KR102381019B1 - Black pigment composition and black coating film formation composition including the black pigment composition - Google Patents

Abstract

[Problem] In the present invention, a black pigment composition capable of absorbing light in the visible region without using black carbon and capable of suppressing absorption of infrared and ultraviolet light, and good solvent resistance, and a composition for forming a black coating film comprising the same The task is to provide
[Solutions] A black pigment composition comprising at least one type of black organic pigment selected from the following formulas (1) and (2), at least two types of colored organic pigments other than the black organic pigment, a dispersant and a solvent, and a black color thereof A black coating film forming composition comprising a pigment composition and a coating film forming component.

Description

A black pigment composition and a black coating film formation composition containing the same

The present invention relates to a black pigment composition and a composition for forming a black coating film comprising the same, and more particularly, to a black pigment composition used for a black column spacer provided in, for example, a flat panel of a liquid crystal display device, and a composition for forming a black coating film comprising the same it's about

A liquid crystal display device has a liquid crystal cell structure in which a liquid crystal substance is filled between two glass substrates provided with opposing transparent electrodes. And between the two glass substrates, a column spacer is inserted in order to keep the gap between the substrates uniformly and to provide a favorable image. Conventionally, bead spacers, such as bead-shaped glass, have been used as such a column spacer. However, in the method using a bead spacer, since the beads are randomly dispersed in the gap, a problem of light leakage may occur, the nonuniformity of the gap distance may become large, and the control of mechanical properties such as elasticity is difficult It is pointed out that there is a problem such as a difficult thing. Moreover, more precise|precise gap control is calculated|required from the market request of the high definition image with respect to the liquid crystal display device in recent years.

As this improvement measure, instead of a bead spacer, a black column spacer using a black photosensitive resin composition has been proposed (see, for example, Patent Documents 1 and 2). According to the black column spacer, it is possible to form the column spacer at a desired position so that the non-uniformity of the gap distance is small, and since it is relatively easy to control the properties such as the photopolymerizable component, it is possible to control the gap more precisely than in the case of the bead spacer. I think it's true In addition, when the black colorant is included in the column spacer, visible light (wavelength is set to 380 nm to 750 nm) is blocked, and improvement in contrast and color development effect can be expected. As such a black colorant, perylene black is exemplified in Patent Documents 1 and 2. Moreover, as an example of perylene black, patent document 3 discloses the pigment of a specific structure.

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 material, resistance to the solvent contained in the liquid crystal material, that is, solvent resistance is required. Moreover, the characteristic which does not give influence to the characteristic of a liquid crystal cell is also required. For example, when the insulating property of the black column spacer is low, the driving of the liquid crystal is affected, and thus the properties of the liquid crystal cell are likely to be affected.

In addition, in the manufacturing process of forming a column spacer, the method of hardening a photopolymerizable component to form a high molecular compound is employ|adopted in many cases. In this case, in order to cure by irradiating an ultraviolet-ray generally, the black photosensitive composition needs to be comprised so that an ultraviolet-ray may be transmitted while absorbing visible light. In addition, in many cases, the alignment key on the panel substrate for determining the exact position of exposure is recognized as infrared rays such as near infrared rays. At this time, it is necessary to configure so that infrared rays are also transmitted.

In Patent Documents 1 and 2, examples of the black pigment include aniline black, perylene black, titanium black, cyanine black, lignin black, lactam organic black, RGB black, carbon black, and the like. However, the use of carbon black is permitted, and there is concern about the influence on the liquid crystal cell in terms of insulating properties. In addition, since carbon black also absorbs ultraviolet rays and infrared rays other than visible light, there is a fear that the polymerization reaction of the photopolymerizable component by ultraviolet rays becomes insufficient, or alignment during exposure using infrared rays becomes difficult, so that the manufacturing process is concerned about the impact of

In view of the above points, an object of the present invention is a black pigment composition capable of absorbing light in the visible region without using black carbon, and capable of suppressing absorption of infrared and ultraviolet rays, and having good solvent resistance, including the same It is to provide the black coating film formation composition which says.

Although perylene black is illustrated as a black pigment in patent documents 1 and 2, it does not describe about the specific example of perylene black. Then, when the present inventors studied earnestly, depending on the kind of perylene black, the thing from which the degree of solvent resistance differs and the thing from which the absorption spectrum of a wavelength differs was acquired. And it discovered that it was possible to solve the said subject by using at least 2 types of perylene black of a specific structure, and other colored pigments, and came to complete this invention. The gist of the present invention is as follows.

1st of this invention is a black pigment composition containing at least 1 type of black organic pigment chosen from following formula (1) and (2), at least 2 types of colored organic pigments other than the black organic pigment, a dispersing agent, and a solvent is about

In a preferable embodiment of this invention, colored organic pigments other than the said black organic pigment are selected from a red organic pigment, a blue organic pigment, and a purple organic pigment. Moreover, in a more preferable embodiment, the said red organic pigment is at least 1 type selected from the following (a) group, The said blue organic pigment is at least 1 type selected from the following (b) group, The said purple organic pigment is It is at least 1 type selected from the following (c) group.

(a) group:

C.I. Pigment Red 149, 179, 254, 255,

(b) group:

C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60,

(c) group:

C.I. Pigment Violet 23, 29.

The 2nd of this invention relates to the black coating film formation composition containing the said black pigment composition and a coating film formation component.

According to the present invention, without using black carbon, a black pigment composition capable of absorbing light in the visible region, capable of suppressing absorption of infrared and ultraviolet light, and good solvent resistance, and a composition for forming a black coating film comprising the same can provide

<Black pigment composition>

The black pigment composition according to the present invention comprises at least one type of black organic pigment selected from the following formulas (1) and (2), and at least two types of colored organic pigments other than the black organic pigment (hereinafter simply referred to as “colored organic pigments”). '), a dispersing agent, and a solvent.

The black organic pigment having a specific structure represented by formulas (1) and (2) effectively absorbs visible light in a wavelength region of 380 nm to 750 nm, and has a low transmittance, and has a low transmittance in an ultraviolet region (a region with a shorter wavelength than 380 nm) and an infrared region. It has the characteristic that absorption of (region of wavelength longer than 750 nm) is suppressed compared with a visible light region, and it is small. The absorption characteristic of light in such a visible region can be confirmed by the optical density (OD value) when measured by the method mentioned later. In addition, by combining with at least two types of colored organic pigments other than the black organic pigment, light in the visible region can be blocked without using black carbon, and absorption of ultraviolet and infrared rays can be more effectively suppressed than in the visible region. For this reason, for example, when forming a column spacer using a photopolymerizable component as a coating film forming component, the photopolymerizable component can fully be polymerized-reacted by ultraviolet-ray, and it is possible to perform alignment at the time of exposure by infrared rays. Moreover, solvent resistance is favorable. The influence on the characteristic of the liquid crystal cell resulting from black carbon can also be avoided.

