JP2016164623A - Photosensitive colored composition, cured product, colored spacer, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored composition excellent in light-shielding property and capable of securing high reliability by suppressing elution of impurities into a solvent.SOLUTION: The photosensitive colored composition contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. The colorant (a) contains an orange pigment and a blue pigment. The photopolymerization initiator (c) contains an oxime ester compound having a diphenyl sulfide skeleton.SELECTED DRAWING: None

Description

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

  A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage to the liquid crystal. On the other hand, many of the members constituting the LCD cell are formed by a method using a photosensitive composition typified by photolithography. The photosensitive composition is expected to be widely applied in the future because it is easy to form a fine structure and can be easily processed to a large area substrate.

  However, due to the electrical reliability of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, the voltage applied to the liquid crystal molecules cannot be maintained, and there are problems with display reliability such as afterimage and image sticking of the LCD. It may occur. In particular, the display reliability of a color LCD is greatly influenced by the alignment film and the sealing material that are in contact with the liquid crystal layer, and the photo spacer used to hold the two substrates in the liquid crystal panel at regular intervals. Has been.

  Further, in a TFT type LCD using a conventional transparent photo spacer, the TFT as a switching element sometimes malfunctions due to light transmitted through the photo spacer. In order to prevent this malfunction, Patent Document 1 describes that a light shielding property is imparted to the photo spacer. A method of adding a colorant such as a pigment to a photosensitive composition in order to produce a photospacer having a light-shielding property is known (see Patent Document 2).

  Furthermore, in order to improve the display reliability of the LCD, a method has been proposed for improving curability while achieving high light shielding properties at a lower pigment concentration (see Patent Document 3).

JP-A-8-234212 International Publication No. 2013/062011 Pamphlet International Publication No. 2013/115268 Pamphlet

As a result of investigations by the present inventors, when a colored spacer is formed using the photosensitive coloring composition described in Patent Document 3, the colorant is derived from the solvent used to form the alignment film as the upper layer film. In addition to the elution of impurities, there are many elutions of impurities derived from the curing component due to the low pigment concentration and the large amount of the curing component, resulting in a problem that the display reliability of the LCD deteriorates. It was issued.
Then, this invention is providing the photosensitive coloring composition which is excellent in light-shielding property, 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 color pigment as a colorant in a photosensitive coloring composition and use a photopolymerization initiator having a specific skeleton structure. The present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention has the following configurations [1] to [14].

[1] Photosensitive coloring containing (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) ethylenically unsaturated compound, (e) solvent, and (f) dispersant. A composition comprising:
The (a) colorant contains an orange pigment and a blue pigment,
The photosensitive coloring composition, wherein the photopolymerization initiator (c) includes an oxime ester compound having a diphenyl sulfide skeleton.
[2] The photosensitive coloring composition according to [1], 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 (a-2) selected from the group consisting of C.I. I. Pigment Blue 60
[3] The photosensitive coloring composition according to [1] or [2], wherein the (a) coloring agent further contains a purple pigment shown in the following (a-3).
(A-3) C.I. I. Pigment violet 23 and C.I. I. [4] At least one selected from the group consisting of CI Pigment Violet 29 [4] The (a) colorant further contains at least one organic color pigment selected from the group shown in (a-4) below. The photosensitive coloring composition in any one of [3].
(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
[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the colorant (a) further contains an organic black pigment.

[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the colorant (a) further contains carbon black.
[7] The photosensitive coloring according to any one of [1] to [6], wherein the content ratio of the colorant (a) 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 of the colorant (a) 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 cured coating has an optical density of 1.0 or more per 1 μm of film thickness.
[10] The photosensitive colored 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 a photolithography method.
[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 this invention is excellent in light-shielding property, can suppress the impurity elution to a solvent, and can ensure high reliability. Further, it is possible to provide a cured product and a colored spacer that are excellent in light-shielding properties and highly reliable, and further, it is possible to provide an image display device including such a colored spacer.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

  The term “(co) polymer” means to include both a single polymer (homopolymer) and a copolymer (copolymer). “Acid (anhydride)”, “(anhydrous) ... acid” , Is meant to include both acids and anhydrides. In the present invention, “acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.

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

  In the present specification, the percentage and part expressed by “mass” are synonymous with the percentage and part expressed by “weight”.

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) a colorant (b) an alkali-soluble resin (c) a photopolymerization initiator (d) an ethylenically unsaturated compound (e) a solvent (f) a dispersant as an essential component, and if necessary, a silane cup It includes adhesion improvers such as ring agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, and other compounding components. Used in a state dissolved or dispersed in a solvent.

<(A) Colorant>
The colorant (a) used in the present invention contains an orange pigment and a blue pigment. As described above, the photosensitive coloring composition of the present invention contains an orange pigment and a blue pigment to increase the light absorption in the visible region and improve the shielding rate while ensuring the light transmittance in the ultraviolet region. Can do. (A) It is preferable to use a pigment as the colorant, and the pigment may be an organic pigment or an inorganic pigment, but it suppresses the decrease in the voltage holding ratio of the liquid crystal and suppresses the absorption of ultraviolet rays. It is more preferable to use an organic pigment from the viewpoint of facilitating control of the step.
The orange pigment may be abbreviated as an orange pigment (hereinafter referred to as “(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. At least one selected from the group consisting of CI Pigment Orange 72

(A-1) Among the orange pigments, C.I. I. It is preferable to use CI Pigment Orange 64.
(A-1) As an orange pigment, one type of orange pigment may be used, but a plurality of types may be used in combination. Specifically, C.I. I. Pigment orange 64 and C.I. I. Pigment Orange 43 combination, C.I. I. Pigment orange 64 and C.I. I. A combination of Pigment Orange 72 can be mentioned.

  In the present invention, in addition to (a-1) the orange pigment, other orange pigments may be used as the orange pigment. Other orange pigments include 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. Of these, C.I. I. And CI pigment oranges 38 and 71.

