TW201819544A - Black pigment composition and black coating film formation composition including the black pigment composition - Google Patents

Abstract

The present invention provides a black pigment composition that can absorb light in a visible light region without using carbon black and can suppress absorption of infrared rays and ultraviolet rays and has good solvent resistance and a black coating film-forming composition containing the black pigment composition. The black pigment composition comprises at least one black organic pigment selected from the following formulas (1) and (2), at least two kinds of 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 particularly to a black pigment composition used in a black column spacer provided in a flat panel of a liquid crystal display device, for example, and A black coating film containing this composition.

The liquid crystal display device has a liquid crystal cell structure in which a liquid crystal substance is filled between two glass substrates provided with opposed transparent electrodes. Then, between two glass substrates, a column spacer was inserted in order to maintain a uniform gap between the substrates and provide a good image. Conventionally, as such a column spacer, a bead spacer using a bead-like glass or the like has been used. However, in the method using a bead spacer, since only the beads are randomly dispersed in the gap, it has been pointed out that there are problems such as the problem of light leakage, the deviation of the gap distance becoming larger, and difficulty in controlling 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, a black column spacer using a black photosensitive resin composition has been proposed in place of the bead spacer (see, for example, Patent Documents 1 and 2). With the black column spacer, the column spacer can be formed in such a manner that the deviation of the gap distance at the desired position becomes smaller, and the control of the characteristics of the photopolymerizable component and the like is relatively easy. Therefore, it is considered that compared with the bead spacer, The gap can be controlled more precisely. Then, by including a black colorant in the column spacer, it is possible to block visible light (wavelength is 380 nm to 750 nm), and it is possible to expect improvement in contrast and color development effect. As such a black colorant, perylene black is exemplified in Patent Documents 1 and 2. In addition, as an example of darkening, Patent Document 3 discloses a pigment having a specific structure.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2015-191234

[Patent Document 2] Japanese Patent Laid-Open No. 2007-71994

[Patent Document 3] Japanese Patent No. 4980727

However, since the column spacer is in contact with the liquid crystal substance, resistance to a solvent contained in the liquid crystal substance, that is, solvent resistance is required. In addition, the characteristics of the column spacer must also have no effect on the characteristics of the liquid crystal cell. For example, when the insulation of the black pillar spacer is low, it will affect the driving of the liquid crystal, and thus may affect the characteristics of the liquid crystal cell.

Furthermore, in the manufacturing steps of forming the column spacer, a method of hardening a photopolymerizable component to form a polymer compound is often adopted. In this case, generally, ultraviolet rays are irradiated to harden. Therefore, the black photosensitive composition must be configured to absorb visible light and transmit ultraviolet rays. In addition, in order to determine a correct exposure position, infrared rays such as near-infrared rays are often used to confirm an alignment key on a panel substrate. In this case, it must be configured so that infrared rays can pass through.

In Patent Documents 1 and 2, examples of the black pigment system include aniline black, perylene black, titanium black, cyanine black, lignin black, lactam organic black, RGB black, and carbon black. However, the use of carbon black is allowed, and in terms of insulation, there is concern about the effect 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 photopolymerizable components by ultraviolet rays becomes insufficient, or alignment during exposure using infrared rays may become difficult, and there are concerns about manufacturing steps. Influence.

In view of the foregoing, an object of the present invention is to provide a black pigment composition and a black coating film-forming composition containing the same, which are black carbon-free, can absorb light in the visible light region, and can suppress absorption of infrared rays and ultraviolet rays. 2. Good solvent resistance.

Although Patent Documents 1 and 2 have exemplified black pigment as a black pigment, specific examples of black pigment are not described. Here, the inventors obtained the following insights through in-depth research and review: "Depending on the type of black, the degree of solvent resistance will vary, and the absorption spectrum of wavelengths will vary." Then, it was found that the above-mentioned problem can be solved by using a black pigment having a specific structure and at least two colored pigments other than the black pigment having a specific structure, and the present invention has been completed. The gist of the present invention is as follows.

The first aspect of the present invention relates to a black pigment composition containing at least one black organic pigment selected from the following formulae (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 pigment other than the black organic pigment is selected from a red organic pigment, a blue organic pigment, and a purple organic pigment. In another preferred embodiment, the red organic pigment is at least one selected from the following (a) group, the blue organic pigment is at least one selected from the following (b) group, and the purple organic The pigment is at least one selected from the group (c) below.

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

(b) Group: color rendering 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.

The second aspect of the present invention relates to a black coating film forming composition including the black pigment composition and a coating film forming component.

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 are free of black carbon, can absorb light in the visible light region, can suppress absorption of infrared rays and ultraviolet rays, and have good solvent resistance .

    [Best Mode for Implementing Invention]         <Black pigment composition>    

The black pigment composition according to the present invention comprises at least one black organic pigment selected from the following formulae (1) and (2), and at least two colored organic pigments (hereinafter referred to as In the case of simply called "colored organic pigment"), dispersant and solvent.

The black organic pigment with a specific structure represented by the formulae (1) and (2) has the following characteristics: "It can effectively absorb visible light and has a low transmittance in a region of a wavelength of 380nm to 750nm, compared with that in the visible light region. Absorption, absorption in the ultraviolet region (a region with a shorter wavelength than 380nm) and the infrared region (a region with a longer wavelength than 750nm) are suppressed to be small. " The absorption characteristics of such light in the visible light region can be confirmed by the optical density (OD value) at the time of measurement by the method described later. In addition, by combining with at least two colored organic pigments other than the black organic pigment, even if black carbon is not used, the light in the visible light region can be blocked, and the absorption of ultraviolet rays and infrared rays can be effectively suppressed compared to the visible light region. . Therefore, for example, when a column spacer is formed using a photopolymerizable component as a coating film-forming component, the photopolymerizable component can be sufficiently polymerized by ultraviolet rays, and at the same time, it can also be used for exposure during infrared rays. Bit. In addition, the solvent resistance was good. The influence on the characteristics of the liquid crystal cell caused by the black carbon can also be avoided.