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

In embodiment of this invention, content of the black organic pigment in a black pigment composition is 1 to 12 weight% from a viewpoint of the balance of absorption of the light ray in a visible region, and suppression of absorption in an ultraviolet-ray and infrared region. is preferable, and 1 to 7% by weight is more preferable.

As a colored organic pigment which can be used by this invention, a red organic pigment, a blue organic pigment, a green organic pigment, a purple organic pigment, a yellow organic pigment, an orange organic pigment, a brown organic pigment, etc. are mentioned. When it shows by color index No., for example, the following can be illustrated.

Red Organic Pigment: 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, the OD value improvement effect and From a viewpoint of the inhibitory effect of ultraviolet-ray and ultraviolet-ray absorption, pigment red 149, 179, 254, and 255 are preferable.

Blue Organic Pigment: 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 these, from the viewpoint of the effect of improving the OD value and the effect of suppressing absorption of ultraviolet and infrared rays according to the combination of the aforementioned black organic pigment and other colored organic pigments, Pigment Blue 15, 15:1, 15:2, 15 :3, 15:4, 15:5, 15:6, 16, 60 are preferable, and pigment blue 15:6, 16, and 60 are more preferable.

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

Violet Organic Pigment: 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 these, from the viewpoint of the effect of improving the OD value and the effect of suppressing absorption of ultraviolet and infrared rays due to the combination of the aforementioned black organic pigment and other colored organic pigments, Pigment Violet 23 and 29 are preferable, and Pigment Violet 29 is more preferable.

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 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 5, 23, 25, 32, 41, 42, etc.

In this invention, it is preferable to contain at least 2 types of the colored organic pigments as mentioned above. Thereby, together with the black organic pigment mentioned above, the light ray of a visible region can be absorbed effectively. Three or more types of colored organic pigments can be contained. This is because, as the number of types of colored pigments increases, the effect of absorbing visible light is greater. However, when there are many kinds, a trouble may arise in the dispersibility of a colored pigment. Then, when the present inventor earnestly studied, by combining at least 2 types selected from a red organic pigment, a blue organic pigment, and a purple organic pigment with the predetermined black organic pigment mentioned above, while suppressing the use of a colored organic pigment, It has been found that it is possible to maintain the absorption characteristics of black organic pigments, and effectively absorb visible light in the entire wavelength range of 380 nm to 750 nm, thereby suppressing the absorption of ultraviolet and infrared regions. In addition, this effect can be attributed to the fact that the red organic pigment is C.I. At least one selected from Pigment Red 149, 179, 254, and 255, and the blue organic pigment is C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, and at least one selected from 60, (c) group C.I. In the case of at least 1 sort(s) chosen from pigment violet 23 and 29, it exists in the tendency exhibited more effectively. In addition, when the red organic pigment and the blue organic pigment are one selected from the group (a) and one selected from the group (b), respectively, and the blue organic pigment and the purple organic pigment are each selected from the group (b) And (c) tends to be more suitable in the case of one selected from the group.

In the embodiment of the present invention, the content of the colored organic pigment is 50 to 100 parts by weight of the black organic pigment from the viewpoint of effectively absorbing visible light in the entire range of 380 to 750 nm and effectively suppressing absorption of ultraviolet and infrared rays. 1000 parts by weight is preferable, and 100 to 700 parts by weight is more preferable. In addition, when using the pigment derivative mentioned later, content of this colored organic pigment means the total amount including a pigment derivative.

As a dispersing agent usable in this invention, a resin type dispersing agent, surfactant type dispersing agent, etc. are mentioned, for example. In addition, in the resin-type dispersant, from the difference between the acid value and the amine value of the resin, an amine value is 0, an acid value type dispersant having an acid value greater than 0, an amine type dispersant having an acid value of 0 and an amine value greater than 0, an acid value and an amine value There is a dispersant greater than zero.

As a resin type dispersing agent, For example, polyurethane; Polyester; unsaturated polyamides; phosphate ester; polycarboxylic acids and their amine salts, ammonium salts, and alkylamine salts; polycarboxylic acid ester; hydroxyl group-containing polycarboxylic acid ester; polysiloxane; modified polyacrylate; water-soluble high molecular compounds such as alginic acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinyl pyrrolidone, and gum arabic; Styrene-acrylic acid resin, styrene-methacrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methacrylic acid ester resin, acrylic acid-acrylic acid ester resin, iso ethylenic double bond-containing resins such as butylene-maleic acid resins, vinyl-ester resins, and rosin-modified maleic acid resins; amine resins such as polyallylamine, polyvinylamine, and polyethyleneimine; and the like.

A commercially available resin type dispersing agent can be used. Although the specific example of a commercial item is as follows, it is not limited to these.

Nippon Lubrizol Corporation Manufactured by: Solpulse 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000,

Big Chemie Japan Co., Ltd. Manufactured by: 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,

Manufactured by BASF: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244, PX4701,

Ajinomoto Fine Techno Co., Ltd. Manufactured by: Ajisper-PB821(F), PB822, PB880,

Kawaken Fine Chemicals Co., Ltd. Manufactured by: Hinoact T-8000,

Kusumoto Kasei Co., Ltd. Manufactured by: Disparon PW-36, Disparon DA-325, 375, 7301;

Otsuka Chemical Co., Ltd. Manufactured by: TERPLUS D2015, MD1000, etc.

In addition, a resin type dispersing agent can synthesize|combine various resins as mentioned above according to a conventional method, and can be used. The various resins as described above are, for example, mixed with one or more monomers or polymerization initiators in a solvent under a nitrogen atmosphere and subjected to polymerization reaction under predetermined conditions, such as homopolymers, random copolymers, block copolymers, graft copolymers, etc. can get

Further, in the embodiment of the present invention, the polymer block (A) includes a structural unit derived from a cyclic amine compound, and a structural unit derived from a nonionic water-soluble compound and a structural unit derived from an anionic water-soluble compound, and the cyclic A resin-type dispersing agent containing, as an active ingredient, a block copolymer (I) of a polymer block (B) that does not contain a structural unit derived from an amine compound can be used. By using the resin type dispersing agent containing this block copolymer (I), the usage-amount of another dispersing agent and the pigment derivative mentioned later can be reduced. Since a pigment derivative introduces a functional group into a pigment, depending on the characteristic of a pigment and a functional group, it may give influence on the characteristic of a liquid crystal cell. However, since the usage-amount of another dispersing agent and a pigment derivative can be reduced by using the resin type dispersing agent containing this block copolymer (I), the influence on the characteristic of a liquid crystal cell can be reduced.

The block copolymer (I) will be described as follows.

