl group or camphenyl group.

  The alkynyl group having 2 to 12 carbon atoms is exemplified by, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl Group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group Group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decin-10-yl group or 1-dodecin-12-yl group.

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

  The organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2).

As a specific example of such an organic black pigment, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation) can be mentioned under the trade name.
The organic black pigment is preferably dispersed by the dispersant, solvent and method described later. When the sulfonic acid derivative of the general formula (2) is present at the time of dispersion, the dispersibility and the storage stability may be improved.

The colorant (a) used in the present invention may contain other colorants in addition to the organic black pigment. As another coloring agent, it is preferable to use a pigment, and the pigment may be either an organic pigment or an inorganic pigment, but it suppresses the decrease in voltage holding ratio of liquid crystal and suppresses the absorption of ultraviolet light. It is more preferable to use an organic pigment from the viewpoint of facilitating control of the shape and the level difference.
Pigments that may be contained as other colorants include orange pigments and blue pigments. Thus, by containing an orange pigment and a blue pigment, there is a tendency to be able to increase the light absorption in the visible region and improve the shielding ratio while securing the light transmittance in the ultraviolet region.
The orange pigment may be abbreviated as an orange pigment (hereinafter, "(a-1) orange pigment") shown in the following (a-1) from the viewpoint of light transmittance in the ultraviolet region and light absorption in the visible region Can be preferably used.
(A-1) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 72 selected from the group consisting of

Among the orange pigments (a-1), from the viewpoint of light shielding and pigment dispersibility, C.I. I. It is preferable to use pigment orange 64.
(A-1) As the orange pigment, one orange pigment may be used, but plural kinds may be used in combination. Specifically, C.I. I. Pigment orange 64 and C.I. I. Pigment orange 43, C.I. I. Pigment orange 64 and C.I. I. And combinations of C.I.

  In the present invention, as the orange pigment, other orange pigments may be used in addition to the (a-1) orange pigment. As other orange pigments, C.I. I. Pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 46, 48, 49, 61, 62, 65, 67, 68, 69, 70, 71, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, preferably, C.I. I. Pigment orange 38, 71 can be mentioned.

Also, the blue pigment is not particularly limited, but from the viewpoint of light transmittance in the ultraviolet region and light absorption in the visible region, a blue pigment shown in the following (a-2) (hereinafter, "(a-2) blue pigment" And the like may be used preferably.
(A-2) C.I. I. Pigment blue 60

Furthermore, in the present invention, it is preferable to use a purple pigment in addition to the orange pigment and the blue pigment. Among the purple pigments, it is preferable to use a purple pigment shown in the following (a-3) (hereinafter sometimes abbreviated as "(a-3) purple pigment"). (A-3) There is a tendency that the shielding rate in the visible light region can be further enhanced by using a purple pigment.
(A-3) C.I. I. Pigment violet 23 and C.I. I. Pigment violet 29 selected from the group consisting of

Among the purple pigments (a-3), from the viewpoint of reliability and pigment dispersibility, C.I. I. It is preferable to use pigment violet 29.
(A-3) As a purple pigment, although 1 type of purple pigment may be used, two types may be used together.

In the present invention, in the case of using the (a-1) orange pigment as the orange pigment and the (a-2) blue pigment as the blue pigment, at least one organic selected from the group shown in the following (a-4) It is preferable to use a colored pigment (hereinafter sometimes abbreviated as “(a-4) organic colored pigment”). (A-4) There is a tendency that the shielding ratio in the visible region can be further enhanced by using the organic coloring pigment.
(A-4)
Blue pigment: C.I. I. Pigment blue 15: 6
Red pigment: C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment red 272

Among the organic color pigments (a-4), C.I. I. It is preferable to use pigment blue 15: 6. Further, from the viewpoint of light transmittance in the ultraviolet region, C.I. I. It is preferable to use pigment red 254.
(A-4) As an organic coloring pigment, although 1 type of organic coloring pigment may be used, you may use multiple types together. Specifically, C.I. I. Pigment blue 15: 6 and C.I. I. Pigment red 254, C.I. I. Pigment blue 15: 6 and C.I. I. And combinations of C.I.

  In the present invention, C.I. I. Pigment blue 60, C.I. I. In addition to pigment blue 15: 6, other blue pigments may be used. Other blue pigments include C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17, 19, 25, 27, 28, 29, 29, 33, 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4 can be mentioned.

  In the present invention, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Other than red pigment, other red pigments may be used. Other red pigments include C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 178, 179, 18 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 208, 209, 210, 210, 214, 216, 220, 221, 224, 230, 231, 233, 235, 236 237, 238, 239, 242, 243, 245, 247, 250, 251, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269 , 270, 271, 273, 274, 275, 276. Among these, preferably C.I. I. Pigment red 48: 1, 122, 168, 202, 206, 207, 209, 224, 242, and more preferably C.I. I. Pigment red 209, 224 can be mentioned.

  In the present invention, organic color pigments other than those described above can also be used. The chemical structure is not particularly limited, but organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene pigments can also be used. Hereinafter, specific examples of usable pigments are shown by pigment numbers. Terms such as "CI pigment red 2" listed below mean color index (CI).

As a green pigment, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned. Among these, preferably C.I. I. Pigment green 7, 36 can be mentioned.
As yellow pigments, C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180 can be mentioned.

  In the present invention, other organic black pigments other than those represented by the general formula (1) can also be used. Other organic black pigments include aniline black, perylene black, cyanine black and the like.

  In the present invention, inorganic black pigments can be used. As the inorganic black pigment, carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black and the like can be mentioned. Among these, carbon black can be preferably used from the viewpoint of light shielding property and image characteristics. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF 88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 30, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, ## 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL 7 B, OIL 9 B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same as the following) 3, Printex 3 OP, Printex 30, Printex 30 OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex P U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Bl ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Made by Cabot: Monarch (registered trademark, the same as the following) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (the same as the following) 99, REGAL 99 R, REGAL 415, REGAL 415 R, REGAL 250, REGAL 250 R, REGAL 330, REGAL 400 R, REGAL 55 R0, REGAL 660 R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark) -8
Columbian Carbon Co., Ltd. product: RAVEN (registered trademark, the same as the following) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500 RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

  The carbon black may be coated with a resin. Use of resin-coated carbon black has the effect of improving the adhesion to a glass substrate and the volume resistance. As carbon black covered with resin, carbon black etc. which are indicated, for example in JP-A-09-71733 can be used conveniently. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

  The carbon black to be subjected to the coating treatment with a resin preferably has a total content of Na and Ca of 100 ppm or less. Carbon black is usually Na mixed in from the raw material oil and combustion oil (or gas) at the time of production, reaction stopped water and granulated water, and further from the furnace material of the reaction furnace, etc., Ca, K, Mg, Al, Fe Etc. is contained in the order of percent. Of these, Na and Ca are generally contained in several hundred ppm or more, respectively, but by reducing them, the permeation to the transparent electrode (ITO) and other electrodes is suppressed, and electricity is reduced. Tend to be able to prevent

  As a method of reducing the content of the ash content containing these Na and Ca, as a raw material oil and fuel oil (or gas) at the time of producing carbon black and reaction stop water, those having the smallest content of these are selected carefully It is possible by reducing the amount of addition of the alkali substance to adjust the volume and the structure as much as possible. Another method is a method of washing carbon black produced from a furnace with water, hydrochloric acid or the like to dissolve and remove Na or Ca.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, a solvent which is poorly soluble in water is added, and the carbon black moves to the solvent side and is completely separated from water At the same time, most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there are cases where it is possible to use only the carbon black production process with carefully selected raw materials or water or acid dissolution method alone. The total amount of Na and Ca can be easily made 100 ppm or less.

The resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the diameter of dispersion in water (agglomerate diameter) is reduced, coating to fine units is possible, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 ml / 100 g or less. By setting the content in the above range, a coating film having a good light shielding property tends to be obtained. The average particle size means a number average particle size, and a particle image analysis is performed by taking several views of photographs taken at several tens of thousands times by electron microscope observation, and measuring about 2000 to 3000 particles of these photographs by an image processing device Means the equivalent circle diameter determined by

  The method for preparing the resin-coated carbon black is not particularly limited. For example, after appropriately adjusting the amounts of the carbon black and the resin, 1. A resin solution prepared by mixing and heating a resin and a solvent such as cyclohexanone, toluene, and xylene, and a suspension obtained by mixing carbon black and water are mixed and stirred to separate carbon black and water, 2. A method of forming a sheet obtained by removing the water and heating and kneading, forming into a sheet, pulverizing and drying it; A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, separating the obtained granular material and heating to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid impregnated carbon black, and then a resin is added thereto. Dry blending method; 4. The reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, cooled after polymerization, and after obtaining a reactive group-containing resin from a polymer suspension, Carbon black may be added and kneaded, and the carbon black and the reactive group may be reacted (grafted with carbon black), followed by cooling and crushing.

The type of resin to be coated is not particularly limited, but synthetic resins are generally used, and furthermore, a resin having a benzene ring in the structure has a stronger amphoteric surfactant action and thus dispersion It is preferable from the point of nature and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene Thermoplastic resins such as oxides, polysulfones, polyparaphenylene terephthalamides, polyamideimides, polyimides, polyaminobismaleimides, polyethersulfopolyphenylenesulfones, polyarylates, and polyetheretherketones can be used. The amount of resin coating on carbon black is preferably 1 to 30% by mass with respect to the total amount of carbon black and resin, and by setting the amount to the above lower limit or more, the coating tends to be sufficient. On the other hand, by setting the content to the upper limit value or less, adhesion between resins can be prevented, and the dispersibility can be made favorable.