As such a black organic pigment, for example, Lumogen Black FK4280 manufactured by BASF can be used.

In the embodiment of the present invention, the content of the black organic pigment in the black pigment composition is preferably from 1 to 1 in terms of the balance between absorption of light in the visible light region and suppression of absorption in the ultraviolet and infrared regions. 12% by weight, and more preferably 1 to 7% by weight.

Examples of the colored organic pigments usable in the present invention include red organic pigments, blue organic pigments, green organic pigments, purple organic pigments, yellow organic pigments, orange organic pigments, and brown organic pigments. When represented by a color index No., examples are as follows.

Red organic pigments: 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 viewpoints of the effect of increasing the OD value obtained by combining with the aforementioned black organic pigment and other colored organic pigments, especially blue organic pigments, and the effect of suppressing absorption of ultraviolet and infrared rays, Pigment reds 149, 179, 254, and 255 are preferred.

Blue organic pigment: pigment blue (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, from the viewpoints of the effect of increasing the OD value obtained by combination with the aforementioned black organic pigment 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 more preferably Pigment Blue 15: 6, 16, 60.

Green organic pigment: Pigment green (pigment green) 1, 4, 7, 8, 10, 36, etc.

Purple organic pigments: pigment violet 1, 2, 3, 3: 1, 1, 3: 3, 5: 1, 13, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50, etc. Among these, from the viewpoints of the effect of increasing the OD value obtained by combining with the aforementioned black organic pigment and other colored organic pigments, and the effect of suppressing the absorption of ultraviolet and infrared rays, pigment violet 23, 29, and more preferably pigment violet 29.

Yellow organic pigment: 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 pigment: Pigment orange (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 and so on.

Brown organic pigment: Pigment brown (pigment brown) 5, 23, 25, 32, 41, 42 and so on.

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. The colored organic pigments may contain three or more kinds. The greater the number of colored pigments, the greater the visible light absorption effect. However, if there are many types, the dispersibility of colored pigments may be poor. Therefore, as a result of intensive research, the present inventors have found that among the aforementioned specified black organic pigments, at least two kinds of organic pigments selected from the group consisting of red organic pigments, blue organic pigments, and purple organic pigments are combined, thereby suppressing Use, while maintaining the absorption characteristics of the specified black organic pigment, it can effectively absorb the visible light in the entire region of the wavelength of 380nm ~ 750nm, and can suppress the absorption in the ultraviolet region and the infrared region. In addition, such an effect is that red organic pigments are at least one kind of color rendering index pigment red 149, 179, 254, and 255 selected from group (a); blue organic pigments are selected from group (b). Color Index Pigment Blue at least one of 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 60; color rendering index pigment purple selected from group (c) In at least one of 23 and 29, there is a tendency to play more effectively. Furthermore, when the red organic pigment and the blue organic pigment are respectively selected from the group (a) and one selected from the group (b), and the blue organic pigment and the purple organic pigment are respectively selected from (b) When there is one kind of group and one kind selected from group (c), there is a tendency that it is more suitable.

In the embodiment of the present invention, the content of the colored organic pigment is 100 parts by weight relative to 100 parts by weight of the black organic pigment in terms of effectively absorbing visible light and effectively suppressing absorption of ultraviolet rays and infrared rays in the entire region of 380 to 750 nm. It is preferably 50 to 1,000 parts by weight, and still more preferably 100 to 700 parts by weight. In the case where a pigment derivative described later is used, the content of the colored organic pigment means a total amount including the pigment derivative.

Examples of the dispersant usable in the present invention include a resin-based dispersant and a surfactant-type dispersant. In addition, resin-based dispersants have different acid values from amine values, so there are acid-value type dispersants having an amine value of 0 and an acid value greater than 0, and amine values of an acid value of 0 and an amine value greater than 0. Type dispersant, dispersant with acid value and amine value greater than 0.

Examples of the resin-based dispersant include polyurethanes; polyesters; unsaturated polyamidoamines; phosphonates; polycarboxylic acids and their amine salts, ammonium salts, and alkylamine salts; polycarboxylic acid esters; Hydroxyl-containing polycarboxylate; 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 acid-acrylate resin, styrene-maleic acid resin, styrene-horse Resins containing ethylenic double bonds, such as maleate 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.

As the resin-based dispersant, a commercially available one 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 .: Ajisper-PB821 (F), PB822, PB880, Kawaken Fine Chemicals Co., Ltd .: Hinoact T-8000, Nanben Chemical Co., Ltd .: DISPARLON PW-36, DISPARLON DA-325, 375, 7301, Otsuka Chemical Co., Ltd .: TERPLUS D2015, MD1000, etc.

The resin-based dispersant can be synthesized by using various resins as described above according to a conventional method. Various resins as described above can be obtained by, for example, mixing one or more monomers or a polymerization initiator in a solvent under a nitrogen environment, and polymerizing them under specified conditions to obtain a homopolymer, Random copolymers, block copolymers, graft copolymers, etc.

In the embodiment of the present invention, a resin-based dispersant containing a polymer block (A) and a block copolymer (I) with the polymer block (B) as an active ingredient may be used. (A) is a structural unit derived from a cyclic amine compound, and the 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 include the aforementioned Structural unit of cyclic amine compound. By using the resin-based dispersant containing the block copolymer (I), it is possible to reduce the amount of other dispersants or pigment derivatives to be described later. Since a pigment derivative introduces a functional group into a pigment, the characteristics of the liquid crystal cell may be affected depending on the characteristics of the pigment and the functional group. However, by using the resin-based dispersant containing the block copolymer (I), since the amount of other dispersants or pigment derivatives 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 any of AB type diblock copolymer, ABA type or BAB type triblock copolymer, ABAB type tetrablock copolymer, ABABA type or BABAB type pentablock. Copolymers, multi-block copolymers, and the like, especially from the viewpoint of dispersibility of a fine pigment, etc., the pigment is such that a polymer block (A) is arranged at one end and the other is The block copolymer (I) in which the polymer block (B) is arranged at the terminal is more preferable.

