TWI735598B - Black pigment composition and black coating film formation composition including the black pigment composition - Google Patents

Abstract

Provided is a black pigment composition and a black coating film forming composition containing the same, which does not use black carbon, can absorb light in the visible light region, can inhibit the absorption of infrared rays and ultraviolet rays, and has good solvent resistance.

A black pigment composition comprising at least one black organic pigment selected from the following formulas (1) and (2), and at least two colored organic pigments other than the black organic pigment, a dispersant, and a solvent; And, a black coating film forming composition containing the black pigment composition and a coating film forming component.

Description

Black pigment composition and black coating film forming composition containing the same

The present invention relates to a black pigment composition and a black coating film forming composition containing the same, and in particular to a black pigment composition used in a black column spacer (black column spacer) provided in a flat panel of a liquid crystal display device, and The black coating film containing this forms a composition.

The liquid crystal display device is provided with a liquid crystal cell structure in which a liquid crystal substance is filled between two glass substrates provided with opposing transparent electrodes. Then, between the two glass substrates, in order to keep the gap between the substrates uniform and provide a good image, a column spacer is inserted. Conventionally, as such a column spacer, bead spacers such as bead glass have been used. However, in the method of using bead spacers, since only the beads are randomly dispersed in the gap, it has been pointed out that there are the following problems: the problem of light leakage, the deviation of the gap distance may increase, and it is difficult to control the elasticity And other mechanical properties. In addition, in recent years, the market has demanded higher image quality of liquid crystal display devices, and more precise gap control has been sought.

As a countermeasure for this improvement, it has been proposed to replace the bead spacer with a black column spacer using a black photosensitive resin composition (see, for example, Patent Documents 1 and 2). With the black column spacer, the column spacer can be formed in such a way that the deviation of the gap distance at the desired position is reduced. The control of the characteristics of the photopolymerizable component and the like is also relatively easy. Therefore, it is considered to be better than the bead spacer. In other words, the gap can be controlled more precisely. Then, by including a black colorant in the column spacer, visible light (wavelengths of 380 nm to 750 nm) can be blocked, and improvement in contrast and color development can be expected. As such a black coloring agent, perylene black is exemplified in Patent Documents 1 and 2. In addition, as an example of perylene black, patent document 3 discloses a pigment with a specific structure.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2015-191234 A

[Patent Document 2] JP 2007-71994 A

[Patent Document 3] Japanese Patent No. 4980727

However, since the column spacer is in contact with the liquid crystal substance, resistance to the solvent contained in the liquid crystal substance, that is, solvent resistance, is required. In addition, the characteristics of the column spacer must also not affect the characteristics of the liquid crystal cell. For example, when the insulation of the black column spacer is low, it will affect the driving of the liquid crystal, which may affect the characteristics of the liquid crystal cell.

Furthermore, in the manufacturing process of forming the column spacer, a method of hardening a photopolymerizable component to form a polymer compound is often used. In this case, it is generally irradiated with ultraviolet rays for curing. Therefore, the black photosensitive composition system must be constructed in a manner that can absorb visible light while allowing ultraviolet rays to pass through. In order to determine the correct exposure position, infrared rays such as near infrared rays are often used to confirm alignment keys on the panel substrate. At this time, it must also be constructed in such a way that infrared rays can penetrate.

In Patent Documents 1 and 2, nigrosine black, perylene black, titanium black, cyanine black, lignin black, endoamide-based organic black, RGB black, carbon black, etc. are exemplified as black pigment systems. However, the use of carbon black is allowed, and in terms of insulation, there is a concern about the influence on the liquid crystal cell. In addition, carbon black also absorbs ultraviolet rays or infrared rays other than visible light, and the polymerization reaction of the photopolymerizable components by ultraviolet rays may become insufficient, or the alignment during exposure using infrared rays may become difficult. The impact.

In view of the above point of view, the object of the present invention is to provide a black pigment composition and a black coating film forming composition containing the same, which does not use black carbon, can absorb light in the visible light region, and can inhibit the absorption of infrared and ultraviolet rays , Solvent resistance is good.

Although Patent Documents 1 and 2 exemplify perylene black as a black pigment, they do not describe specific examples of perylene black. Here, the inventors have obtained the following insights through in-depth research and review: "Depending on the type of perylene black, the degree of solvent resistance will vary, and the wavelength absorption spectrum will vary." Then, it was discovered that the above-mentioned problems can be solved by using perylene black of a specific structure and at least two colored pigments other than perylene black of the specific structure, thus completing the present invention. The gist of the present invention is as follows.

The first aspect of the present invention relates to a black pigment composition comprising at least one black organic pigment selected from the following formulas (1) and (2), and at least two colored organic pigments other than the black organic pigment Pigments, dispersants and solvents.

In a preferred embodiment of the present invention, the colored organic pigments other than the aforementioned black organic pigments are selected from the group consisting of red organic pigments, blue organic pigments, and purple organic pigments. In another preferred embodiment, the red organic pigment is selected from at least one of the following (a) group, the blue organic pigment is selected from at least one of the following (b) group, and the purple organic The pigment system is at least one selected from the following (c) group.

(a) Group: color index (pigment red) 149, 179, 254, 255.

(b) Group: color rendering index pigment blue (pigment blue) 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16,60.

(c) Group: Pigment violet 23, 29 color rendering index.

The second aspect of the present invention relates to a black coating film forming composition comprising the aforementioned black pigment composition and coating film forming components.

According to the present invention, it is possible to provide a black pigment composition and a black coating film forming composition containing the same, which does not use black carbon, can absorb light in the visible light region, can inhibit the absorption of infrared rays and ultraviolet rays, and has good solvent resistance .

[Best form to implement the invention] <Black pigment composition>

The black pigment composition related to the present invention contains at least one black organic pigment selected from the following formulas (1) and (2), and at least two colored organic pigments other than the black organic pigment (there are below: Simply referred to as "colored organic pigments"), dispersants and solvents.

The black organic pigments with specific structures represented by formulas (1) and (2) have the following characteristics: "In the wavelength range of 380nm~750nm, it can effectively absorb visible light and has a low transmittance, which is compared to the visible light range. Absorption, the absorption in the ultraviolet region (shorter wavelength than 380nm) and infrared region (longer wavelength than 750nm) is suppressed to be small.” Such absorption characteristics of light in the visible light region can be confirmed by the optical density (OD value) when measured by the method described later. In addition, by combining with at least two kinds of colored organic pigments other than the black organic pigments, even if black carbon is not used, it can still block light in the visible light region, and can effectively inhibit the absorption of ultraviolet and infrared rays than the visible light region. . Therefore, for example, when a photopolymerizable component is used as a coating film forming component to form a column spacer, the photopolymerizable component can be sufficiently polymerized by ultraviolet rays, and at the same time, the photopolymerizable component can also be used for exposure by infrared rays. Bit. In addition, the solvent resistance is good. It can also avoid the influence on the characteristics of the liquid crystal cell caused by the black carbon.

For such black organic pigments, for example, Lumogen Black FK4280 manufactured by BASF Corporation can be used.

In the embodiment of the present invention, the content of the black organic pigment in the black pigment composition is preferably 1~ 12% by weight, and preferably 1 to 7% by weight.

Examples of colored organic pigments that can be used in the present invention include red organic pigments, blue organic pigments, green organic pigments, purple organic pigments, yellow organic pigments, orange organic pigments, brown organic pigments, and the like. When expressed as a color index No., the following can be exemplified.

Red organic pigments: pigment red (pigment red) 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 52, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 81: 1, 83, 88, 89, 95, 112, 114, 119, 122, 123, 129, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 181, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 214, 216, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279. Among them, from the viewpoint of the effect of increasing the OD value and the effect of suppressing the absorption of ultraviolet and infrared rays by combining with the aforementioned black organic pigments and other colored organic pigments, especially blue organic pigments, Preferably, it is Pigment Red 149, 179, 254, and 255.