In addition, the blue pigment is not particularly limited, but from the viewpoint of light transmittance in the ultraviolet region and light absorbability in the visible region, the blue pigment shown below (a-2) (hereinafter, “(a-2) blue pigment”) May be abbreviated to be preferred).
(A-2) C.I. I. Pigment Blue 60

In the present invention, it is further preferable to use a purple pigment in addition to the orange pigment and the blue pigment. Among the violet pigments, it is preferable to use the violet pigment shown in the following (a-3) (hereinafter sometimes abbreviated as “(a-3) violet pigment”). (A-3) By using a violet pigment, there exists a tendency which can further improve the shielding rate of visible region.
(A-3) C.I. I. Pigment violet 23 and C.I. I. At least one selected from the group consisting of CI Pigment Violet 29

(A-3) Among purple pigments, from the viewpoint of reliability and pigment dispersibility, C.I. I. Pigment violet 29 is preferably used.
(A-3) One type of purple pigment may be used as the purple pigment, but two types may be used in combination.

In the present invention, when (a-1) an orange pigment is used as the orange pigment and (a-2) a blue pigment is used as the blue pigment, at least one organic compound selected from the group shown in (a-4) below is further used. It is preferable to use a colored pigment (hereinafter sometimes abbreviated as “(a-4) organic colored pigment”). (A-4) By using an organic coloring pigment, there exists a tendency which can further improve the shielding rate of a visible region.
(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

(A-4) Among the color pigments, C.I. I. Pigment Blue 15: 6 is preferably used. From the viewpoint of light transmittance in the ultraviolet region, C.I. I. Pigment Red 254 is preferably used.
(A-4) As an organic coloring pigment, one kind of organic coloring pigment may be used, but a plurality of kinds may be used in combination. Specifically, C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Red 254 combination, C.I. I. Pigment blue 15: 6 and C.I. I. And a combination of CI Pigment Red 177.

  In the present invention, C.I. I. Pigment blue 60, C.I. I. Other than blue pigment 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, 33, 35, 36, 56, 56: 1, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4.

  In the present invention, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Other than red pigment 272, 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: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 178, 179, 18 , 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269 270, 271, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 202, 206, 207, 209, 224, 242 and more preferably C.I. I. And CI Pigment Red 209 and 224.

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

Examples of green pigments include 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. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include 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: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

Furthermore, in addition to the organic coloring pigment, an organic black pigment can be used. By using an organic black pigment, the shielding rate tends to increase.
Among organic black pigments, from the viewpoint of light-shielding properties and dispersibility, an organic black pigment that is a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer is used. preferable.

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 are independently of each other a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ⁻ , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N = CH ₂ , N = CHR ¹¹ , N = CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ¹¹ , SO ₃ R ¹¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
And 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 , Can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ¹¹ and R ¹² are independently of each other 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 formula 2-12.

  The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. .

  When the compound represented by general formula (1) is anionic, its charge can be any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal. A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium, or trialkylammonium, a quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the following is preferable because the shielding ratio tends to be high. This is because the following substituents are considered not to absorb and affect the hue of the pigment.
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are independently of each other preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ³ and R ⁸ are preferably independently of each other 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 are preferably each independently a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, more preferably R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ Are the same.

  Examples of the alkyl group having 1 to 12 carbon atoms include 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 Group, nonyl group, decyl group, undecyl group or dodecyl group.

  Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.

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

  Examples of the C3-C12 cycloalkenyl group include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, and 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -An yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

  Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl. Group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-in-1-yl Group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiin-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).

Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later. In addition, when the sulfonic acid derivative of the general formula (2) is present during dispersion, dispersibility and storage stability may be improved.

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

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

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBl4, ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, REGAL 99) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark; the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Colombian Carbon: RAVEN (registered trademark; the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA10850RA, RA10850RA, RA40850RA RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As carbon black coated with resin, for example, carbon black described in JP-A No. 09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

  As carbon black to be subjected to a coating treatment with a resin, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe. The ash content of etc. is contained on the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.

  As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw oil, fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from the furnace is washed with water, hydrochloric acid or the like, and Na or Ca is dissolved and removed.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, carbon black moves to the solvent side and is completely separated from water when a solvent that is hardly soluble in water is added. At the same time, most of Na and Ca present in the 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 may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained. The average particle diameter means the number average particle diameter. Particle images are analyzed by taking several fields of photographs taken at tens of thousands of times by electron microscope observation, and measuring about 2000 to 3000 particles of these photographs with an image processing apparatus. This means the equivalent circle diameter obtained by.

  The method of preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and the resin, and then the resulting granular material is separated and heated to remove the remaining solvent and water; 3. Dissolve carboxylic acid such as maleic acid and fumaric acid in the above-mentioned solvent, add carbon black, mix and dry, remove the solvent to obtain carboxylic acid-impregnated carbon black, and then add resin to it. 3. dry blending method; A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension, and after polymerization, the reactive group-containing resin is obtained from the polymer suspension by cooling. A method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.

The type of resin to be coated is not particularly limited, but a synthetic resin is common, and a resin having a benzene ring in its structure has a stronger function as an amphoteric surfactant. From the viewpoints of stability and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used. The coating amount of the resin with respect to the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and there is a tendency that the coating can be made sufficiently by setting the amount to the lower limit value or more. On the other hand, by setting it to the upper limit value or less, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

  Carbon black formed by coating with a resin in this manner can be used as a light shielding material for a colored spacer according to a conventional method, and a color filter having this colored spacer as a constituent element can be prepared by a conventional method. When such carbon black is used, there is a tendency that a colored spacer having a high light shielding rate and a low surface reflectance can be achieved at a low cost. It is also speculated that by covering the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

In addition to the organic color pigment, organic black pigment, and inorganic black pigment described above, a dye may be used. Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include 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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

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 etc. are mentioned.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as 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, more preferably 0.25 μm or less. Here, the standard of the average particle diameter is the number of pigment particles.
In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS). The particle size is measured by fully diluting the photosensitive coloring composition (usually diluted and adjusted to a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, According to concentration) and measured at 25 ° C.

<(B) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. For example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin is used. A urethane resin, a novolac resin, a polyvinylphenol resin, and the like can be given. Among them, an epoxy (meth) acrylate resin and an acrylic resin are preferable. These can be used individually by 1 type or in mixture of multiple types.

