JPWO2017110893A1 - Photosensitive coloring composition, cured product, colored spacer, image display device - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition that can form a pattern with high light-shielding properties, high reliability, and excellent surface smoothness, and that is particularly preferably used for forming colored spacers. . The photosensitive coloring composition of the present invention comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersion. (A) the colorant contains an organic pigment and carbon black, (b) an alkali-soluble resin, (b-I) an epoxy (meth) acrylate resin, and (b-II) an ethylenic side chain (Meth) acrylic copolymer resin containing repeating unit α having an unsaturated bond and repeating unit β derived from unsaturated carboxylic acid, and (b-II) the repeating unit in (meth) acrylic copolymer resin The α content is 12 mol% or more.

Description

  The present invention relates to a photosensitive coloring composition and the like. Specifically, the present invention relates to a photosensitive coloring composition that is preferably used for forming a colored spacer or the like in a color filter such as a liquid crystal display, a coloring spacer obtained by curing the photosensitive coloring composition, and an image display device including the coloring spacer. .

  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, each member constituting the LCD cell is often formed by a method using a photosensitive composition represented by a photolithography method. This photosensitive composition tends to form a fine structure and is easy to process a substrate for a large screen, and its application range tends to further expand in the future.

  However, an LCD manufactured using a photosensitive composition does not maintain the voltage applied to the liquid crystal due to the electrical characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, thereby causing the display to display. Problems such as display unevenness may occur. In particular, a member closer to the liquid crystal layer in a color liquid crystal display, for example, a so-called columnar spacer, photospacer or the like used to keep the distance between two substrates constant in a liquid crystal panel has a great influence.

  Conventionally, when a spacer having no light-shielding property is used in a TFT (Thin Film Transistor) type LCD, the TFT as a switching element sometimes malfunctions due to light transmitted through the spacer. In order to prevent this, for example, Patent Document 1 describes a method using a light-shielding spacer (colored spacer).

  On the other hand, in recent years, a method has been proposed in which colored spacers having different heights are collectively formed by a photolithography method as the structure of the panel changes. For example, in Patent Document 2, a plurality of specific pigment types having different light absorption characteristics are combined, and while maintaining the light absorption balance in the ultraviolet region and the visible region, while maintaining the light shielding property and the voltage holding ratio of the liquid crystal, It is disclosed that shape and level difference control and adhesion to a substrate can be realized.

  On the other hand, Patent Document 3 discloses that an alkali-soluble resin having a specific structure can be used to achieve light-shielding properties, step control, and adhesion to a substrate.

Japanese Unexamined Patent Publication No. 8-234212 International Publication No. 2013/115268 Japanese Unexamined Patent Publication No. 2013-134263

In recent years, with the change in the panel structure, there is a demand for further enhancing the light shielding property of the colored spacer. Examples of the method for increasing the light shielding property include a method using a pigment having a high light shielding property and a method for increasing the pigment content ratio in the photosensitive coloring composition. As a result of studies by the present inventors, in the photosensitive coloring composition described in Patent Document 2, when the light shielding property of the colored spacer is further increased by using a pigment having a high light shielding property, the vicinity of the film surface is determined. It was found that the difference in crosslink density between the vicinity of the bottom of the film was increased, wrinkles were generated on the surface of the coating film due to thermal shrinkage during the thermosetting process, and the surface smoothness was insufficient.
Moreover, when a highly light-shielding colored spacer is formed using the photosensitive coloring composition described in Patent Document 3, impurities derived from the colorant are present in the solvent for forming the alignment film as the upper layer film. In addition to elution, it has been found that there are many elutions of impurities due to a high pigment concentration and a small amount of curing components, resulting in a deterioration in LCD display reliability.
This invention is made | formed in view of the said situation, and this invention provides the photosensitive coloring composition which can form a pattern with high light-shielding property, high reliability, and excellent surface smoothness. For the purpose.

As a result of intensive studies by the present inventors to solve the above-mentioned problems, an epoxy (meth) acrylate resin and a specific (meth) acrylic copolymer resin are combined as an alkali-soluble resin in the photosensitive coloring composition. It was found that the above-described problems can be solved by using the present invention, and the present invention has been achieved.
That is, the present invention has the following configurations [1] to [9].

[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 organic pigment and carbon black,
The (b) alkali-soluble resin comprises (b-I) an epoxy (meth) acrylate resin, (b-II) a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. (Meth) acrylic copolymer resin containing, and
The photosensitive coloring composition, wherein the content ratio of the repeating unit α in the (b-II) (meth) acrylic copolymer resin is 12 mol% or more.

[2] The organic pigment is at least one selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound The photosensitive coloring composition as described in [1] containing an organic black pigment.

(In formula (1), R ¹¹ and R ¹⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = CH ₂ , N = CHR ²¹ , N = CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ , It can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ²¹ bridges;
R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or carbon. It is an alkynyl group of formula 2-12. )

[3] 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 colorant (a) includes at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment,
The (b) alkali-soluble resin comprises (b-I) an epoxy (meth) acrylate resin, (b-II) a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. (Meth) acrylic copolymer resin containing, and
The photosensitive coloring composition, wherein the content ratio of the repeating unit α in the (b-II) (meth) acrylic copolymer resin is 12 mol% or more.
[4] The photosensitive coloring composition according to any one of [1] to [3], wherein the repeating unit α has a chemical structure represented by the following general formula (I).

(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ³ represents a divalent linking group.)
[5] Any of [1] to [4], wherein the content ratio of the (b-II) (meth) acrylic copolymer resin is 1% by mass or more based on the total solid content in the photosensitive coloring composition. The photosensitive coloring composition as described in any one.
[6] The photosensitive coloring composition according to any one of [1] to [5], wherein an optical density per 1 μm film thickness of the cured coating film is 1.0 or more.
[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6].
[8] A colored spacer formed from the cured product according to [7].
[9] An image display device comprising the colored spacer according to [8].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition which can form a pattern with high light-shielding property, high reliability, and excellent surface smoothness can be provided. In addition, a cured product and a colored spacer that are excellent in light shielding properties and surface smoothness can be provided, and further, an image display device including such a colored spacer can be provided.

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”.

  In the present invention, the term “(co) polymer” means that both a single polymer (homopolymer) and a copolymer (copolymer) are included, and “acid (anhydride)”, “(anhydrous). "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.

In the photosensitive coloring composition according to the first aspect of the present invention, (a) the colorant contains an organic pigment and carbon black. In the photosensitive coloring composition according to the second aspect of the present invention, (a) the colorant is selected from the group consisting of at least one selected from the group consisting of a red pigment and an orange pigment, and a group consisting of a blue pigment and a purple pigment. Containing at least one selected. Furthermore, the photosensitive coloring composition according to the third aspect of the present invention is for forming a colored spacer.
Hereinafter, unless otherwise specified, the “photosensitive coloring composition of the present invention” refers to the photosensitive coloring composition according to the first aspect, the photosensitive coloring composition according to the second aspect, and the third aspect. All the photosensitive coloring compositions which concern on are pointed out.

<(A) Colorant>
The (a) colorant used in the photosensitive coloring composition of the present invention is not particularly limited as long as it is a colorant that can color the photosensitive coloring composition or a cured product obtained by curing the photosensitive coloring composition. From the viewpoint of durability, pigments can be preferably used.
Examples of the pigment include organic pigments and inorganic pigments. From the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to make it easier to control the shape and level difference, use the organic pigment. Is preferred.

The (a) colorant used in the photosensitive coloring composition according to the first aspect of the present invention contains an organic pigment and carbon black. In this way, it is easy to control the shape and steps by using an organic pigment that absorbs less ultraviolet light, and it is easy to improve the surface smoothness. In addition to the organic pigment, high blackness is achieved by using carbon black. can do.
Although the kind of organic pigment is not particularly limited, it is preferable to contain at least one organic coloring pigment selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a purple pigment from the viewpoint of adhesion. Moreover, it is preferable to contain an organic black pigment from a light-shielding viewpoint.

  The chemical structure of these pigments is not particularly limited, but various other than organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Inorganic pigments 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 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, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272, more preferably C.I. I. Pigment red 149, 177, 179, 194, 209, 224, 254. In terms of dispersibility and light shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used. In the case of curing with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. I. More preferably, CI pigment red 254 and 272 are used.