Blue organic pigments: pigment blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1, 24, 24:1 , 25, 26, 56, 60, 61, 62, 63, 75, 79, 80, etc. Among them, in terms of the effect of increasing the OD value obtained by the combination with the aforementioned black organic pigments and other colored organic pigments, and the effect of suppressing the absorption of ultraviolet and infrared rays, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60, and preferably pigment blue 15:6, 16, 60.

Green organic pigments: pigment green 1, 4, 7, 8, 10, 36, etc.

Purple organic pigments: pigment violet (pigment violet) 1, 2, 3, 3: 1, 3: 3, 5: 1, 13, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50, etc. Among them, in terms of the effect of increasing the OD value obtained by the combination with the aforementioned black organic pigments and other colored organic pigments, and the effect of suppressing the absorption of ultraviolet and infrared rays, pigment violet 23, 29, Pigment Violet 29 is more preferred.

Yellow organic pigments: pigment yellow (pigment yellow) 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 49, 55, 60, 61, 61: 1, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 185, 191, 191-1, 193, 194, 199, 205, 206, 209, 209: 1, 212, 213, 214, 215, 219, etc.

Orange organic pigments: pigment orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81, etc.

Brown organic pigments: pigment brown (pigment brown) 5, 23, 25, 32, 41, 42, etc.

In the present invention, it is preferable to contain at least two kinds of colored organic pigments as described above. In this way, it complements the aforementioned black organic pigments and can effectively absorb light in the visible light region. Colored organic pigments may contain 3 or more types. The more types of colored pigments, the greater the absorption effect of visible light. However, if there are many types, the dispersibility of the colored pigment may be poor. Therefore, as a result of in-depth research, the inventors found that in the aforementioned designated black organic pigments, by combining at least two selected from the group consisting of red organic pigments, blue organic pigments and purple organic pigments, the color organic pigments are suppressed. Used, while maintaining the absorption characteristics of the specified black organic pigments, it can effectively absorb the visible light in the entire range of wavelengths from 380nm to 750nm, and can inhibit the absorption in the ultraviolet and infrared regions. In addition, such an effect is that the red organic pigment is selected from the group (a) of the color rendering index pigment red 149, 179, 254, 255 at least one; the blue organic pigment is selected from the group (b) At least one of color index pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60; color rendering index pigment violet selected from group (c) When there is at least one of 23 and 29, there will be a tendency to play more effectively. Furthermore, when the red organic pigment and the blue organic pigment are each selected from one species selected from the group (a) and one species selected from the group (b), and the blue organic pigment and the purple organic pigment are each selected from the group (b) There will be a tendency to be more suitable when one of the group and one selected from the (c) group.

In the embodiment of the present invention, the content of the colored organic pigment is based on 100 parts by weight of the black organic pigment in terms of effectively absorbing visible light in the entire region of 380 to 750 nm and effectively suppressing the absorption of ultraviolet and infrared rays. It is preferably 50 to 1000 parts by weight, and more preferably 100 to 700 parts by weight. In the case of using the pigment derivative described later, the content of the colored organic pigment means the total amount including the pigment derivative.

Examples of the dispersant that can be used in the present invention include resin-type dispersants, surfactant-type dispersants, and the like. In addition, among resin-based dispersants, because the acid value of the resin is different from the amine value, there are acid value type dispersants with an amine value of 0 and an acid value greater than 0, and an amine value with an acid value of 0 and an amine value greater than 0. Type of dispersant, dispersant with acid value and amine value greater than 0.

Examples of resin-type dispersants include polyurethane; polyester; unsaturated polyamide; sulfonate; polycarboxylic acid and its amine salt, ammonium salt, and alkylamine salt; polycarboxylate; Polycarboxylate containing hydroxyl; polysiloxane; modified polyacrylate; alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, poly Water-soluble polymer compounds such as vinylpyrrolidone and gum arabic; styrene-acrylic resin, styrene-methacrylic resin, styrene-acrylic-acrylate resin, styrene-maleic acid resin, styrene-horse Resins containing ethylenic double bonds such as acrylate resin, methacrylic acid-methacrylate resin, acrylic acid-acrylate resin, isobutylene-maleic acid resin, vinyl-ester resin, rosin-modified maleic acid resin, etc. ; Amine-based resins such as polyallylamine, polyvinylamine, and polyethyleneimine.

Commercially available resin-type dispersants can be used. Specific examples of commercially available products are as follows, but they are not limited to these.

Japan Lubrizol Co., Ltd.: Solsperse 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000, BYK‧JAPAN Co., Ltd.: Disperbyk 108 , 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2015, 2050, 2070, 2150, LPN6919, LPN22101, LPN21116, BASF Company system: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244, PX4701, Ajinomoto Fine-Techno Co., Ltd. system: Ajisper-PB821 (F), PB822, PB880, manufactured by Kawaken Fine Chemicals Co., Ltd.: Hinoact T-8000, manufactured by Kusumoto Chemical Co., Ltd.: DISPARLON PW-36, DISPARLON DA-325, 375, 7301, manufactured by Otsuka Chemical Co., Ltd.: TERPLUS D2015, MD1000, etc.

In addition, the resin-type dispersant system can be used after synthesizing various resins as described above according to a conventional method. Various resins as described above, for example, by mixing one or more monomers or polymerization initiators in a solvent in a nitrogen environment, and polymerizing them under specified conditions to obtain homopolymers, Random copolymers, block copolymers, graft copolymers, etc.

In addition, in the embodiment of the present invention, a resin-type dispersant containing a polymer block (A) and a block copolymer (I) with the polymer block (B) as an effective ingredient can be used. (A) is a structural unit derived from a cyclic amine compound, and the aforementioned polymer block (B) is a structural unit derived from a nonionic water-soluble compound and a structural unit derived from an anionic water-soluble compound, and does not contain the aforementioned structural unit derived from The structural unit of cyclic amine compounds. By using a resin-type dispersant containing the block copolymer (I), the amount of other dispersants or pigment derivatives used as described later can be reduced. Since the pigment derivative introduces functional groups into the pigment, it may affect the characteristics of the liquid crystal cell according to the characteristics of the pigment and the functional group. However, by using a resin-type dispersant containing the block copolymer (I), since the amount of other dispersants or pigment derivatives used can be reduced, the influence on the characteristics of the liquid crystal cell can be reduced.

The detailed description of the block copolymer (I) is as follows.

The block copolymer (I) can be arbitrarily AB type diblock copolymer, ABA type or BAB type triblock copolymer, ABAB type tetrablock copolymer, ABABA type or BABAB type pentablock In particular, from the viewpoint of the dispersibility of finely divided pigments, the pigment system has a polymer block (A) arranged on one end and a polymer block (A) on the other end. The block copolymer (I) in which the polymer block (B) is arranged on the terminal is preferable.

The polymer block (A) is a block composed of a homopolymer of a cyclic amine compound or a copolymer of a cyclic amine compound and a compound copolymerizable therewith. The copolymer may be a random copolymer or a block copolymer. The cyclic amine units contained in the aforementioned homopolymers and copolymers can also be quaternized as needed. As the cyclic amine compound, in particular, a nitrogen heterocyclic compound having a group containing a polymerizable double bond (hereinafter sometimes referred to as a "polymerizable group") can be used without limitation. Member nitrogen-containing heterocyclic compounds are more preferred. The polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

Specific examples of the 5-membered or 6-membered nitrogen-containing heterocyclic compound having a polymerizable group include, for example, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, and 1-vinyl-1H-pyridine. Azole, 1-vinyl-2-imidazoline, 2-vinyl-2-imidazoline, 2-vinylpyrazine, 2-vinyl-4,6-diamino-1,3,5-triazine Wait. Among these, from the viewpoint of dispersibility and the like, 2-vinylpyridine, 4-vinylpyridine, etc. are preferred. The cyclic amine compound system can be used individually by 1 type or in combination of 2 or more types.