The block copolymer (I) is an AB type diblock copolymer, ABA type or BAB type triblock copolymer, ABAB type tetrablock copolymer, ABABA type or BABAB type pentablock copolymer, and more Block copolymers and the like may be used, but a block in which a polymer block (A) is disposed at one end and a polymer block (B) is disposed at the other end from the viewpoint of dispersibility of the pigment, particularly the fine pigment, etc. Copolymer (I) is preferred.

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. This copolymer may be a random copolymer or a block copolymer. The cyclic amine unit contained in the said homopolymer and copolymer may be quaternized as needed. As the cyclic amine compound, a nitrogen heterocyclic compound having a group containing a polymerizable double bond (hereinafter, may be referred to as a "polymerizable group") can be used without particular limitation, but among them, a 5-membered or 6-membered compound having a polymerizable group A heterocyclic compound containing a nitrogenous member is more preferable. The polymerizable group is preferably an alkenyl group, more preferably a vinyl group.

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

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

Moreover, the compound copolymerizable with a cyclic amine compound can be copolymerized with a cyclic amine compound in the range which does not impair the effect by a block copolymer (I). As a copolymerizable compound, the nonionic water-insoluble compound mentioned later is mentioned, for example, Among these, butyl acrylate, methyl methacrylate, styrene, etc. are preferable. These copolymerizable compounds can be used individually by 1 type or in combination of 2 or more type.

On the other hand, the polymer block (B) contains a nonionic water-soluble unit and an anionic water-soluble unit, preferably a nonionic water-soluble unit, an anionic water-soluble unit, and a structural unit derived from a nonionic water-insoluble compound (hereinafter referred to as "nonionic ratio"). water-soluble unit"), and a block comprising a copolymer that does not contain a cyclic amine unit. Although the polymer block (B) may be a random copolymer or a block copolymer, it is preferable that it is a random copolymer from a viewpoint of compatibility with resin, photopolymer, dispersion resin, etc. of the resin of a coating film formation component mentioned later, etc.

The nonionic water-soluble unit is a divalent structural unit derived from a nonionic water-soluble compound. The nonionic water-soluble compound is not particularly limited as long as it is a nonionic, water-soluble, and polymerizable organic compound, but at least one hydrophilic group selected from the group consisting of a hydroxyl group and an amide group (hereinafter simply referred to as “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, more preferably a vinyl group.

Examples of the nonionic water-soluble organic compound that has a hydrophilic group and can be polymerized include polyalkylene glycol, polyalkylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide compound, N-vinyl p Rollidone, an alkylene oxide, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more type.

Examples of polyalkylene glycol include polyalkylene glycol 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 monofunctional 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, phenoxy polyethylene glycol acrylate, polypropylene glycol monomethacrylate, polypropylene glycol diacrylate, etc. are mentioned.

As hydroxyalkyl (meth)acrylate, an alkyl part, such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, has 1 C1 and hydroxyalkyl (meth)acrylates which are ∼4 chain alkyl.

As (meth)acrylamide compound, For example, (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth) Acrylamide, Nn-butylacryl(meth)amide, Nt-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N- Dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzyl (meth)acrylamide, diacetone acrylamide, etc. are mentioned.

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

The content of the nonionic water-soluble unit in the block copolymer (I) is based on the total amount of the block copolymer (I) from the viewpoint of developability when, for example, a column spacer is formed using the coating film forming composition described later. relative to, preferably 40 to 80% by weight, more preferably 45 to 75% by weight, still 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 at least one acid group selected from the group consisting of a carboxylic acid group, a sulfonic acid group and a phosphoric acid group (hereinafter simply referred to as “acid group”) ) and an anionic water-soluble organic acid compound having a polymerizable group in one molecule are preferable. Moreover, Preferably a polymeric group is an alkenyl group, More preferably, it is 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 can be used individually by 1 type or in combination of 2 or more type.

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, 2-methylitaconic acid, sorbic acid, α,β- methylglutaric acid, maleic anhydride, itaconic anhydride, acrylic acid anhydride, methacrylic acid anhydride, and salts thereof, and the like.

Examples of the sulfonic acid compound include vinylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallylsulfonic acid, (meth)allyloxybenzenesulfonic acid, 2-allyloxy-2-hydroxypropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-methacryloyloxyethanesulfonic acid and salts thereof, and the like.

Examples of the phosphoric acid compound include 2-methacryloyloxyethyl phosphoric acid, 2-methacryloyloxyethylphenyl phosphoric acid, 10-methacryloyloxydecamethylene phosphoric acid, 4-vinylbenzyl phosphoric acid, and pentaacryloyldipentaerythritol. Phosphoric acid and its salts, 2-(meth)acryloyloxyethyl phosphate, diethyl (vinylphenyl) phosphate, 4-vinylbenzene phosphinic acid diethyl ester, diphenyl-2-methacryloyloxyethyl phosphate, etc. of phosphoric acid ester, etc. are mentioned.

Since the phosphoric acid group can also be a polymerizable group [=P(O)(OH)], phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphoric acid esters, such as tricrezyl phosphate, crezyl diphenyl phosphate, and octyl diphenyl phosphate, may also be used as an anionic water-soluble organic acid compound.

The content of the anionic water-soluble unit in the block copolymer (I) is preferably 0.5 to 20 wt%, more preferably 0.5 to 20 wt%, based on the total amount of the block copolymer (I) from the viewpoint of dispersibility and the like. 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). Moreover, when the hydrophilicity of a nonionic water-insoluble unit is higher, there exists an effect|action which improves the hydrophilicity of a polymer block (B). The nonionic water-insoluble compound is not particularly limited as long as it is an organic compound that is nonionic and water-insoluble and has a polymerizable group. At least one hydrophobic group selected from the group consisting of a chain hydrocarbon group, a cyclic hydrocarbon group, and an aromatic hydrocarbon group (hereinafter A nonionic water-insoluble organic compound having a "hydrophobic group" in some cases) and a polymerizable group in one molecule is preferable. In addition, a polymeric group becomes like this. Preferably it is an alkenyl group, More preferably, it is 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, an aryl (meth) acrylate, and a styrenic compound. . These can be used individually by 1 type or in combination of 2 or more type.

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, glycidyl (meth) acrylate, the number of carbon atoms in the alkyl moiety and alkyl (meth)acrylates having 1 to 17.

As cycloalkyl (meth)acrylate, for example, cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate and cycloalkyl (meth)acrylates having 3 to 10 carbon atoms in the cycloalkyl moiety, such as , cyclooctyl (meth)acrylate, cyclononyl (meth)acrylate, and cyclodecyl (meth)acrylate.

As an aryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. are mentioned, for example.

Examples of the styrene compound include styrene, α-methylstyrene, methylstyrene, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-aminostyrene, 4-dimethylaminostyrene, and methoxystyrene. , chloromethylstyrene, chlorostyrene, 4-tert-butylstyrene, vinyltoluene, vinyltoluene, etc., 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 selected from the group consisting of The styrene compound which has at least 1 as a substituent is mentioned.