  Examples of orange (orange) pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. Pigment orange 38, 43, 64, 71, 72. In terms of dispersibility and light shielding properties, C.I. I. Pigment Oranges 43, 64, and 72 are preferably used. In the case of curing with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. I. More preferably, CI pigment oranges 64 and 72 are used.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, more preferably C.I. I. Pigment blue 15: 6.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. In the case of curing with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. I. More preferably, CI Pigment Blue 60 is used.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, 29, more preferably C.I. I. And CI Pigment Violet 23.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Violet 23 and 29 are preferably used. In the case of curing with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. I. More preferably, pigment violet 29 is used.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
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.

Among these, it is preferable to contain at least one or more of the following pigments from the viewpoint of light shielding properties, shape and step control.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. Pigment Blue 15: 6, 60
Purple pigment: C.I. I. Pigment Violet 23, 29

Further, from the viewpoint of light shielding properties, shape and step control, the red pigment is preferably the following (1), the orange pigment is preferably the following (2), and the blue pigment is the following ( 3) is preferable, and the purple pigment is preferably the following (4).
(1) C.I. I. At least one selected from CI Pigment Red 177 and 254 (2) C.I. I. At least one selected from Pigment Orange 43 and 64 (3) C.I. I. Pigment blue 15: 6, at least one selected from 60 (4) C.I. I. At least one selected from Pigment Bio Red 23 and 29

In the photosensitive coloring composition according to the first aspect, there is no particular limitation on the combination when a plurality of organic pigments are used in combination. From the viewpoint of light shielding properties in the visible region, particularly in the long wavelength region, a blue pigment is used. And / or a violet pigment is preferably used. In particular, the absorption spectrum of carbon black has a decreasing absorbance from short wavelength to long wavelength, and the absorbance in the ultraviolet region is higher than that of organic pigments. From this point of view, it is preferable to use a blue pigment and / or purple pigment and carbon black in combination, and it is more preferable to use a blue pigment and purple pigment and carbon black in combination.
On the other hand, when a small amount of carbon black is used, from the viewpoint of light shielding properties, at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment, Specific examples of combinations thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a purple pigment.

Furthermore, in addition to these organic coloring pigments, a black color material can be further used. Examples of the black color material include inorganic black pigments such as carbon black and organic black pigments.
On the other hand, an organic black pigment can be used instead of the organic coloring pigment.

  The photosensitive coloring composition which concerns on a 1st aspect contains carbon black as a black color material. Thus, high light-shielding property can be achieved by using carbon black in addition to the organic pigment. In the case of using carbon black, the surface smoothness tends to be deteriorated, so that it tends to be improved by applying the present invention. 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, same hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, RE, 99, REGAL 99, REGAL 99, REGAL 99, REGAL (99, REGAL 99). REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Made by Colombian Carbon: RAVEN (registered trademark, the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA10850RA, RA101000RA, V40 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 the carbon black coated with resin, for example, carbon black described in Japanese Patent Application Laid-Open 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 for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, 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. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and then a resin is added thereto. 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. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. 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, and 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.

  The carbon black formed by coating with a resin in this way 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 presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

  As a black color material other than carbon black, an organic black pigment is used from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and controlling the shape and level difference by suppressing the absorption of ultraviolet rays. Preferably, particularly from the viewpoint of light-shielding properties, at least selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound It is preferable to use one organic black pigment (hereinafter sometimes abbreviated as “organic black pigment represented by the general formula (1)”).

In formula (1), R ¹¹ and R ¹⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = CH ₂ , N = CHR ²¹ , N = CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ , It can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ²¹ bridges;
R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or carbon. It is an alkynyl group of formula 2-12.

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

  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 ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are preferably each independently a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ¹³ and R ¹⁸ are preferably independently of each other a 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 ¹¹ and R ¹⁶ are preferably each independently a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, and more preferably R ¹¹ is the same as R ¹⁶ ; R ¹² is the same as R ¹⁷ ; R ¹³ is the same as R ¹⁸ ; R ¹⁴ is the same as R ¹⁹ ; and R ¹⁵ is the same as R ²⁰ 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 cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tuzyl group, norbornyl group, bornyl group, 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.

  Examples of the black color material other than the organic black pigment represented by the general formula (1) include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black. .

In addition to the pigments described above, dyes 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.
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 diluted photosensitive coloring composition (usually diluted 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.

  The (a) colorant used in the photosensitive coloring composition according to the second aspect is at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a violet pigment. Containing. Thus, the photosensitive coloring composition which concerns on the 2nd aspect of this invention can achieve high light-shielding property by containing the combination of a specific organic coloring pigment.

As the red pigment, orange pigment, blue pigment, and purple pigment, the same pigments as those described in the first embodiment can be preferably used. The combination of colors is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of an orange pigment and a blue pigment, a combination of an orange pigment, a blue pigment, and a purple pigment.
In addition, the photosensitive coloring composition according to the second embodiment may contain a pigment other than a red pigment, an orange pigment, a blue pigment and a violet pigment, and preferably contains a black color material from the viewpoint of light shielding properties. . As the black color material, the same materials as those described in the first embodiment can be suitably used.

  The photosensitive coloring composition which concerns on a 3rd aspect is a photosensitive coloring composition for coloring spacer formation, (a) A coloring agent is not specifically limited. For example, what contains at least any one of the above-mentioned organic coloring pigment, a black color material, and dye is mentioned. Moreover, (a) As a coloring agent, what was described as a 1st aspect and a 2nd aspect can also be used, and the organic black pigment represented by the said General formula (1) from a light-shielding viewpoint can be used. Coloring agents can also be used.

<(B) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is a resin containing a carboxyl group or a hydroxyl group, and in particular, (b-I) an epoxy (meth) acrylate resin and (b-II) an ethylenically unsaturated bond in the side chain. And a (meth) acrylic copolymer resin containing a repeating unit α and a repeating unit β derived from an unsaturated carboxylic acid, and the content ratio of the repeating unit α in the (b-II) (meth) acrylic copolymer resin Is 10 mol% or more, preferably 12 mol% or more.

(B) When the (b-I) epoxy (meth) acrylate resin is used alone as the alkali-soluble resin, the resin generally has a structure such as aromatic in the main chain. Heat flow is likely to occur, wrinkles are likely to occur, and surface smoothness is likely to deteriorate. Since the light-shielding property is also reduced by wrinkles, the desired light-shielding property cannot be obtained and problems such as light leakage tend to occur.
In addition, the colored spacer is often used with a higher film thickness than the black matrix. Further, in order to provide a desired level difference, it is desirable that the photosensitive coloring composition has a coating characteristic that is difficult to be thermally deformed. However, in order to ensure compression characteristics or reliability, the pigment concentration is set lower than that of the black matrix. It is preferable. As a result, in the colored spacer, the difference in crosslink density between the vicinity of the film surface and the vicinity of the film bottom is further increased, and wrinkles are easily generated. Moreover, there is a tendency that sufficient step forming property cannot be ensured due to such thermal deformation.

  In order to achieve both of these various performances, the main chain contains an acrylic resin that does not contain an aromatic ring or the like and has little heat shrinkage, and particularly contains a repeating unit derived from an unsaturated carboxylic acid that has a high glass transition temperature and is difficult to heat flow. By using a specific (meth) acrylic copolymer resin in combination, it is considered that the heat flow can be reduced, the generation of wrinkles can be suppressed, and the surface smoothness can be improved. However, when a (meth) acrylic copolymer resin with low sensitivity is used in combination, the reliability tends to deteriorate. Therefore, by introducing a predetermined amount of an ethylenically unsaturated bond into the (meth) acrylic copolymer resin, It is considered that sufficient sensitivity can be secured and reliability can be improved, and as a result, both surface smoothness and reliability can be achieved.

<(B-I) Epoxy (meth) acrylate resin>
(B-I) Epoxy (meth) acrylate resin is a reaction product of an epoxy compound and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety; It is a resin obtained by further reacting a hydroxyl group produced by the reaction with a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and / or an anhydride thereof.