The polymer block (A) is a block formed from a homopolymer of a cyclic amine compound or a copolymer of a cyclic amine compound and a copolymerizable compound 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 required. 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. Among them, 5 members or 6 members having a polymerizable group are used. N-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- or 6-membered nitrogen-containing heterocyclic compound having a polymerizable group include 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, 2-vinylpyridine, 4-vinylpyridine, and the like are preferred from the viewpoint of dispersibility and the like. The cyclic amine compound may be used alone or in combination of two or more.

The content of the cyclic amine unit in the block copolymer (I) is not particularly limited. From the viewpoint of dispersibility and the like, it is preferably 5 to 30% by weight based on the total amount of the block copolymer (I). It is also preferably 5 to 25% by weight, and more preferably 7 to 20% by weight.

Moreover, the compound which can be copolymerized with a cyclic amine compound and a cyclic amine compound can be copolymerized within the range which does not impair the effect of a block copolymer (I). Examples of the copolymerizable compound include nonionic water-insoluble compounds described below, and among them, butyl acrylate, methyl methacrylate, and styrene are preferred. These copolymerizable compounds can be used individually by 1 type or in combination of 2 or more types.

On the other hand, the polymer block (B) is composed of a nonionic water-soluble unit and an anionic water-soluble unit, and preferably contains a nonionic water-soluble unit and an anionic water-soluble unit and a nonionic non-water-soluble unit. A block formed by a copolymer of a structural unit (hereinafter, sometimes referred to as a "nonionic and water-insoluble unit") of a chemical compound and not including a cyclic amine unit. The polymer block (B) may be a random copolymer or a block copolymer, but from the viewpoint of compatibility with resins, photopolymers, dispersion resins, and the like of 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 has a hydrophilic property selected from at least one selected from the group consisting of a hydroxyl group and an amido group. A nonionic water-soluble organic compound that can be polymerized (hereinafter sometimes simply referred to as "hydrophilic group") and can be polymerized. The nonionic water-soluble organic compound may have a polymerizable group. The polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

Examples of the polymerizable nonionic water-soluble organic compound having a hydrophilic group include polyalkylene glycol, polyalkylene glycol (meth) acrylate, and hydroxyalkyl (meth) acrylate. , (Meth) acrylamide compounds, N-vinylpyrrolidone, epoxyalkylene, and the like. These systems can be used alone or in combination of two or more.

Examples of the polyalkylene glycol include polyalkylene glycols having 2 to 4 carbon atoms in the alkylene chain, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol.

Examples of the polyalkylene glycol (meth) acrylate include mono- or polyfunctional esters of polyalkylene glycol having 2 to 4 carbon atoms in the alkylene chain 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, and the like.

Examples of the hydroxyalkyl (meth) acrylate include alkyl groups such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. The hydroxyalkyl (meth) acrylate is partially 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 (meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyliso ( (Meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (methyl Group) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, diacetone acrylamide, and the like.

Examples of the epoxyalkylene group include ethylene oxide, propylene oxide, and butylene oxide.

The content of the nonionic water-soluble unit in the block copolymer (I) is higher than that of the block copolymer from the viewpoint of using a coating film-forming composition to be described later to form, for example, developability in the case of a column spacer. 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 anionic and water-soluble organic compound having a polymerizable group, but it has a molecule selected from a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group in one molecule. Groups of at least one type of acid group (hereinafter sometimes referred to simply as "acid group") and an anionic water-soluble organic acid compound of a polymerizable group are preferred. The polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

Specific examples of the anionic water-soluble organic acid compound having an acid group and a polymerizable group include a carboxylic acid compound, a sulfonic acid compound, and a phosphoric acid compound. These systems can be used alone or in combination of two or more.

Examples of the carboxylic acid compound include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, and 2-methyliconic acid. Acids, sorbic acid, α, β-methylglutaric acid, maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride, and salts thereof.

Examples of the sulfonic acid compound include ethylene sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, and methallylsulfonic acid. Acid, allyl hydroxybenzophenone sulfonic acid, methacrylic sulfonic acid, (meth) propenyl benzophenone sulfonic acid, 2-allyloxy-2-hydroxypropanesulfonic acid, 3-allyl Oxy-2-hydroxy-1-propanesulfonic acid, 2-methacryloxyoxyethanesulfonic acid, and salts thereof.

Examples of the phosphoric acid compound include 2-methacryloxyethylphosphonic acid, 2-methacryloxyethylphenylphenyl phosphate, 10-methacryloxydecylmethylene phosphate, 4-ethylene Benzyl benzyl phosphoric acid, pentapropenyl dipentaerythritol phosphoric acid, and salts thereof or 2- (meth) acryl ethoxyethyl phosphate, diethyl (vinylphenyl) phosphate, 4 -Phosphates such as diethyl vinyl phenylphosphinate, diphenyl-2-methacryloxyethyl phosphate, and the like.

Since the phosphate group can be a polymerizable group [= P (O) (OH)], phosphoric acid, or trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, Phosphates such as tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and octyl diphenyl phosphate can also be used as anionic water-soluble In the case of organic acid compounds.

The content of the anionic water-soluble unit in the block copolymer (I) is preferably 0.5 to 20% by weight relative to the total amount of the block copolymer (I) in terms of dispersibility and the like. It is preferably 0.5 to 15% by weight, and 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). When the hydrophilicity of the nonionic and water-insoluble unit is higher, the hydrophilicity of the polymer block (B) is increased. 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 has one molecule selected from a chain hydrocarbon group, a cyclic hydrocarbon group, A nonionic water-insoluble organic compound of at least one type of a hydrophobic group (hereinafter sometimes simply referred to as a "hydrophobic group") grouped by an aromatic hydrocarbon group and a polymerizable group is preferable. The polymerizable group is preferably an alkenyl group, and more preferably a vinyl group.