The content of the cyclic amine unit in the block copolymer (I) is not particularly limited, but from the viewpoint of dispersibility and the like, it is preferably 5 to 30% by weight relative to the total amount of the block copolymer (I) , And more preferably 5-25% by weight, more preferably 7-20% by weight.

In addition, within a range that does not impair the effect of the block copolymer (I), a compound that can be copolymerized with a cyclic amine compound can be copolymerized with a cyclic amine compound. As the copolymerizable compound, for example, the following nonionic water-insoluble compound can be mentioned, and among them, butyl acrylate, methyl methacrylate, styrene, etc. are preferred. These copolymerizable compounds can be used alone or in combination of two or more.

On the other hand, the polymer block (B) is composed of nonionic water-soluble units and anionic water-soluble units, and preferably contains nonionic water-soluble units and anionic water-soluble units and nonionic non-water-soluble units. The structural unit of a sexual compound (hereinafter sometimes referred to as a "nonionic water-insoluble unit") and a block formed by a copolymer that does not include a cyclic amine unit. The polymer block (B) may be a random copolymer or a block copolymer. However, from the viewpoint of compatibility with the resin or photopolymer, dispersion resin, etc. of the coating film forming components described later, Random copolymers are preferred.

The nonionic water-soluble unit is a divalent structural unit derived from a nonionic water-soluble compound. The non-ionic water-soluble compound is not particularly limited as long as it is a non-ionic, water-soluble, and polymerizable organic compound, but it has at least one hydrophilicity selected from the group consisting of a hydroxyl group and an amide group. A group (hereinafter sometimes referred to simply as a "hydrophilic group") and a polymerizable nonionic water-soluble organic compound is preferred. The nonionic water-soluble organic compound may have a polymerizable group, and the polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

Examples of the nonionic water-soluble organic compound that has a hydrophilic group and can polymerize include polyalkylene glycol, polyalkylene glycol (meth)acrylate, and hydroxyalkyl (meth)acrylate. , (Meth)acrylamide compounds, N-vinylpyrrolidone, alkylene oxide, etc. These systems can be used individually by 1 type or in combination of 2 or more types.

As the polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like, polyalkylene glycols having an alkylene chain of 2 to 4 carbon atoms.

Examples of polyalkylene glycol (meth)acrylates include monofunctional or polyfunctional esters of polyalkylene glycol having an alkylene chain of 2 to 4 carbon atoms and acrylic acid or methacrylic acid. More specifically, polyethylene glycol monomethacrylate, methoxy polyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, and phenoxy polyethylene glycol acrylate , Polypropylene glycol monomethacrylate, polypropylene glycol diacrylate, etc.

Examples of hydroxyalkyl (meth)acrylates include alkyl groups such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Part of the hydroxyalkyl (meth)acrylate is a chain alkyl group having 1 to 4 carbon atoms.

Examples of the (meth)acrylamide compound include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl( Meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl acrylate (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl iso( (Meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide Yl)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, diacetone acrylamide, etc.

As an alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned, for example.

The content of the nonionic water-soluble unit in the block copolymer (I) is relative to the block copolymer from the viewpoint of, for example, the developability when forming the column spacer using the coating film forming composition described later The total amount of (I) is preferably 40 to 80% by weight, more preferably 45 to 75% by weight, and more preferably 45 to 73% by weight.

The anionic water-soluble unit is a divalent structural unit derived from an anionic water-soluble compound. The anionic water-soluble compound is not particularly limited as long as it is an organic compound that is anionic, water-soluble, and has a polymerizable group. A group of at least one acid group (hereinafter sometimes referred to as "acid group") and an anionic water-soluble organic acid compound of a polymerizable group are preferable. Furthermore, the polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

As a specific example of the anionic water-soluble organic acid compound which has an acid group and a polymerizable group, a carboxylic acid compound, a sulfonic acid compound, a phosphoric acid compound, etc. are mentioned, for example. These systems can be used individually by 1 type or in combination of 2 or more types.

As the carboxylic acid compound, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, 2-methylikon Acid, sorbic acid, α,β-methylglutaric acid, maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride, and their salts.

Examples of sulfonic acid compounds include vinylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-propenamide-2-methylpropanesulfonic acid, allylsulfonic acid, and methallylsulfonic acid. Acid, allyloxybenzophenone sulfonic acid, methacrylic acid, (meth)propenyloxybenzophenone sulfonic acid, 2-allyloxy-2-hydroxypropane sulfonic acid, 3-allyl Oxy-2-hydroxy-1-propane sulfonic acid, 2-methacryloxy ethane sulfonic acid, and their salts.

As the phosphoric acid compound, for example, 2-methacryloxyethyl phosphoric acid, 2-methacryloxyethyl phenyl phosphoric acid, 10-methacryloxydecamethylene phosphoric acid, 4-ethylene Benzyl benzyl phosphoric acid, pentapropenyl dineopentyl erythritol phosphoric acid, and their salts or 2-(meth)acryloyloxyethyl phosphate, diethyl (vinylphenyl) phosphate, 4 -Phosphate esters such as diethyl vinylbenzene phosphonite, diphenyl-2-methacryloxyethyl phosphate and the like.

Still, the phosphoric acid group can become a polymerizable group [=P(O)(OH)], so phosphoric acid, or trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, Phosphate esters such as tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresolyl diphenyl phosphate, and octyl diphenyl phosphate are also available as anionic water-soluble The case of organic acid compounds.

The content of the anionic water-soluble unit in the block copolymer (I), from the viewpoint of dispersibility, etc., is preferably 0.5 to 20% by weight relative to the total amount of the block copolymer (I). It is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.

The nonionic water-insoluble unit is a divalent structural unit derived from a nonionic water-insoluble compound. The nonionic water-insoluble unit is used, for example, to adjust the degree of hydrophilicity of the polymer block (B). In addition, when the hydrophilicity of the nonionic water-insoluble unit is higher, it has the effect of increasing the hydrophilicity of the polymer block (B). The nonionic water-insoluble compound is not particularly limited as long as it is a nonionic and water-insoluble organic compound having a polymerizable group, but it has a chain hydrocarbon group, a cyclic hydrocarbon group, and a cyclic hydrocarbon group in one molecule. At least one type of hydrophobic group (hereinafter sometimes referred to as "hydrophobic group") among the group of aromatic hydrocarbon groups and nonionic water-insoluble organic compounds of polymerizable groups are preferred. Furthermore, the polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

As the nonionic water-insoluble organic compound having a hydrophobic group and a polymerizable group in one molecule, for example, chain alkyl (meth)acrylate, cycloalkyl (meth)acrylate, (methyl) ) Aryl acrylate, styrenic compound, etc. These systems can be used individually by 1 type or in combination of 2 or more types.

Examples of chain alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, N-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Alkyl (meth)acrylates such as glycerol meth)acrylate having 1 to 17 carbon atoms in the alkyl moiety.

Examples of cycloalkyl (meth)acrylates include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, Cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, cyclodecyl (meth)acrylate, etc., whose cycloalkyl moiety has 3 to 10 carbon atoms ( Cycloalkyl meth)acrylate.