  The carbon black thus coated with the resin can be used as a light shielding material for the colored spacer according to the conventional method, and a color filter having this colored spacer as a component can be prepared by the conventional method. When such carbon black is used, a colored spacer having a high light-shielding rate and a low surface reflectance tends to be achievable at low cost. In addition, it is also speculated that coating the carbon black surface with a resin has the function of containing Ca and Na in the carbon black.

In addition to the above-mentioned organic color pigments, organic black pigments, and inorganic black pigments, dyes may be used. Examples of dyes that can be used as color materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like.
As an azo dye, for example, C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct red 28, C.I. I. Direct red 83, C.I. I. Direct Yellow 12, C.I. I. Direct orange 26, C.I. I. Direct green 28, C.I. I. Direct green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant tread 7, C.I. I. Mordant yellow 5, C.I. I. Mordant Black 7 and the like.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.
In addition to these, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are, for example, C.I. I. Solvent yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

These pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles.
In the present invention, the average particle size of the pigment is a value determined from the pigment particle size measured by dynamic light scattering (DLS). For particle size measurement, a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring equipment, (According to concentration) and measured at 25.degree.

<(B) Alkali-soluble resin>
The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group. For example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing resin Although a urethane resin, novolak resin, polyvinyl phenol resin, etc. are mentioned, epoxy (meth) acrylate resin and acrylic resin are preferable among them. These may be used alone or in combination of two or more.

  Especially as (b) alkali-soluble resin used by this invention, the following alkali-soluble resin (b1) and / or alkali-soluble resin (b2) (Hereafter, it may be called "carboxyl group containing epoxy (meth) acrylate resin.") Is preferably used from the viewpoint of excellent platemaking properties.

<Alkali-soluble resin (b1)>
Obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting a polybasic acid and / or an anhydride thereof Alkali soluble resin.
<Alkali-soluble resin (b2)>
An epoxy resin is added with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof Alkali-soluble resin obtained by

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, "Epicoat (registered trademark. The same applies hereinafter) 828" manufactured by Mitsubishi Chemical Corporation, "Epicoat 1001", "Epicoat 1002", "Epicoat 1004", etc. ), An epoxy obtained by the reaction of an alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C. manufactured by Nippon Kayaku Co., Ltd.)), bisphenol F type resin ( For example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004, etc." manufactured by Mitsubishi Chemical Corporation, an epoxy resin obtained by the reaction of the alcoholic hydroxyl group of a bisphenol F-type epoxy resin and epichlorohydrin (For example, “NER-7 manufactured by Nippon Kayaku Co., Ltd. 06 ”(epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example,“ YX-4000 ”manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd. Product “EPPN-201”, Mitsubishi Chemical Co. “EP-152”, “EP-154”, Dow Chemical Co. “DEN-438”), (o, m, p-) cresol novolac epoxy resin (For example, "EOCN (registered trademark. Same as the following)-102S" manufactured by Nippon Kayaku Co., Ltd., "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC" manufactured by Nissan Chemical Industries, Ltd. (Registered trademark)), trisphenol methane type epoxy resin (for example, “EPPN (registered trademark), manufactured by Nippon Kayaku Co., Ltd.) A) -501 "," EPN-502 "," EPPN-503 "), alicyclic epoxy resin (" CELLOXIDE 2021 P "manufactured by Daicel Chemical Industries, Ltd.," CELLOXIDE (registered trademark; hereinafter the same) EHPE ") An epoxy resin (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.) obtained by glycidylating a phenol resin by the reaction of dicyclopentadiene and phenol, the following general formula (B1) ̃ The epoxy resin etc. which are represented by (B4) can be used suitably. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), "NDC Co., Ltd." as an epoxy resin represented by the following general formula (B2) NC-3000 ”,“ ESF-300 ”manufactured by Nippon Steel Sumikin Chemical Co., Ltd., etc. may be mentioned as an epoxy resin represented by the following general formula (B4).

In the said General formula (B1), a shows an average value and shows the number of 0-10. 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. The plurality of R ¹¹¹ present in one molecule may be the same or different.

In the said General formula (B2), b shows an average value and shows the number of 0-10. R ¹²¹ 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. The plurality of R ¹²¹ present in one molecule may be the same or different.

  In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, one or more adamantane structures are included in the molecular structure. c represents an integer of 2 or 3;

In the general formulas (B3-1) and (B3-2), each of R ^{131 to} R ¹³⁴ and R ^{135 to} R ¹³⁷ independently represents an adamantyl group which may have a substituent, a hydrogen atom, a substituent And an optionally substituted alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent. * Indicates a bonding hand.

In General Formula (B4), 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> respectively independently represent a C1-C4 alkylene group. Each of x and y independently represents an integer of 0 or more.

  Among these, it is preferable to use an epoxy resin represented by any of the general formulas (B1) to (B4).

Examples of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, ) Α-position haloalkyl of acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acid such as cyano, cyano substituted etc, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (meth) Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloylate Roxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid to ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomer to which lactones such as δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate (anhydride) succinic acid, (anhydride) phthalic acid, (anhydride) Monomer to which acid (anhydride) such as maleic acid is added, (meth) acrylic acid dimer And the like.
Among these, particularly preferred in view of sensitivity is (meth) acrylic acid.

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

The epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two. The above may be used in combination.
The amount of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to be used 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, it is in the range of 0.7 to 1.1 equivalents. When the amount of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the introduction amount of unsaturated group is insufficient, and the polybasic acid and / or the anhydride thereof are subsequently formed. The reaction with is also inadequate. It is also not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted material. In any case, the curing characteristics tend to deteriorate.

  As a polybasic acid and / or its anhydride, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid 1 type, or 2 or more types selected from an acid, endo methylene tetrahydro phthalic acid, chlorendic acid, methyl tetrahydro phthalic acid, biphenyl tetracarboxylic acid, these anhydrides, etc. are mentioned.

  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 is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  Known methods can be used also for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid to epoxy resin or α, β-unsaturated monocarboxylic acid having a carboxyl group The desired product can be obtained by continuous reaction under the same conditions as in the ester addition reaction. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxyl group-containing epoxy (meth) acrylate resin to be produced is in the range of 10 to 150 mg KOH / g, and more preferably 20. It is preferable that it is a grade which becomes -140 mgKOH / g. The alkali developability tends to be good by setting the content to the lower limit or more, and the curing performance tends to become good by setting the content to the upper limit or less.

A multi-branched structure may be introduced by adding a polyfunctional alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol at the time of addition reaction of this polybasic acid and / or its anhydride.
The carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing the anhydride or / or the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, polybasic acid and / or Or after mixing the anhydride and polyfunctional alcohol, it is obtained by heating. 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, any hydroxyl group present in a mixture of a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group and a polyfunctional alcohol The addition reaction of the polybasic acid and / or the anhydride thereof is carried out.

  The polystyrene equivalent weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, and usually 10000 or less, preferably 8000 Or less, more preferably 6000 or less. When the weight average molecular weight is small, the solubility in the developer is high, and when the weight average molecular weight is too large, the solubility in the developer is low.

The carboxyl group-containing epoxy (meth) acrylate resin may be used singly or in combination of two or more resins.
In addition, a part of the above-mentioned carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin and used. That is, the 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 (b) alkali-soluble resin is preferably 50% by mass or more, particularly 80% by mass or more.

  There is no restriction | limiting in the other binder resin which can be used together with a carboxyl group containing epoxy (meth) acrylate resin, What is necessary is just to select from resin normally used to a photosensitive coloring composition. For example, the binder resin etc. which are described in Unexamined-Japanese-Patent No. 2007-217727, 2007-316620, 2007-334290 grade | etc., Are mentioned. The other binder resins may be used alone or in combination of two or more.

  Moreover, as a (b) alkali-soluble resin, it is preferable to use acrylic resin from a viewpoint of platemaking property, and the thing as described in Unexamined-Japanese-Patent No. 2014-137466 can be used preferably.

As an acrylic resin, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)") and other ethylenically unsaturated monomers that can be copolymerized Copolymers with monomers (hereinafter referred to as "unsaturated monomers (b2)") can be mentioned.
Examples of unsaturated monomers (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid and itaconic acid. Acid, itaconic anhydride, citraconic acid, citraconic anhydride, unsaturated dicarboxylic acids such as mesaconic acid or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acid Mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having 2 or more valences such as acryloyloxyethyl]; having a carboxy group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate Polymer mono (meth) acrylate; p-vinyl benzoic acid etc. can be mentioned.
These unsaturated monomers (b1) can be used alone or in combination of two or more.

  Also, as the unsaturated monomer (b2), for example, N-position substituted maleimide such as N-phenyl maleimide, N-cyclohexyl maleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α- Aromatic vinyl compounds such as methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (polymerization degree 2 To 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10 ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumyl phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyl oxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyl oxetane And polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polysiloxane and the like.
These unsaturated monomers (b2) can be used alone or in combination of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass More preferably, it is 10-40 mass%. By copolymerizing the unsaturated monomer (b1) in such a range, a photosensitive coloring composition having excellent alkali developability and storage stability tends to be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876 and JP-A-10-31308. Japanese Patent Laid-Open Publication Nos. 10-300922, 11-174224, 11-258415, 2000-56118, 2004-101728, etc. It can be mentioned coalescence.
Although the copolymer of unsaturated monomer (b1) and unsaturated monomer (b2) can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680 The structure, Mw and Mw / Mn can also be controlled by the methods disclosed in the publication, WO 2007/029871 and the like.