  As the (b-I) epoxy (meth) acrylate resin used in the present invention, the following epoxy (meth) acrylate resin (b1) and / or epoxy (meth) acrylate resin (b2) (hereinafter referred to as “carboxyl group-containing epoxy (meth) )) Acrylate resin ”is sometimes used from the viewpoint of reliability.

<Epoxy (meth) acrylate 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.
<Epoxy (meth) acrylate 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.

Here, the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
The types of epoxy resins used as raw materials are cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolak type An epoxy resin, an epoxy resin that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, and the like can be suitably used. Those having an aromatic ring in the main chain can be suitably used.

  Specific examples of the epoxy resin include bisphenol A type epoxy resin (for example, “Epicoat (registered trademark), 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), epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin Resin (for example, “NER-74 manufactured by Nippon Kayaku Co., Ltd. 6 ”(epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example,“ YX-4000 ”manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd.) "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) ”), trisphenol methane type epoxy resin (for example,“ EPPN (registered trademark) manufactured by Nippon Kayaku Co., Ltd. ) -501 "," EPN-502 "," EPPN-503 "), cycloaliphatic epoxy resins (" Celoxide 2021P "," Celoxide (registered trademark, the same applies hereinafter) EHPE "manufactured by Daicel Chemical Industries, Ltd.), Epoxy resins obtained by glycidylation of 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 NS

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.

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

  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, from the viewpoint of reliability, 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. When the amount is not less than the lower limit, the amount of unsaturated groups introduced is sufficient, and the subsequent reaction with the polybasic acid and / or anhydride thereof tends to be sufficient. Moreover, there exists a tendency which can suppress that (alpha), (beta)-unsaturated monocarboxylic acid or (alpha), (beta)-unsaturated monocarboxylic acid ester which has a carboxyl group remains as an unreacted substance by setting it as the said upper limit or less.

  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 chemical structure of the repeating unit contained in the carboxyl group-containing epoxy (meth) acrylate resin is not particularly limited, and examples thereof include the following chemical structures.

  However, in said formula (C-1)-(C-15), X shows the following structures.

(In the structure X, R ¹¹ represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a residue of a polybasic acid. The polybasic acids may be cross-linked to each other.)

  Examples of the carboxyl group-containing epoxy (meth) acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955, in addition to the above-mentioned ones.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, Particularly preferably, it is 5000 or more, usually 10,000 or less, preferably 8000 or less, more preferably 7000 or less. When it is at least the lower limit value, the reliability tends to be improved, and when it is at most the upper limit value, the solubility tends to be good.

  The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mg · KOH / g or more, more preferably 20 mg · KOH / g or more, further preferably 40 mg · KOH / g or more, and 60 mg · KOH / g or more. Is more preferably 80 mg · KOH / g or more, preferably 200 mg · KOH / g or less, more preferably 150 mg · KOH / g or less, still more preferably 120 mg · KOH / g or less, and 100 mg · KOH / g or less. Particularly preferred is g or less. When the amount is not less than the lower limit value, moderate development solubility tends to be obtained, and when the value is not more than the upper limit value, the development tends to be excessive and the film dissolution tends to be suppressed.

  The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of reliability, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (b-I-I) (hereinafter, “ (B-I-I) Epoxy (meth) acrylate resin ”and / or epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b-I-II) ( Hereinafter, it may be preferable to contain “(b-I-II) epoxy (meth) acrylate resin”.

In formula (b-I-I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (b-I-I) may be further substituted with an arbitrary substituent. * Represents a bond.

In formula (b-I-II), each R ¹³ independently represents a hydrogen atom or a methyl group. R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ¹⁵ and R ¹⁶ each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represents an integer of 0 to 2. * Represents a bond.

<(B-I-I) Epoxy (meth) acrylate resin>
First, the epoxy (meth) acrylate resin having a repeating unit structure represented by the general formula (b-I-I) will be described in detail.

In formula (b-I-I), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (b-I-I) may be further substituted with an arbitrary substituent. * Represents a bond.

^{(R 12)}
In the formula (b-I-I), R ¹² represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Examples of the divalent branched aliphatic group include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group. Examples include structures having a -butyl group, a sec-butyl group, a tert-butyl group, and the like.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting the lower limit value or more, a strong film tends to be obtained and the substrate adhesion tends to be good. By setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film reduction during development, and resolution. Tend to improve. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom. And a group in which two are removed. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, naphthalene ring, anthracene having one free valence And groups such as a ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. The aromatic heterocyclic ring in 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 benzoic ring having one free valence. Thiophene ring, pyrrole ring, 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 , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoints of development solubility and moisture absorption resistance.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

  Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the following formulas (b-I-A) to (b-I-I- And the group represented by F). Among these, a group represented by the following formula (b-I-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.

As described above, the benzene ring in the formula (b-I-I) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.

  The repeating unit structure represented by the formula (b-I-I) is a repeating unit structure represented by the following formula (b-I-I-1) from the viewpoint of simplicity of synthesis. preferable.

In formula (b-I-1), R ¹¹ and R ¹² have the same meanings as those in formula (b-I-I). R ^X represents a hydrogen atom or a polybasic acid residue. * Represents a bond. The benzene ring in formula (b-I-I-1) may be further substituted with an arbitrary substituent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The repeating unit structure represented by the formula (b-I-I-1) contained in one molecule of the (b-I-I) epoxy (meth) acrylate resin may be one type or two or more types. , R ^X may be a hydrogen atom, and R ^X may be a polybasic acid residue.

  The number of repeating unit structures represented by the formula (b-I-I) contained in one molecule of the (b-I-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more. 3 or more is more preferable, 20 or less is preferable, and 15 or less is more preferable. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.

  The polystyrene-converted weight average molecular weight (Mw) of (bII) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. Preferably, 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, and 8000 or less is particularly preferable. preferable. There exists a tendency for the remaining film rate of the photosensitive coloring composition to become favorable by setting it as the said lower limit or more, and there exists a tendency for resolution to become favorable by setting it as the said upper limit or less.

  The acid value of the (b-I-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and 50 mgKOH / g or more. Is more preferable, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 130 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable. When the amount is not less than the lower limit, the development solubility is improved and the resolution tends to be good, and when the amount is not more than the upper limit, the remaining film ratio of the photosensitive coloring composition tends to be good. There is.

  Specific examples of the (b-I-I) epoxy (meth) acrylate resin are given below. In addition, * in an example shows a bond.

<(B-I-II) Epoxy (meth) acrylate resin>
Next, the epoxy (meth) acrylate resin having the partial structure represented by the general formula (b-I-II) will be described in detail.

In formula (b-I-II), each R ¹³ independently represents a hydrogen atom or a methyl group. R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. R ¹⁵ and R ¹⁶ each independently represents a divalent aliphatic group which may have a substituent. m and n each independently represents an integer of 0 to 2. * Represents a bond.

(R ¹⁴ )
In the general formula (b-I-II), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the photosensitive coloring composition.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, preferably 4 or less. Is more preferable. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.

  Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are linked to each other.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Examples of the divalent branched aliphatic group include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group. Examples include structures having a -butyl group, a sec-butyl group, a tert-butyl group, and the like.
The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the value is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good. When the value is not more than the upper limit value, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution. Tend to improve. Specific examples of the divalent aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms. Group. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, naphthalene ring, anthracene having one free valence And groups such as a ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring. The aromatic heterocyclic ring in 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 benzoic ring having one free valence. Thiophene ring, pyrrole ring, 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 , Benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, Nazorin ring, quinazolinone ring, groups such as azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring is preferable, and a fluorene ring is more preferable.

  Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of development solubility.

In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include those represented by the above formulas (b-I-A) to (b-I-I- And the group represented by F). Among these, the group represented by the formula (b-I-I-C) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.

  The bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is formed.

^{(R 15, R 16)}
In the general formula (b-I-II), R ¹⁵ and R ¹⁶ each independently represents a divalent aliphatic group which may have a substituent.

  Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Examples of the divalent branched aliphatic group include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso group. Examples include structures having a -butyl group, a sec-butyl group, a tert-butyl group, and the like.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. By setting the lower limit value or more, a strong film tends to be obtained and the substrate adhesion tends to be good. By setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film reduction during development, and resolution. Tend to improve. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom. And a group in which two are removed. Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.

  Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, amyl group, iso-amyl group and other alkyl groups having 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl groups; nitro groups; cyano groups; carboxyl groups and the like. . Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

(M, n)
In the said general formula (b-I-II), m and n represent the integer of 0-2. When it is at least the lower limit, patterning suitability is good and surface roughness tends to be less likely to occur, and when it is at most the upper limit, developability tends to be good. M and n are preferably 0 from the viewpoint of developability, and m and n are preferably 1 or more from the viewpoint of patterning suitability and surface roughness.

  The partial structure represented by the general formula (b-I-II) is a partial structure represented by the following general formula (b-I-II-1) from the viewpoint of adhesion to the substrate. Is preferred.

In the formula (b-I-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are as defined in the formula (b-I-II). R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. p is an integer of 1 or more. The benzene ring in formula (b-I-II-1) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^α )
In the general formula (b-I-II-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development solubility.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.

  p represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for a film hardening degree and a residual film rate to become favorable, and there exists a tendency for developability to become favorable by setting it as the said upper limit or less.

Among these, from the viewpoint of a strong film curing degree, R ^α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

As described above, the benzene ring in the formula (b-I-II-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.

  Specific examples of the partial structure represented by the formula (b-I-II-1) are given below.

  The partial structure represented by the general formula (b-I-II) is a moiety represented by the following general formula (b-I-II-2) from the viewpoints of skeleton rigidity and membrane hydrophobization. A structure is preferred.

In the formula (b-I-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are as defined in the formula (b-I-II). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (b-I-II-2) may be further substituted with an arbitrary substituent. * Represents a bond.

(R ^β )
In the formula (b-I-II-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
Moreover, carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable. By setting it to the lower limit value or more, there is a tendency to suppress film deterioration during development. By setting the upper limit value or less, it is easy to suppress deterioration in sensitivity and film reduction during development, and resolution is improved. Tend.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of storage stability.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. By setting the lower limit value or more, a strong film is likely to be obtained, and there is a tendency that surface roughness is less likely to occur, and by setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film loss, and resolution. Tend to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. Preferably, 15 or less is particularly preferable. By setting the lower limit value or more, a strong film is likely to be obtained, and there is a tendency that surface roughness is less likely to occur, and by setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film loss, and resolution. Tend to improve.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of developability.

  Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, C1-C5 alkyl groups, such as an amyl group and an iso-amyl group; C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; A nitro group; A cyano group; A carboxyl group etc. are mentioned. Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of storage stability and electrical properties, it is preferred that R ^beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of low hygroscopicity and patterning properties of the coating film, it is preferred that R ^beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in formula (b-I-II-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Moreover, two benzene rings may be connected via a substituent. Examples of the substituent in this case include divalent groups such as —O—, —S—, —NH—, and —CH ₂ —.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics. Moreover, it is preferable that it is methyl group substitution from a viewpoint of making it hard to produce film reduction.

  Specific examples of the partial structure represented by the formula (b-I-II-2) are given below. In addition, * in an example shows a bond.

  On the other hand, the partial structure represented by the formula (b-I-II) is a partial structure represented by the following formula (b-I-II-3) from the viewpoint of the coating film residual film ratio and patterning characteristics. Preferably there is.

In the formula (b-I-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n are as defined in the formula (b-I-II). R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. In addition, another OH group may be removed and shared with R ^Z in other molecules represented by the formula (b-I-II-3), that is, a plurality of formulas are formed via R ^Z. (B-I-II-3) may be linked.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The partial structure represented by the formula (b-I-II-3) contained in one molecule of (b-I-II) epoxy (meth) acrylate resin may be one type or two or more types. R ^Z may be a hydrogen atom and R ^Z may be a polybasic acid residue.

  The number of partial structures represented by the formula (b-I-II) contained in one molecule of the (b-I-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more. 3 or more are more preferable, 20 or less are preferable, 15 or less are more preferable, and 10 or less are more preferable. By setting it above the lower limit value, it is easy to obtain a strong film, surface roughness is unlikely to occur, and electric characteristics tend to be good, and by setting the upper limit value or less, deterioration of sensitivity and film loss are suppressed. The resolution tends to improve.

  The polystyrene-converted weight average molecular weight (Mw) of the (b-I-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more. It is preferably 30000 or less, more preferably 20000 or less, further preferably 10,000 or less, still more preferably 7000 or less, and particularly preferably 5000 or less. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at most the upper limit value, a strong film is likely to be obtained and surface roughness tends not to occur.

  The acid value of the (b-I-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and 60 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, and 120 gKOH / g or less is more preferable. When the amount is not less than the lower limit, a strong film tends to be easily obtained, and when the amount is not more than the upper limit, the development solubility is improved and the resolution tends to be good.

<(B-II) (Meth) acrylic copolymer resin containing repeating unit α having ethylenically unsaturated bond in side chain and repeating unit β derived from unsaturated carboxylic acid>
The (b-II) (meth) acrylic copolymer resin contains a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. It is considered that reliability can be ensured by having the repeating unit α, and surface smoothness can be improved by having the repeating unit β.

  The repeating unit α is not particularly limited as long as it has an ethylenically unsaturated bond in the side chain, and examples thereof include those having a chemical structure represented by the following general formula (I).

In the formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ³ represents a divalent linking group.
As a bivalent coupling group, the alkylene group which may have a substituent, or the bivalent aromatic ring group which may have a substituent is mentioned.

  Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably 20 or less, more preferably 15 or less, It is more preferably 10 or less, still more preferably 8 or less, and particularly preferably 5 or less. The reactivity tends to be improved by setting it to the lower limit value or more, and the thermal fluidity tends to decrease by setting the upper limit value or less.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, and a cyclohexylene group. Among these, from the viewpoint of reactivity, a methylene group, an ethylene group or a propylene group is preferable, and a propylene group is more preferable.

  Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, More preferably, it is more preferably 10 or less. The reactivity tends to be improved by setting it to the lower limit value or more, and the thermal fluidity tends to decrease by setting the upper limit value or less.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene. And groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
In addition, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, or a 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, benzoiso Thiazole 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, quinazolino Rings include groups such as azulene ring.

In addition, examples of the substituent that the alkylene group and the divalent aromatic ring group may have include a halogen atom, a phenyl group, a hydroxyl group, and a carboxyl group. Among these, a hydroxyl group is preferable from the viewpoint of reactivity. preferable.
Moreover, as a chemical structure represented by the said general formula (I), the chemical structure represented by the following general formula (I-1) or (I-2) from a reactive viewpoint is preferable, and the following general formula ( The chemical structure represented by I-1) is more preferable.

In the formula (I-1) and formula (I-2), R ¹ represents a hydrogen atom or a methyl group.

  The chemical structures represented by the general formulas (I-1) and (I-2) can be formed by adding an epoxy group-containing unsaturated compound to a repeating unit derived from (meth) acrylic acid.

  On the other hand, as the repeating unit β derived from unsaturated carboxylic acid, for example, a repeating unit derived from acrylic acid, a repeating unit derived from methacrylic acid, a repeating unit derived from crotonic acid, a repeating unit derived from itaconic acid, a repeating unit derived from maleic acid Units, repeating units derived from fumaric acid, and the like. Among these, from the viewpoint of thermal fluidity, repeating units derived from acrylic acid and repeating units derived from methacrylic acid are preferred, and the chemistry represented by the following general formula (II) A structure is more preferable.

In said formula (II), R < ³ > represents a hydrogen atom or a methyl group each independently.

  The (b-II) (meth) acrylic copolymer resin may further contain a repeating unit γ in addition to the repeating units α and β. Examples of the repeating unit γ include repeating units derived from ethylenically unsaturated compounds such as (meth) acrylic acid esters. For example, from the viewpoint of adjustment of reliability and development time, the repeating unit γ is represented by the following formula (IIIa). A repeating unit having a partial structure is preferred.