Examples of the aryl (meth)acrylate include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

Examples of styrene compounds include styrene, α-methylstyrene, methylstyrene, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, and 4-ethylstyrene. , 4-aminostyrene, 4-dimethylaminostyrene, methoxystyrene, chloromethylstyrene, chlorostyrene, 4-tert-butylstyrene, vinyl toluene, vinyl toluene Such as a styrene compound having at least one substituent selected from the group consisting of a chain alkyl group having 1 to 4 carbon atoms, a chain alkoxy group having 1 to 4 carbon atoms, a halogen atom, and an amino group.

The content of the nonionic water-insoluble unit in the block copolymer (I) is preferably 10 to 50% by weight relative to the total amount of the block copolymer (I) from the viewpoint of dispersibility and the like. It is more preferably 15 to 45% by weight, more preferably 20 to 40% by weight.

As described above, the block copolymer (I) has a preferable form as the content of each unit, and contains cyclic amine units at 5 to 30% by weight (more preferably 5 to 25% by weight, more preferably 7-20% by weight), the nonionic water-soluble unit is 40-80% by weight (more preferably 45-75% by weight, more preferably 45-73% by weight), and the anionic water-soluble unit is 0.5-20 % By weight, (more preferably 0.5-15% by weight, more preferably 1-10% by weight) of the first form; according to the same ratio as the first form, it contains cyclic amine units, non-ionic water-soluble units, And anionic water-soluble units, and further include the second form of nonionic water-insoluble units 10-50% by weight (more preferably 15-45% by weight, more preferably 20-40% by weight).

The block copolymer (I) can be synthesized by a known polymerization method such as living (controlled) radical polymerization. The living radical polymerization method generally includes ATRP (atom transfer radical polymerization) method, RAFT (reversible addition-fragmentation type chain transfer polymerization) method, NMP (nitrogen oxide-mediated radical polymerization) method, TERP (organic tellurium) Mediated radical polymerization) method, RTCP (reversible transfer catalyst polymerization) method, etc., may be appropriately selected and synthesized.

The living radical polymerization system can be, for example, -100~250°C, preferably 0~200°C, more preferably room temperature~200°C, more preferably 50~150°C, in solvent-free (block polymerization) ) Or in a solvent.

As the solvent system, a solvent which is inert in the polymerization reaction can be used without particular limitation. Examples include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, dichloromethane, chloroform, etc. Halogenated hydrocarbon solvents, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, Nitrile solvents such as acetonitrile, propionitrile and benzonitrile, ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, N,N-dimethyl Amine-based solvents such as formamide and N,N-dimethylacetamide.

When the block copolymer (I) is produced by the living radical polymerization method, it can be mentioned: a method of successively adding a specified amount of a raw material compound that becomes the base of each structural unit, and using a previously synthesized polymer block as A method of polymerizing a polymer polymerization initiator to polymerize the other polymer block, a method of combining each polymerized polymer block by reaction, etc. In the case of adding the raw material compound successively, it is better to first charge the next raw material compound at a time point when the conversion rate of the charged raw material compound is 80 to 95%. The conversion rate can be obtained by, for example, gas chromatography, nuclear magnetic resonance spectroscopy, gravimetric method, etc.

As a method of using one polymer block synthesized in advance as a polymer initiator and polymerizing the other polymer block, for example, at a desired time point when one polymer block is polymerized Next, in the active state, the temperature is first lowered to stop the polymerization, the raw material compound of one polymer block is distilled off under reduced pressure, and then the raw material compound of the other polymer block is added. Even in the case of polymerizing the third and subsequent polymer blocks, it is sufficient to perform the same operation as this one.

The molecular weight of the resin-type dispersant is not particularly limited, but the weight average molecular weight is preferably 1,000 to 100,000. However, for the aforementioned block copolymer (I), from the viewpoint of dispersibility, it is not the weight average molecular weight, but the peak top molecular weight is preferably 30 to 1 million, more preferably 30 to 500,000, more preferably It is 4,000~100,000, particularly preferably 4,000~50,000, and most preferably 5,000~30,000. The molecular weight of the block copolymer (I) can be adjusted by appropriately selecting the type and content of each structural unit, the timing of stopping the polymerization reaction, and the like.

The acid value and amine value of the resin-type dispersant can be determined in accordance with the functional groups contained in the resin constituting the resin-type dispersant and its content. The acid value (acid value in solid content conversion) can be obtained by, for example, the method according to DIN EN ISO 2114, and the amine value (amine value in solid content conversion) can be obtained, for example, by the method according to DIN 16945. have to. The acid value of the acid type dispersant is not particularly limited, but is preferably 20 to 150 mgKOH/g. The amine value of the amine type dispersant is not particularly limited, but is preferably 5 to 30 mgKOH/g. In the case of a dispersant having an acid value and an amine value greater than 0, there is no particular limitation, but the acid value is preferably 5-50 mgKOH/g, and the amine value is preferably 5-50 mgKOH/g. However, for the aforementioned block copolymer (I), from the viewpoint of dispersibility, the acid value is preferably 20 mgKOH/g or more, more preferably 20 to 80 mgKOH/g, more preferably 25 to 75 mgKOH/g, And the amine value is 40 mgKOH/g or more, preferably 40 to 100 mgKOH/g, and more preferably 42 to 98 mgKOH/g.

As surfactant-type dispersants, anionic active agents (anionic) such as naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl sulphate ester, etc. (anionic), polyoxyethylene Nonionic active agents (nonionic) such as oxyethylene alkyl ethers, cationic active agents (cationic) such as alkylamine salts and quaternary ammonium salts, etc. There are various types of surfactant-type dispersants on the market, and specific examples thereof are as follows, but they are not limited to these.

Kao Corporation: DEMOL N, RN, MS, SN-B, EMULGEN 120, 430, Acetamin 24, 86, Quartamin 24P, Nikko CHEMICALS Corporation: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25, manufactured by First Industrial Pharmaceutical Co., Ltd.: Plysurf AL, A208F, manufactured by Lion Co., Ltd.: Arquad C-50, T-28, T-50, etc.

The above-mentioned dispersing agent system may be 1 type, or may combine 2 or more types. In the case of combining two or more types, for example, in the case of a resin-based dispersant, it can be a combination of different resins, an acid value type, and an amine-based type, and in the case of a surfactant-type dispersant, it can be combined with each other. They are those with different ionic properties (for example, anionic type and non-ionic type, etc.), but are not limited to these.

The content of the dispersant (solid content or active ingredient) in the black pigment composition, from the standpoint of dispersion stability, is 2-20 parts by weight relative to the total of 100 parts by weight of the black organic pigment and colored organic pigment Preferably, it is more preferably 5-10 parts by weight. However, the most suitable amount of dispersant can be adjusted appropriately by combining the types of organic pigments used. In the case of using the pigment derivative described later, the content of the colored organic pigment means the total amount including the pigment derivative.

In the embodiment of the present invention, in addition to the aforementioned dispersant, in order to stabilize and disperse the black organic pigment and the colored organic pigment in the black pigment composition, a pigment derivative may also be used as a dispersion aid. When a pigment derivative is used, the part having affinity with the dispersant or the pigment derivative introduced with a polar group will be adsorbed on the surface of each organic pigment, and this can become the adsorption point of the dispersant. In this case, since the dispersant is present on the surface of the organic pigment by the pigment derivative, each organic pigment can be more stable with fine particles and dispersed in the black pigment composition. Moreover, this reaggregation can also be prevented more effectively. However, as mentioned above, depending on the characteristics of the pigment or the introduced functional group, there is a possibility that the characteristics of the liquid crystal cell may be affected. Therefore, in the case of using pigment derivatives, it is appropriate to determine the type or amount of use in consideration of this point and dispersibility.