  The alkali-soluble resin (b) used in the present invention is particularly the following alkali-soluble resin (b1) and / or alkali-soluble resin (b2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). Is preferably used from the viewpoint of excellent plate-making property.

<Alkali-soluble resin (b1)>
It was 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 α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.

  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”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)), 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 an alcoholic hydroxyl group of bisphenol F type epoxy resin with 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 (eg“ YX-4000 ”manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (eg Nippon Kayaku Co., Ltd.) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolac type epoxy resin (For example, “EOCN (registered trademark) manufactured by Nippon Kayaku Co., Ltd.”) “102S”, “EOCN-1020”, “EOCN-104S”), triglycidyl isocyanurate (for example, “TEPIC manufactured by Nissan Chemical Co., Ltd.) (Registered trademark) ”), trisphenolmethane type epoxy resin (for example,“ EPPN (registered trademark) manufactured by Nippon Kayaku Co., Ltd. ) -501 "," EPN-502 "," EPPN-503 "), cycloaliphatic epoxy resin (" Celoxide 2021P "," Celoxide (registered trademark, the same applies hereinafter) EHPE "manufactured by Daicel Chemical Industries, Ltd.) An epoxy resin obtained by glycidylation of a phenol resin by reaction of dicyclopentadiene and phenol (for example, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), the following general formulas (B1) to An epoxy resin represented by (B4) can be preferably used. Specifically, “XD-1000” manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), and “XD-1000” manufactured by Nippon Kayaku 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., and the like can be given 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 any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group. A plurality of R ¹¹¹ present in one molecule may be the same or different from each other.

In the said general formula (B2), b shows an average value and shows the number of 0-10. R ¹²¹ represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group. A plurality of R ¹²¹ present in one molecule may be the same or different from each other.

  In the 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), R ^{131 to} R ¹³⁴ and R ^{135 to} R ¹³⁷ are each independently an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. The alkyl group of C1-C12 which may have this, or the phenyl group which may have a substituent is shown. * Indicates a bond.

In the 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 each independently represents an alkylene group having 1 to 4 carbon atoms. x and y each independently represents an integer of 0 or more.

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

Examples of 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, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 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- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomer with added acid (anhydride) such as maleic acid, (meth) acrylic acid dimer And the like.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

  As a method of adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin, a known method 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, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .

In addition, the epoxy resin, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two types. You may use the above together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

  Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal Examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

  A known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid having carboxyl group to epoxy resin. The target product can be obtained by continuing the 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 resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mg KOH / g, and further 20 It is preferable that it is a grade which becomes the range of -140 mgKOH / g. There exists a tendency for alkali developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for hardening performance to become favorable by setting it as the said upper limit or less.

In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure 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 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. Or after mixing the anhydride, or 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 with a polybasic acid and / or Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. To the polybasic acid and / or its anhydride.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1000 or more, preferably 1500 or more, and usually 10,000 or less, preferably 8000. Below, more preferably 6000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.

The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
Moreover, you may replace and use a part of above-mentioned carboxyl group-containing epoxy (meth) acrylate resin for another binder resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, it is preferable that the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in (b) the alkali-soluble resin is 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 for the photosensitive coloring composition. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like. In addition, all other binder resins may be used alone or in combination of two or more.

  Further, as the (b) alkali-soluble resin, it is preferable to use an acrylic resin from the viewpoint of plate-making property, and those described in JP-A-2014-137466 can be preferably used.

Examples of the acrylic resin include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”) and other copolymerizable ethylenically unsaturated monomers. Examples thereof include a copolymer with a monomer (hereinafter referred to as “unsaturated monomer (b2)”).
Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl]; having carboxy groups and hydroxyl groups at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate Polymer mono (meth) acrylate; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

  Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; 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 (degree of polymerization 2 -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 paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane A macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, and the like.
These unsaturated monomers (b2) can be used alone or in admixture 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 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, there is a tendency that a photosensitive coloring composition excellent in alkali developability and storage stability can 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. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.
The copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method. For example, JP 2003-222717 A, JP 2006-259680 A The structure, Mw, and Mw / Mn can also be controlled by the method disclosed in Japanese Patent Publication No. 2007/029871.

<(C) Photopolymerization initiator>
(C) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or 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. Thus, by including the oxime ester compound having a diphenyl sulfide skeleton, light absorption at a short wavelength is strong and surface curability is improved, so that it is difficult to dissolve in a solvent and solvent resistance is considered to increase. Moreover, it is thought that it can control that a coloring agent melt | dissolves also from the inside of a coating film by preventing permeation of a solvent. The oxime ester-based compound having a diphenyl sulfide skeleton has a short conjugated system, increases the energy of the whole molecule, increases the radical generation efficiency by thermal decomposition, promotes the polymerization reaction, and further unreacted initiator. Therefore, it is considered that elution of the initiator itself into the solvent can be suppressed.

  The chemical structure of the oxime ester-based compound having a diphenyl sulfide skeleton is not particularly limited, but from the viewpoint of solvent resistance, it is preferable to use one represented by the following general formula (I).

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, or an aromatic ring 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 the 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 part of R ^25b may be interrupted 1 to 5 times by —O—, —S—, —COO— or —OCO—. The alkylene part of R ²⁵ may have a branched side chain or cyclohexylene.
R ^25c represents a hydroxyl group or a carboxyl group.

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

Specific examples of the alkyl group include a methyl group, a hexyl group, and a cyclopentylmethyl group. Among these, a methyl group or a hexyl group is preferable, and a methyl group is more preferable from the viewpoint of developability.
Examples of the substituent that 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. A carboxyl group is more preferred. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ²³ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms 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 further 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, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable. 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 even more preferably a methyl group. .

The number of carbon atoms 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, further preferably 5 or less, and particularly preferably 3 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable from the viewpoint of sensitivity.
Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, and an amide 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 ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ²⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. When the amount is not more than the upper limit value, the sensitivity tends to be high, and when the value is not less than the lower limit value, there is a tendency to be low sublimation.