<(C) Photopolymerization initiator>
The photopolymerization initiator (c) is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added and used.
The photopolymerization initiator (c) in the photosensitive coloring composition of the present invention contains an oxime ester compound having a diphenyl sulfide skeleton represented by the following general formula (I). As described above, by including a specific oxime ester compound having a diphenyl sulfide skeleton, light absorption at short wavelengths is strong, and surface curability is improved, so it is considered that dissolution in a solvent is difficult and solvent resistance is enhanced. . In particular, by setting the group to be bonded to the oxime ester to be an alkyl group which may have a substituent, it is considered that the mobility of the radical is high and the sensitivity is high, so that the surface curability is further improved.
Moreover, it is thought that it becomes possible to suppress that a coloring agent etc. dissolve out also from the inside of a coating film by preventing the penetration of a solvent. The oxime ester compound having a diphenyl sulfide skeleton has a short length of the conjugated system, the energy of the whole molecule is high, the radical generation efficiency by thermal decomposition is high, and the polymerization reaction is promoted, and the unreacted initiator It is considered that the elution of the initiator itself to the solvent can also be suppressed.

In the above general formula (I), R ²³ represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ²⁴ represents an alkyl group which may have a substituent.
R ²⁵ represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (I-1), and h represents an integer of 0 to 5.
The benzene ring shown in Formula (I) may further have a substituent.

In formula (I-1), R ^25a represents -O-, -S-, -OCO- or -COO-.
R ^25b represents an alkylene group which may have a substituent.
The alkylene moiety of R ^25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The alkylene moiety of R ²⁵ may be branched side chain and may be cyclohexylene.
R ^25c represents a hydroxyl group or a carboxyl group.

The number of carbon atoms in the alkyl group in R ²³ is not particularly limited, is preferably 1 or more from the viewpoint of solubility of the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 5 or less, particularly preferably 3 or less. preferable.

A methyl group, a hexyl group, a cyclopentyl methyl group etc. are mentioned as a specific example of an alkyl group, Among these, a viewpoint to developability to a methyl group or a hexyl group is preferable, and a methyl group is more preferable.
Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability Carboxyl groups are more preferred. In addition, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

The aromatic ring group in R ^23, an aromatic hydrocarbon ring group and aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, etc. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl Groups are more preferred.
Among these, from the viewpoint of developability, R ²³ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. .

The carbon number of the alkyl group in R ²⁴ is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.

A methyl group, an ethyl group, a propyl group etc. are mentioned as a specific example of an alkyl group, From these, a viewpoint of a sensitivity to a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
Examples of the substituent which the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group and an amido group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.

Among these, from the viewpoint of sensitivity, R ²⁴ is more preferably an unsubstituted alkyl group, and still more preferably a methyl group.

R ²⁵ is a hydroxyl group, a carboxyl group or a group represented by the general formula (I-1), and among them, from the viewpoint of sensitivity and developability, R ²⁵ is represented by the general formula (I-1) It is preferably a group.
In the general formula (I-1), as described above, R ^25a represents -O-, -S-, -OCO- or -COO-, but among them, from the viewpoint of sensitivity and developability,- O- or -OCO- is preferable, and -O- is more preferable.

As described above, R ^25b represents an alkylene group which may have a substituent.
The carbon number of the alkylene group in R ^25b is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 20 or less from the viewpoint of solubility in the photosensitive coloring composition. Is more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
The alkylene group may be linear, branched or may contain an aliphatic ring. Among these, from the viewpoint of solubility in the photosensitive coloring composition, linear is preferable.

  A methylene group, ethylene group, a propylene group etc. are mentioned as a specific example of an alkylene group, Among these, a methylene group is more preferable from a soluble viewpoint to a photosensitive coloring composition.

As mentioned above, R ^25c is a hydroxyl group or a carboxyl group. From the viewpoint of solvent resistance (liquid crystal contamination), R ^25c is preferably a hydroxyl group.

In the said General formula (I), h represents the integer of 0-5. In particular, h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, or 1 from the viewpoint of developability. Most preferred.
On the other hand, h is preferably 0 from the viewpoint of synthesisability.

  The following can be mentioned as specific examples of the oxime ester compound represented by the above general formula (I).

  Although it does not specifically limit about the manufacturing method of the oxime ester-type compound represented by said general formula (I), For example, it can manufacture by the method of Unexamined-Japanese-Patent No. 2000-080068.

The photopolymerization initiator (c) in the photosensitive coloring composition of the present invention contains the oxime ester compound represented by the above general formula (I), but further contains other photopolymerization initiators. It is also good.
Other photopolymerization initiators include, for example, metallocene compounds containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; a hexaary described in JP-A-2000-56118 Rubiimidazole derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts described in JP-A No. 10-39503 Radical active agents such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP-A-2000-80068, JP-A-2006-36750, WO 2008/075564, WO 2009/131189 brochure, special table 2 Such oxime ester derivatives as described in 14-500852 JP, and the like.

The photopolymerization initiator may be used alone or in combination of two or more.
In the photopolymerization initiator, a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source can be blended, if necessary, for the purpose of enhancing sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarins having a heterocycle described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, and the like JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005. Patent Publications JP-A-59-56403, JP-A-2-692, JP-A-57-168088, JP-A-5-10761 JP-5-210240 discloses, mention may be made of dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

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, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone And benzophenone series compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5. ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethy) 2-aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds and the like. The most preferable of these is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may also be used alone or in combination of two or more.

  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, and mercapto compounds described later. Be The polymerization accelerator may be used alone or in combination of two or more.

<(D) Ethylenically Unsaturated Compound>
The photosensitive coloring composition of the present invention comprises (d) an ethylenically unsaturated compound. (D) It is considered that high sensitivity is obtained by including the ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenic unsaturated bond, monoester of polyvalent or monohydric alcohol, etc. It can be mentioned.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 3 or more, more preferably 5 or more, and preferably 15 or less. More preferably, it is 10 or less. By setting the content to the above lower limit or more, the polymerizability tends to be improved and the sensitivity becomes high, and by setting the content to the above upper limit or less, the developability tends to be better.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly The ester etc. which are obtained by the esterification reaction of polyvalent hydroxy compounds, such as a hydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid are mentioned.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate. Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylates wherein acrylates of these exemplified compounds are replaced by methacrylates , Itaconic acid ester similarly substituted for itaconate Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

As esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcine diacrylate, resorcine dimethacrylate, pyrogallol triacrylate and the like Etc.
The esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single substances, but acrylic acid, phthalic acid, and acrylic acid, phthalic acid, and so on. A condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin, and the like can be mentioned.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; Acrylamides such as ethylene bis acrylamide; Diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
As said urethane (meth) acrylates, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (made by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U, for example -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Japan Synthetic Chemical Industry Co., Ltd.), and the like.

Among these, it is preferable to use ester (meth) acrylates or urethane (meth) acrylates as the (d) ethylenically unsaturated compound from the viewpoint of sensitivity, and dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta It is more preferable to use (meth) acrylate or the like.
One of these may be used alone, or two or more may be used in combination.

<(E) Solvent>
The photosensitive coloring composition of the present invention contains (e) a solvent. (E) Function to adjust viscosity by dissolving or dispersing (a) coloring agent, (b) alkali soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound etc. by containing solvent You can have
The photosensitive coloring composition of the present invention generally comprises (a) a colorant, (b) an alkali-soluble resin, (d) an ethylenically unsaturated compound, (f) a dispersant, and other optional ingredients. Various materials are used in a state of being dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoint of solubility and dispersibility.

  Among the organic solvents, it is preferable to select one having a boiling point in the range of 100 to 300 ° C. from the viewpoint of dispersibility and coatability, and it is more preferable to select one having a boiling point in the range of 120 to 280 ° C. Here, the boiling point means a boiling point at a pressure of 1013.25 hPa.

Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-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, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as 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, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, glycerin and benzyl alcohol;
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, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
Ether ketones such as methoxymethyl pentanone;
Acetonitrile, nitriles such as benzonitrile, etc.

The commercially available organic solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apcosynner, Socar Solvent No. 1 and No. 1 2, Solvesso # 150, Shell TS 28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosorb" is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (any one Are also trade names).
These organic solvents may be used alone or in combination of two or more.

  When forming a colored spacer by the photolithography method, it is preferable to select an organic solvent having a boiling point of 100 to 200 ° C. (pressure 1013.25 hPa condition, hereinafter, all the same regarding the boiling point). More preferably, it has a boiling point of 120 to 170 ° C.

Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coating properties, surface tension and the like and relatively high solubility of the components in the composition.
Moreover, although glycol alkyl ether acetates may be used independently, you may use another organic solvent together. Particularly preferable organic solvents to be used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferable in view of the solubility of the component in the composition. In addition, since the glycol monoalkyl ethers have high polarity and the addition amount is too large, the pigment tends to aggregate, and the storage stability tends to decrease such as the viscosity of the photosensitive coloring composition to be obtained later increases. The proportion of glycol monoalkyl ethers in the solvent 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 ° C. or higher (hereinafter sometimes referred to as “high-boiling point solvent”) in combination. The combined use of such a high boiling point solvent makes it difficult to dry the photosensitive coloring composition, but it has the effect of preventing the uniform dispersion of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the generation of foreign matter defects at the tip of the slit nozzle due to the precipitation and solidification of the coloring material and the like. Among the various solvents described above, 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 such effects being high.

  3 mass%-50 mass% are preferable, as for the content rate of the high boiling point solvent in the organic solvent, 5 mass%-40 mass% is more preferable, and 5 mass%-30 mass% is especially preferable. By setting the lower limit value or more, for example, there is a tendency that it is possible to suppress that a coloring material etc. precipitates and solidifies at the tip of the slit nozzle and causes foreign matter defects, and by setting the upper limit value or less. Tends to be able to suppress problems such as tact defects in the vacuum drying process and pin marks on prebaking

The high boiling point solvent having a boiling point of 150 ° C. or more may be a glycol alkyl ether acetate or may be a glycol alkyl ether, and in this case, a high boiling point solvent having a boiling point of 150 ° C. or more is separately contained You don't have to.
As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate Acetate, triacetin and the like can be mentioned.