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

As described above, in the block copolymer (I), as a preferred form of the content of each unit, 5 to 30% by weight of cyclic amine units (more preferably 5 to 25% by weight, still more preferably 7 to 20% by weight) , 40 to 80% by weight of nonionic water-soluble units (more preferably 45 to 75% by weight, still more preferably 45 to 73% by weight) and 0.5 to 20% by weight of anionic water-soluble units (more preferably 0.5 to 15% by weight) %, more preferably from 1 to 10% by weight), cyclic amine units, nonionic water-soluble units and anionic water-soluble units in the same proportions as those of the first form, and nonionic water-insoluble units from 10 to It has a second form further comprising 50% by weight (more preferably 15 to 45% by weight, still more preferably 20 to 40% by weight).

The block copolymer (I) can be synthesized using, for example, a known polymerization method such as living (controlled) radical polymerization. Living radical polymerization methods can be roughly divided into ATRP (atom transfer radical polymerization) method, RAFT (reversible addition cleavage type chain transfer polymerization) method, NMP (nitroxide mediated radical polymerization) method, TERP (organotellurium mediated radical polymerization) method, RTCP (Reversible Transfer Catalyst Polymerization), etc., may be appropriately selected and synthesized.

Living radical polymerization is, for example, -100 to 250 ° C., preferably 0 to 200 ° C., more preferably room temperature to 200 ° C., still more preferably 50 to 150 ° C. in a solvent-free (block polymerization) or It can be carried out in a solvent.

As the solvent, a solvent that is inert to the polymerization reaction can be used without any particular limitation. For example, hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform , ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, nitriles such as acetonitrile, propionitrile, and benzonitrile solvents, ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide A solvent etc. are mentioned.

In order to produce the block copolymer (I) according to the living radical polymerization method, a method in which a predetermined amount of a raw material compound serving as a basis for each structural unit is sequentially added, one polymer block synthesized in advance is used as a polymer polymerization initiator in the other The method of superposing|polymerizing the polymer block of , the method of bonding the polymer block superposed|polymerized separately by reaction, etc. are mentioned. In the case of sequential addition of the raw material compound, it is preferable to inject the next raw material compound when the conversion ratio of the raw material compound injected earlier is 80 to 95%. The conversion ratio is determined according to, for example, a gas chromatograph method, a nuclear magnetic resonance spectrum method, a gravimetric method, or the like.

As a method for polymerizing one polymer block synthesized in advance as a polymer initiator for the other polymer block, for example, at a desired time point during polymerization of one polymer block, once the temperature is lowered to a living state, polymerization is stopped, After distilling off the raw material compound of a polymer block under reduced pressure, the method of adding the raw material compound of the other polymer block is mentioned. Also in the case of polymerizing the third and subsequent polymer blocks, the same operation may be performed.

Although there is no limitation in particular as for the molecular weight of a resin type dispersing agent, 1000-100000 of weight average molecular weights are preferable. However, from the viewpoint of dispersibility, the above-mentioned block copolymer (I) has a peak top molecular weight, not a weight average molecular weight, of preferably 30 to 1 million, more preferably 30 to 500,000, still more preferably 4000 to 100,000, particularly preferably from 4000 to 50,000, and most preferably from 5000 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 resinous dispersant are determined by the functional group contained in the resin constituting the resinous dispersant and the content thereof. The acid value (acid value in terms of solid content) can be obtained by, for example, a method conforming to DIN EN ISO 2114, and the amine value (amine value in terms of solid content) can be determined, for example, by a method conforming to DIN 16945 can be saved Although the acid value of an acid value type dispersing agent is not specifically limited, 20-150 mgKOH/g is preferable, Although the amine value of an amine value type dispersing agent is not specifically limited, 5-30 mgKOH/g is preferable. Although there is no limitation in particular in the case of a dispersing agent with an acid value and an amine value larger than 0, An acid value of 5-50 mgKOH/g is preferable, and an amine value of 5-50 mgKOH/g is preferable. However, with respect to the above-mentioned 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, still more preferably 25 to 75 mg It is KOH/g, and an amine titer is 40 mgKOH/g or more, More preferably, it is 40-100 mgKOH/g, More preferably, it is 42-98 mgKOH/g.

As the surfactant type dispersant, depending on the ionicity, anionic active agents (anionic type) such as naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, and nonionic active agents such as polyoxyethylene alkyl ether (nonionic type), an alkylamine salt, and a cation activator (cation type), such as a quaternary ammonium salt, etc. are mentioned. Various surfactant-type dispersants are also marketed, Although the specific example is as follows, it is not limited to these.

Produced by Kao Corporation: Demol N, RN, MS, SN-B, Emulgen 120, 430, Acetamine 24, 86, Cotamine 24P,

Nikko Chemicals Co., Ltd. Manufactured by: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25,

Daiichi Kogyo Seiyaku Co., Ltd. Manufactured by: Flysurf AL, A208F,

Manufactured by Lion Corporation: Aquad C-50, T-28, T-50, etc.

One type may be sufficient as the above dispersing agents, and what combined 2 or more types may be sufficient as it. In the case of combining two or more types, for example, in the case of a resin-type dispersant, those having different resins, combining an acid value type and an amine value type, and in the case of a surfactant type dispersing agent, those having different ionicity (eg, combination of an anionic type and a nonionic type), but is not limited thereto.

From the viewpoint of dispersion stability, the content (solid content or active ingredient) of the dispersant in the black pigment composition is preferably 2 to 20 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight in total of the black organic pigment and the colored organic pigment. Do. However, what is necessary is just to adjust the optimal addition amount of a dispersing agent suitably according to the combination etc. with the kind of organic pigment to be used. In addition, when using the pigment derivative mentioned later, content of this colored organic pigment means the total amount including a pigment derivative.

In the embodiment of the present invention, in addition to the dispersing agent described above, a pigment derivative may be used as a dispersing aid in order to more stably disperse the black organic pigment and the colored organic pigment in the black pigment composition. When a pigment derivative is used, a portion having affinity with the dispersing agent or a pigment derivative having a polar group introduced thereto is adsorbed to the surface of each organic pigment, which may serve as an adsorption point for the dispersant. In that case, since the dispersing agent can be made to exist on the surface of the organic pigment through the pigment derivative, each organic pigment can be more stably dispersed in the black pigment composition as fine particles. Moreover, the re-agglomeration 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, when using a pigment derivative, it is preferable to determine the kind and usage-amount in consideration of this point and dispersibility.