Examples of the nonionic water-insoluble organic compound having a hydrophobic group and a polymerizable group in one molecule include a chain (alkyl) (meth) acrylate, a cycloalkyl (meth) acrylate, and (meth) ) Aryl acrylate, styrenic compounds, etc. These systems can be used alone or in combination of two or more.

Examples of the chain alkyl (meth) acrylate 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, ( (Meth) acrylic acid alkyl esters having 1 to 17 carbon atoms in the alkyl portion such as glyceryl (meth) acrylate.

Examples of the cycloalkyl (meth) acrylate 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, and the like have 3 to 10 carbon atoms in the cycloalkyl moiety ( Cycloalkyl meth) acrylate.

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

Examples of the styrene compound 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 And the like have a styrene compound having at least one 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 amine group as a substituent.

The content of the nonionic water-insoluble unit in the block copolymer (I) is preferably from 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, and 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 the cyclic amine unit is 5 to 30% by weight (also preferably 5 to 25% by weight, and more preferably 7 ~ 20% by weight), nonionic water-soluble unit is 40 ~ 80% by weight (also preferably 45 ~ 75% by weight, more preferably 45 ~ 73% by weight), and anionic water-soluble unit is 0.5 ~ 20 % By weight, (also preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight) of the first aspect; cyclic amine units, non-ionic water-soluble units, And anionic water-soluble units, and further includes a second form of nonionic water-insoluble units of 10 to 50% by weight (also preferably 15 to 45% by weight, more preferably 20 to 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 (atomic mobile radical polymerization) method, RAFT (reversible addition-fragmentation type chain transfer polymerization) method, NMP (nitrogen oxide-mediated radical polymerization) method, and TERP (organic tellurium) It can be synthesized by appropriately selecting these, such as a radical radical polymerization (mediated polymerization) method, an RTCP (reversible transfer catalyst polymerization) method, or the like.

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

As the solvent system, a solvent that is inert during the polymerization reaction is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, methylene chloride, and chloroform. Halogenated hydrocarbon solvents, ketone solvents such as acetone, methyl ethyl ketone, 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 ethyl carbonate and propyl carbonate; N, N-dimethyl Amidamine-based solvents such as formamide, N, N-dimethylacetamide, and the like.

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

As a method of using one polymer block synthesized in advance as a polymer initiator and polymerizing the other polymer block, for example, a desired point in time when one polymer block is polymerized. Then, in a living state, the temperature is first lowered to stop polymerization, and 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, the same operation can be performed with this.

The molecular weight of the resin-based 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 3,000 to 1,000,000, and more preferably 3,000 to 500,000, more preferably It ranges from 4,000 to 100,000, especially from 4,000 to 50,000, and most preferably from 5,000 to 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 the amine value of the resin-based dispersant can be determined in accordance with the functional groups contained in the resin constituting the resin-based dispersant and the content thereof. The acid value (acid value at the time of solid content conversion) can be obtained by a method according to DIN EN ISO 2114, and the amine value (the amine value at the time of solid content conversion) can be obtained by a method according to DIN 16945, for example. Got. The acid value of the acid value type dispersant is not particularly limited, but it is preferably 20 to 150 mgKOH / g, and the amine value of the amine value type dispersant is not particularly limited, but 5 to 30 mgKOH / g is preferable. 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 to 50 mgKOH / g, and the amine value is preferably 5 to 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, The amine value is more than 40 mgKOH / g, more preferably 40 to 100 mgKOH / g, and even more preferably 42 to 98 mgKOH / g.

Examples of the surfactant dispersant include anionic activators (anionic) such as formalin naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkylphosphonate, and the like in response to ionicity. Nonionic activators (nonionic) such as oxyethylene alkyl ethers, cationic activators (cationic) such as alkylamine salts and quaternary ammonium salts, and the like. There are various commercially available surfactant-type dispersants, and specific examples 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, made by Daiichi Industries Pharmaceutical Co., Ltd .: Plysurf AL, A208F, Lion Co., Ltd .: Arquad C-50, T-28, T-50, etc.

The dispersant system as described above may be used alone or in combination of two or more. In the case of combining two or more types, for example, in the case of a resin-based dispersant, a combination of resins, acid-value types, and amine-value types that are different from each other may be cited. In the case of a surfactant-type dispersant, combinations of each other may be mentioned. Those having different ionicities (for example, anionic and nonionic) are not limited to these.

The content (solid content or active ingredient) of the dispersant in the black pigment composition is 2 to 20 parts by weight relative to 100 parts by weight of the total of the black organic pigment and the colored organic pigment, from the viewpoint of dispersion stability. Preferably, 5 to 10 parts by weight is more preferred. However, the most suitable addition amount of the dispersant can be appropriately adjusted by combining the types of organic pigments used. In the case where a pigment derivative described later is used, the content of the colored organic pigment means a 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, a portion having an affinity with the dispersant or a pigment derivative introduced with a polar group is adsorbed on the surface of each organic pigment, and this can become an adsorption point of the dispersant. In this case, since a dispersant is present on the surface of the organic pigment by a pigment derivative, each organic pigment can be more stably dispersed in the black pigment composition with fine particles. Moreover, this re-aggregation can also be prevented more effectively. However, as described 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 are affected. Therefore, in the case of using a pigment derivative, it is appropriate to determine the type or amount to be used in consideration of this point and dispersibility.

The pigment derivative is specifically a compound in which an organic pigment is used as a parent skeleton, and an acidic group, a basic group, or an aromatic group is introduced as a substituent in a side chain. The organic pigments serving as the parent skeleton include, specifically, quinacridone-based pigments, phthalocyanin-based pigments, azo-based pigments, quinoline yellow-based pigments, isoindoline-based pigments, and isoindolinone-based pigments. , Quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, dioxazine-based pigments, and the like. In addition, the parent skeleton may generally include a pale yellow aromatic polycyclic compound such as a naphthalene-based, anthraquinone-based, triazine-based, or quinoline-based compound not referred to as a dye.