<(F) Dispersant>
In the photosensitive coloring composition of the present invention, (a) dispersing the coloring agent finely and stabilizing the dispersion state is important for securing the stability of the quality, and therefore (f) contains a dispersing agent. .
(F) The dispersant is preferably a polymer dispersant having a functional group, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or these bases; primary, secondary or tertiary Polymeric dispersants having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine are preferable. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine disperses the pigment. From the viewpoint of being able to be dispersed with a small amount of dispersing agent.

  Further, as the polymer dispersant, for example, a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant comprising an amino group-containing monomer and a macromonomer, a polyoxyethylene alkyl ether A system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, an aliphatic modified polyester dispersant, and the like can be mentioned.

Specific examples of such dispersants are trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BIC Chemie Co., Ltd.), Disperon (registered trademark, manufactured by Kushimoto Chemical Co., Ltd.), SOLSPERSE (registered trademark) Lublisol Co., Ltd., KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Addispar (registered trademark, manufactured by Ajinomoto Co., Ltd.), and the like.
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

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 these, from the viewpoint of dispersion stability, the (f) dispersant preferably contains a urethane-based polymer dispersant having a functional group and / or an acrylic polymer dispersant, and includes an acrylic-based polymer dispersant. Is particularly preferred.
Also, from the viewpoint of dispersibility and storage property, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of urethane type and acrylic type polymer dispersants include DISPERBYK 160 to 166, 182 series (all urethane type), DISPERBYK 2000, 2001, LPN 21116 etc. (all are acrylic type) (all manufactured by Bick Chemie Co., Ltd.).
If a chemical structure preferable as a urethane type polymer dispersing agent is specifically illustrated, for example, it is the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule. Examples thereof include dispersion resins having a weight average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.

  Examples of the above-mentioned polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, etc. Aliphatic diisocyanates such as aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanatodimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetrame Aliphatic diisocyanates having an aromatic ring such as lxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecanetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatophenylmethane) and tris (isocyanatophenyl) thiophosphate, and trimers, water adducts thereof, and polyol adducts thereof. Preferred as polyisocyanates are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. One of these may be used alone, or two or more may be used in combination.

  As a method for producing a trimer of isocyanate, a portion of an isocyanate group using the above-mentioned polyisocyanate with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like After the trimerization is terminated by addition of a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain a desired polyisocyanate containing isocyanurate group.

As compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol etc., and one terminal hydroxyl group of these compounds have carbon atoms The thing alkoxylated with the 1-25 alkyl group and the mixture of 2 or more types of these are mentioned.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. As polyether diols, those obtained by homopolymerization or copolymerization of alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and those And mixtures of two or more thereof.

  As polyether ester diols, those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or reacting polyester glycols with alkylene oxides, such as poly (poly (poly) Oxytetramethylene) adipate and the like. Most preferred as the polyether glycol are 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.

  Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-hexanediol, 2-methyl-2,4- Intandiol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -Those obtained by polycondensation of N-alkyl dialkanolamines such as methyldiethanolamine etc., such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate etc., or the above-mentioned diols or carbon number 1 25 monovalent Polylactone diol or polylactone monool obtained by using the call as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferable as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Can be mentioned.
One of these may be used alone, or two or more may be used in combination.

  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.

The compound which has an active hydrogen and a tertiary amino group in the same molecule used for this invention is demonstrated.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a thiol group, among which an amino group, especially primary Preferred is a hydrogen atom of the amino group of

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.
If the compound which has active hydrogen and a tertiary amino group in such a same molecule is illustrated, N, N- dimethyl- 1, 3- propane diamine, N, N- diethyl 1, 3- propane diamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  When the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero five-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc. Pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, six-membered nitrogen-containing hetero ring such as isoquinoline ring There is a ring. Among these nitrogen-containing heterocycles, preferred is an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specifically illustrating a compound having a triazole ring and an amino group, 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 And 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
One of these may be used alone, or two or more may be used in combination.

  The compounding ratio of the raw material at the time of manufacturing a urethane type polymer dispersing agent is the compound of the number average molecular weights 300-10,000 which has one or two hydroxyl groups in the same molecule with respect to 100 mass parts of polyisocyanate compounds. -200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 And 24 parts by mass.

  The production of the urethane-based polymer dispersant is carried out according to a known method of polyurethane resin production. As the solvent for production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve, benzene, toluene, xylene and hexane are usually used. Some hydrocarbons such as diacetone alcohol, isopropanol, secondary butanol, tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. One of these may be used alone, or two or more may be used in combination.

  In the above production, a urethanization reaction catalyst is usually used. As this catalyst, for example, tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannas octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, and 3 such as triethylamine and triethylenediamine And the like. One of these may be used alone, or two or more may be used in combination.

  The introduced amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg KOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mg KOH / g. The amine value is a value obtained by neutralizing titration of a basic amino group with an acid and expressing the acid value in mg of KOH corresponding to the acid value. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when the above range is exceeded, the developability tends to be lowered.

In the case where the isocyanate group is left in the polymer dispersant in the above reaction, it is preferable to destroy the isocyanate group with an alcohol or an amino compound because the temporal stability of the product is increased.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and the dispersion stability will be poor, and if it exceeds 200,000, the solubility will be reduced, the dispersibility will be poor and the control of the reaction will be difficult.

  As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group as referred to herein is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use a random copolymer, a graft copolymer or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

  As the unsaturated group-containing monomer having a functional group, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acrylic acid Unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and tertiary amino groups such as quaternary compounds thereof An unsaturated monomer having a quaternary ammonium base is mentioned as a specific example. One of these may be used alone, or two or more may be used in combination.

  Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl ( Meta) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and derivatives thereof, α-methylstyrene, N-cyclohexene N-substituted maleimide such as syl maleimide, N-phenyl maleimide, N-benzyl maleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Macromonomers, macromonomers such as polypropylene glycol macromonomers, polycaprolactone macromonomers, etc. may be mentioned. One of these may be used alone, or two or more may be used in combination.

  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, but in this case, A The block may contain, in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, a partial structure derived from the unsaturated group-containing monomer not containing the functional group, May be contained in any form of random copolymerization or block copolymerization in the A block. The content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block consists of a partial structure derived from the unsaturated group-containing monomer not containing the above functional group, but a partial structure derived from two or more kinds of monomers is contained in one B block. They may also be contained in any mode of random copolymerization or block copolymerization in the B block.
The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method described below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, in the anion living polymerization method, a polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above 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 integers of 1 or more.

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

In the above 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, and R ^a is a hydrogen atom or 1 R ^b is ^a hydrogen atom or a monovalent organic group different from R ^a .

  In synthesizing this acrylic polymer dispersant, those disclosed in JP-A-9-62002, P.I. 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. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatata, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Articles, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takizo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D., et al. Y. Sogoh, W. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) may be employed.

The acrylic polymer dispersant that can be used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block constituting the copolymer / B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio), and by setting it within this range, good heat resistance and dispersion stability can be secured. There is.
The amount of quaternary ammonium base in 1 g of the A-B block copolymer or B-A-B block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol in general. Within the range, good heat resistance and dispersion stability tend to be secured.

Although such a block copolymer may usually contain an amino group generated in the production process, its amine value is about 1 to 100 mg KOH / g, and from the viewpoint of dispersibility, The amount is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, preferably 90 mg KOH / g or less, more preferably 80 mg KOH / g or less, still more preferably 75 mg KOH / g or less.
Here, the amine value of dispersants such as these block copolymers is represented by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
In a 100 mL beaker, precisely weigh 0.5 to 1.5 g of the dispersant sample and dissolve with 50 mL of acetic acid. This solution is neutralized titrated with 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following equation.

Amine value [mg KOH / g] = (561 x V) / (W x S)
[Wherein W represents the amount by which the dispersant sample is weighed [g], V represents the titration amount at the titration end point [mL], and S represents the solid concentration [% by mass] of the dispersant sample. ]
The acid value of this block copolymer is generally lower, though it depends on the presence or absence and type of the acid group which is the origin of the acid value, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw Is preferably in the range of 1000 to 100,000. There exists a tendency which can ensure favorable developability and dispersion stability by setting it in the said range.

  When it has a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the repeating unit represented by the following formula (i) (hereinafter referred to as “repeating unit It is preferable to have a unit (i).

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

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

The number of carbon atoms of the aryl group which may have a substituent in R ^{31 to} R ³³ in the above formula (i) is not particularly limited, but is usually 6 or more and preferably 16 or less, 12 It is more preferable that Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl 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 in the above formula (i) is not particularly limited, but is usually 7 or more, and preferably 16 or less, 12 It is more preferable that Specific examples of the aralkyl group include phenylmethylene group, phenylethylene group, phenylpropylene group, phenylbutylene group, phenylisopropylene group and the like, and among these, phenylmethylene group, phenylethylene group, phenylpropylene group, or It is preferably a phenyl butylene group, and more preferably a phenyl methylene group or a phenyl ethylene group.

Among these, from the viewpoint of dispersibility, R ^{31 to} R ³³ are preferably each independently an alkyl group or an aralkyl group, and specifically, R ³¹ and R ³³ are each independently a methyl group or ethyl And R ³² is preferably a phenylmethylene group or a phenylethylene group, more preferably R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethylene group.