A pigment derivative is specifically, the compound which made the organic pigment into a parent structure, and introduce|transduced the acidic group, the basic group, and the aromatic group as a substituent in the side chain. The organic pigment serving as the parent skeleton is, specifically, a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindoline pigment, an isoindolinone pigment, a quinoline pigment, and a diketopyrrolopyrrole. A pigment, a benzimidazolone pigment, a dioxazine type pigment, etc. are mentioned. The parent skeleton also includes pale yellow aromatic polycyclic compounds, which are not generally called dyes, such as naphthalene-based, anthraquinone-based, triazine-based and quinoline-based compounds.

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

From a viewpoint of dispersion stability, 2-15 weight part is preferable with respect to a total of 100 weight part of a black organic pigment and a colored organic pigment, and, as for content (solid content) of the pigment derivative in a black pigment composition, 5-10 weight part is more preferable. However, what is necessary is just to adjust the optimal addition amount of a pigment derivative suitably according to the combination with the kind of organic pigment and dispersing agent to be used, the influence on the characteristic of a liquid crystal cell, etc. In addition, "a total of 100 weight part of a black organic pigment and a colored organic pigment" means the total amount which does not contain a pigment derivative.

The particle diameters of the black organic pigment and the colored organic pigment can be appropriately determined depending on the application or the like, and those having an average particle diameter of approximately primary particles, ie, an average primary particle diameter of 20 to 200, can be preferably used. Moreover, for example, in the use of a column spacer or a black matrix, it is more preferable that an average primary particle diameter is 20-80 nm from a viewpoint of obtaining a higher OD value at the time of coating film formation. In addition, an average primary particle diameter is computable as an arithmetic mean of the largest width of a plurality (eg, 50) primary particles during imaging with a transmission electron microscope (TEM), for example.

In the embodiment of the present invention, depending on the type of the organic pigment, the milling treatment may be performed beforehand from the viewpoint of adjusting the average particle diameter or the like. The milling treatment can be performed according to a conventional method depending on the type of organic pigment or the like. As such a milling process, the solvent salt milling method etc. are mentioned, for example.

In embodiment of this invention, in addition to the dispersing agent mentioned above from a viewpoint of improving more dispersibility, such as an organic pigment in a black pigment composition and a black coating film formation composition, you may use dispersion resin as a dispersion aid. It is suitable to use this dispersion resin especially when the coating film formation component used in the black coating film formation composition mentioned later is a polymeric component, especially a photopolymerizable component. As a dispersion resin usable in this invention, alkali-soluble resin mentioned later is mentioned. The resin type of the same kind as alkali-soluble resin used for the black coating film formation composition may be sufficient as dispersion resin, and the resin type of a different type may be sufficient as it. The content of the dispersion resin is preferably 10 to 50 parts by weight with respect to 100 parts by weight in total of the black organic pigment and the colored organic pigment. In addition, when using a pigment derivative, content of a black organic pigment and a colored organic pigment means the total amount including a pigment derivative.

The solvent that can be used in the present invention can be appropriately selected according to the type of coating film forming component described later, and for example, various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic solvents. can be heard Among these, the organic solvent chosen from an aromatic type, a ketone type, an ester type, and a glycol ether type is preferable from a viewpoint of coating-film formation property. The number of organic solvents may be one, and what combined 2 or more types may be sufficient as them.

As an aromatic organic solvent, aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene, are mentioned, for example.

Examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, 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, ethyl glycol acetate, and propylene glycol monomethyl ether acetate (PMA). , propylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, monochloromethyl acetate, monochloroethyl acetate, monochlorobutyl acetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, Ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butylene glycol diacetate, etc. are mentioned.

As the glycol ether 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 water-soluble glycol ethers such as ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether;

Ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl Water-insoluble glycol ethers, such as ether, dipropylene glycol propyl ether, and propylene glycol methyl ether propionate, etc. are mentioned.

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, pentamethylene 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-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6- Hexanediol, glycerin, mesoerythritol, pentaerythritol, etc. are mentioned.

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

When using for preparation of the black coating film formation composition mentioned later, the addition amount of a solvent can be added so that the solid content concentration containing a black organic pigment etc. may become 50 to 85 weight% from a viewpoint of handleability.

In embodiment of the black pigment composition of this invention, you may contain other additives other than the component mentioned above.

A black pigment composition can be obtained by adding and disperse|distributing each component mentioned above to well-known dispersers, such as a bead mill, a sand mill, and a disper, for example. That is, a black pigment composition is the dispersion which solid content, such as a black organic pigment and a colored organic pigment, was disperse|distributed as particle|grains to the solvent. Here, the particle means secondary particles formed by aggregation of primary particles of the aforementioned black organic pigment or colored organic pigment. In addition, the method of addition of each component is not specifically limited, You may carry out the dispersion process of mixing each component simultaneously. Moreover, after dispersing what mixed each organic pigment and a solvent, a dispersing agent and/or another arbitrary component, preparing a pigment composition for every pigment, and mixing these pigment compositions, you may disperse|distribute again. Any other method is fine.

The average particle diameter of the particles dispersed in the black pigment composition obtained as described above (hereinafter, may be referred to as "dispersion average particle diameter") is not particularly limited, but those of approximately 30 to 300 nm can be preferably used. . Moreover, for example, in the use of a column spacer or a black matrix, it is more preferable that a dispersion average particle diameter is 30-150 nm from a viewpoint of the surface smoothness of a coating film. In addition, the dispersion average particle diameter can be measured with a particle size measuring device, for example. Moreover, as a particle size measuring device, the Otsuka Electronics Co., Ltd. make, FPAR-1000, etc. are mentioned.

<Black coating film forming composition>

Embodiment of the black coating film formation composition of this invention contains the black pigment composition and coating film formation component mentioned above. Thus, by including the black pigment composition as mentioned above, visible light can be effectively absorbed in the area|region of wavelength 380nm - 750nm by the action|action of the above-mentioned black organic pigment in a coating film. Moreover, absorption in the ultraviolet region (region of wavelength shorter than 380 nm) and infrared region (region of wavelength longer than 750 nm) can be suppressed to such an extent that there is no influence on the manufacture of the flat panel. In addition, by combining with at least two types of colored organic pigments other than the black organic pigment, light in the visible region can be blocked without using black carbon in the coating film, and absorption of ultraviolet and infrared rays can be suppressed more effectively than in the visible region. can Moreover, the solvent resistance of a coating film can also be improved by the action|action of the above-mentioned black organic pigment. In addition, the influence on the characteristic of the liquid crystal cell resulting from black carbon can also be avoided.