The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Ring, quinazo Non rings include groups such as azulene ring.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a halogen atom, a hydroxyl group, and a carboxyl group.
Among these, from the viewpoint of sensitivity, R ²⁴ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.
On the other hand, from the viewpoint of plate-making property, R ²⁴ is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent. Further, an unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group is particularly preferable.

R ²⁵ is a hydroxyl group, a carboxyl group or a group represented by the general formula (I-1). Among these, from the viewpoints 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—. Among these, from the viewpoints 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 number of carbon atoms of the alkylene group in R ^25b is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in the photosensitive coloring composition, more preferably 2 or more, and 20 or less. Is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less.
The alkylene group may be a straight chain, may be branched, or may contain an aliphatic ring. Among these, a straight chain is preferable from the viewpoint of solubility in the photosensitive coloring composition.

  Specific examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Among these, a methylene group is more preferable from the viewpoint of solubility in the photosensitive coloring composition.

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

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

  Specific examples of the oxime ester compound represented by the general formula (I) include the following.

  Although it does not specifically limit about the manufacturing method of the oxime ester type compound represented by the 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 an oxime ester compound represented by the general formula (I), but further contains another photopolymerization initiator. Also good.
Other photopolymerization initiators include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarynes described in JP-A-2000-56118. Rubiimidazole derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, and N-aryl-α-amino acid salts described in JP-A-10-39503 , Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP 2000-80068 A, JP 2006-36750 A, International Publication No. 2008/077554, International Publication 2009/131189 pamphlet, Special Table 2 Such oxime ester derivatives as described in 14-500852 JP, and the like.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
A sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity. Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarins having a heterocyclic ring 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, pyromethene dyes described in JP-A-6-19240, and others, JP-A-47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Examined Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005. JP, 59-56403, JP 2-69, JP 57-168888, JP 5-107761. 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. Benzophenone 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-diethyl) Ruaminophenyl) 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 such as Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

  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. It is done. A polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

<(D) Ethylenically unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (D) It is thought that it becomes high sensitivity by including an 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, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. 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 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 it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.
Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound. Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate 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 ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (made by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).

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. Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta It is more preferable to use (meth) acrylate or the like.
These may be used alone or in combination of two or more.

<(E) Solvent>
The photosensitive coloring composition of the present invention contains (e) a solvent. (E) A function of adjusting viscosity by dissolving or dispersing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, etc. by including a solvent. Can have.
The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (d) an ethylenically unsaturated compound, (f) a dispersant, and other used as necessary. Various materials are used in a state of being dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoints of solubility and dispersibility.

  Among organic solvents, those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of dispersibility and coating properties, and those having a boiling point in the range of 120 to 280 ° C. are more preferable. The boiling point here means the 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, methoxymethylpentanol, 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;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, 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 Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

Commercially available organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve" is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).
These organic solvents may be used alone or in combination of two or more.

  When the colored spacer is formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ° C. (under pressure of 101.25 hPa, hereinafter the same for the boiling point). More preferably, it has a boiling point of 120 to 170 ° C.

Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the photosensitive coloring composition obtained later tends to decrease. 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”). By using such a high boiling point solvent in combination, the photosensitive coloring composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to the lower limit value or more, for example, there is a tendency to suppress the occurrence of foreign matter defects due to precipitation and solidification of color materials at the tip of the slit nozzle, and by setting the lower limit value or less, the drying temperature of the composition Tends to be able to suppress slowing down and to prevent problems such as tact failure in the vacuum drying process and pre-baked pin marks

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

<(F) Dispersant>
In the photosensitive coloring composition of the present invention, (a) it is important to finely disperse the colorant and stabilize its dispersion state to ensure the stability of the quality. .
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant 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, or pyrazine is preferable. In particular, 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. In particular, it is particularly preferable from the viewpoint that it can be dispersed with a small amount of a dispersant.

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), SOLPERSE. (Registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like.
These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of dispersion stability, (f) the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group, and includes an acrylic polymer dispersant. It is particularly preferred.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.

Examples of the urethane-based and acrylic polymer dispersant include DISPERBYK160 to 166, 182 series (all are urethane-based), DISPERBYK2000, 2001, LPN21116 and the like (all are acrylic-based) (all manufactured by Big Chemie).
If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, 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 a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an 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 polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 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 -N-alkyl dialkanolamine such as methyldiethanolamine) obtained by polycondensation such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the above diols or carbon number 1 ~ 25 monovalent a 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 preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
These may be used alone or in combination of two or more.

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

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
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, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-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.

  In addition, 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 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are 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, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-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.
These may be used alone or in combination of two or more.

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. To 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3. -24 parts by mass.

  Manufacture of a urethane type polymer dispersing agent is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., 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. These may be used alone or in combination of two or more.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned. These may be used alone or in combination of two or more.

  The introduction 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 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time 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, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

  As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here 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 a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) 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 its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

  The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group. May be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, content in the A block of the partial structure which does not contain a functional group is 80 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less.

The B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.

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 each an integer of 1 or more.

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

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 different from R ^a or a monovalent organic group.

  In synthesizing this acrylic polymer dispersant, JP-A-9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

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

In addition, in such a block copolymer, an amino group generated in the production process may be usually contained, but the amine value is about 1 to 100 mgKOH / g, from the viewpoint of dispersibility, Preferably it is 10 mgKOH / g or more, More preferably, it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more, Preferably it is 90 mgKOH / g or less, More preferably, it is 80 mgKOH / g or less, More preferably, it is 75 mgKOH / g or less.
Here, the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, 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. When the amount falls within the above range, good developability and dispersion stability tend to be ensured.

  In the case of having 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, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating” It is preferable to have a unit (i) ”.

In the above formula (i), R ^{31 to} R ³³ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group that may be present, 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. The following is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

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

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

  In addition, when the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, it may be a repeating unit represented by the following formula (ii) (hereinafter, referred to as “repeating unit (ii)”). .).