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

In the above formula (ii), each of R ³⁵ and R ³⁶ independently has a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent And R ³⁵ and R ³⁶ may combine with each other to form a cyclic structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

In addition, as the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above-mentioned formula (ii), those exemplified as R ^{31 to} R ³³ of the above-mentioned formula (i) are preferably adopted it can.
Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above-mentioned formula (ii), those exemplified as R ^{31 to} R ³³ of the above-mentioned formula (i) are preferably adopted Can. In addition, as the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above-mentioned formula (ii), those exemplified as R ^{31 to} R ³³ of the above-mentioned formula (i) are preferably adopted it can.

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

Examples of the substituent which may be possessed by the alkyl group, the aralkyl group or the aryl group in R ^{31 to} R ³³ of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group etc. are mentioned.

In the above formulas (i) and (ii), examples of the divalent linking group X and Z include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and a -CONH-R ⁴³ -group, -COOR ⁴⁴ -group [wherein R ⁴³ and R ^{44 each} represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] is -COO-R ⁴⁴ - a group.
In the above formula (i), the counter anion of Y ^{- The, Cl -, Br -, I} -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - , and the like.

  The content of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, it is represented by the content of the repeating unit represented by the formula (i) and the formula (ii) Preferably it is 60 mol% or less with respect to the sum total of the content rate of a repeating unit, More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, Especially preferably, it is 35 mol% or less Preferably it is 5 mol% or more, More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more, Especially preferably, it is 30 mol% or more.

  Further, the content ratio of the repeating unit represented by the above formula (i) to the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, 5 mol % Or more is more preferable, 10 mol% or more is more preferable, 50 mol% or less is preferable, 30 mol% or less is more preferable, and 20 mol% or less Is more preferable, and 15 mol% or less is particularly preferable.

  Further, the content ratio of the repeating unit represented by the formula (ii) to the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, 10 mol % Is more preferably, 15 mol% or more is more preferable, 20 mol% or more is particularly preferable, and 60 mol% or less is preferable, and 40 mol% or less. Is more preferable, 30 mol% or less is more preferable, and 25 mol% or less is particularly preferable.

  Further, the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii), from the viewpoint of enhancing the compatibility with a binder component such as a solvent and improving the dispersion stability. It is preferable to have "."

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

  Further, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. And 5 or less are more preferable.

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

  In addition, the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv) from the viewpoint of enhancing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability. It is preferable to have “)”.

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

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but it is usually 6 or more, preferably 16 or less, and 12 or less Is more preferable, and 8 or less is more preferable. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ³⁸ of the above formula (iv) is not particularly limited, but it is usually 7 or more, preferably 16 or less, and 12 or less Is more preferably 10 or less. Specific examples of the aralkyl group include phenylmethylene group, phenylethylene group, phenylpropylene group, phenylbutylene group, phenylisopropylene group and the like, and among these, phenylmethylene group, phenylethylene group, phenylpropylene group, or It is preferably a phenyl butylene group, and more preferably a phenyl methylene group or a phenyl ethylene group.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
As a substituent which the alkyl group in R ³⁸ may have, a halogen atom, an alkoxy group and the like can be mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain | strand-shaped alkyl group, a halogen atom, an alkoxy group etc. are mentioned. In addition, the linear alkyl group represented by R ³⁸ includes both linear and branched.

  In addition, the content ratio of the repeating unit represented by the formula (iv) to the total repeating units of the polymer dispersant is preferably 30 mol% or more, and 40 mol% or more from the viewpoint of dispersibility. Is more preferably 50 mol% or more, and preferably 80 mol% or less, 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 α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide type monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units derived from monomers such as N-methacryloyl morpholine and the like.

  The polymer dispersant is an A block having the repeating unit (i) and the repeating unit (ii), and a B block not having the repeating unit (i) and the repeating unit (ii) from the viewpoint of further enhancing the dispersibility. It is preferable that it is a block copolymer which has The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Unexpectedly, the dispersing ability of the dispersant tends to be remarkably improved by introducing not only the quaternary ammonium base but also the tertiary amino group into the A block. The B block preferably has the repeating unit (iii), more preferably the repeating unit (iv).

  In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any mode of random copolymerization and block copolymerization. Moreover, repeating unit (i) and repeating unit (ii) may each be contained 2 or more types in 1 A block, In that case, each repeating unit is a random copolymerization in this A block, You may contain in any aspect of block copolymerization.

  Moreover, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in A block, As an example of such a repeating unit, the above-mentioned (meth) acrylic acid ester type single is mentioned. The repeating unit derived from a monomer etc. are mentioned. The content of the repeating unit 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, it is not contained in the block.

  Repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth) acrylate based monomers such as acrylic acid chloride; (meth) acrylamide based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ethers; repeating units derived from monomers such as N-methacryloyl morpholine. 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, it is not contained in the block.

  Further, from the viewpoint of improving the dispersion stability, it is preferable to use the (f) dispersant in combination with a pigment derivative described later.

<Other components of photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, in addition to the components described above, adhesion improvers such as silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives Etc. can be blended appropriately.

(1) Adhesion Improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, silane coupling agents, phosphoric acid group-containing compounds and the like are preferable.
As a kind of a silane coupling agent, various things, such as an epoxy type, a (meth) acrylic type, an amino type, can be used individually by 1 type or in mixture of 2 or more types.

As preferable silane coupling agents, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, it is a silane coupling agent of epoxy silanes.
As a phosphoric acid group containing compound, (meth) acryloyl group containing phosphates are preferable and what is represented with the following general formula (g1), (g2) or (g3) is preferable.

In the general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, 1 and l ′ are integers of 1 to 10, and m is 1, 2 or 3.
These phosphate group-containing compounds may be used alone or in combination of two or more.

(2) Surfactant The photosensitive coloring composition of the present invention may contain a surfactant to improve the coatability.

As surfactant, various things, such as an anionic type, a cationic type, a nonionic type, an amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant in that the possibility of adversely affecting various properties is low, and a fluorine-based or silicon-based surfactant is particularly effective in terms of coatability.
As such surfactant, for example, TSF 4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by Bick Chemie Co., Ltd.), KP340 (Shin Etsu Silicone) , F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar) And FC 4430 (manufactured by Sumitomo 3M).
In addition, surfactant may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(3) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid for the purpose of improving dispersibility and storage stability.
As a pigment derivative, azo type, phthalocyanine type, quinacridone type, benzimidazolone type, quinophthalone type, isoindolinone type, dioxazine type, anthraquinone type, indanthrene type, perylene type, perinone type, perinone type, diketopyrrolopyrrole type, dioxazine There may be mentioned derivatives of such as systems, among which phthalocyanines and quinophthalones are preferred.
As a substituent of the pigment derivative, 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 amido group, etc. directly on the pigment skeleton or an alkyl group, an aryl group or a complex What is bonded via a ring group etc. is mentioned, Preferably it is a sulfonic acid group. Moreover, these substituents may be multiply substituted by one pigment frame.

  Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. One of these may be used alone, or two or more may be used in combination.

(4) Photo-acid generator The photo-acid generator is a compound capable of generating an acid by ultraviolet light, and the presence of a crosslinking agent such as a melamine compound by the action of the acid generated upon exposure. The crosslinking reaction will proceed. Among the photoacid generators, those having high solubility in solvents, particularly high solubility in solvents used for photosensitive coloring compositions, are preferred. For example, diphenyliodonium, ditollylodonium, phenyl (p-anisyl) are preferable. Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p -Diaryliodoniums such as isopropylphenyl (p-tolyl) iodonium, chlorides, bromides or borofluoride salts of triarylsulfoniums such as triphenylsulfonium, hexafluorophosphate salts, Sulfonium organoboron complexes such as senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts, etc., diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Although triazine compounds, such as bis trichloromethyl triazine and 2- (4-methoxyphenyl) -4,6-bis trichloromethyl triazine, etc. can be mentioned, it is not this limitation.

(5) Crosslinking agent A crosslinking agent can be further added to the photosensitive coloring composition of the present invention, and for example, a melamine or guanamine compound can be used. As these crosslinking agents, the compound of the melamine or guanamine type shown by following General formula (6) can be mentioned, for example.

In formula (6), R ⁶¹ represents a —NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms, and when R ⁶¹ is an —NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and the rest of R ⁶⁷ independently of each other 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 Represent.
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 an alkyl group, an alkoxy group, a halogen atom, etc. are exemplified as the phenyl group and the naphthyl group. The substituent of may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, especially a methyl group.

  The melamine compounds corresponding to the general formula (6), that is, the compounds of the following general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxylmelamine Methylmelamine, hexaethoxymethylmelamine and the like are included.

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 It represents oR ⁶⁸ group, the remaining ^{R 62, R 63, R 64} , R 65, R 66 and R ⁶⁷ each independently represent a hydrogen atom or a -CH ₂ oR ⁶⁸ group, wherein the R ⁶⁸ is a hydrogen atom or Represents an alkyl group.

In addition, guanamine compounds corresponding to the general formula (6), that is, compounds in which R ⁶¹ in the general formula (6) is aryl, include tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine. Etc. are included.

Furthermore, crosslinking agents having methylol groups or methylol alkyl ether groups can also be used. An example is given below.
2,6-Bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 3,5-Triazin-2-one (generally called N-ethyldimethylol triazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (generally called dimethylol urone) or its dimethyl ether, tetramethylol glyoxal diurein or its tetramethyl ether.

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

(6) Mercapto Compound It is also possible to add a mercapto compound as a polymerization accelerator or to improve the adhesion to a substrate.

  Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, and butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis 3-Mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3) -Mercapto butyrate), pentaerythritol tris (3-mercapto butyrate), ethylene glycol bis (3- mercapto isobutyrate), butanediol bis (3- mercapto isobutyrate), trimethylolpropane tris (3-mercaptoiso) Butyrate), 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triquinone and other mercapto compounds having a heterocyclic ring Or aliphatic polyfunctional mercapto compounds etc. It is. These can be used singly or in combination of two or more.

<Composition of Component in Photosensitive Coloring Composition>
In the photosensitive coloring composition of the present invention, the content ratio of the (a) colorant is usually 10% by mass or more, preferably 20% by mass or more based on the total solid content in the photosensitive coloring composition. , More preferably 25% by mass or more, and usually 50% by mass or less, preferably 45% by mass or less, more preferably 40% by mass or less, and 35% by mass or less Is more preferable, and 30% by mass or less is particularly preferable. (A) A sufficient optical density (OD) tends to be obtained by setting the content ratio of the coloring agent to the above lower limit value, and a sufficient image formability can be obtained by setting the content ratio to the above upper limit value. It tends to be easy.

  The content of the organic black pigment represented by the general formula (1) with respect to 100 parts by mass of the (a) colorant is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. 20 parts by mass or more is further preferable, 90 parts by mass or less is preferable, 80 parts by mass or less is more preferable, 60 parts by mass or less is more preferable, and 40 parts by mass or less It is more preferable to be present, and particularly preferably 30 parts by mass or less. There is a tendency that the light shielding property can be improved by setting it to the above lower limit value, and there is a tendency to be able to suppress the reliability decrease by setting it to the above upper limit value.

  When the colorant (a) contains an orange pigment, the content of the orange pigment per 100 parts by mass of the colorant (a) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more It is more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 90 parts by mass or less, 80 parts by mass The content is more preferably the following, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less. The light blocking property around 400 nm to 550 nm tends to be improved by setting the lower limit value or more, and by setting the upper limit value or less, the entire visible light range tends to be able to be balanced in a balanced manner when combined with other pigments. .

  The content of the (a-1) orange pigment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass or more based on 100 parts by mass of the colorant (a). Is more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less The content is more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less. The light blocking property around 400 nm to 550 nm tends to be improved by setting the lower limit value or more, and by setting the upper limit value or less, the entire visible light range tends to be able to be balanced in a balanced manner when combined with other pigments. .

  When the colorant (a) contains a blue pigment, the content of the blue pigment relative to 100 parts by mass of the colorant (a) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more 20 parts by mass or more is more preferable, 30 parts by mass or more is further more preferable, 40 parts by mass or more is particularly preferable, and 90 parts by mass or less is preferable, and 80 parts by mass The content is more preferably the following, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less. By setting the lower limit value or more, the light shielding property in the vicinity of 550 nm to 700 nm tends to be able to be improved, and by setting the upper limit value or less, the transmittance in the ultraviolet light range tends to be able to be improved.

  The content of the (a-2) blue pigment relative to 100 parts by mass of the colorant (a) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass or more Is more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and preferably 90 parts by mass or less, more preferably 80 parts by mass or less The content is more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less. By setting the lower limit value or more, the light shielding property in the vicinity of 550 nm to 700 nm tends to be able to be improved, and by setting the upper limit value or less, the transmittance in the ultraviolet light range tends to be able to be improved.

  Furthermore, the content of the blue pigment relative to 100 parts by mass of the orange pigment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and 900 It is preferable that it is a mass part or less, It is more preferable that it is 800 mass parts or less, It is more preferable that it is 600 mass parts or less, It is still more preferable that it is 300 mass parts or less, It is 100 mass parts or less Is particularly preferred. By setting the lower limit value or more, the entire visible light region tends to be shielded in a balanced manner, and by setting the upper limit value or less, the transmittance of the ultraviolet light range tends to be able to be improved.

  When the colorant (a) contains a violet pigment (a-3), the content of the violet pigment (a-3) relative to 100 parts by mass of the colorant (a) is preferably 10 parts by mass or more, It is more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 90 parts by mass or less, and 80 parts by mass or less Some are more preferable, 60 parts by mass or less is more preferable, and 50 parts by mass or less is particularly preferable. By setting the content to the above lower limit or more, there is a tendency to improve the light shielding property in the vicinity of 500 nm to 600 nm where light can not be blocked sufficiently by only the orange pigment and the blue pigment. Tend.

  Moreover, when (a) coloring agent contains (a-4) organic coloring pigment, the content of (a-4) organic coloring pigment with respect to 100 parts by mass of (a) coloring agent is 10 parts by mass or more Preferably, 20 parts by mass or more is more preferable, 30 parts by mass or more is further preferable, 90 parts by mass or less is preferable, 80 parts by mass or less is more preferable, and 60 parts by mass It is more preferable that it is the following. In the case of the red pigment, the transmittance in the ultraviolet light region tends to be able to be improved by setting it to the above lower limit value, and in the case of the blue pigment, the light blocking property in the visible light region tends to be improved. In the case of a red pigment, there is a tendency to be able to suppress the decrease in light shielding property in the visible light region, and in the case of a blue pigment, there is a tendency to be able to suppress a decrease in transmittance in the ultraviolet light region.

  When the colorant (a) contains carbon black, the content of carbon black relative to 100 parts by weight of the colorant (a) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more 20 parts by mass or more is more preferable, 60 parts by mass or less is preferable, 50 parts by mass or less is more preferable, and 40 parts by mass or less is more preferable. The light shielding property tends to be improved by setting the lower limit value or more, and the increase in the relative dielectric constant tends to be suppressed by setting the upper limit value or less.

  The content ratio of the (b) alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably, based on the total solid content of the photosensitive coloring composition of the present invention. It is 30% by mass or more, usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less. (B) By setting the content of the alkali-soluble resin to the lower limit value or more, it is possible to suppress the decrease in the solubility of the unexposed area in the developer and to suppress the development failure. Further, by setting the upper limit value or less, it is possible to suppress the increase in the permeability of the developing solution to the exposed portion, and to suppress the reduction in sharpness and adhesion of the pixels.

  The content ratio of the photopolymerization initiator (c) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass, based on the total solid content of the photosensitive coloring composition of the present invention It is the above, Usually 15 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. (C) There is a tendency that the sensitivity decrease can be suppressed by setting the content ratio of the photopolymerization initiator to the above lower limit value, and by setting the content ratio to the above upper limit value, the decrease in the solubility of the unexposed part in the developer is suppressed. And development defects tend to be suppressed.

(C) When using a polymerization accelerator together with a photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the photosensitive coloring composition of the present invention, and usually 10% % Or less, preferably 5% by mass or less, and the polymerization accelerator is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of (c) photopolymerization initiator It is preferred to use. By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency to suppress the decrease in sensitivity to the exposure light, and by setting the content ratio to the above upper limit value, the decrease in the solubility of the unexposed area in the developer is suppressed. Tend to be able to suppress development defects.
In addition, the blending 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, based on the total solid content of the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.

  The content ratio of the (d) ethylenically unsaturated compound is usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. (D) By setting the content ratio of the ethylenically unsaturated compound to the upper limit value or less, it is possible to suppress the increase in the permeability of the developer to the exposed area and to easily obtain a good image. is there. The lower limit value of the content ratio of the (d) ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more.

  The photosensitive coloring composition of the present invention has a solid content concentration of usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30 by using a solvent (e). The mixture is adjusted to be mass%.

  The content ratio of the dispersant (f) is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less in the solid content of the photosensitive coloring composition. 20 mass% or less is preferable, and 15 mass% or less is especially preferable. In addition, the content ratio of the (f) dispersant to 100 parts by mass of the colorant (a) is usually preferably 5 parts by mass or more and 10 parts by mass or more, and usually 50 parts by mass or less, particularly 30 parts by mass or less preferable. (F) By setting the content ratio of the dispersant to the lower limit value or more, sufficient dispersibility tends to be easily obtained, and by setting the content ratio to the upper limit value or less, the ratio of the other components relatively decreases. There is a tendency to be able to suppress that sensitivity, plate-making property etc. decline.

  When the adhesion improver is used, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 based on the total solids in the photosensitive coloring composition. It is -2 mass%. There is a tendency that the adhesion improvement effect can be sufficiently obtained by setting the content ratio of the adhesion improving agent to the above lower limit value, and the sensitivity is lowered by setting the content ratio to the above upper limit value, or the residue remains after development. There is a tendency to be able to suppress becoming a defect.

  When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0 based on the total solid content in the photosensitive coloring composition. 0.1 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. By setting the content of the surfactant to the lower limit value or more, the smoothness and uniformity of the coating film tend to be easily expressed, and by setting the content to the upper limit value or less, the smoothness and uniformity of the coating film are expressed It tends to be easy to suppress deterioration of other characteristics.

<Physical Properties of Photosensitive Colored Composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a coloring spacer, and from the viewpoint of using as a coloring spacer, it is preferable to exhibit black. Further, the optical density (OD) per 1 μm of the film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and usually It is less than 4.0.

<Method of producing photosensitive coloring composition>
The photosensitive coloring composition (hereinafter sometimes referred to as "resist") of the present invention is produced according to a conventional method.
In general, the colorant (a) is preferably dispersed 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. By the dispersion treatment, (a) the colorant is micronized, the coating characteristics of the resist are improved.

The dispersion treatment is usually preferably performed in a system in which a part or all of (a) colorant, (e) solvent, and (f) dispersant, and (b) alkali-soluble resin are used in combination (hereinafter, dispersion) The mixture to be subjected to the treatment, and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion". In particular, the use of a polymer dispersant as the dispersant (f) is preferable because thickening of the obtained ink and resist with time is suppressed (the dispersion stability is excellent).
Thus, in the step of producing the resist, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, the (e) organic solvent, and the (f) dispersant which can be used for the pigment dispersion, those described as ones which can be used for the photosensitive coloring composition are preferably employed. Can.