As a coating film formation component usable in embodiment of the black coating film formation composition of this invention, solvent resistance is good, the influence on the characteristic of a liquid crystal cell is suppressed, If it is a component which can form a coating film, there is no particular limitation, A polymerizable component may be sufficient and a polymer may be sufficient. As a polymerizable component, since it is easy to pattern by image development (negative image development), a photopolymerizable component is preferable. Further, as the polymer, for example, a thermoplastic urethane-based resin, (meth)acrylic-based resin, polyamide-based resin, polyimide-based resin, styrene/maleic acid-based resin, polyester-based resin, silicone resin, cardo resin, etc. can be heard

A photopolymerizable compound and a photoinitiator are included as a photopolymerizable component which can be used. As such a photopolymerizable compound and a photoinitiator, the thing of Unexamined-Japanese-Patent No. 2009-179789 can be used, for example. Specifically, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. These compound groups are widely known in the art, and in the present invention, they can be used without particular limitation. Photopolymerizable compounds have chemical forms such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

Examples of the monomer and its copolymer include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably For silver, esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and amides of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound are used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, and a monofunctional or polyfunctional carboxyl group A dehydration-condensation reaction product with an acid and the like are also suitably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, and thiols, and also a halogen group, tosyloxy group, etc. Substitution products of unsaturated carboxylic acid esters or amides having a sexual substituent and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. In addition, as another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, etc. instead of the unsaturated carboxylic acid.

In addition, although these specific examples are as described in Unexamined-Japanese-Patent No. 2009-179789, As a specific example of the monomer of the ester of an aliphatic polyhydric alcohol compound and unsaturated carboxylic acid, As an acrylic acid ester, ethylene glycol diacrylate, triethylene Glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri(acryloyloxy Propyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate; Polyester acrylate oligomer, isocyanuric acid EO modified triacrylate, and the like.

About these addition polymeric compounds, the detail of usage methods, such as the structure, single use or combined use, addition amount, can be set arbitrarily according to the performance design of the final black coating film formation composition.

For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in many cases, more than bifunctionality is preferable. In addition, in order to increase the strength of the cured film, it is preferable to have three or more functions, and by using a combination of a different number of functions and a different polymerizable group (eg, acrylic acid ester, methacrylic acid ester, styrene-based compound, vinyl ether-based compound), A method of adjusting both sensitivity and intensity is also effective.

In addition, with respect to the compatibility and dispersibility of other components in the black coating film-forming composition (eg, binder polymer such as alkali-soluble resin, photopolymerization initiator, colorant (pigment)), the selection and usage method of the addition polymerization compound are important factors, such as , compatibility can be improved by use of a low-purity compound or by using two or more types of combined use.

In addition, there may be a case where a specific structure is selected for the purpose of improving adhesion to a substrate or the like. A photopolymerizable compound becomes like this with respect to the nonvolatile component in a coating-film formation composition, Preferably it is 5-70 weight%, More preferably, 10-60 weight% is contained. In addition, these may be used independently or may use 2 or more types together. In addition, as for how to use a photopolymerizable compound, an appropriate structure, compounding, and addition amount can be arbitrarily selected from viewpoints of the magnitude of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, etc.

As said photoinitiator, what was described in Unexamined-Japanese-Patent No. 2009-179789 can be used.

That is, the photopolymerization initiator that can be suitably used in the present invention includes, for example, acetophenone-based, ketal-based, benzophenone-based, benzoin-based, benzoyl-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 include, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4 as specific examples of the benzophenone-based photopolymerization initiator. '-dichlorobenzophenone etc. are mentioned.

As content in the black coating film formation composition of a photoinitiator, 0.1-10.0 mass % is preferable with respect to the total solid of a black coating film formation composition, More preferably, it is 0.5-5.0 mass %. When the content of the photopolymerization initiator is within the range, the polymerization reaction proceeds favorably and a film having good strength can be formed.

In embodiment of the black coating film formation composition which concerns on this invention, when a photopolymerizable component is included, you may contain alkali-soluble resin other than the black pigment composition and photopolymerizable component mentioned above.

When an alkali-soluble resin is contained in the black coating film-forming composition, for example, in the production of a column spacer by a photolithography process, when the black coating film-forming composition is applied to pattern formation, the pattern formability can be further improved. .

As such alkali-soluble resin, the thing of Unexamined-Japanese-Patent No. 2009-179789 can be used. Briefly, the alkali-soluble resin that can be used in the present invention is, for example, a linear organic high molecular polymer, wherein at least one alkali-soluble in a molecule (preferably a molecule having an acrylic copolymer or a styrenic copolymer as a main chain) is It can select suitably from alkali-soluble resin which has a group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) which accelerates|stimulates. Among these, more preferably, it is soluble in an organic solvent and can develop with weak alkali aqueous solution.

As a preferable thing of alkali-soluble resin, the copolymer of (meth)acrylic acid and the other monomer copolymerizable with this is mentioned especially. Here, (meth)acrylic acid is a generic term that combined acrylic acid and methacrylic acid, and (meth)acrylate is a generic name of acrylate and methacrylate in the same manner below.

As another monomer copolymerizable with (meth)acrylic acid, an alkyl (meth)acrylate, an aryl (meth)acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atoms of the alkyl group and the aryl group may be substituted with 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, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) ) acrylate, cyclohexyl (meth)acrylate, and the like.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylic rate, polystyrene macromonomer, polymethylmethacrylate macromonomer, CH ₂ =CR ⁵ R ⁶ , CH ₂ =C(R ⁵ )(COOR ⁷ ) (where R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and R ⁶ represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ⁷ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.) and the like.

These copolymerizable other monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

As for the weight average molecular weight of alkali-soluble resin, 5000-50000 are preferable from a developable viewpoint.

Although various alkali-soluble resins are marketed and the specific example is as follows, it is not limited to these.

Showa Kobunshi Co., Ltd. Manufactured by: Lipoxy SPC-2000;

Mitsubishi Rayon Co., Ltd. Manufactured by: Diana NR series,

Diamond hamrock Co.Ltd., manufactured by: Photomer 6173 (polyurethane acrylic oligomer containing COOH);

Osaka Yuki Chemical Co., Ltd. Manufactured by: Viscot R-264, KS Resist 106, SOP-005,

Daisel Chemicals Co., Ltd. Manufactured by: Cyclomer P series, Fraxel CF200 series,

Daicel Yushibi Co., Ltd. Manufactured by: Ebecryl 3800,

Corporation Nihon Shokubai: RD-Y-503, etc.

As content in the black coating film formation composition of alkali-soluble resin, 1 to 20 weight% is preferable in the total solid of a black coating film formation composition, More preferably, it is 2 to 15 weight%, Especially preferably, 3 -12% by weight. When contained in a black pigment composition as dispersion resin, it is a total amount.

In embodiment of the black coating film formation composition which concerns on this invention, when a photopolymerizable component is included, you may contain a solvent other than the black pigment composition mentioned above, a photopolymerizable component, and alkali-soluble resin. By using a solvent, it can prepare suitably.