In the formula (ii), R ³⁵ and R ³⁶ each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. And may be an aralkyl group, and R ³⁵ and R ³⁶ may be bonded to each other to form a cyclic structure. ^R37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

Further, for R ³⁵ and R ³⁶ in the formula (ii), as the alkyl group which may have a substituent, may be preferably used those exemplified as R ³¹ to R ³³ in the formula (i) it can.
Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ^{31 to} R ^{33 in} the above formula (i) should be preferably employed. Can do. In addition, as R ³⁵ and R ³⁶ in the above formula (ii) which may have a substituent, those exemplified as R ^{31 to} R ^{33 in} the above formula (i) may be preferably employed. 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 that the alkyl group, aralkyl group or aryl group in R ^{31 to} R ³³ of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) may have 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 groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ⁴³ — group, —COOR ⁴⁴ — group (wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and the like are preferable. Is a —COO—R ⁴⁴ — group.
In the above formula (i), Y ⁻ of the counter anion includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  Although the content rate of the repeating unit represented by the said formula (i) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (i), and the said formula (ii). Preferably it is 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, based on the total content of repeating units. The amount is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

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

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

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

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 1-20.

The number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, 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 viewpoints of compatibility with a binder component such as a solvent and dispersibility. More preferably, it is 5 or less.

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

  The polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv)” from the viewpoint of improving the compatibility of the dispersing agent with a binder component such as a solvent and improving dispersion stability. ) ").).

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

The number of carbon atoms of the aryl group which may have a substituent in R ³⁸ in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , 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 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

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

  In addition, the content of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is more preferably 50 mol% or more, more preferably 80 mol% or less, and even 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 monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- Examples include (meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

  From the viewpoint of further improving dispersibility, the polymer dispersant is composed of 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). It is preferable that it is a block copolymer which has these. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved. The B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).

  In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization and block copolymerization. In addition, the repeating unit (i) and the repeating unit (ii) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized in the A block. It may be contained in any form of block copolymerization.

  A repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block. Examples of such a repeating unit include the aforementioned (meth) acrylic acid ester-based unit. Examples include a repeating unit derived from a monomer. 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 monomers such as styrene and α-methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine. The content in the B block of the repeating units other than the repeating unit (iii) and the repeating unit (iv) 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 dispersion stability, (f) the dispersant is preferably used in combination with a pigment derivative described later.

<Other compounding components of photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative. Etc. can be suitably blended.

(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, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
As the type of silane coupling agent, various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.

Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 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 the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

In the general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2, or 3.
These phosphoric acid 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 in order to improve coatability.

As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (DIC), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 (Nihon Unicar) ), FC4430 (manufactured by Sumitomo 3M), and the like.
In addition, 1 type may be used for surfactant and it 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 dispersion aid in order to improve dispersibility and storage stability.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are preferable.
Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.

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

(4) Photoacid generator A photoacid generator is a compound capable of generating an acid by ultraviolet rays, and has a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure. The crosslinking reaction will proceed. Among such photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a photosensitive coloring composition, are preferable. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p -Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine can be exemplified, but not limited thereto.

(5) Crosslinking agent A crosslinking agent can be further added to the photosensitive coloring composition of the present invention. For example, a melamine or guanamine compound can be used. Examples of these cross-linking agents include melamine or guanamine compounds represented by the following general formula (6).

In the 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 a —NR ⁶⁶ R ⁶⁷ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , one of R ⁶⁶ and R ^67, and R ⁶¹ represents R ^62, R ^63, one of R ⁶⁴ and R ⁶⁵ are -CH ₂ oR ⁶⁸ group in the case of an aryl group having from 6 to 12 carbon atoms, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ , independently of one another, 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 these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom, and the like. May be bonded to each other. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Alkyl group represented by R ⁶⁸ is, among the above, methyl group or an ethyl group, especially a methyl group.

  Melamine compounds corresponding to the general formula (6), that is, compounds of the following general formula (6-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.

In the formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH _2. Represents an OR ⁶⁸ group, and the remainder of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of one another represents a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ represents a hydrogen atom or Represents an alkyl group.

Further, guanamine compounds corresponding to the general formula (6), that is, compounds in which R ⁶¹ in the general formula (6) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are 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 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.

  In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. 0.1-15 mass% is preferable with respect to the total solid of a photosensitive coloring composition, and, as for the quantity at the time of using a crosslinking agent, Most preferably, it is 0.5-10 mass%.

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

  Mercapto compound types include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, 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 -Mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoiso) Butyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like mercapto compounds Or aliphatic polyfunctional mercapto compounds It is. These can be used alone or in combination of two or more.

<Ingredient compounding amount in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content ratio of (a) the colorant is usually 10% by mass or more and preferably 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. 25% by mass or more, 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) By making the content rate of a coloring agent more than the said lower limit, there exists a tendency for sufficient optical density (OD) to be obtained, and sufficient image formability is obtained by making it below the said upper limit. It tends to be easy.

  Further, (a) the content of the orange pigment with respect to 100 parts by mass of the colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. More preferably, it is 20 parts by mass or more, particularly preferably 30 parts by mass or more, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 60 parts by mass or less. More preferably, it is particularly preferably 50 parts by mass or less. By setting it to the lower limit value or more, there is a tendency that the light shielding property in the vicinity of 400 nm to 550 nm can be improved. By setting the upper limit value or less, there is a tendency that the entire visible light region can be shielded in a balanced manner when combined with other pigments. .

  Further, the content of the (a-1) orange pigment with respect to 100 parts by mass of the (a) colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass or more. Is more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less. 60 parts by mass or less is more preferable, and 50 parts by mass or less is particularly preferable. By setting it to the lower limit value or more, there is a tendency that the light shielding property in the vicinity of 400 nm to 550 nm can be improved. By setting the upper limit value or less, there is a tendency that the entire visible light region can be shielded in a balanced manner when combined with other pigments. .

  Further, the content of the blue pigment with respect to (a) 100 parts by mass of the colorant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more. The amount is particularly preferably 40 parts by mass or more, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less. There exists a tendency which can improve the light-shielding property of 550 nm to 700 nm vicinity by setting it as the said lower limit or more, and there exists a tendency which can improve the transmittance | permeability of an ultraviolet region by setting it as the said upper limit or less.