In addition, when a dispersion process is performed with respect to the liquid containing all the components mix | blended with a photosensitive coloring composition, there is a possibility that a highly reactive component may be denatured due to the heat generated during the dispersion process. Therefore, it is preferable to carry out dispersion treatment in a system containing a polymer dispersant.
When the colorant (a) is dispersed by a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. Dispersion treatment conditions are usually a temperature of 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. Controlling the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300 is a measure of dispersion. When the glossiness 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, resolution, etc. . In addition, when the dispersion process is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so the dispersion stability tends to be impaired.

The dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the above dispersion treatment and the other components described above contained in the resist are mixed to form a uniform solution. In the resist manufacturing process, it is desirable to filter the obtained resist with a filter or the like because fine dust is often mixed in the solution.

[Cured product]
A cured product can be obtained by curing the photosensitive coloring composition of the present invention. A cured product obtained by curing the photosensitive coloring composition can be suitably used as a coloring spacer, and in particular, it can be suitably used to collectively form colored spacers having different heights by photolithography.

[Coloring spacer]
Next, the coloring spacer using the photosensitive coloring composition of this invention is demonstrated according to the manufacturing method.

(1) Support As a support for forming a colored spacer, the material is not particularly limited as long as it has appropriate strength. A transparent substrate is mainly used, and as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy Thermosetting resin sheets, such as resin, unsaturated polyester resin, poly (meth) acrylic resin, or various glass etc. are mentioned. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In addition, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. It is also possible to form on a TFT array other than a transparent substrate.

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, for improvement of 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. Moreover, when performing the thin film formation process of various resin, the film thickness is the range of 0.01-10 micrometers normally, Preferably it is 0.05-5 micrometers.

(2) Colored Spacer The photosensitive colored composition of the present embodiment is used in the same manner as a known photosensitive colored composition for color filter, but the case of use for colored spacer will be described below. Usually, a photosensitive coloring composition solution is supplied in the form of a film or pattern by a method such as coating on a substrate on which a coloring spacer is to be provided, and the solvent is dried. Subsequently, exposure and development are performed. A pattern is formed by photolithography or the like. Thereafter, a colored spacer is formed on the substrate by performing additional exposure and thermosetting treatment as necessary.

(3) Formation of Colored Spacer (3-1) Application of Photosensitive Colored Composition The photosensitive colored composition of the present embodiment is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. The application of the photosensitive coloring composition for a coloring spacer onto a 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. Above all, according to the die coating method, the amount of coating solution used is significantly reduced, and there is no influence of mist etc. adhering when using the spin coating method, and the generation of foreign matter is suppressed, and so on. It is preferable from

  When the thickness of the coating film is too thick, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation step may become difficult, and when it is too thin, it becomes difficult to increase the pigment concentration and 1 to 10 μm It is preferably in the range, more preferably in the range of 1 to 9 μm, and still more preferably in the range of 1 to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer be uniform over the entire substrate. If the variation is large, nonuniformity defects of the liquid crystal panel will occur. Moreover, you may supply in pattern shape by the inkjet method, the printing method, etc.

(3-2) Drying of Coating Film Drying of the coating film after the photosensitive coloring composition is applied to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but if it is too high, the (b) alkali-soluble resin may be decomposed to induce thermal polymerization to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating of the photosensitive coloring composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. In the case of performing exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or placing the exposure mask at a position away from the coating film of the photosensitive coloring composition It may be a method of projecting exposure light through a mask. Alternatively, a scanning exposure method using laser light without using a mask pattern may be used. Under the present circumstances, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen as needed, you may expose after forming oxygen blocking layers, such as a polyvinyl alcohol layer, on a photopolymerizable coating film. The light source used for the above-mentioned image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, lamp light sources such as fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers and the like can be mentioned. An optical filter can also be used when irradiating and using the light of a specific wavelength. The optical filter may be, for example, a thin film which can control the light transmittance at the exposure wavelength, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), MoSi, Si, W, Al etc. are mentioned.

  Also, in recent years, a method of collectively forming colored spacers having different heights has been proposed for producing the colored spacers by photolithography. Also in the embodiment of the present invention, as disclosed in Japanese Patent Application Laid-Open Nos. 2003-344860 and 2004-45757, the average light transmission is performed as the light shielding portion (0% light transmittance) and the plurality of openings. Of forming colored spacers of different heights at a time by using an exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to the highest opening (full transmission opening) ing. If it is a negative photosensitive coloring composition, the degree of cure and the residual film rate of the pattern are changed by the difference in the average transmittance between the intermediate transmission aperture and the complete transmission aperture, that is, the difference in exposure amount, Through the development and heat curing process, steps of the colored spacer can be formed.

Exposure is usually normal, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 300 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably It is 150 mJ / cm ² or less. In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less It is.

(3-4) Development The colored spacer according to the present invention is an aqueous solution containing an organic solvent or a surfactant and an alkaline compound after image exposure of the coated film of the photosensitive coloring composition with the above light source. Can be produced by forming an image on a substrate. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

  As the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-.di- or triethanolamine, mono-.di- or trimethylamine Mono-.di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-.di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkyl benzene sulfonic acid Anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts, and 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 conditions for development are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., preferably 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development method is immersion development, spray development, brush It can be by any method such as a developing method or an ultrasonic developing method.

(3-5) Thermal Curing Treatment The substrate after development is subjected to a thermal curing treatment or a light curing treatment, preferably a thermal curing treatment. In this case, the temperature of the thermosetting treatment is selected in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
The size, shape, and the like of the colored spacer of the present invention formed as described above are appropriately adjusted in accordance with the specification and the like of the color filter. However, the photosensitive coloring composition of the present invention is effective for collectively forming colored spacers having different heights of spacer and sub-spacer by photolithography as described above, and the height of the spacer is usually 2 to 7 μm. The sub-spacer has a height which is usually about 0.2 to 1.5 μm lower than that of the spacer.

[Color filter]
The color filter of the present invention is provided with the colored spacer of the present invention as described above, and for example, on a glass substrate as a transparent substrate, a black matrix, red, green and blue pixel coloring layers, and an overcoat layer Are laminated to form a colored spacer, and then an orientation film is formed. As the alignment film, a resin film such as polyimide is suitable.

[Image display device]
The image display device of the present invention is not particularly limited as long as it is a device for displaying an image or a video, but includes a liquid crystal display device described later, an organic electro luminescence (EL) display, and the like.

[Liquid crystal display device]
The liquid crystal display device of the present invention is manufactured using the above-mentioned colored spacer of the present invention, and is not particularly limited in the formation order or formation position of color pixels or black matrix.
For example, a black matrix is provided on a TFT element substrate, red, green and blue pixels are formed, and if necessary, an overcoat layer is formed, and then ITO, IZO, etc. transparent on the image. An electrode is formed and used as a part of parts, such as a color display and a liquid crystal display. In addition, in some applications such as a planar orientation drive method (IPS mode), the transparent electrode may not be formed.

  In the liquid crystal display device, usually, an alignment film is formed on a color filter, and a spacer is dispersed on the alignment film, or the colored spacer of the present invention is formed, and then bonded to an opposing substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell, and wire connection is completed to the opposite electrode. As the alignment film, a resin film such as polyimide is suitable. For forming the alignment film, usually, a gravure printing method and / or a flexo printing method is adopted, and the thickness of the alignment film is several tens nm. After curing treatment of the alignment film by thermal baking, the alignment film is subjected to surface treatment by irradiation with ultraviolet light or treatment with a rubbing cloth to be processed into a surface state capable of adjusting the inclination of the liquid crystal.

The bonding gap with the opposing substrate is usually selected in the range of 2 to 8 μm, although it varies depending on the application of the liquid crystal display device. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units and then decompressed in a vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and then liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of pressure reduction in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat the liquid crystal cell at the time of pressure reduction, and the heating temperature is usually 30 to 100 ° C., more preferably 50 to 90 ° C. The heating and holding at the time of pressure reduction is usually in the range of 10 to 60 minutes, and then it is immersed in the liquid crystal. The liquid crystal cell in which the liquid crystal is injected is sealed with a UV curable resin which cures the liquid crystal injection port, thereby completing the liquid crystal display (panel).

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

Next, the present invention will be more specifically described by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.
The components of the photosensitive coloring composition used in the following examples and comparative examples are as follows.

<Organic black pigment>
BASF Corporation Irgaphor® Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Alkali-soluble resin-I>
It stirred, nitrogen-substituting 145 mass parts of propylene glycol monomethyl ether acetate, and it heated up at 120 degreeC. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped, and 2,2'-azobis-2-methyl 8.47 mass parts of butyronitrile were dripped over 3 hours, and also stirring was continued at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was replaced with air, 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 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, and the acid value was 80 mg KOH / g.

<Alkali-soluble resin-II>
Nippon Kayaku Co., Ltd. “ZCR-1642H” (MW = 6500, acid value = 98 mg-KOH / g)
<Alkali-soluble resin-III>

  Attach a thermometer, a stirrer, and a cooling pipe to 50 g of the epoxy compound of 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 paramethoxyphenol The mixture was placed in a flask and allowed to react at 90 ° C. with stirring until the acid value became 5 mg KOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the above epoxy acrylate solution, 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), 2.8 parts by mass of tetrahydrophthalic anhydride (THPA) The mixture was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was raised to 105.degree. C. with stirring to cause a reaction.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, an acid value of 131 mg KOH / g, and a carboxyl group having a polystyrene-equivalent weight average molecular weight (Mw) of 4000 as measured by GPC. The contained epoxy acrylate resin was obtained.