The pigment derivative is specifically a compound in which an organic pigment is used as a matrix skeleton and an acidic group, a basic group, or an aromatic group is introduced into the side chain as a substituent. The organic pigments that form the matrix skeleton, specifically, quinacridone-based pigments, phthalocyanine-based pigments, azo-based pigments, quinoline yellow-based pigments, isoindoline-based pigments, and isoindolinone-based pigments , Quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, dioxazine pigments, etc. In addition, generally, a naphthalene-based, anthraquinone-based, triazine-based, quinoline-based, and other light-yellow aromatic polycyclic compounds that are not called dyes may be included as the host skeleton.

As a pigment derivative, it can be used in Japanese Patent Application Publication No. 11-49974, Japanese Patent Application Publication No. 11-189732, Japanese Patent Application Publication No. 10-245501, Japanese Patent Application Publication No. 2006-265528, Japanese Patent Application Publication No. 8-295810 No., Japanese Patent Application Publication No. 11-199796, Japanese Patent Application Publication No. 2005-234478, Japanese Patent Application Publication No. 2003-240938, Japanese Patent Application Publication No. 2001-356210, etc.

The content (solid content) of the pigment derivative in the black pigment composition, from the viewpoint of dispersion stability, is preferably 2 to 15 parts by weight relative to 100 parts by weight of the total of black organic pigments and colored organic pigments. It is more preferably 5-10 parts by weight. However, the most suitable addition amount of the pigment derivative can be appropriately adjusted in accordance with the type of organic pigment and dispersant used in combination and the effect on the characteristics of the liquid crystal cell. Note that "100 parts by weight of the total of black organic pigments and colored organic pigments" means the total amount that does not include pigment derivatives.

The particle size of the black organic pigment and the colored organic pigment can be appropriately determined depending on the application, etc. It is preferable to use approximately the average particle diameter of the primary particles (ie, the average primary particle diameter) of 20 to 200. Moreover, in the use of, for example, a column spacer or a black matrix, from the viewpoint that a higher OD value can be obtained when the coating film is formed, the average primary particle size is preferably 20 to 80 nm. Furthermore, the average primary particle size can be calculated, for example, by the arithmetic average form of the maximum width of a plurality of (for example, 50) primary particles in a transmission electron microscope (TEM) photograph.

In the embodiment of the present invention, according to the type of organic pigment, from the viewpoint of adjusting the average particle size, etc., grinding treatment may be performed in advance. The grinding treatment system can be carried out according to the type of organic pigments and the like and according to a conventional method. Examples of such a polishing treatment system include the solvent salt milling method.

In the embodiment of the present invention, from the viewpoint of further enhancing the dispersibility of the organic pigments in the black pigment composition and the black coating film forming composition, in addition to the aforementioned dispersing agent, a dispersing resin may also be used as a dispersing aid. Agent. Such a dispersion resin is particularly suitable for use when the coating film forming component used in the black coating film forming composition described later is a polymerizable component, and is particularly suitable for use in the case of a photopolymerizable component. Examples of the dispersion resin that can be used in the present invention include alkali-soluble resins described later. The dispersion resin may be the same type of resin as the alkali-soluble resin used in the black coating film forming composition, or may be a different type of resin. The content of the dispersing resin is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total of the black organic pigment and the colored organic pigment. However, when pigment derivatives are used, the content of black organic pigments and colored organic pigments means the total amount including the pigment derivatives.

The solvent that can be used in the present invention can be appropriately selected according to the types of coating film forming components described later, and examples thereof include aromatic, ketone, ester, glycol ether, alcohol, and aliphatic Various organic solvents. Among them, from the viewpoint of coating film formation properties, organic solvents selected from aromatic, ketone, ester, and glycol ether systems are preferred. The organic solvent system may be only one type, or two or more types may be combined.

Examples of aromatic organic solvents include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

Examples of ketone-based organic solvents include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetone, isophorone, acetophenone, and cyclohexanone.

Examples of ester-based organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, and ethyl ethylene glycol. Ester, propylene glycol monomethyl ether acetate (PMA), propylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate Ester, Butyl Monochloroacetate, Methyl Acetate, Ethyl Acetate, Butyl Carbitol Acetate, Butyl Lactate, Ethyl-3-ethoxypropionate, Ethylene Glycol Monobutyl Base ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butanediol diacetate, etc.

As the glycol ether-based organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1- Methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl Water-soluble glycol ethers such as base ethers, ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethyl Water-insoluble glycol ethers such as glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, and propylene glycol methyl ether propionate.

Examples of alcohol-based organic solvents include, for example, C1-C4 alkyl alcohols such as ethanol, methanol, butanol, propanol, and isopropanol, ethylene glycol, propylene glycol, diethylene glycol, pentamethylene Base glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol , Polyethylene glycol with molecular weight below 2000, 1,3-propanediol, isopropanediol, isobutanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1, 6-Hexanediol, glycerol, mesoerythritol, neopentylerythritol, etc.

Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

If the amount of solvent added can be used in the preparation of the black coating film forming composition described later, from the viewpoint of operability, the solid content concentration including black organic pigments can be 50 to 85% by weight. Way to add.

In the embodiment of the black pigment composition of the present invention, other additives may be included in addition to the aforementioned components.

The black pigment composition system can be obtained by adding the aforementioned components to a well-known dispersing machine such as a bead mill, a sand mixer, and a dispersion-type stirring blade, and dispersing, for example. That is, the black pigment composition disperses solid components such as black organic pigments and colored organic pigments in a solvent as a dispersion of particles. Here, the term “particles” means secondary particles formed by agglomeration of the aforementioned black organic pigments or primary particles of colored organic pigments. However, the method of adding each component is not particularly limited, and the components may be mixed simultaneously to perform dispersion treatment. In addition, it is possible to disperse each organic pigment and solvent, and a dispersant and/or other optional components, prepare a pigment composition for each pigment, and mix the pigment composition, and then disperse again. Other methods can also be used.

The average particle diameter of the particles dispersed in the black pigment composition obtained by the above method (hereinafter sometimes referred to as "dispersed average particle diameter") is not particularly limited, but it may preferably be approximately 30 to 300 nm . Moreover, in the use of, for example, a column spacer or a black matrix, from the viewpoint of the surface smoothness of the coating film, the average dispersed particle diameter is preferably 30 to 150 nm. In addition, the dispersed average particle size can be measured by, for example, a particle size measuring machine. In addition, as a particle size measuring machine, FPAR-1000 manufactured by Otsuka Electronics Co., Ltd., and the like can be cited.

<Black coating film forming composition>

The embodiment of the black coating film forming composition of the present invention includes the aforementioned black pigment composition and coating film forming components. In this way, by including the aforementioned black pigment composition, the coating film can effectively absorb visible light in the wavelength range of 380nm~750nm due to the effect of the aforementioned black organic pigment. In addition, the absorption in the ultraviolet region (the region with a wavelength shorter than 380 nm) and the infrared region (the region with a wavelength longer than 750 nm) can be suppressed to the extent that it has no effect on the manufacture of the flat panel. In addition, by combining at least two kinds of colored organic pigments other than the black organic pigments, black carbon is not used in the coating film, which can block light in the visible light region, and can effectively suppress the absorption compared to the visible light region. Absorption of ultraviolet and infrared rays. Furthermore, the solvent resistance of the coating film can also be improved by the effect of the aforementioned black organic pigment. In addition, the effect of black carbon on the characteristics of the liquid crystal cell can also be avoided.

As the coating film forming component that can be used in the embodiment of the black coating film forming composition of the present invention, as long as it has good solvent resistance, can suppress the influence on the characteristics of the liquid crystal cell, and is a component that can form a coating film That is, it is not particularly limited, and it may be a polymerizable component or a polymer. As a polymerizable component, since it is easy to apply a pattern by development (negative development), a photopolymerizable component is preferred. In addition, examples of polymers include thermoplastic urethane resins, (meth)acrylic resins, polyamide resins, polyimide resins, styrene·maleic acid resins, and polyesters. Series resin, silicone resin, cardo resin, etc.