In formula (IIIa), R ^{1d to} R ^4d each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^5d and R ^6d each independently represent a hydrogen atom or 1 carbon atom. Represents 10 to 10 alkyl groups. R ^5d and R ^6d may be linked to form a ring. The ring formed by connecting R ^5d and R ^6d is preferably an aliphatic ring, which may be either saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

The carbon number of the alkyl group in R ^{1d to} R ^4d is usually 1 or more, and usually 10 or less, preferably 8 or less, more preferably 5 or less. There exists a tendency for it to become suitable image development solubility by setting it as the said upper limit or less.
Among these, R ^{1d to} R ^4d are preferably hydrogen atoms from the viewpoint of solubility.

The carbon number of the alkyl group in R ^5d and R ^6d is usually 1 or more, and is usually 10 or less, preferably 8 or less, more preferably 5 or less. There exists a tendency which shows appropriate solubility by setting it as the said lower limit or more, and there exists a tendency for hydrophilicity to be hold | maintained by setting it as the said upper limit or less.
Among these, from the viewpoint of development solubility, it is preferable that R ^5d and R ^6d are hydrogen atoms or R ^5d and R ^6d are connected to form an aliphatic ring having 5 to 6 carbon atoms.

  Among the above formulas (IIIa), those having a structure represented by the following formula (IIIb), (IIIc), or (IIId) are preferable. By introducing these partial structures, there is a tendency that heat resistance and strength can be increased.

  As the repeating unit having a partial structure represented by the formula (IIIa), those represented by the following formula (III) are preferable from the viewpoint of curability.

In the formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a partial structure represented by the formula (IIIa).

  On the other hand, as the ethylenically unsaturated compound from which the repeating unit γ is derived, in addition to the (meth) acrylate having the partial structure represented by the above formula (IIIa), for example, α-, o-, m of styrene -, P-alkyl, styrenes such as nitro, cyano, amide, ester derivatives, dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (Meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid Xylyl, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, ( (Meth) acrylic acid dicyclohexyl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, (meth) acrylic acid allyl, (meth) acrylic acid propargyl, (meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meta) ) Anthracenyl acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (Meth) acrylic Pyranyl, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, ( (Meth) acrylic acid perfluoro-n-propyl, (meth) acrylic acid perfluoro-iso-propyl, (meth) acrylic acid triphenylmethyl, (meth) acrylic acid cumyl, (meth) acrylic acid 3- (N, N -(Meth) acrylic acid esters such as (dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid amide, (meth) acrylic acid N , N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dip (Meth) acrylic acid amides such as pyramide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide, (meth) acrylic acid anilide, (meth) acryloylnitrile, Vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, and the like, diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Radical polymerization such as saturated dicarboxylic acid diesters, N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, monomaleimides such as N- (4-hydroxyphenyl) maleimide, N- (meth) acryloylphthalimide, etc. Compound Also mentioned.

  Among these, in order to impart superior heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the ethylenically unsaturated compound. is there.

  (B-II) The manufacturing method of (meth) acrylic copolymer resin is not specifically limited, It can obtain by copolymerizing the (meth) acrylate compound corresponding to each of repeating unit (alpha)-(gamma). Also, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether First, a copolymer of an epoxy group-containing (meth) acrylate and an ethylenically unsaturated compound such as (meth) acrylic acid or (meth) acrylic acid ester is obtained, and an epoxy group contained in the copolymer is obtained. It can also be obtained by adding ethylenically unsaturated monocarboxylic acid.

  (B-II) The content ratio of the repeating unit α in the (meth) acrylic copolymer resin is usually 10 mol% or more, preferably 12 mol% or more, more preferably 15 mol% or more, and more preferably 18 mol% or more. More preferably, 20 mol% or more is still more preferred, 22 mol% or more is particularly preferred, 25 mol% or more is most preferred, 40 mol% or less is preferred, 35 mol% or less is more preferred, and 30 mol% or less is preferred. More preferably, it is more preferably 25 mol% or less. When it is at least the lower limit value, it tends to be easy to ensure reliability, and when it is at most the upper limit value, surface smoothness tends to be ensured.

  Further, the content ratio of the repeating unit β in the (b-II) (meth) acrylic copolymer resin is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, and 50 mol%. The above is most preferable, 70 mol% or less is preferable, 60 mol% or less is more preferable, and 50 mol% or less is more preferable. When it is at least the lower limit value, the development solubility tends to be ensured, and when it is at most the upper limit value, reliability tends to be ensured.

  In addition, the content of the repeating unit γ in the (b-II) (meth) acrylic copolymer resin is usually 0 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 30 mol%. The above is more preferable, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 40 mol% or less is more preferable. There exists a tendency for adhesiveness to become favorable by setting it as the said lower limit or more, and there exists a tendency which is easy to ensure reliability by setting it as the said upper limit or less.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the (b-II) (meth) acrylic copolymer resin is usually 3000 or more, preferably 5000 or more, more preferably 10,000. It is above, More preferably, it is 15000 or more, Usually 50000 or less, Preferably it is 30000 or less, More preferably, it is 20000 or less. When it is at least the lower limit, the reliability tends to be good, and when it is at most the upper limit, the development solubility tends to be good.

  The acid value of the (b-II) (meth) acrylic copolymer resin is not particularly limited, but is preferably 100 mg · KOH / g or more, more preferably 130 mg · KOH / g or more, further preferably 160 mg · KOH / g or more, 180 mg · KOH / g or more is particularly preferred, 400 mg · KOH / g or less is preferred, 300 mg · KOH / g or less is more preferred, and 200 mg · KOH / g or less is even more preferred. When it is at least the lower limit value, the development solubility tends to be ensured, and when it is at most the upper limit value, reliability tends to be ensured.

  In the photosensitive coloring composition of the present invention, (b-II) (meth) acrylic copolymer resin containing a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid is 1 Types may be included, or two or more types may be included. When two or more types are included, from the viewpoint of easily obtaining the effect of the present invention, in at least one type of resin, the content of the repeating unit α is preferably within the above range.

  On the other hand, in the photosensitive coloring composition which concerns on another aspect, it contains the repeating unit (alpha) which has an ethylenically unsaturated bond in a side chain, and the repeating unit (beta) derived from unsaturated carboxylic acid (b-II) (meta). When two or more kinds of acrylic copolymer resins are contained, the content ratio of the repeating unit α contained therein is within the above range on the basis of all repeating units of the (b-II) (meth) acrylic copolymer resin of all kinds. It can also be. Similarly, the content ratio of the repeating unit β can be based on all repeating units of all types of (b-II) (meth) acrylic copolymer resins. Similarly, when the repeating unit γ is included, the content can be based on all repeating units of all types of (b-II) (meth) acrylic copolymer resins.

<Other alkali-soluble resins>
The (b) alkali-soluble resin used in the present invention contains other alkali-soluble resins in addition to the (b-I) epoxy (meth) acrylate resin and the (b-II) (meth) acrylic copolymer resin. Also good.

  There is no restriction | limiting in other alkali-soluble resin, What is necessary is just to select from resin normally used for the photosensitive coloring composition. Examples thereof include binder resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, Japanese Patent Application Publication No. 2007-334290, and the like. Moreover, it is preferable to use an acrylic resin from a compatible viewpoint with a pigment, a dispersing agent, etc., and what is described in Japan Unexamined-Japanese-Patent No. 2014-137466 can be used more preferably.

<(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.
Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; Japanese Patent Application Laid-Open No. 2000-56118 N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N -Radical activators such as aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750, etc. And the oxime ester derivatives described in the above.

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclo Tantadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

  Examples of α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Eat, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( 4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is below.

  As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making property, and when using an alkali-soluble resin containing a phenolic hydroxyl group, it is disadvantageous in terms of sensitivity. Such an oxime ester compound having excellent sensitivity is useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in a small amount and stable against thermal reactions. It is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.

  Examples of the oxime ester compound include compounds represented by the following general formula (IV).

In the above formula (IV), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. It is. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
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 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a 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 ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .

R ^21b is preferably an optionally substituted carbazole group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group. Among these, an optionally substituted diphenyl sulfide group is preferable from the viewpoint of suppressing N-methylpyrrolidone (NMP) elution.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

  Among the compounds represented by the general formula (IV), the compound represented by the following general formula (V) is preferable from the viewpoint of suppressing NMP elution.