  Further, the content of (a-2) the blue pigment with respect to 100 parts by mass of (a) the colorant is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 30 parts by mass or more. Is more preferably 40 parts by mass or more, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less. There exists a tendency which can improve the light-shielding property of 550 nm to 700 nm vicinity by setting it as the said lower limit or more, and there exists a tendency which can improve the transmittance | permeability of an ultraviolet region by setting it as the said upper limit or less.

  Furthermore, the content of the blue pigment with respect 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, further preferably 30 parts by mass or more, and 900 It is preferably no greater than part by mass, more preferably no greater than 800 parts by mass and even more preferably no greater than 600 parts by mass. 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 in the ultraviolet light region tends to be improved.

  When (a) the colorant contains (a-3) a violet pigment, the content of (a-3) the violet pigment with respect to 100 parts by mass of (a) the colorant is preferably 10 parts by mass or more, More preferably, it is 15 parts by mass or more, further preferably 20 parts by mass or more, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 60 parts by mass or less. More preferably it is. There is a tendency to improve the light-shielding property in the vicinity of 500 nm to 600 nm, which cannot be sufficiently shielded by only the orange pigment and the blue pigment by setting the lower limit value or more. By setting the upper limit value or less, the entire visible light region can be shielded in a balanced manner. Tend.

  When (a) the colorant contains (a-4) an organic color pigment, the content of (a-4) the organic color pigment relative to 100 parts by mass of (a) the colorant may be 10 parts by mass or more. Preferably, it is 20 parts by mass or more, more preferably 30 parts by mass or more, preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and 60 parts by mass. More preferably, it is as follows. In the case of a red pigment by setting it to the lower limit value or more, there is a tendency to improve the transmittance in the ultraviolet region, and in the case of a blue pigment, there is a tendency to improve the light-shielding property in the visible light region, and the upper limit value or less. Thus, in the case of a red pigment, there is a tendency that it is possible to suppress a decrease in the light shielding property in the visible light region, and in the case of a blue pigment, there is a tendency that a decrease in the transmittance in the ultraviolet region can be suppressed.

  Moreover, when (a) a coloring agent contains an organic black pigment, it is preferable that content of the organic black pigment with respect to 100 mass parts of (a) coloring agents is 5 mass parts or more, and it is 10 mass parts or more. More preferably, it is 20 parts by mass or more, more preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 60 parts by mass or less, and 40 parts by mass. It is particularly preferred that the amount is not more than parts. There exists a tendency which can improve light-shielding property by setting it as the said lower limit or more, and there exists a tendency which can suppress a reliability fall by setting it as the said upper limit or less.

  Further, when (a) the colorant contains carbon black, the content of carbon black with respect to 100 parts by mass of (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, more preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less. There exists a tendency which can improve light-shielding property by setting it as the said lower limit or more, and there exists a tendency which can suppress an increase in a dielectric constant by setting it as the said upper limit or less.

  (B) The content rate of alkali-soluble resin is 5 mass% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably It is 30 mass% or more, and is 85 mass% or less normally, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less. (B) By making content of alkali-soluble resin more than the said lower limit, there exists a tendency which can suppress the fall of the solubility with respect to the developing solution of an unexposed part, and can suppress image development defect. Moreover, by setting it as the said upper limit or less, there exists a tendency which can suppress that the permeability | transmittance of the developing solution to an exposure part becomes high, and can suppress the sharpness of a pixel, or the fall of adhesiveness.

  (C) The content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 mass%. These are usually 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less. (C) There exists a tendency which can suppress a sensitivity fall by making the content rate of a photoinitiator more than the said lower limit, and the fall of the solubility with respect to the developing solution of an unexposed part is suppressed by making it the said upper limit or less. There is a tendency that development defects can be suppressed.

(C) When a polymerization accelerator is used together with a photopolymerization initiator, the content ratio of the polymerization accelerator is preferably 0.05% by mass or more and usually 10% with respect to the total solid content of the photosensitive coloring composition of the present invention. % By mass or less, preferably 5% by mass or less. 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 the photopolymerization initiator (c). It is preferable to use in. 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 beam, and by setting the content ratio to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer is suppressed. However, there is a tendency that development defects can be suppressed.
Further, 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 in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.

  (D) The content rate of an ethylenically unsaturated compound is 30 mass% or less normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 20 mass% or less. (D) By making the content rate of an ethylenically unsaturated compound below the said upper limit, it becomes the tendency which suppresses that the permeability of the developing solution to an exposure part becomes high, and obtains a favorable image easily. is there. In addition, the lower limit of the content rate of (d) ethylenically unsaturated compound is 1 mass% or more normally, Preferably it is 5 mass% or more, More preferably, it is 10 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 the solvent (e). It is prepared so that it may become the mass%.

  (F) The content of the dispersant 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. Further, the content ratio of the (f) dispersant with respect to 100 parts by mass of the (a) colorant 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 making the content rate of a dispersing agent more than the said lower limit, there exists a tendency for sufficient dispersibility to be easy to be obtained, and the ratio of another component reduces relatively by making it below the said upper limit. There exists a tendency which can suppress that a sensitivity, platemaking property, etc. fall.

  When using an adhesion improving agent, the content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4% with respect to the total solid content in the photosensitive coloring composition. It is -2 mass%. There is a tendency that the effect of improving the adhesion can be sufficiently obtained by setting the content ratio of the adhesion improver to the above lower limit value or more, and the sensitivity is lowered by setting it to the upper limit value or less, or a residue remains after development. There exists a tendency which can suppress becoming a defect.

  Moreover, when using surfactant, the content rate is 0.001-10 mass% normally with respect to the total solid in a photosensitive coloring composition, Preferably it is 0.005-1 mass%, More preferably, it is 0. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. By making the content of the surfactant more than the lower limit value, there is a tendency that the smoothness and uniformity of the coating film tend to be expressed, and by setting it 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 coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a colored spacer, and is preferably black from the viewpoint of being used as a colored spacer. Further, the optical density (OD) per 1 μm of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, 4.0 or less.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, (a) the colorant 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. Since the colorant (a) is finely divided by the dispersion treatment, the resist coating characteristics are improved.