Examples of the solvent include esters such as ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters. , methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-Methoxy methyl propionate, 3-methoxyethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, 2-oxymethyl methyl propionate, 2-oxypropionate ethyl, 2-oxypropionate propyl, 2-methoxy Methyl propionate, 2-methoxyethylpropionate, 2-methoxypropylpropionate, 2-ethoxymethylpropionate, 2-ethoxypropionate ethyl, 2-oxy-2-methylpropionate, 2-oxy-2-methylpropionate ethyl , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobu methyl carbonate, ethyl 2-oxobutanoate, etc.; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve 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, and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; aromatic hydrocarbons such as toluene, xylene; and the like.

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

As the content of the solvent in the black coating film-forming composition, in consideration of the type and content of the solvent in the black pigment composition, the total solid content (nonvolatile component) content in the black coating film-forming composition is 15 to 50% by weight. it is preferable

When using a polymer as a coating-film formation component, you may use a solvent similarly to the case of using a photopolymerizable component. As such a solvent, the thing which can be used for the black pigment composition mentioned above, and the thing which can be used with a photopolymerizable component can be used.

Also in this case, as content in the black coating film formation composition of a solvent, the kind and content of the solvent in a pigment dispersion are considered, and the total solid content (non-volatile component) content in a black coating film formation composition is 15 to 50 weight%. It is preferable to be included so that

In the black coating film-forming composition of the present invention, if necessary, a dispersing aid, a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a surfactant, an adhesion promoter, an antioxidant, You may add various additives, such as an aggregation inhibitor and a surface conditioning agent (leveling agent). When contained in a black pigment composition, what is necessary is just to adjust an addition amount.

The black coating film formation composition which concerns on this invention is obtained by adding a coating film formation component to a black pigment composition, and stirring with a disper etc.

As mentioned above, the black coating film formation composition which concerns on this invention absorbs light only in a visible region without using black carbon in a coating film, and has favorable solvent resistance. Moreover, alignment using infrared rays in a manufacturing process is possible. Moreover, when a photopolymerizable component is used as a coating-film formation component, the polymerization reaction by an ultraviolet-ray is favorable, and there is also no influence on a manufacturing process. Therefore, for example, it is especially suitable as a black column spacer of the flat panel used for a liquid crystal display device. In addition, it is suitable also as a black matrix of the color filter of an image display apparatus.

[Example]

(Preparation Example 1) Preparation 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 Irgajin Red L3551HD) and 10 parts by weight of thionyl chloride were added, reacted at 60° C. for 5 hours, and then 2 liters of After discharging into ice water, passing through and washing with water, 26.9 parts by weight of a chlorosulfonate of Pigment Red 255 was obtained. This is dispersed in 200 parts by weight of water, 8.3 parts by weight of diethylaminopropylamine is added, reacted at 80° C. for 1 hour, followed by filtration, washing with water, drying and pulverization to obtain a pigment derivative 1 represented by the following formula (3) 31.5 parts by weight were obtained.

(Preparation Example 2) Preparation of Pigment Derivative 2

With respect to 200 parts by weight of chlorosulfonic acid, 20.4 parts by weight of PIGMENT VIOLET 23 (manufactured by DIC, product name Violet 23 Crude) and 20 parts by weight of thionyl chloride were added, reacted at 60° C. for 5 hours, and then 2 liters of It discharged|emitted in ice water, draining and washing with water were performed, and 27.2 weight part of chlorosulfonates of Pigment VIOLET 23 were obtained. This is dispersed in 200 parts by weight of water, 15 parts by weight of diethylaminopropylamine is added, reacted at 80° C. for 1 hour, followed by filtration, washing with water, drying and pulverization to obtain the pigment derivative 2 represented by the following formula (4) 31.9 parts by weight were obtained.

(Preparation Example 3) Preparation of Pigment Derivative 3

After injecting 200 parts by weight of 88% sulfuric acid into a 300 ml three-necked flask, 20 parts by weight of PIGMENT RED 255 (manufactured by BASF, product name Irgajin Red L3551HD) was injected under water cooling, and reacted at 40 to 45° C. for 3 hours. Sulfonation was performed. Next, the synthetic stock solution is discharged into a beaker containing 1 L of water, filtered, the paste is transferred to a 2 L beaker, 1.5 L of water is added, stirred at 60 to 70° C. for 1 hour, and then fully dispersed. , 1 part by weight of cetyltrimethylammonium chloride was added to form a salt. After stirring for about 10 minutes, the paste obtained by filtering and washing with water was dried at 100°C to obtain a pigment derivative 3 represented by the following formula (5).

(DM-3)

(Preparation Example 4) Preparation of Pigment Derivative 4

In 200 parts by weight of chlorosulfonic acid, 40.2 parts by weight of copper phthalocyanine crude (manufactured by Shukaitoyo, product name T-99 crude blue, Pigment Blue 15:3) and 10 parts by weight of thionyl chloride were added, and reacted at 60° C. for 5 hours. After washing, it was discharged into 2 liters of ice water, and washed with water to obtain 47 parts by weight of a chlorosulfonate of Pigment Blue 15. This was dispersed in 200 g of water, 8.3 parts by weight of dimethylaminopropylamine was added, reacted at 80° C. for 1 hour, followed by filtration, washing with water, drying and pulverization, and 51.5 weight of the pigment derivative 4 represented by the following formula (6) got wealth

(Preparation Example 5) Preparation of resin-type dispersant 1

Butyl acrylate (nonionic water-soluble organic compound) 192.8 parts by weight, methoxypolyethylene glycol (n≒9) methacrylate (nonionic water-soluble organic compound) 321.9 parts by weight, acrylic acid (anionic water-soluble organic compound) 59.2 parts by weight, N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxylprop-2-yl)hydroxyamine (polymerization modifier) 15.0 weight Part, 370 parts by weight of propylene glycol monomethyl ether acetate (reaction solvent) is poured into a 2 L capacity stainless steel separable flask, and while nitrogen bubbling and stirring, the system is heated to 125 ° C in an oil bath, and after the temperature rise is finished It was made to react for 6.5 hours, and the polymer block B was synthesize|combined. A small amount of the contents was sampled and GPC measurement was performed. As a result, 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, followed by nitrogen bubbling and stirring, followed by reaction at 125° C. for 4 hours. When the contents were sampled and GPC measurement was performed, the peak top molecular weight was 10140 and Mw/Mn was 1.45.

Subsequently, the system internal temperature was raised to 210 degreeC, the system internal pressure was reduced to 2.0 kPa, the solvent was distilled off, and the block copolymer (I) was taken out. As a result of GPC measurement of the obtained block copolymer (I), the peak top molecular weight was 10990 and Mw/Mn was 1.49. In addition, the acid value was 74.0 mgKOH/g, and the amine value was 52.9 mgKOH/g.