As a pigment derivative, it can be used in Japanese Patent Laid-Open No. 11-49974, Japanese Patent Laid-Open No. 11-189732, Japanese Patent Laid-Open No. 10-245501, Japanese Patent Laid-Open No. 2006-265528, and Japanese Patent Laid-Open No. 8-295810. It is described in Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2005-234478, Japanese Patent Laid-Open No. 2003-240938, and Japanese Patent Laid-Open No. 2001-356210.

The content (solid content) of the pigment derivative in the black pigment composition is preferably 2 to 15 parts by weight based on 100 parts by weight of the total of the black organic pigment and the colored organic pigment. It is more preferably 5 to 10 parts by weight. However, the most suitable addition amount of the pigment derivative may 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. In addition, "the total of 100 parts by weight of the black organic pigment and the colored organic pigment" means that the total amount of the pigment derivative is not included.

The particle size of the black organic pigment and the colored organic pigment can be appropriately determined according to the application and the like, and it is preferable that the average particle diameter of the primary particles (that is, the average primary particle diameter) is 20 to 200. In addition, for applications such as a column spacer or a black matrix, from the viewpoint that a higher OD value can be obtained when a coating film is formed, an average primary particle diameter of 20 to 80 nm is more preferable. The average primary particle diameter can be calculated, for example, from the arithmetic mean of the maximum widths of a plurality of (for example, 50) primary particles in a transmission electron microscope (TEM) photography.

In the embodiment of the present invention, a grinding treatment may be performed in advance in terms of adjusting the average particle diameter in accordance with the type of the organic pigment. The polishing treatment can be performed in accordance with a conventional method in accordance with the type of the organic pigment and the like. Examples of such a polishing treatment system include a solvent salt milling method.

In the embodiment of the present invention, from the viewpoint of further improving the dispersibility of the organic pigment and the like in the black pigment composition and the black coating film forming composition, in addition to the dispersant described above, a dispersing resin may be used as a dispersing aid. Agent. Such a dispersing resin, particularly a coating film forming component used in a 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 usable in the present invention include alkali-soluble resins described later. The dispersing resin may be the same kind of resin as the alkali-soluble resin used in the black coating film forming composition, or it may be a different kind of resin. The content of the dispersed resin is preferably 10 to 50 parts by weight based on 100 parts by weight of the total of the black organic pigment and the colored organic pigment. In the case where a pigment derivative is used, the content of the black organic pigment and the colored organic pigment means the total amount including the pigment derivative.

The solvent that can be used in the present invention can be appropriately selected according to the type of the coating film forming component described later, and examples thereof include aromatic, ketone, ester, glycol ether, alcohol, and aliphatic And other various organic solvents. Among these, an organic solvent selected from the group consisting of an aromatic system, a ketone system, an ester system, and a glycol ether system is preferred from the viewpoint of coating film formability. Only one type of organic solvent may be used, or two or more types may be combined.

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

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

Examples of the ester-based organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, and ethylene glycol. Acid 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 ethyl acetate, ethyl acetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypropionate, ethylene glycol monobutyl Ether ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butanediol diacetate, and the like.

Examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and 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 ethylene ethers, ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, and diethyl ether Glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, propylene glycol Ether propionate water-insoluble glycol ethers.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol, ethylene glycol, propylene glycol, diethylene glycol, and pentylene. Glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol , Polyethylene glycol with a molecular weight of 2000 or less, 1,3-propanediol, isopropanediol, isobutanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1, 6-hexanediol, glycerol, mesoerythritol, neopentyl tetraol and the like.

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

When the amount of the solvent added can be used for the preparation of a black coating film-forming composition described later, from the viewpoint of operability, the solid content concentration including a black organic pigment 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 contained in addition to the aforementioned components.

The black pigment composition is obtained, for example, by adding the aforementioned components to a well-known disperser such as a bead mill, a sand mixer, and a dispersing stirring blade. That is, the black pigment composition is a dispersion in which solid components such as black organic pigments and colored organic pigments are dispersed in a solvent as particles. Here, the term “particles” means secondary particles formed by aggregating the aforementioned primary particles of a black organic pigment or a colored organic pigment. The method of adding the components is not particularly limited, and the components may be mixed simultaneously to perform a dispersion treatment. In addition, the organic pigments and solvents are mixed and dispersed with a dispersant and / or other optional components, and a pigment composition is prepared for each pigment, and these pigment compositions are mixed and then dispersed again. Other methods can also be used.

The average particle diameter of the particles dispersed in the black pigment composition obtained as described above (hereinafter sometimes referred to as the "dispersed average particle diameter") is not particularly limited, but those having a size of approximately 30 to 300 nm can be preferably used. . In addition, for applications such as a column spacer or a black matrix, from the viewpoint of the surface smoothness of the coating film, the dispersed average particle diameter is more preferably 30 to 150 nm. The dispersed average particle diameter can be measured by, for example, a particle diameter measuring machine. Examples of the particle size measuring machine include Fuza-1000 manufactured by Otsuka Electronics Co., Ltd. and the like.

    <Black coating film forming composition>    

An embodiment of the black coating film forming composition of the present invention includes the black pigment composition and the coating film forming component described above. In this way, by including the black pigment composition as described above, the coating film can effectively absorb visible light in the region of a wavelength of 380 to 750 nm due to the effect of the black organic pigment. In addition, absorption in an ultraviolet region (a region shorter than a wavelength of 380 nm) and an infrared region (a region longer than a wavelength of 750 nm) can be suppressed to such an extent that they have no influence on the manufacture of a flat panel. In addition, because at least two kinds of colored organic pigments other than the black organic pigment are combined, the coating film can block light in the visible light region without using black carbon, and can effectively suppress absorption in the visible light region compared to absorption in the visible light region. Absorption of ultraviolet and infrared. Furthermore, the solvent resistance of the coating film can be improved by the action of the black organic pigment. In addition, the influence of black carbon on the characteristics of the liquid crystal cell can also be avoided.