As the photopolymerizable component that can be used, a photopolymerizable compound and a photopolymerization initiator are included. Such a photopolymerizable compound and photopolymerization initiator system can be used, for example, those described in JP 2009-179789 A. In detail, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from having at least one, preferably two or more terminal ethylenic compounds. Compounds with saturated bonds. Such a group of compounds is widely known in this technical field, and they can be used in the present invention without particular limitation. The photopolymerizable compound has chemical forms such as monomers, prepolymers (ie, dimers, trimers, and oligomers), or mixtures of these, and copolymers of these.

Examples of monomers and their copolymers include unsaturated carboxylic acids (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or their esters and amides. Preferably, esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds can be used. In addition, addition reactants of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amine, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxy, and with monofunctional or poly The dehydration condensation reaction product of functional carboxylic acid and the like can also be suitably used. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols may also be used Suitable for use. Furthermore, the substitution reaction of unsaturated carboxylic acid esters or amides having a halogen group, or a toluene sulfonyloxy group with a detachable substituent, and monofunctional or polyfunctional alcohols, amines, and thiols Things can also be suitable for use. In addition, as another example, a group of compounds substituted into unsaturated phosphonic acid, styrene, vinyl ether, etc. may be used instead of the above-mentioned unsaturated carboxylic acid.

However, these specific examples are as described in JP 2009-179789 A. As specific examples of monomers of esters of aliphatic polyol compounds and unsaturated carboxylic acids, as acrylates, for example, ethylene dichloride Alcohol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol Trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, neopentaerythritol diacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dineopentylerythritol diacrylate, dineopentaerythritol hexaacrylate , Sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(acryloxyethyl) isocyanurate, polyester acrylate oligomer Compounds, isocyanuric acid EO modified triacrylate, etc.

For these addition polymerizable compounds, the details of the structure, use alone or in combination, and the amount of use, etc., can be arbitrarily set in accordance with the performance design of the final black coating film forming composition.

For example, it can be selected from the following general viewpoints. In terms of sensitivity, a structure with a large amount of unsaturated groups per molecule is preferable, and in most cases, it is preferable to have two or more functional groups. In addition, in order to increase the strength of the cured film, it is preferable to use one with three or more functionalities. Furthermore, by using different functional numbers and different polymerizable groups (e.g., acrylate, methacrylate, styrene-based compound, vinyl ether-based Compound), the method of adjusting both sensitivity and strength is also effective.

In addition, the compatibility and dispersibility with other components in the black coating film forming composition (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, and colorants (pigments)) are added The choice of the polymer compound and the method of use are also important factors. For example, by using a low-purity compound or using two or more of them in combination, the compatibility can be improved.

In addition, a specific structure can also be selected for the purpose of improving adhesion to the base material. The photopolymerizable compound is preferably contained at 5 to 70% by weight, and more preferably 10 to 60% by weight with respect to the nonvolatile components in the coating film forming composition. Moreover, these systems may be used individually or in combination of 2 or more types. In addition, the use of the photopolymerizable compound can be arbitrarily selected from the viewpoints of the size, resolution, fogging property, refractive index change, and surface adhesion of oxygen polymerization inhibition. quantity.

As the aforementioned photopolymerization initiator, those described in JP 2009-179789 A can also be used.

That is, as photopolymerization initiators that can be suitably used in the present invention, there are, for example, acetophenone-based, ketal-based, benzophenone-based, benzoin-based, benzophenone-based, xanthone-based, and active halogen compounds. (Triazine series, oxadiazole series, coumarin series), acridine series, biimidazole series, oxime ester series, etc.

These specific examples are taken as specific examples of benzophenone-based photopolymerization initiators, such as benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4,4'-bis (Diethylamine) benzophenone, 4,4'-dichlorobenzophenone, etc.

In the black coating film forming composition, the content of the photopolymerization initiator relative to the total solid content of the black coating film forming composition is preferably 0.1 to 10.0% by mass, and more preferably 0.5 to 5.0% by mass. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well, and a film with good strength can be formed.

In the embodiment of the black coating film forming composition according to the present invention, if it contains a photopolymerizable component, it may contain an alkali-soluble resin in addition to the aforementioned black pigment composition and photopolymerizable component.

When an alkali-soluble resin is contained in the black coating film forming composition, for example, when the black coating film forming composition is applied to the pattern formation in the manufacture of the column spacer by the photolithography step, the pattern can be formed Sex is improved.

As such an alkali-soluble resin, what is described in JP 2009-179789 A can be used. In simple terms, the alkali-soluble resins that can be used in the present invention, such as linear organic high-molecular polymers, can be used with molecules (preferably acrylic copolymers or styrene copolymers as the main chain). The molecule) has at least one alkali-solubility-promoting group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) among alkali-soluble resins, and is appropriately selected. Among them, those that are soluble in organic solvents and can be developed by weak alkali aqueous solutions are more preferred.

As a suitable one of alkali-soluble resin, the copolymer of (meth)acrylic acid and other monomers copolymerizable with this can be mentioned especially. Here, the term “(meth)acrylic acid” refers to the general term combining acrylic acid and methacrylic acid, and the same applies to the general term of (meth)acrylate acrylate and methacrylate hereinafter.

Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. Here, the hydrogen atoms of the alkyl group and the aryl group may also be substituted with a substituent.

Specific examples of the aforementioned alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, ( Benzyl meth)acrylate, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

Examples of the aforementioned vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, vinyl acetate, and N-vinylpyrrolidone , Tetrahydrofuran methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ⁵ R ⁶ , CH ₂ =C(R ⁵ )(COOR ⁷ ) (here, R ⁵ It represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R ⁶ represents an aromatic hydrocarbon ring with 6 to 10 carbon atoms, and R ⁷ represents an alkyl group with 1 to 8 carbon atoms or an arane with 6 to 12 carbon atoms.基) etc.

These other single systems that can be copolymerized may be used alone or in combination of two or more types.

The weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 50,000 from the viewpoint of developability.

Alkali-soluble resin has various commercial products, and its specific examples are as follows, but it is not limited to these.

Showa Polymer Co., Ltd. product: RipoxySPC-2000, Mitsubishi Rayon Co., Ltd. product: Daiyana-Le NR series, Diamond hamrock Co. Ltd., product: Photomer6173 (COOH contains Polyurethane acrylic oligomer), Osaka Organic Chemical Industry Co., Ltd. Manufacturing: Viscoat R-264, KS Resist106, SOP-005, Daicel Chemical Industry Co., Ltd.: cyclomerP series, PLACCEL CF200 series, Daicel-UCB Co., Ltd.: Ebecryl 3800, Nippon Shokubai Co., Ltd.: RD-Y -503, etc.

In the black coating film forming composition, the content of the alkali-soluble resin in the total solid content of the black coating film forming composition is preferably 1-20% by weight, more preferably 2-15% by weight, particularly preferred It is 3-12% by weight. When contained in the black pigment composition as a dispersion resin, it is the total amount.

In the embodiment of the black coating film forming composition according to the present invention, if a photopolymerizable component is included, it may contain a solvent in addition to the aforementioned black pigment composition, photopolymerizable component, and alkali-soluble resin. It can be suitable for preparation by using a solvent.

Examples of such solvents include esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, butyl acetate, and butyl acetate. Isopropyl acid, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; 3-hydroxypropionic acid such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc. Alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxypropionic acid Methyl ester, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methyl Methyl oxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, acetylacetate Ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.; ethers, such as: diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, methylcellulose acetate, ethylceloxol acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptan Ketones, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.