The dispersion treatment is usually preferably carried out in a system in which a part or all of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) an alkali-soluble resin are used together (hereinafter referred to as dispersion). The mixture subjected to the treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”). In particular, it is preferable to use a polymer dispersant as the dispersant (f) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
Thus, in the step of producing a 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, (e) organic solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive coloring composition are preferably employed. Can do.

In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When (a) the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from 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. The standard of dispersion is to control 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. 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, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.

[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 colored spacer, and in particular, can be suitably used to collectively form colored spacers having different heights by photolithography.

[Coloring spacer]
Next, a colored spacer using the photosensitive coloring composition of the present invention will be described according to its production method.

(1) Support As long as the support for forming the colored spacer has an appropriate strength, the material thereof is not particularly limited. Transparent substrates are mainly used. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets made of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy. Examples thereof include thermosetting resin sheets such as resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.

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, in order to improve surface properties such as adhesiveness. .
The thickness of the transparent substrate is usually 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 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Colored spacer Although the photosensitive coloring composition of this embodiment is used by the method similar to the well-known photosensitive coloring composition for color filters, the case of a coloring spacer use is demonstrated below. Usually, a photosensitive coloring composition solution is supplied in a film or pattern by a method such as coating on a substrate on which a colored 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. Then, a coloring spacer is formed on this board | substrate by performing additional exposure and a thermosetting process as needed.

(3) Formation of colored spacer (3-1) Application of photosensitive coloring composition The photosensitive coloring composition of the present embodiment is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. The photosensitive coloring composition for the coloring spacer can be applied on the transparent substrate 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. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming step, and if it is too thin, it is difficult to increase the pigment concentration, and the thickness is 1 to 10 μm. The range is preferable, more preferably 1 to 9 μm, and still more preferably 1 to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect of the liquid crystal panel is generated. Further, it may be supplied in a pattern by an inkjet method or a printing method.

(3-2) Drying of coating film It is preferable to dry the coating film after applying the photosensitive coloring composition to the substrate by a drying method using a hot plate, IR oven, or convection oven. 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 a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 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. However, if the drying temperature is too high, (b) the alkali-soluble resin is decomposed, which may cause thermal polymerization and cause poor development. 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 increasing the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the photosensitive coloring composition, or the exposure mask is arranged at a position away from the coating film of the photosensitive coloring composition. A method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength. The optical filter may be of a type that can control the light transmittance at an exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
In recent years, a method has been proposed in which colored spacers having different heights are collectively formed when the colored spacers are manufactured by a photolithography method. Also in the embodiment of the present invention, as disclosed in Japanese Patent Application Laid-Open No. 2003-344860 and Japanese Patent Application Laid-Open No. 2004-45757, the light shielding portion (light transmittance 0%) and the plurality of openings are used as the average light transmission. The method of forming colored spacers with different heights at once using an exposure mask that has an opening (intermediate transmission opening) with a low average light transmittance relative to the opening with the highest rate (complete transmission opening) is suitable. ing. If it is a negative photosensitive coloring composition, the degree of curing of the pattern and the remaining film rate are changed by the difference in average transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount, The steps of the colored spacer can be formed through a development and thermosetting process.
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 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-exposing the coating film of the photosensitive coloring composition with the above light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 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 the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines 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.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is 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 according to the specifications of the color filter. However, the photosensitive coloring composition of the present invention is effective for collectively forming colored spacers having different spacer and sub-spacer heights by photolithography as described above, and the spacer height is usually 2 to 7 μm. The sub-spacer has a height that is usually about 0.2 to 1.5 μm lower than the spacer.

[Color filter]
The color filter of the present invention is provided with the colored spacer of the present invention as described above. For example, on a glass substrate as a transparent substrate, a black matrix, a red, green, and blue pixel coloring layer, and an overcoat layer Are stacked to form a colored spacer, and then an alignment 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 that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL (Electro Luminesence) display described later.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described colored spacer of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
For example, a black matrix is provided on a TFT element substrate, red, green, and blue pixels are formed, an overcoat layer is formed as necessary, and a transparent material such as ITO or IZO is further formed on the image. Electrodes are formed and used as part of components such as color displays and liquid crystal display devices. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

  The liquid crystal display device usually forms an alignment film on the color filter, and after dispersing the spacer on the alignment film or forming the colored spacer of the present invention, it is bonded to the counter substrate to form a liquid crystal cell, Liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an 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, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure 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 a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is sealed with a UV curable resin in which the liquid crystal injection port is cured, thereby completing a liquid crystal display device (panel).

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

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The components of the photosensitive coloring composition used in the following examples and comparative examples are as follows.

<Organic black pigment>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 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 mgKOH / g.

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

  50 g of an epoxy compound having the above structure (epoxy equivalent 247), 14.3 g of acrylic acid, 59.5 g of methoxybutyl acetate, 1.29 g of triphenylphosphine, and 0.05 g of paramethoxyphenol were attached to a thermometer, a stirrer, and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the above-mentioned epoxy acrylate solution, 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 2.8 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, the resin solution is diluted with methoxybutyl acetate and prepared to have a solid content of 50% by mass. The carboxyl group has an acid value of 131 mgKOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 4000 measured by GPC. A containing epoxy acrylate resin was obtained.

<Dispersant-I>
"DISPERBYK-LPN21116" manufactured by BYK Chemie Co., Ltd. (Acrylic AB block consisting of an A block having a quaternary ammonium base and a tertiary amino group in the side chain and a B block having no quaternary ammonium base and an amino group) Polymer)

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxybutanol

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

<Photopolymerization initiator-II>
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., KAYAMER PM-21 (phosphate containing methacryloyl group)

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

<Surfactant-I>
DIC Corporation Mega Fuck 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 with a spin coater so that the final film thickness was 2 μm, dried under reduced pressure for 1 minute, and then dried at 80 ° C. for 70 seconds with a hot plate. A resist-coated substrate was obtained by heating at 230 ° C. for 20 minutes. The optical density (OD) of the obtained substrate was measured with a transmission densitometer Gretag Macbeth D200-II, and the film thickness was measured with a non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd. The optical density per unit film thickness was calculated from the measured optical density (OD) and 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 property.