As a 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 and can suppress the influence on the characteristics of the liquid crystal cell, it is a component that can form a coating film. It is not particularly limited, and it may be a polymerizable component or a polymer. As the polymerizable component, it is easy to pattern the application by development (negative development), and therefore a photopolymerizable component is preferable. Examples of the polymer include thermoplastic urethane resins, (meth) acrylic resins, polyamide resins, polyimide resins, styrene and maleic resins, and polyesters. Resin, silicone resin, Cardo resin, etc.

The photopolymerizable component that can be used includes a photopolymerizable compound and a photopolymerization initiator. Such a photopolymerizable compound and a photopolymerization initiator can be used, for example, as described in Japanese Patent Application Laid-Open No. 2009-179789. In detail, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from at least one terminal, preferably two or more terminal ethylenic compounds. Saturated compound. Such a group of compounds is widely known in the technical field, and these can be used without particular limitation in the present invention. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer (that is, a dimer, a trimer, and an oligomer), a mixture thereof, and a copolymer thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or their esters and amines Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amine of an unsaturated carboxylic acid and an aliphatic polyamine compound can be used. In addition, unsaturated carboxylic acid esters or amidoamines having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, and an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy, and A functional dehydration condensation reactant of a carboxylic acid can also be suitably used. Also, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol may be used. Suitable for use, and further, the substitution reaction of unsaturated carboxylic acid esters or amidoamines having a detachable substituent such as a halogen group or tosylsulfonyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols Also suitable for use. In addition, as another example, a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether, or the like may be used instead of the unsaturated carboxylic acid described above.

The specific examples of these are as described in Japanese Patent Application Laid-Open No. 2009-179789. As specific examples of the monomer of an aliphatic polyalcohol compound and an ester of an unsaturated carboxylic acid, examples of the acrylate include ethylene oxide. Alcohol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol Propane triacrylate, trimethylolpropane tris (propyleneoxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, neopentaerythritol diacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dinepentaerythritol diacrylate, dinepentaerythritol hexaacrylate , Sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris (acryloxyethyl) isocyanurate, polyester acrylate oligomerization Materials, isocyanuric acid EO modified triacrylate and so on.

The details of the structure of the addition polymerizable compound, the method of using it alone or in combination, and the amount of addition can be arbitrarily set in accordance with the performance design of the final black coating film forming composition.

For example, you can choose from the following viewpoints. In terms of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in most cases, a bifunctional or higher function is preferable. In order to increase the strength of the cured film, it is preferable to use three or more functional groups, and to use different functional numbers and different polymerizable groups (for example, acrylate, methacrylate, styrene-based compound, vinyl ether-based). (Compound), which is also effective for adjusting both sensitivity and intensity.

In addition, for compatibility and dispersibility with other components in the black coating film-forming composition (for example, a binder polymer such as an alkali-soluble resin, a photopolymerization initiator, and a colorant (pigment)), The choice and use of the polymer compound is also an important factor. For example, compatibility can be improved by using a low-purity compound or using two or more types in combination.

In addition, it is possible to select a specific structure for the purpose of improving the adhesion to the substrate and the like. The photopolymerizable compound is preferably contained in an amount of 5 to 70% by weight, and more preferably 10 to 60% by weight based on the nonvolatile component in the coating film forming composition. These systems can be used alone or in combination of two or more. In addition, the method of using the photopolymerizable compound can arbitrarily select an appropriate structure, formulation, and addition from the viewpoints of the size, resolution, haze, refractive index change, and surface adhesion of the polymerization inhibition of oxygen. the amount.

The photopolymerization initiator can also be used as described in Japanese Patent Application Laid-Open No. 2009-179789.

That is, examples of the photopolymerization initiator that can be suitably used in the present invention include acetophenone-based, ketal-based, benzophenone-based, benzoin-based, benzophenone-based, xanthone-based, and active halogen compounds (Triazine-based, oxadiazole-based, coumarin-based), acridine-based, biimidazole-based, oxime ester-based, and the like.

Specific examples of these are specific examples of benzophenone-based photopolymerization initiators, and examples include benzophenone, 4,4'-bis (dimethylamine) benzophenone, and 4,4'-bis (Diethylamine) benzophenone, 4,4'-dichlorobenzophenone, and the like.

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

In the embodiment of the black coating film-forming composition according to the present invention, if a photopolymerizable component is included, an alkali-soluble resin may be contained in addition to the black pigment composition and the photopolymerizable component described above.

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 more improved.

Such an alkali-soluble resin can be used in those described in Japanese Patent Application Laid-Open No. 2009-179789. If briefly described, examples of the alkali-soluble resins that can be used in the present invention include linear organic high molecular polymers, and those having a molecular (preferably an acrylic copolymer or a styrene copolymer as a main chain) can be used. Among the alkali-soluble resins having at least one group (for example, carboxyl group, phosphate group, sulfonic acid group, etc.) which promotes alkali-solubility in the molecule), an appropriate choice is made. Among them, those which are soluble in an organic solvent and capable of being developed by a weak alkaline aqueous solution are more preferable.

Examples of suitable alkali-soluble resins include copolymers of (meth) acrylic acid and other monomers copolymerizable therewith. Here, the (meth) acrylic acid refers to a general term for combining acrylic acid and methacrylic acid, and the same applies hereinafter to the general term for (meth) acrylic acid ester-based acrylate and methacrylic acid ester.

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

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (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 vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, ethylene 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 Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁶ is an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ⁷ is an alkyl group having 1 to 8 carbon atoms or an arane having 6 to 12 carbon atoms Base) etc.