A solvent system may be used individually by 1 type, and may be used in combination of 2 or more types.

In the black coating film forming composition, as the content of the solvent, consider the type and content of the solvent in the black pigment composition, and the total solid content (non-volatile content) content in the black coating film forming composition is 15-50 It is better to include in the form of weight %.

When using a polymer as a coating film forming component, a solvent can also be used in the same way as when using a photopolymerizable component. As such a solvent, it can be used in the aforementioned black pigment composition and can be used with the photopolymerizable component.

Even in this case, as the content of the solvent in the black coating film forming composition, consider the type and content of the solvent in the pigment dispersion, and use the total solid content (non-volatile content) in the black coating film forming composition It is preferable to include it so that the content becomes 15-50 weight%.

In the black coating film forming composition of the present invention, dispersing aids, sensitizers (sensitizing dyes), chain transfer agents, fluorine-based organic compounds, thermal polymerization initiators, thermal polymerization components, and fillers can also be added as required. Various additives such as surfactants, surfactants, adhesion promoters, antioxidants, aggregation inhibitors, and surface regulators (leveling agents). When it is contained in the black pigment composition, the addition amount may be adjusted.

The black coating film forming composition according to the present invention can be obtained by adding a coating film forming component to a black pigment composition and stirring by a dispersion-type stirring blade or the like.

The composition system for forming a black coating film related to the present invention does not use black carbon in the coating film, absorbs only light in the visible light region, and has good solvent resistance as described above. In addition, it will be possible to use infrared alignment in the manufacturing process. Furthermore, when a photopolymerizable component is used as a coating film forming component, the polymerization reaction by ultraviolet rays is good, and there is no influence on the manufacturing process. Therefore, for example, it is particularly suitable as a black column spacer of a flat panel used in a liquid crystal display device. In addition, a black matrix as a color filter of an image display device is also suitable.

[Example] (Manufacturing Example 1) Manufacturing of Pigment Derivative 1

With respect to 200 parts by weight of chlorosulfonic acid, 20 parts by weight of PIGMENT RED 255 (manufactured by BASF, product name IRGAZIN RED L3551HD) and 10 parts by weight of sulfuryl chloride were added, and the mixture was heated at 60°C. After reacting for 5 hours, it was discharged into 2 liters of ice water, passed over and washed with water to obtain 26.9 parts by weight of Pigment Red 255 chlorosulfonate. Disperse this into 200 parts by weight of water, add 8.3 parts by weight of diethylaminopropylamine, and react at 80°C for 1 hour, followed by filtration, washing, drying and pulverization to obtain 31.5 parts by weight of the following The pigment derivative 1 represented by formula (3).

(Manufacturing Example 2) Manufacturing of Pigment Derivative 2

With respect to 200 parts by weight of chlorosulfonic acid, 20.4 parts by weight of PIGMENT VIOLET 23 (product name Violet 23 crude product manufactured by DIC Corporation) and 20 parts by weight of sulfuryl chloride were added, and the temperature was maintained at 60°C. After making it react for 5 hours, it was discharged into 2 liters of ice water, spent and washed with water, and 27.2 parts by weight of the chlorosulfonate of PIGMENT VIOLET 23 was obtained. Disperse this in 200 parts by weight of water, add 15 parts by weight of diethylaminopropylamine, and react at 80°C for 1 hour, followed by filtration, washing, drying and pulverization to obtain 31.9 parts by weight of the following The pigment derivative 2 represented by formula (4).

(Manufacturing Example 3) Manufacturing of Pigment Derivative 3

After putting 200 parts by weight of 88% sulfuric acid into a 300 ml 3-necked flask, 20 parts by weight of PIGMENT RED 255 (manufactured by BASF, product name IRGAZIN RED L3551HD) was charged under water cooling, and it was heated at 40 to 45°C. It reacts for 3 hours for sulfonation. Next, after discharging the synthetic stock solution into a beaker with 1L of water, filter it, transfer the paste to a 2L beaker and add 1.5L of water, stir at 60~70℃ for 1 hour and fully make After the dispersion, 1 part by weight of cetyltrimethylammonium chloride was added to form a salt. After stirring for about 10 minutes, the paste obtained after filtering and washing with water is dried at 100°C to obtain the pigment derivative 3 represented by the following formula (5).

(DM-3) (Production Example 4) Production of Pigment Derivative 4

To 200 parts by weight of chlorosulfonic acid, 40.2 parts by weight of crude copper phthalocyanine (manufactured by Zhuhai Toyo Co., Ltd., product name T-99 crude product blue, Pigment Blue 15: 3) and 10 parts by weight of thiol chlorinate were added, After reacting at 60°C for 5 hours, it was discharged into 2 liters of ice water, spent and washed with water, and 47 parts by weight of Pigment Blue 15 chlorosulfonate were obtained. Disperse this into 200 g of water, add 8.3 parts by weight of dimethylaminopropylamine, and react at 80°C for 1 hour, followed by filtration, washing, drying, and pulverization to obtain 51.5 parts by weight of the following formula (6) The pigment derivative 4 represented.

(Production Example 5) Production of Resin-type Dispersant 1

Mix 192.8 parts by weight of butyl acrylate (nonionic water-insoluble organic compound), 321.9 parts by weight of methoxy polyethylene glycol (n≒9) methacrylate (nonionic water-soluble organic compound), acrylic acid (anionic Water-soluble organic compound) 59.2 parts by weight, N-(2-methylpropyl)-N-(1-diethylphosphino-2,2-dimethylpropyl)-O-(2-carboxyl 15.0 parts by weight of propan-2-yl)hydroxylamine (polymerization regulator) and 370 parts by weight of propylene glycol monomethyl ether acetate (reaction solvent) were put into a 2L-capacity stainless steel separatory flask, while nitrogen was bubbled and stirred, The temperature of the system was raised to 125°C in an oil bath, and the reaction was allowed to react for 6.5 hours after the completion of the temperature rise, thereby synthesizing the polymer block B. When a small amount of content was sampled and GPC measurement was performed, the peak top molecular weight was 9570 and Mw/Mn=1.43.

Next, 56.1 parts by weight of 4-vinylpyridine (cyclic amine compound) and 50 parts by weight of propylene glycol monomethyl ether acetate (reaction solvent) were put into the flask. Next, while the nitrogen was bubbled and stirred, It was allowed to react at °C for 4 hours. When the contents were sampled and subjected to GPC measurement, the peak top molecular weight was 10140 and Mw/Mn was 1.45.

Next, the temperature in the system was increased to 210°C, the pressure in the system was reduced to 2.0 kPa, the solvent was distilled off, and the block copolymer (I) was taken out. When the obtained block copolymer (I) was subjected to GPC measurement, the peak top molecular weight was 10990 and the Mw/Mn was 1.49. In addition, the acid value was 74.0 mgKOH/g, and the amine value was 52.9 mgKOH/g.

(Manufacturing Example 6) Manufacturing of blue organic pigment 2

Add 300 parts by weight of color rendering index pigment blue 15:6 (trade name: FASTOGEN Blue EP-207, manufactured by DIC), 3,000 parts by weight of neutral Glauber's anhydride (average particle size of about 20μm, manufactured by Sandajiri Chemical Co., Ltd.), As a solvent, 750 parts by weight of diethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) is placed in a 5L kneader (manufactured by Moriyama Co., Ltd., S5-2GH-S type), while the temperature of the kneaded product becomes 50°C. Way to do temperature control, while mixing and grinding for 9 hours. The kneaded ground product was stirred and dispersed in 30 L of warm water at 40°C, and then transferred to nutsche and filtered, and washing with water was repeated until Glauber's salt was completely removed, thereby obtaining a pigment water paste. The pigment water paste was dried at 105°C for 2 hours. The dried product was pulverized with a pulverizer (manufactured by Kyoritsu Riko Co., Ltd., small pulverizer, sample mill SK-M2), and 330 parts by weight of blue organic pigment 2 was obtained. The average particle diameter of the primary particles of the obtained blue organic pigment 2 was 40 nm. The average particle size is the result of measurement and calculation by TEM photography.