In the general formula (V), 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 (V-1), and h represents an integer of 0 to 5.
The benzene ring shown in the formula (V) may further have a substituent.

In Formula (V-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 number of carbon atoms 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 number of carbon atoms 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.

An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene. Ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
An aromatic heterocyclic group means an aromatic heterocyclic ring having one free valence. The aromatic heterocyclic ring of the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an 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, benzo Imidazole 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, quinazolinone ring, azulene ring Such And the like.
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 further 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 (V-1), and among these, from the viewpoints of sensitivity and developability, it is represented by the general formula (V-1). It is preferably a group.
In the general formula (V-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 reliability (liquid crystal contamination), R ^25c is preferably a hydroxyl group.

In the general formula (V), h represents an integer of 0 to 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 (IV) or (V) 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 (V), For example, it can manufacture by the method of Japan Unexamined-Japanese-Patent No. 2000-080068.

  Further, as the oxime ester compound, compounds other than the above general formulas (IV) and (V) can be used. For example, Japanese Unexamined Patent Publication No. 2000-80068, Japanese Unexamined Patent Publication No. 2006-36750, Oxime ester derivatives and the like described in International Publication No. 2008/077554, International Publication No. 2009/131189, Japanese Special Tables No. 2014-500852, and the like can also be used.

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. As sensitizing dyes, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335 A coumarin dye having a heterocyclic ring described in JP-A-3-239703, a 3-ketocoumarin compound described in JP-A-5-289335, and a pyromethene described in JP-A-6-19240. Dye, etc., Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. Sho 48-84183, Japanese Special Publication Japanese Unexamined Patent Publication No. 52-112682, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403. Japanese Laid-Open Patent Publication No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088, Japanese Laid-Open Patent Publication No. 5-107761, Japanese Laid-Open Patent Publication No. 5-210240, Japanese Laid-Open Patent Publication No. 4-288818. And dyes having a dialkylaminobenzene skeleton described in Japanese Patent Application Publication No. H10.

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-die) Tilaminophenyl) 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) Sensitivity improves 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. It is done.

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 possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less. Yes, more preferably 7 or less. There exists a tendency which becomes high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve 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, from the viewpoint of curability, it is preferable to use (meth) acrylic acid alkyl ester as (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate.
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) By containing a solvent, a pigment can be disperse | distributed in a solvent and application | coating becomes easy.
The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary. Various other materials used according to the above are used in a state dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferable from the viewpoints of dispersibility and coatability.

  Among organic solvents, those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of applicability, 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 colored resin 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 or solidification of a color material or the like 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. Is suppressed, and there is a tendency that problems such as a tact defect in the reduced-pressure drying process and a pin mark of prebaking can be suppressed.

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), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), 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 the dispersibility of the pigment, (f) the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group. It is particularly preferable to include it.
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-based polymer dispersants include DISPERBYK 160 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 those 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 by reacting polyester glycols with alkylene oxides, such as poly ( And polyoxytetramethylene) 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 dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol 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.

Although a tertiary amino group is not specifically limited, For example, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring etc. are mentioned.
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 catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. And tertiary amine catalysts. 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 tend to be inferior. If the molecular weight exceeds 200,000, the solubility is lowered and the dispersibility is inferior, and at the same time, the reaction tends to be difficult to control.

  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, Japanese Patent Application Laid-Open No. 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, more preferably 5/95 to 60/40 (mass ratio), and within this range, a balance between dispersibility and storage stability can be ensured. Tend.
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 dispersibility 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. ]
Further, the amine value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. There exists a tendency which can ensure favorable dispersibility by setting it as the said range.

  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, 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. And 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. R ³⁵ and R ³⁶ may be bonded to each other to form a cyclic structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

Moreover, as the alkyl 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) may be preferably employed. 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 the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ^{31 to} R ^{33 in} the above formula (i) 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), etc. Is a —COO—R ⁴⁴ — group.
In the above formula (i), examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ⁻ .

  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, 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 that 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, 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 dispersion stability and solvent compatibility, it is preferred that R ³⁸ is an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
In R ^38, a substituent which may have an alkyl group, a halogen atom, an alkoxy group, and the like. 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. , A photoacid generator, a crosslinking agent, a polymerization accelerator and the like can be appropriately 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 kind of the silane coupling agent, various kinds such as epoxy, (meth) acrylic and amino 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 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 , R ⁶⁶ and R ⁶⁷ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a —CH ₂ OR ⁶⁸ group, and 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 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 the OR ⁶⁸ group, 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 the 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 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. Preferably, it is more preferably 30% by mass or more, still more preferably 35% by mass or more, particularly preferably 40% by mass or more, and usually preferably 60% by mass or less, The content is more preferably at most mass%, further preferably at most 48 mass%, particularly preferably at most 46 mass%. (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 plate-making characteristic is easy to be obtained by making it below the said upper limit. Tend.

  When (a) the colorant contains an organic pigment, the content ratio of the organic pigment to the (a) colorant is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass. More preferably, it is more preferably 30% by mass or more, particularly preferably 50% by mass or more, most preferably 70% by mass or more, and usually 100% by mass or less. It is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, still more preferably 85% by mass or less, and 80% by mass or less. It is particularly preferred that There exists a tendency for sufficient optical density (OD) to be acquired by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.

  When (a) the colorant contains an organic color pigment, the content ratio of the organic color pigment to (a) the colorant is preferably 1% by mass or more, more preferably 5% by mass or more. More preferably, it is more preferably 30% by mass or more, still more preferably 30% by mass or more, particularly preferably 50% by mass or more, most preferably 70% by mass or more, and usually 100% by mass. It is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, still more preferably 85% by mass or less, and 80% by mass. % Or less is particularly preferable. There exists a tendency for sufficient optical density (OD) to be acquired by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.

  When (a) the colorant contains at least one pigment selected from the group consisting of a red pigment and an orange pigment, (a) at least one pigment selected from the group consisting of a red pigment and an orange pigment for the colorant Is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and preferably 30% by mass or less, 20% by mass. % Or less, more preferably 15% by weight or less, still more preferably 10% by weight or less, particularly preferably 7% by weight or less, and 5% by weight or less. Is most preferred. There exists a tendency for sufficient optical density (OD) to be acquired by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.

  When (a) the colorant contains at least one pigment selected from the group consisting of a blue pigment and a purple pigment, (a) at least one pigment selected from the group consisting of a blue pigment and a purple pigment with respect to the colorant Is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, and 60% by mass. % Or more, particularly preferably 65% by weight or more, more preferably 90% by weight or less, more preferably 80% by weight or less, and 70% by weight or less. Is more preferable. There exists a tendency which can ensure light-shielding property by setting it as the said lower limit or more, and there exists a tendency which can ensure plate-making characteristic by setting it as the said upper limit or less.

  When (a) the colorant contains a black color material, the content ratio of the black color material to (a) the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass. % Or more, more preferably 20% by weight or more, more preferably 50% by weight or less, more preferably 40% by weight or less, and 35% by weight or less. Is more preferable, and it is still more preferable that it is 30 mass% or less. There exists a tendency for sufficient optical density (OD) to be obtained by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.

  Further, when (a) the colorant contains an organic black pigment, the content ratio of the black organic pigment to (a) the colorant is preferably 1% by mass or more, more preferably 5% by mass or more. More preferably, it is more preferably at least 20% by mass, particularly preferably at least 20% by mass, more preferably at most 50% by mass, more preferably at most 40% by mass, and at most 30% by mass. More preferably, it is particularly preferably 20% by mass or less. There exists a tendency for sufficient optical density (OD) to be obtained by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.

  When (a) the colorant contains carbon black, the content ratio of carbon black to (a) the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass or more. Is more preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. It is preferably 30% by mass or less. There exists a tendency for sufficient optical density (OD) to be obtained by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics 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 25 It is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass. It is as follows. (B) By making the content rate 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.

  The content of the (b-I) epoxy (meth) acrylate resin is usually 3% by mass or more, preferably 6% by mass or more, more preferably 8% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. It is usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. There is a tendency that reliability can be ensured by setting it to the lower limit value or more, and there is a tendency that surface smoothness can be ensured by setting the upper limit value or less.