<NMP dissolution test>
The N-methylpyrrolidone (NMP) dissolution test was performed according to the following procedure.
First, the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2 μm, dried under reduced pressure for 1 minute, and then dried at 80 ° C. for 70 seconds at a hot plate. After passing through the exposure and development steps, it was heated in an oven at 230 ° C. for 20 minutes to obtain a resist-coated substrate. Two measurement substrates (2.5 cm × 1.0 cm square) were cut out from the prepared 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 container containing the board | substrate for a measurement for 40 minutes in a 80 degreeC heat bath. After leaving still for 40 minutes, the vial was taken out from the heat bath, and the absorbance of the NMP elution solution was measured every 1 nm in the wavelength range of 300 to 800 nm with a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). A halogen lamp and a deuterium lamp (switching wavelength: 360 nm) are used as the light source, a photomultiplier is used as the detector, and the slit width is 2 nm. 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 indicating how much light intensity is attenuated 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, when light is incident on the sample solution and NMP alone from the same light source, it can be regarded as light intensity I ₀ transmitted through NMP alone and light intensity I transmitted through the sample solution. Therefore, (I / I ₀ ) in the above formula represents the light transmittance, and the absorbance A is a value obtained by logarithmically expressing the reciprocal of the transmittance. Absorbance A is a notation used when calculating the concentration of a substance contained in a sample solution. When absorbance A = 0, it indicates a state that does not absorb light at all (transmittance 100%), and when absorbance A = ∞, it indicates a state that does not transmit light at all (transmittance 0%). become. That is, the stronger the absorbance, the more resist coating film components are eluted in NMP, indicating that NMP resistance is poor. The spectrum area (nm) of the measured absorbance was calculated, and NMP resistance was evaluated with an area value less than 30 (nm) as ◯, 30 (nm) or more and less than 50 (nm) as Δ, and 50 (nm) or more as x. . The spectral area of absorbance, which is the evaluation criterion, can be expressed as the sum of absorbance at each wavelength, and means the total sum of the eluted resist components.

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

<Preparation of pigment dispersions-1 to 7>
The pigment, dispersant, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was achieved. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 7.

[Example 1 and Comparative Example 1]
Using the pigment dispersion prepared above, add each component so that the ratio in the solid content becomes the blending ratio in Table 2, and further add PGMEA so that the solid content is 17% by mass, stir and dissolve. A photosensitive coloring composition was prepared. The solid content ratio of the prepared composition is shown in Table 2. Table 2 shows the unit OD values and NMP dissolution test results measured by the above-described method. In addition, the mass part of the photosensitive coloring composition in Table 2 shows the mass of solid content.

[Examples 2 to 5 and Comparative Examples 2 and 3]
Using the pigment dispersion prepared above, add each component so that the ratio in the solid content is the blending ratio in Table 3, add PGMEA so that the solid content is 17% by mass, stir and dissolve. A photosensitive coloring composition was prepared. The solid content ratio of the prepared composition is shown in Table 3. Table 3 shows the unit OD value and NMP dissolution test results measured by the above-described method. In addition, the mass part of the photosensitive coloring composition in Table 3 shows the mass of solid content.

  From the comparison between Example 1 and Comparative Example 1 in Table 2, a photosensitive coloring composition containing an orange pigment and a blue pigment uses a photopolymerization initiator having a diphenyl sulfide skeleton among oxime ester photopolymerization initiators. Therefore, light absorption at short wavelengths is strong and surface curability is improved, so that it is difficult to dissolve in NMP, and solvent resistance is considered to have increased. Moreover, it is thought that by preventing the penetration of NMP, it was possible to suppress the dissolution of the coloring agent from the inside of the coating film. The photopolymerization initiator having a diphenyl sulfide skeleton has a short conjugated system, the energy of the whole molecule is high, the radical generation efficiency by thermal decomposition is high, and the polymerization reaction is accelerated. It is thought that the elution of the initiator itself into NMP could be suppressed.

Furthermore, it has been found that combining not only the light-shielding property and NMP resistance but also the plate-making characteristics of the colored spacer, it is more effective to combine an oxime ester compound having a diphenyl sulfide skeleton and a specific pigment. From the comparison between Example 1 and Example 2, by using a specific pigment, there is an advantage that ultraviolet transmittance can be secured and desired functions such as sensitivity can be secured even with a small amount of initiator.
From the above, the photosensitive coloring composition of the present invention containing a photopolymerization initiator having a diphenyl sulfide skeleton and containing an orange pigment and a blue pigment has excellent light shielding properties and suppresses impurity elution into a solvent. It was found useful.

  According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a colored spacer that have excellent light shielding properties and high reliability, and further provide an image display device including such a colored spacer. Can do. Therefore, the present invention has very high industrial applicability in the fields of photosensitive coloring composition, cured product, coloring spacer and image display device.

Claims (14)

A photosensitive coloring composition containing (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 (a) colorant contains an orange pigment and a blue pigment,
The photosensitive coloring composition, wherein the photopolymerization initiator (c) includes an oxime ester compound having a diphenyl sulfide skeleton. The photosensitive coloring composition of Claim 1 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 (a-2) selected from the group consisting of C.I. I. Pigment Blue 60 The photosensitive coloring composition of Claim 1 or 2 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. At least one selected from the group consisting of CI Pigment Violet 29 The photosensitive coloring composition of any one of Claims 1-3 in which the said (a) coloring agent contains the at least 1 sort (s) of organic coloring pigment chosen from the group shown to the following (a-4) further.
(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 of any one of Claims 1-4 in which the said (a) coloring agent contains an organic black pigment further.   The photosensitive coloring composition in any one of Claims 1-5 in which the said (a) coloring agent contains carbon black further.   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 content in a photosensitive coloring composition.   The photosensitive coloring composition of any one of Claims 1-7 whose content rate of the said (a) coloring agent is 50 mass% or less with respect to the total solid content in a photosensitive coloring composition.   The photosensitive coloring composition of any one of Claims 1-8 whose optical density per 1 micrometer of film thickness of the hardened 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 of Claim 10 used in order to collectively form the coloring spacer from which height differs by the photolithographic 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.   An image display device comprising the colored spacer according to claim 13.