These other copolymerizable single systems may be used alone or in combination of two or more.

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

There are various commercially available alkali-soluble resins. Specific examples are as follows, but they are not limited to these.

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

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

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

Examples of such solvents include esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyl acetate. Isopropyl ester, 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, pyruvate Esters, ethyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethyl acetate Glycol monomethyl ether, ethylene glycol monoethyl ether, methylcellulose acetate, ethelussel acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, for example: methyl ethyl ketone, cyclohexane Ketones, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, such as toluene, xylene and the like.

The solvent may be used singly or in combination of two or more kinds.

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

When a polymer is used as a coating film forming component, a solvent may be used similarly to the case where a photopolymerizable component is used. As such a solvent, a user who can use the black pigment composition and a user who can use the photopolymerizable component can be used.

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

In the black coating film forming composition of the present invention, a dispersing aid, a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, and a filler may be added as required. Various additives such as agents, surfactants, adhesion promoters, antioxidants, agglutination inhibitors, and surface conditioners (leveling agents). When it is contained in the black pigment composition, the amount of addition 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 it with a dispersion type stirring blade or the like.

The black coating film-forming composition according to the present invention is as described above. The coating film does not use black carbon and only absorbs light in the visible light region, and has good solvent resistance. In addition, alignment using infrared rays in the manufacturing steps will be possible. Furthermore, when using a photopolymerizable component as a coating-film formation component, the polymerization reaction by an ultraviolet-ray is good, and it does not affect a manufacturing process. Therefore, for example, a black pillar spacer as a flat panel used in a liquid crystal display device is particularly suitable. In addition, a black matrix as a color filter of an image display device is also suitable.

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

With respect to 200 parts by weight of chlorosulfonic acid, PIGMENT RED 255 (manufactured by BASF, product name IRGAZIN RED L3551HD) was added in an amount of 20 parts by weight and thiosulfenyl chloride was 10 parts by weight, and the mixture was added at 60C After reacting for 5 hours, it was discharged into 2 liters of ice water, and 26.9 parts by weight of chlorosulfonate of Pigment Red 255 was obtained by passing and washing with water. This was dispersed into 200 parts by weight of water, 8.3 parts by weight of diethylaminopropylamine was added, and the mixture was reacted at 80 ° C for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain 31.5 parts by weight of the following: Pigment derivative 1 represented by formula (3).

    (Production Example 2) Production of Pigment Derivative 2    

With respect to 200 parts by weight of chlorosulfonic acid, PIGMENT VIOLET 23 (manufactured by DIC Corporation, product name Violet 23) was added to 20.4 parts by weight and thiosulfenyl chloride was 20 parts by weight, and the mixture was added at 60 ° C After allowing to react for 5 hours, it was discharged into 2 liters of ice water, and was passed through and washed with water to obtain 27.2 parts by weight of a chlorosulfonate of Pigment Violet 23. This was dispersed into 200 parts by weight of water, 15 parts by weight of diethylaminopropylamine was added, and the mixture was reacted at 80 ° C for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain 31.9 parts by weight of the following Pigment derivative 2 represented by formula (4).

    (Production Example 3) Production of Pigment Derivative 3    

200 parts by weight of 88% sulfuric acid was charged into a 300 ml 3-necked flask, and then 20 parts by weight of Pigment Red 255 (manufactured by BASF Corporation, product name IRGAZIN RED L3551HD) was placed under water cooling, and the temperature was adjusted at 40 to 45 ° C It was reacted for 3 hours to perform sulfonation. Next, after draining the synthetic stock solution into a beaker of 1L of water, filter this, transfer the paste to a 2L beaker, add 1.5L of water, and stir at 60 to 70 ° C for 1 hour to fully 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 was dried at 100 ° C. to obtain a 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 a crude copper phthalocyanin product (manufactured by Zhuhai Toyo Corporation, product name T-99 Crude Blue, Pigment Blue 15: 3) and 10 parts by weight of thiosulfenyl chloride, After reacting at 60 ° C. for 5 hours, it was discharged into 2 liters of ice water, and was passed through and washed with water to obtain 47 parts by weight of chlorosulfonate of Pigment Blue 15. This was dispersed in 200 g of water, 8.3 parts by weight of dimethylaminopropylamine was added, and the mixture was reacted at 80 ° C. for 1 hour, and then filtered, washed with water, dried, and pulverized to obtain 51.5 parts by weight of the following formula (6) Pigment derivative 4 shown.

    (Production Example 5) Production of Resin Dispersant 1    

192.8 parts by weight of butyl acrylate (nonionic and water-insoluble organic compound), 321.9 parts by weight of methoxypolyethylene glycol (n ≒ 9) methacrylate (non-ionic water-soluble organic compound), and acrylic acid (anion Water-soluble organic compound) 59.2 parts by weight, N- (2-methylpropyl) -N- (1-diethylphosphinofluorenyl-2,2-dimethylpropyl) -O- (2-carboxyl 15.0 parts by weight of propyl-2-yl) hydroxylamine (polymerization regulator) and 370 parts by weight of propylene glycol monomethyl ether acetate (reaction solvent) were put into a 2L stainless steel separatory bottle, and 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 proceed for 6.5 hours after the temperature increase was completed, thereby polymer block B was synthesized. When the contents were sampled in small amounts and measured by GPC, 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 a flask. Next, while foaming and stirring with nitrogen, the amount of 125 was 125. It was made to react at 4 degreeC for 4 hours. When the contents were sampled and measured by GPC, the peak top molecular weight was 10140 and Mw / Mn was 1.45.

Next, the temperature in the system was raised to 210 ° C, and 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 measured by GPC, the peak top molecular weight was 10990, and Mw / Mn was 1.49. The acid value was 74.0 mgKOH / g and the amine value was 52.9 mgKOH / g.