<Dispersant-I>
Bic Chemie “DISPERBYK-LPN 21116” (acrylic A-B block co-made of A block having quaternary ammonium base and tertiary amino group in side chain and B block having no quaternary ammonium base and amino group) Polymer)

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <solvent-II>
MB: 3-methoxy butanol

<Photoinitiator-I>
A compound having the following chemical structure was used.

<Photopolymerizable Monomer-I>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate

<Additive-I>
Nippon Kayaku Co., Ltd. product KAYAMER PM-21 (methacryloyl group-containing phosphate)

<Additive-II>
Toray Dow Corning Co., Ltd. SH6040

<Surfactant-I>
DIC Corporation made Megafuck F-559

<Measurement of optical density (unit OD value) per unit film thickness>
The optical density per unit film thickness was measured by the following procedure.
First, the prepared photosensitive coloring composition was applied to a glass substrate by a spin coater so as to give a final film thickness of 2 μm, dried under reduced pressure for 1 minute, and dried at 80 ° C. for 70 seconds on a hot plate. The resist coating board | substrate was obtained by heating at 230 degreeC for 20 minutes. The optical density (OD) of the obtained substrate is measured with a transmission densitometer Gretag Macbeth D200-II, and the film thickness is measured with a non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka Systems Co., Ltd. The optical density per unit film thickness was calculated from the optical density (OD) and the film thickness. The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding ability.

<NMP dissolution test>
The N-methyl pyrrolidone (NMP) elution test was performed according to the following procedure.
First, the prepared photosensitive coloring composition was coated on a glass substrate by a spin coater so as to give a final film thickness of 2 μm, dried under reduced pressure for 1 minute, and dried at a hot plate at 80 ° C. for 70 seconds. After the exposure and development steps, the substrate was heated at an oven temperature of 230 ° C. for 20 minutes to obtain a resist coated substrate. Two substrates for measurement (2.5 cm × 1.0 cm square) were cut out from the produced resist-coated substrate and immersed in a 10 mL vial containing 8 mL of N-methylpyrrolidone (NMP). And the NMP elution test was implemented in the state which left the vial bottle containing the substrate for measurement in a 80 degreeC heat bath for 40 minutes. After standing for 40 minutes, the vial was removed from the heat bath, and the NMP-eluted solution was measured for absorbance at 1 nm intervals in a wavelength range of 300 to 800 nm using a spectrophotometer ("UV-3100 PC" manufactured by Shimadzu Corporation). A halogen lamp and a deuterium lamp (switching wavelength: 360 nm) are used as a light source, and a photomar is used as a detector, and a slit width of 2 nm is used as a measurement condition. In the case of a liquid, the sample solution is placed in a 1 cm square quartz cell and measured. Absorbance is a dimensionless quantity that indicates how much the light intensity attenuates when light passes through an object in spectroscopy, and is defined by the following equation.

A (absorbance) = -log ₁₀ (I / I ₀ ) (I: transmitted light intensity, I ₀ : incident light intensity)

Further, the same time of each light is incident to the sample solution and NMP alone from the light source can be regarded as the light intensity I transmitted through the light intensity I ₀ and the sample solution having passed through the NMP alone. Therefore, (I / I ₀ ) in the above equation represents the light transmittance, and the absorbance A is a value obtained by logarithmically expressing the reciprocal of the transmittance. The absorbance A is a notation used when calculating the concentration or the like of a substance contained in a sample solution. In the case of the absorbance A = 0, it shows a state of not absorbing light at all (transmission rate 100%), and in the case of the absorbance A = ∞, it shows a state of not transmitting light at all (transmission rate 0%). become. That is, the stronger the absorbance, the more the resist coating component dissolves into NMP, indicating that the NMP resistance is worse. The spectrum area (nm) of the measured absorbance was calculated, and the area value less than 30 (nm) was evaluated as ○, 30 (nm) or more and less than 50 (nm) as Δ, and 50 (nm) or more as x . The spectral area of the absorbance, which is the evaluation criterion, can be represented by the sum of absorbance at each wavelength, and means the sum of the eluted resist components.

NMP resistance evaluation criteria: Determination by the area value of absorption spectrum of NMP elution solution (wavelength 300 to 800 nm)
○: less than 30 (nm) Δ: 30 (nm) or more and 50 (nm) or less ×: 50 (nm) or more

Preparation of Pigment Dispersion 1 and 2
The pigments described in Table 1, the dispersant, the alkali-soluble resin, and the solvent were mixed to achieve the mass ratio described in Table 1. The solution was dispersed for 3 hours in the range of 25 to 45 ° C. with a paint shaker. As beads, 0.5 mm diameter zirconia beads were used, and 2.5 times the mass of the dispersion were added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare pigment dispersions 1 and 2.

Example 1
Using the pigment dispersion prepared above, each component is added so that the ratio in solid content becomes the blending ratio in Table 2, and then PGMEA is added so that the solid content becomes 17 mass%, stirred and dissolved , A photosensitive coloring composition was prepared. The solid content ratio of the prepared composition is shown in Table 2. Moreover, the unit OD value measured by the above-mentioned method and the NMP dissolution test result are shown in Table 2. In addition, the mass part of the photosensitive coloring composition in Table 2 shows the mass of solid content.

  From Example 1 in Table 2, in the photosensitive coloring composition containing a specific organic black pigment, a short wavelength can be obtained by using a specific photopolymerization initiator having a diphenyl sulfide skeleton among the oxime ester photopolymerization initiators. It is considered that the light absorption of the above is strong and the surface curability is improved, so that it is difficult to be dissolved in NMP and the solvent resistance is enhanced. In particular, by setting the group to be bonded to the oxime ester to be an alkyl group which may have a substituent, the mobility of the radical is high and the sensitivity is high, so it is considered that the surface curability is further improved. Further, it is considered that the prevention of the permeation of NMP can suppress the dissolution of the coloring agent and the like even from the inside of the coating film. Then, the photopolymerization initiator having a diphenyl sulfide skeleton has a short length of the conjugated system, the energy of the whole molecule is high, the radical generation efficiency by thermal decomposition is high, and the polymerization reaction is promoted, and the unreacted matter of the initiator It is considered that the elution of the initiator itself to NMP was also suppressed.

  From the above, the photosensitive coloring composition of the present invention, which contains a photopolymerization initiator having a diphenyl sulfide skeleton and contains a specific organic black pigment, is excellent in the light shielding property and suppresses the elution of impurities into the solvent. It turned out to be useful.

  According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a colored spacer which are excellent in light-shielding property and highly reliable, and to provide an image display device provided with such a colored spacer. Can. Therefore, the present invention has extremely high industrial applicability in the fields of photosensitive coloring composition, cured product, coloring spacer and image display device.

Claims (14)

A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. There,
The organic black pigment, wherein the colorant (a) is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer thereof,
The photosensitive coloring composition characterized by the said (c) photoinitiator containing the oxime ester type compound which has a diphenyl sulfide frame represented by following General formula (I).

[In the above general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ independently of each other are each independently a hydrogen atom, a halogen atom, R ¹¹ COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCN HR 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 , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And 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 , They can also be directly linked to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or carbon It is an alkynyl group of several 2-12. ]

[In the above general formula (I), R ²³ represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ²⁴ represents a methyl group .
R ²⁵ represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (I-1), and h represents an integer of 0 to 5.
The benzene ring shown in Formula (I) may further have a substituent. ]

[In the above general formula (I-1), R ^25a represents -O-, -S-, -OCO- or -COO-.
R ^25b represents an alkylene group which may have a substituent.
The alkylene moiety of R ^25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The alkylene moiety of R ²⁵ may be branched side chain and may be cyclohexylene.
R ^25c represents a hydroxyl group or a carboxyl group. ]   The photosensitive coloring composition according to claim 1, wherein the (a) colorant further comprises an orange pigment and a blue pigment. The photosensitive coloring composition of Claim 2 whose said orange pigment is an orange pigment shown to the following (a-1), and whose said blue pigment is a blue pigment shown to the following (a-2).
(A-1) C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 72 selected from the group consisting of C.I. I. Pigment blue 60 The photosensitive coloring composition of any one of Claims 1-3 in which the said (a) coloring agent contains the purple pigment further shown to the following (a-3).
(A-3) C.I. I. Pigment violet 23 and C.I. I. Pigment violet 29 selected from the group consisting of The photosensitive coloring composition of any one of Claims 1-4 in which the said (a) coloring agent contains the at least 1 sort (s) of organic coloring pigment further chosen from the group shown to the following (a-4).
(A-4)
Blue pigment: C.I. I. Pigment blue 15: 6
Red pigment: C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment red 272   The photosensitive coloring composition according to any one of claims 1 to 5, wherein the (a) colorant further contains carbon black.   The photosensitive coloring composition of any one of Claims 1-6 whose content rate of the said (a) coloring agent is 10 mass% or more with respect to the total solid amount in a photosensitive coloring composition.   The photosensitive coloring composition according to any one of claims 1 to 7, wherein the content ratio of the (a) coloring agent is 50% by mass or less based on the total solid content in the photosensitive coloring composition.   The photosensitive coloring composition of any one of Claims 1-8 whose optical density per film thickness of 1 micrometer of the hardened | cured coating film is 1.0 or more.   The photosensitive coloring composition of any one of Claims 1-9 used in order to form a coloring spacer.   The photosensitive coloring composition according to claim 10, which is used to collectively form colored spacers having different heights by a photolithography method.   Hardened | cured material obtained by hardening | curing the photosensitive coloring composition of any one of Claims 1-11.   A colored spacer formed from the cured product according to claim 12.   The image display apparatus provided with the coloring spacer of Claim 13.