  (B) The content ratio of the (b-I) epoxy (meth) acrylate resin contained in the alkali-soluble resin is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30%. % By mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass. Hereinafter, it is particularly preferably 40% by mass or less. There is a tendency that reliability can be ensured by setting it to the lower limit value or more, and there is a tendency that surface smoothness can be ensured by setting the upper limit value or less.

  The content ratio of the (b-II) (meth) acrylic copolymer resin is usually 1% by mass or more, preferably 3% by mass or more, more preferably 6% by mass with respect to the total solid content of the photosensitive coloring composition of the present invention. More preferably, it is 8% by mass or more, usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. There exists a tendency which can ensure surface smoothness by setting it as the said lower limit or more, and there exists a tendency which can ensure reliability by setting it as the said upper limit or less.

  (B) The content ratio of the (b-II) (meth) acrylic copolymer resin contained in the alkali-soluble resin is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably. 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass. It is as follows. There exists a tendency which can ensure surface smoothness by setting it as the said lower limit or more, and there exists a tendency which can ensure reliability by setting it as the said upper limit or less.

  (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% or more. More preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, Preferably it is 7 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 it suppresses the fall of the solubility with respect to the developing solution of an unexposed part 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 with respect to the total solid content of the photosensitive coloring composition of the present invention. It is 10 mass% or less, Preferably it is 5 mass% or less, and a polymerization accelerator is 0.1-50 mass parts normally with respect to 100 mass parts of (c) photoinitiators, Especially 0.1-20 mass parts. It is preferable to use in proportion. 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.
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, More preferably, it is 15 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.

  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, more preferably 15% by mass or more, even more preferably, by using (e) a solvent. Is adjusted to be 20% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less.

  (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, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable. Further, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less. In particular, it is preferably 30 parts by mass or less. (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 thickness of the coating film obtained by curing the photosensitive coloring composition is preferably 1.0 or more, more preferably 1.2 or more, and 1.5 or more. More preferably, it is particularly preferably 1.8 or more, usually 4.0 or less, preferably 3.0 or less, and more preferably 2.5 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.

[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 The photosensitive colored composition of the present invention is used for the same applications as known photosensitive colored compositions for color filters. Hereinafter, it is used as a colored spacer (black photospacer). The method for forming a black photospacer using the photosensitive coloring composition of the present invention will be described below.

  Usually, a photosensitive coloring composition is supplied into a film or pattern by a method such as coating on a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermosetting treatment as necessary.

(3) Formation of colored spacer [1] Supplying method to substrate The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as 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 can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.

  The coating amount varies depending on the application. For example, in the case of a black photospacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm 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 occurs in the liquid crystal panel.

  However, when the black photo spacers having different heights are collectively formed by the photolithography method using the photosensitive coloring composition of the present invention, the heights of the black photo spacers finally formed are different.

  A known substrate such as a glass substrate can be used as the substrate. The substrate surface is preferably a flat surface.

[2] Drying method Drying after supplying the photosensitive coloring composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.

  Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used. The temperature is selected in the range of 30 seconds to 3 minutes.

[3] Exposure Method Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating with 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, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.

As a preferred embodiment of the present invention, when black photo spacers having different heights are simultaneously formed by a photolithography method, for example, a light shielding portion (light transmittance 0%) and a plurality of openings have the highest average light transmittance. An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a high opening (complete transmission opening) is used. By this method, a difference in the residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount.
For example, a method of producing the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.

  The light source used for said exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared 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 the 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.

Energy of exposure generally, 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 target 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.

[4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, 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; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; 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 can 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.

[5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature ranges from 100 ° C. to 280 ° C., preferably from 150 ° C. to 250 ° C., and the time ranges from 5 minutes to 60 minutes.

The size and shape of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which the colored spacer is applied, but the photosensitive colored composition of the present invention is particularly suitable for the height of the spacer and the sub-spacer by photolithography. It is useful for simultaneously forming different black photo spacers, in which case the height of the spacer is usually about 2 to 7 μm, and the sub-spacer is usually about 0.2 to 1.5 μm lower than the spacer. Have
Moreover, the optical density (OD) per 1 μm of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, further preferably 1.8 or more, from the viewpoint of light-shielding properties. It is 0 or less, and preferably 3.0 or less. Here, the optical density (OD) is a value measured by a method described later.

[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.

  The liquid crystal provided with the colored spacer of the present invention is formed by bonding the color filter having the colored spacer of the present invention and the liquid crystal driving side substrate to form a liquid crystal cell, and injecting the liquid crystal into the formed liquid crystal cell. An image display device such as a display device can be manufactured.

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

<Alkali-soluble resin-A>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of 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 the mixture was further stirred 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-A thus obtained was about 8400, and the acid value was 80 mgKOH / g.

<Alkali-soluble resin-B>
A mixed liquid of 217.6 parts by mass of propylene glycol monomethyl ether acetate and 53.9 parts by mass of propylene glycol monomethyl ether was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 3.52 parts by mass of benzyl methacrylate, 58.5 parts by mass of methacrylic acid, 66.1 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2'-azobis-2- A mixed solution of 3.8 parts by mass of methylbutyronitrile 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 replaced with air, 27.3 parts by mass of glycidyl methacrylate, 0.6 part by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. The alkali-soluble resin-B thus obtained had a weight average molecular weight Mw of 16,500 and an acid value of 176 mgKOH / g.

<Alkali-soluble resin-C>
A mixed liquid of 303.5 parts by mass of propylene glycol monomethyl ether acetate and 75.9 parts by mass of propylene glycol monomethyl ether was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 10.4 parts by mass of styrene, 34.4 parts by mass of methacrylic acid, 66.1 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2,2′-azobis-2-methyl A mixed solution of 8.7 parts by mass of butyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 9.9 parts by mass of glycidyl methacrylate, 0.2 parts by mass of trisdimethylaminomethylphenol and 0.04 parts by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. The alkali-soluble resin-C thus obtained had a weight average molecular weight Mw of 7200 and an acid value of 86 mgKOH / g.

<Alkali-soluble resin-D>
“ZCR-1642H” manufactured by Nippon Kayaku Co., Ltd. (Mw = 6500, acid value = 98 mgKOH / g)

  <Alkali-soluble resin-E>

50 g of an epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were added to a thermometer, a stirrer, and a cooling pipe. It put into the attached flask, and it was made to react at 90 degreeC, stirring until an acid value became 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 3.5 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 became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, acid value 113 mgKOH / g, weight average molecular weight (Mw) 2600 in terms of polystyrene measured by GPC, double A carboxyl group-containing epoxy methacrylate resin (alkali-soluble resin-E) having a binding equivalent of 520 g / mol was obtained.

<Alkali-soluble resin-F>
A mixed solution of 214.5 parts by mass of propylene glycol monomethyl ether acetate and 53.6 parts by mass of propylene glycol monomethyl ether was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 68.7 parts by mass of benzyl methacrylate, 43.9 parts by mass of methacrylic acid, 22.0 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2′-azobis-2- A mixture of 1.4 parts by mass of methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 21.3 parts by mass of glycidyl methacrylate, 0.5 part by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. The alkali-soluble resin-F thus obtained had a weight average molecular weight Mw of 44100 and an acid value of 130 mgKOH / g.

<Alkali-soluble resin-G>
A mixture of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2'-azobis-2- A mixed solution of 3.3 parts by mass of methylbutyronitrile was dropped over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 38.4 parts by mass of glycidyl methacrylate, 0.8 part by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. The alkali-soluble resin-G thus obtained had a weight average molecular weight Mw of 19100 and an acid value of 198 mgKOH / g.

<Dispersant-I>
“DISPERBYK-LPN21116” manufactured by Big Chemie Co., Ltd. (acrylic AB composed of an A block having a quaternary ammonium base and a tertiary amino group in a side chain and a B block having no quaternary ammonium base and a tertiary amino group Block copolymer, amine value is 70 mgKOH / g, acid value is 1 mgKOH / g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.