The components used in the following test examples, examples, and comparative examples are as follows.

(a) At least one black organic pigment selected from the aforementioned formulas (1) and (2)

Black organic pigment 1: made by BASF, Lumogen Black FK4280

(b) Black organic pigments other than (a) above

Black organic pigment 2: manufactured by BASF, Paliogen Black S0084

(c) Colored organic pigments

Red organic pigment 1: DIC Co., Ltd. product, PERRINDO Maroon 179 229-6438, Pigment Red 179 (PR179)

Red organic pigment 2: made by Clariant, PV Fast Red B, Pigment Red 149 (PR149)

Red organic pigment 3: manufactured by CINIC, Cinilex DPP Red SR2P, Pigment Red 254 (PR254)

Red organic pigment 4: made by BASF, Irgazine Red L3551HD, Pigment Red 255 (PR255)

Blue organic pigment 1: manufactured by DIC Co., Ltd., EP-210, pigment blue 15: 6 (PB15: 6)

Blue Organic Pigment 2: Manufacturing Example 6

Blue organic pigment 3: manufactured by BASF Co., Ltd., Heliogen Blue D7490, pigment blue 16 (PB16)

Blue organic pigment 4: made by BASF Co., Ltd., Paliogen Blue EH1900, Pigment Blue 60 (PB60)

Purple organic pigment: manufactured by DIC Co., Ltd., PERRINDO VIOLET 29 229-4050, pigment VIOLET 29 (PV29)

(d) Dispersant

Resin type dispersant 1: Production Example 5

Resin type dispersant 2: manufactured by BYK‧JAPAN Co., Ltd., Disperbyk LPN22102, acrylic resin, acid value 0mgKOH/g, amine value 32mgKOH/g

Resin type dispersant 3: manufactured by Otsuka Chemical Co., Ltd., TERPLUS D2015, acrylic resin, acid value 30mgKOH/g, amine value 63mgKOH/g

Resin type dispersant 4: manufactured by Otsuka Chemical Co., Ltd., TERPLUS MD1000, acrylic resin, acid value 30mgKOH/g, amine value 63mgKOH/g

(e) Dispersing additives

Dispersion resin 1: Nippon Shokubai Co., Ltd. product, RD-Y-503, alkali-soluble acrylic resin

Dispersing resin 2: manufactured by Osaka Organic Chemical Corporation, SOP-005, alkali-soluble acrylic resin, acid value 29mgKOH/g, amine value 116mgKOH/g, weight average molecular weight 19,000

(f) Solvent

Propylene glycol monomethyl ether acetate (PMA)

(g) Coating film forming ingredients

Coating film forming resin: Nippon Shokubai Co., Ltd., RD-Y-507, acrylic resin

(Examples 1-7, Comparative Example 1) <Preparation of black pigment composition>

The components of the composition shown in Table 1 (except for the solvent are based on solid content) were mixed and dispersed with a bead mill to obtain a black pigment composition. The grinding medium of the bead mill uses zirconia beads having a particle diameter of 0.3 mm, and is added so as to be 400 parts by weight with respect to 100 parts by weight of the grinding material. This medium is removed after the dispersion treatment. In addition, the compositions shown in Table 1 are parts by weight.

<Preparation of black coating film forming composition>

To each of the obtained black pigment compositions, the aforementioned coating film-forming resin is added and stirred by a dispersion-type stirring blade to obtain a black coating film-forming composition. The addition amount of the coating film forming resin is 100 parts by weight of all the organic pigments (including pigment derivatives) contained in each black pigment composition, and 200 parts by weight of the total of the dispersant, the dispersion resin and the coating film forming resin Way to make it.

<Formation of Coating Film>

Using each obtained black coating film forming composition, each composition was spin-coated on a glass plate so that the film thickness became 1 μm and 3 μm. The pre-baking is 90°C for 2.5 minutes, and the subsequent baking is 230°C for 30 minutes to heat to form a coating film.

<Measurement of Optical Density (OD Value)>

The coating film formed by adjusting the film thickness to 3 μm was used, and the measurement was performed with an OD measuring device (X-Rite 361T). The OD values of three coating films whose film thicknesses were changed centered on 1 µm were measured, and the value when the film thickness was 1 µm was used as the OD value from the slope and the slice. The evaluation results are shown in Table 1.

<Solvent resistance>

The coating film formed by adjusting the film thickness to 1μm was cut into a size of 2×4cm and immersed in 50g of 1-methyl-2-pyrrolidone (NMP) at 80°C for 1 hour, and then confirmed by visual inspection Whether the NMP liquid is colored or not. The evaluation results are shown in Table 1. In Table 1, if there is no coloring, set it as "○", and if coloring is observed, set it as "×".

(Example 8) <Preparation of black pigment composition>

The components of the composition shown in Table 2 (except for the solvent are based on solid content) were mixed, and dispersed with a bead mill to obtain pigment compositions 1 to 3 for each pigment. The grinding medium of the bead mill uses zirconia beads having a particle diameter of 0.3 mm, and is added so as to be 400 parts by weight with respect to 100 parts by weight of the grinding material. This medium is removed after the dispersion treatment. The composition shown in Table 2 is parts by weight. 13.3 g of the pigment composition 1, 1.25 g of the pigment composition 2, and 2.55 g of the pigment composition 3 were mixed, and stirred with a dispersion-type stirring blade to obtain a black pigment composition.

<Preparation of black coating film forming composition>

To the obtained black pigment composition, 18.72 g of the aforementioned coating film-forming resin was added and stirred by a dispersion-type stirring blade to obtain a black coating film-forming composition.

<Formation and Evaluation of Coating Film>

In the same manner as in Example 1, coating films with different film thicknesses were formed. Using the obtained coating film, the OD value and solvent resistance were evaluated in the same manner as in Example 1. The OD value is 1.24 (/μm). Also, there is no coloring of NMP.

From the results of Examples 1 to 8 and Comparative Example 1, it can be seen that compared with the comparative example, the OD value of the example is higher, and there is no coloration of NMP in the example. Therefore, it can be seen that by using a specific black organic pigment and at least two kinds of colored organic pigments as in the embodiment, the OD value is high, that is, the absorption of light in all wavelengths of the visible light region is good, and Solvent resistance is also good. In addition, compared with the absorption of visible light, the absorption of ultraviolet and infrared is suppressed for the pigments used in Examples 1 to 8, which is obvious to those with ordinary knowledge in the relevant technical field. Furthermore, comparing Examples 1-7 and Example 8, when the designated dispersant is used, the use of dispersant or pigment derivatives can be reduced.

Claims (3)

A black pigment composition comprising at least one black organic pigment selected from the following formulas (1) and (2), and at least two organic pigments selected from the group consisting of red organic pigments, blue organic pigments, and purple organic pigments Colored organic pigments, dispersants and solvents,

The black pigment composition of claim 1, wherein the red organic pigment is selected from at least one of the following (a) group, and the blue organic pigment is selected from at least one of the following (b) group, and The purple organic pigment is selected from at least one of the following (c) group, (a) group: color index (color index) pigment red 149, 179, 254, 255; (b) group: color index pigment blue 15 , 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 60; (c) group: color rendering index pigment violet 23, 29. A black coating film forming composition comprising the black pigment composition of claim 1 or 2 and a coating film forming component, wherein the coating film forming component is selected from polymerizable components and polymers.