(Preparation Example 6) Preparation of blue organic pigment 2

C.I. Pigment Blue 15:6 (trade name: FASTOGEN Blue EP-207, manufactured by DIC) 300 parts by weight, neutral anhydrous algae (average particle size about 20 μm, manufactured by Mitaji Rika Chemicals Co., Ltd.) 3000 parts by weight, diethylene as a solvent 750 parts by weight of glycol (manufactured by Nippon Shokubai Co., Ltd.) was added to a 5 L kneader (manufactured by Moriyama Co., Ltd., S5-2GH-S type), and kneaded and ground for 9 hours while controlling the temperature so that the temperature of the kneaded product was 50 ° C. did The kneaded and pulverized product was stirred and dispersed in 30 L of warm water at 40°C, then transferred to a Nutche for filtration, and washed with water until complete removal of the black pepper, to obtain 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 Rico Co., Ltd., small pulverizer, sample mill SK-M2) to obtain 330 parts by weight of blue organic pigment 2. The average particle diameter of the primary particles of the obtained blue organic pigment 2 was 40 nm. This average particle diameter is the result of measuring and calculating from imaging by TEM.

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

(a) at least one type of black organic pigment selected from the formulas (1) and (2)

Black organic pigment 1: Lumogen Black FK4280 manufactured by BASF

(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 Corporation make, PERRINDO Maroon 179 229-6438, Pigment Red 179 (PR179)

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

Red organic pigment 3: Synylex DPP Red SR2P, Pigment Red 254 (PR254) manufactured by Scenic Co., Ltd.

Red organic pigment 4: BASF company make, Irgazine Red L 3551 HD, Pigment Red 255 (PR255)

Blue organic pigment 1: DIC Corporation make, EP-210, Pigment Blue 15:6 (PB15:6)

Blue organic pigment 2: Preparation 6

Blue organic pigment 3: BASF Corporation make, Heliogen Blue D7490, Pigment Blue 16 (PB16)

Blue organic pigment 4: BASF Corporation make, Paliogen Blue EH1900, Pigment Blue 60 (PB60)

Purple organic pigment: manufactured by DIC Corporation, PERRINDO VIOLET 29 229-4050, Pigment Violet 29 (PV29)

(d) dispersants

Resin-type dispersant 1: Preparation Example 5

Resin type dispersant 2: Biccheme Japan Co., Ltd. make, Disperbyk LPN22102, acrylic resin, acid value 0 mgKOH/g, amine value 32 mgKOH/g

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

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

(e) dispersing aids

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

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

(f) solvents

Propylene glycol monomethyl ether acetate (PMA)

(g) coating film forming component

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

(Examples 1 to 7, Comparative Example 1)

<Preparation of black pigment composition>

Each component was mixed so that it might become the composition (a solid content basis except a solvent) shown in Table 1, it disperse|distributed with a bead mill, and obtained the black pigment composition. The grinding medium of the bead mill was added so that it might become 400 weight part with respect to 100 weight part of mill base amounts using the zirconia bead with a particle diameter of (phi) 0.3 mm. This medium was removed after dispersion treatment. In addition, the composition shown in Table 1 is a weight part.

<Preparation of the composition for forming a black coating film>

The above-mentioned coating film formation resin was added to each obtained black pigment composition, it stirred with a disper, and the black coating film formation composition was obtained. The amount of the coating film-forming resin added was such that the total of the dispersant, the dispersion resin and the coating film-forming resin was 200 parts by weight with respect to 100 parts by weight in total of all organic pigments (including the pigment derivative) contained in each black pigment composition. .

<Formation of coating film>

Using each obtained black coating film formation composition, it spin-coated on the glass plate so that the film thickness might be set to 1 micrometer and 3 micrometers about each composition. As a prebaking, it heated at 90 degreeC, 2.5 minutes, and 230 degreeC, 30 minutes as a post-baking, and formed the coating film.

<Measurement of optical density (OD value)>

It measured with the OD measuring apparatus (X-Rite 361T) using the coating film which adjusted to the film thickness of 3 micrometers and was formed. The OD values of the three coating films in which the film thicknesses were changed centering on 1 µm were measured, and the value at a film thickness of 1 µm from the slope and intercept was used as the OD value. An evaluation result is 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, followed by coloring of the NMP solution. The presence or absence of was confirmed by visually inspecting. An evaluation result is shown in Table 1. In Table 1, a thing in which there was no coloring was shown as "○", and a thing in which coloring was observed was shown as "x".

(Example 8)

<Preparation of black pigment composition>

Each component was mixed so that it might become the composition (a solid content basis except a solvent) shown in Table 2, it disperse|distributed with a bead mill, and obtained the pigment compositions 1-3 about each pigment. The grinding medium of the bead mill was added so that it might become 400 weight part with respect to 100 weight part of mill base amounts using the zirconia bead with a particle diameter of (phi) 0.3 mm. This medium was removed after dispersion treatment. In addition, the composition shown in Table 2 is a weight part. 13.3 g of pigment composition 1, 1.25 g of pigment composition 2, and 2.55 g of pigment composition 3 were mixed and stirred with a disper to obtain a black pigment composition.

<Preparation of the composition for forming a black coating film>

18.72 g of coating film formation resin mentioned above was added to the obtained black pigment composition, it stirred with a disper, and the black coating film formation composition was obtained.

<Formation and evaluation of coating film>

It carried out similarly to Example 1, and formed the coating film from which film thickness differs. Using the obtained coating film, it carried out similarly to Example 1, and evaluated the OD value and solvent resistance. The OD value was 1.24 (/µm). Moreover, there was no coloring of NMP.

From the results of Examples 1 to 8 and Comparative Example 1, the Example had an OD value higher than that of the Comparative Example, and there was no coloring of NMP in the Example. Therefore, by using a specific black organic pigment and at least two types of colored organic pigments as in Examples, the OD value is high, that is, light absorption is good in all wavelengths of the visible region, and furthermore, solvent resistance is good. it can be seen that In addition, in each pigment used in Examples 1-8, it is clear to those skilled in the art that absorption of ultraviolet-ray and infrared rays is suppressed rather than visible light. Moreover, from the contrast of Examples 1-7 and Example 8, when a predetermined dispersing agent is used, it is possible to reduce use of a dispersing agent and a pigment derivative.

Claims (4)

At least one type of black organic pigment selected from the following formulas (1) and (2), at least two types of colored organic pigments other than the black organic pigment, a dispersant, and a solvent,
The black pigment composition in which at least 2 types of colored organic pigments other than the said black organic pigment are chosen from a red organic pigment, a blue organic pigment, and a purple organic pigment.

The organic pigment according to claim 1, wherein the red organic pigment is at least one selected from the following group (a), the blue organic pigment is at least one selected from the following group (b), and the purple organic pigment is selected from the following group (b): c) at least one black pigment composition selected from the group;
(a) group:
CI Pigment Red 149, 179, 254, 255,
(b) group:
CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 60,
(c) group:
CI Pigment Violet 23, 29. A black coating film forming composition comprising the black pigment composition according to claim 1 or 2 and a coating film forming component. delete