    (Production Example 6) Production 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 diameter of about 20 μm, manufactured by Sanda Chemical Industries, Ltd.) As a solvent, 750 parts by weight of diethylene glycol (manufactured by Nihon Shokusen) in a 5L kneading machine (manufactured by Moriyama, S5-2GH-S type), while the temperature of the kneaded product becomes 50 ° C Way to do temperature control, kneading and grinding for 9 hours. The kneaded and ground product was stirred and dispersed in 30 L of warm water at 40 ° C., then moved to a nutsche and filtered, and repeatedly washed with water until thenardite was completely removed, thereby obtaining a pigment water paste. This pigment water paste was dried at 105 ° C for 2 hours. The dried product was pulverized with a pulverizer (manufactured by Kyoritsu Science & Technology Co., Ltd., a small pulverizer, and a sample mill SK-M2) to obtain 330 parts by weight of a blue organic pigment 2. The average particle diameter of the primary particles of the obtained blue organic pigment 2 was 40 nm. The average particle diameter is a result of measurement and calculation by TEM imaging.

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 formulae (1) and (2)

Black organic pigment 1: BASF, Lumogen Black FK4280

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

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

(c) Colored organic pigments

Red organic pigment 1: manufactured by DIC Corporation, 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: CINIC Corporation, Cinilex DPP Red SR2P, Pigment Red 254 (PR254)

Red organic pigment 4: manufactured by BASF, Irgazine Red L3551HD, pigment red 255 (PR255)

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

Blue Organic Pigment 2: Manufacturing Example 6

Blue organic pigment 3: 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 Corporation, PERRINDO VIOLET 29 229-4050, pigment VIOLET 29 (PV29)

(d) Dispersant

Resin-based dispersant 1: Production example 5

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

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

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

(e) Dispersion aid

Dispersion resin 1: made by Japan Catalyst Co., Ltd., RD-Y-503, alkali-soluble acrylic resin

Dispersion resin 2: manufactured by Osaka Organic Chemical Co., Ltd., SOP-005, alkali-soluble acrylic resin, acid value 29mgKOH / g, amine value 116mgKOH / g, weight average molecular weight 19000

(f) Solvent

Propylene glycol monomethyl ether acetate (PMA)

(g) Coating film forming component

Coating film forming resin: made by Japan Catalyst Co., Ltd., RD-Y-507, acrylic resin

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

The black pigment composition can be obtained by mixing the components having the composition shown in Table 1 (based on solid content other than the solvent) and dispersing them with a bead mill. The pulverizing medium of the bead mill uses zirconia beads having a diameter of 0.3 mm in diameter, and is added so as to become 400 parts by weight based on 100 parts by weight of the amount of the abrasive. This medium is removed after the dispersion treatment. The compositions shown in Table 1 are parts by weight.

    <Preparation of black coating film forming composition>    

A black coating film-forming composition can be obtained by adding the aforementioned coating film-forming resin to each of the obtained black pigment compositions and stirring them with a dispersion-type stirring blade. The amount of the coating film-forming resin added is 100 parts by weight of the total organic pigments (including pigment derivatives) contained in each black pigment composition, and the total amount of the dispersant, the dispersion resin, and the coating film-forming resin is 200 parts by weight. Way to make.

    <Formation of Coating Film>    

Each of the obtained black coating film-forming compositions was used, and each composition was spin-coated on a glass plate so that the film thickness became 1 μm and 3 μm. The coating film was formed by pre-baking at 90 ° C for 2.5 minutes, and then baking at 230 ° C for 30 minutes.

    <Measurement of optical density (OD value)>    

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

    <Solvent resistance>    

The coating film formed by adjusting the film thickness to 1 μm was cut to a size of 2 × 4 cm, and immersed in 50 g of 1-methyl-2-pyrrolidone (NMP) at 80 ° C. for 1 hour, and then confirmed by visual inspection. The color of NMP fluid. The evaluation results are shown in Table 1. In Table 1, those with no coloring are indicated by "○" and those with observed coloring are indicated by "X".

    (Example 8)         <Preparation of black pigment composition>    

Each component of the composition shown in Table 2 (except the solvent is based on the solid content) was mixed and dispersed with a bead mill to obtain pigment compositions 1 to 3 for each pigment. The pulverizing medium of the bead mill uses zirconia beads having a diameter of 0.3 mm in diameter, and is added so as to become 400 parts by weight based on 100 parts by weight of the amount of the abrasive. This medium is removed after the dispersion treatment. The composition shown in Table 2 is parts by weight. A black pigment composition can be obtained by mixing 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, and stirring with a dispersion stirring blade.

    <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 with a dispersion 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 having 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 was 1.24 (/ μm). In addition, there is no color of NMP.

It can be known from the results of Examples 1 to 8 and Comparative Example 1 that compared with the comparative example, the OD value of the example is high, and the color of NMP is not present 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 is good in all wavelengths in the visible light region, and The solvent resistance is also good. In addition, the pigments used in Examples 1 to 8 have suppressed the absorption of ultraviolet and infrared rays compared to the absorption of visible light. This is obvious to those skilled in the art in the field. Furthermore, when Comparative Examples 1 to 7 and Example 8 are used, when a specified dispersant is used, the use of a dispersant or a pigment derivative can be reduced.

Claims (4)

A black pigment composition comprising at least one black organic pigment selected from the following formulae (1) and (2), and at least two colored organic pigments, dispersants, and solvents other than the black organic pigment,     The black pigment composition according to claim 1, wherein the colored organic pigment other than the black organic pigment is selected from the group consisting of a red organic pigment, a blue organic pigment, and a purple organic pigment.         The black pigment composition according to claim 2, wherein the red organic pigment is at least one selected from the following (a) group, the blue organic pigment is at least one selected from the following (b) group, the aforementioned The purple organic pigment is selected from at least one of the following (c) group, (a) group: color index pigment red 149, 179, 254, 255; (b) group: color rendering 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 according to any one of claims 1 to 3 and a coating film-forming component.