<Dispersant-II>
“DISPERBYK-167” manufactured by Big Chemie (urethane polymer dispersant)

<Pigment derivative>
Lubrizol “Solsperse 12000”
<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxybutanol

<Photopolymerization initiator>
Compounds with the following structure

<Photopolymerizable monomer>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Additives>
Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacryloyl group-containing phosphate)
<Surfactant>
DIC 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 a hot plate temperature of 80 ° C. for 70 seconds. After passing through the exposure and development steps, a resist coated substrate was obtained by heating at an oven temperature of 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. The optical density per unit film thickness was calculated from the optical density (OD) and the film thickness. The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding 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 a hot plate temperature of 80 ° C. for 70 seconds. After passing through the exposure and development steps, it was heated at an oven temperature of 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. The sample solution (NMP elution solution) was 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 the NMP single solution from the same light source, the light intensity transmitted through the NMP single solution can be regarded as I _0, and the light intensity transmitted through the sample solution can be regarded as I. 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 the NMP resistance was evaluated by setting the area value less than 20 (nm) to ◯ and 20 (nm) or more to 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: Determination by spectral area value of absorbance (wavelength 300 to 800 nm)
○: Less than 20 (nm) ×: 20 (nm) or more

<Evaluation of surface smoothness>
Evaluation of surface smoothness and the following surface roughness was performed in the following procedures.
First, the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 3 μm, dried under reduced pressure for 1 minute, and then dried at a hot plate temperature of 80 ° C. for 70 seconds. After passing through the exposure and development steps, it was heated at an oven temperature of 230 ° C. for 20 minutes to obtain a resist-coated substrate. About the produced resist coating board | substrate, the presence or absence of wrinkle generation | occurrence | production on the surface after a heating was observed with the optical microscope in the visual field of 70 micrometers x 70 micrometers. The evaluation criteria are as follows.
○: Micron-order wrinkles are not observed on the pattern surface ×: Micron-order wrinkles are noticeable on the pattern surface

<Evaluation of surface roughness>
With respect to the resist coated substrate prepared in the above <Evaluation of surface smoothness>, a three-dimensional non-contact surface shape measurement system Micromap manufactured by Ryoka System Co., Ltd. is used with a 50 × optical lens and 70 μm × 70 μm in Focus mode. The surface roughness Sa (arithmetic mean roughness, μm) was measured in the visual field.

<Preparation of pigment dispersions 1, 3 and 4>
The pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was obtained. This mixed solution was subjected to a dispersion treatment in a 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 were separated by a filter to prepare pigment dispersions 1, 3, and 4.

<Pigment dispersion 2 (coated carbon black dispersion)>
Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small amount of Na, Ca, and S was used, and a coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Mitsubishi Chemical Corporation) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.

Next, after draining with a 60 mesh wire net, it was put into a vacuum dryer and dried at 70 ° C. for 7 hours to completely remove toluene and water.
The obtained coated carbon black, a dispersant, a pigment derivative, and a solvent were mixed so as to have a mass ratio shown in Table 1.

  This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same mass as the dispersion was added. After the completion of dispersion, the beads and dispersion were separated by a filter to prepare pigment dispersion 2.

[Examples 1-6, Comparative Examples 1-3]
Each component was added so that the solid content ratio was the blending ratio shown in Table 2, and PGMEA was further added so that the solid content was 22% by mass, followed by stirring and dissolution to prepare a photosensitive coloring composition. The solid content ratio of the prepared composition is shown in Table 2. Table 2 shows the evaluation results of the unit OD value, NMP dissolution test, surface smoothness and surface roughness measured by the above-described method. In addition, the mass part of the photosensitive coloring composition in Table 2 represents a mass part of solid content.

  From a comparison between Example 1 and Comparative Examples 1 and 2 in Table 2, 12 mol% or more of (b-I) epoxy (meth) acrylate resin and (b-II) repeating unit α having an ethylenically unsaturated bond were used. And a photosensitive coloring composition containing a (meth) acrylic copolymer resin containing a repeating unit β derived from an unsaturated carboxylic acid has high light-shielding properties and at the same time has reliability and surface smoothness. It was suggested that it was excellent. On the other hand, Comparative Example 1 in which the repeating unit α is less than 12 mol% has poor reliability, and Comparative Example 2 that does not contain (b-II) (meth) acrylic copolymer resin has poor surface smoothness. there were.

  When the main resin component is (b-I) epoxy (meth) acrylate resin as in Comparative Example 2, it is considered that the surface smoothness becomes poor due to the heat flow resulting from the structure. Therefore, in addition to the epoxy (meth) acrylate resin, by using a (meth) acrylic copolymer resin containing a repeating unit derived from an unsaturated carboxylic acid that is difficult to heat flow, the heat flow is reduced and the surface smoothness is improved. it is conceivable that. However, since such (meth) acrylic copolymer resins are generally less sensitive than epoxy (meth) acrylate resins, curability is reduced and reliability may deteriorate as in Comparative Example 1. is there. Therefore, by increasing the content ratio of the repeating unit α having an ethylenically unsaturated bond in the (meth) acrylic copolymer resin, sufficient curability can be ensured, and both reliability and surface smoothness can be achieved. Conceivable.

From the comparison of Examples 1 to 3, when the colorant includes an organic pigment and carbon black, or at least one selected from the group consisting of a red pigment and an orange pigment, and a group consisting of a blue pigment and a purple pigment. When at least one selected one was included, it was suggested that high light-shielding properties were ensured and reliability and surface smoothness were excellent regardless of specific pigment types.
On the other hand, Comparative Example 3 in which the colorant is carbon black having a high ultraviolet absorption property has insufficient surface smoothness.

  On the other hand, the comparison between Examples 2 and 4 suggested that the (b-I) epoxy (meth) acrylate resin was excellent in reliability regardless of the type. On the other hand, if the content ratio of the repeating unit α having an ethylenically unsaturated bond in the (b-II) resin is 12 mol% or more from the comparison of Examples 1, 5, and 6, the value of the specific content ratio It was suggested that it is excellent in reliability and surface smoothness regardless of the above.

  Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2015-252149) for which it applied on December 24, 2015, The whole is used by reference.

  According to the photosensitive coloring composition of the present invention, it is possible to provide a cured product and a colored spacer that have high light-shielding properties, high reliability, and excellent surface smoothness, and an image display including such a colored spacer. An apparatus can be provided. 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 (9)

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 organic pigment and carbon black,
The (b) alkali-soluble resin comprises (b-I) an epoxy (meth) acrylate resin, (b-II) a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. (Meth) acrylic copolymer resin containing, and
The photosensitive coloring composition, wherein the content ratio of the repeating unit α in the (b-II) (meth) acrylic copolymer resin is 12 mol% or more. The organic pigment is at least one organic black pigment selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound The photosensitive coloring composition of Claim 1 containing this.

(In formula (1), R ¹¹ and R ¹⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OCONH ₂ , OCONHR ²¹ , OCONR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = CH ₂ , N = CHR ²¹ , N = CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;
And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ , It can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR ²¹ bridges;
R ²¹ and R ²² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or carbon. It is an alkynyl group of formula 2-12. ) 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 colorant (a) includes at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment,
The (b) alkali-soluble resin comprises (b-I) an epoxy (meth) acrylate resin, (b-II) a repeating unit α having an ethylenically unsaturated bond in the side chain and a repeating unit β derived from an unsaturated carboxylic acid. (Meth) acrylic copolymer resin containing, and
The photosensitive coloring composition, wherein the content ratio of the repeating unit α in the (b-II) (meth) acrylic copolymer resin is 12 mol% or more. The photosensitive coloring composition of any one of Claims 1-3 in which the said repeating unit (alpha) has a chemical structure represented by the following general formula (I).

(In formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. R ³ represents a divalent linking group.)   The content rate of the said (b-II) (meth) acrylic copolymer resin is 1 mass% or more with respect to the total solid in a photosensitive coloring composition, The any one of Claims 1-4. Photosensitive coloring composition.   The photosensitive coloring composition of any one of Claims 1-5 whose optical density per 1 micrometer of film thickness of the hardened coating film is 1.0 or more.   Hardened | cured material obtained by hardening | curing the photosensitive coloring composition of any one of Claims 1-6.   A colored spacer formed from the cured product according to claim 7.   An image display device comprising the colored spacer according to claim 8.