KR20210134230A - Pigment dispersion composition for black matrix, resist composition for black matrix and black matrix - Google Patents

Abstract

Provided is a pigment dispersion composition for a black matrix capable of forming a black matrix with excellent sealing strength without degrading a surface resistance value even after high-temperature and long-term post-baking. The present invention provides the pigment dispersion composition for a black matrix comprising a black colorant, an epoxy resin, an oxazine compound, and an organic solvent, wherein the epoxy resin has an aromatic ring.

Description

The pigment dispersion composition for black matrices, the resist composition for black matrices, and a black matrix TECHNICAL FIELD

This invention relates to the pigment dispersion composition for black matrices, the resist composition for black matrices, and a black matrix.

In an image display device using liquid crystal or plasma, a light shielding film (black matrix) is provided in gaps in the coloring pattern in the display area of the screen or at the edges of the display area periphery, or on the external light side of the TFT in a liquid crystal display using TFT.

In addition, in the liquid crystal display device, mainly leakage light from the backlight, and in the plasma display device, the blur caused by the turbidity of each color light is prevented from being reflected on the screen, thereby improving the display characteristics (contrast and color purity).

For example, a color filter used to convert white light of a backlight of a liquid crystal display device into colored light is a process in which pixels of different colors of red, green, and blue are sequentially placed on the surface of a transparent substrate such as a glass or plastic sheet having a black matrix formed thereon. As such, it is manufactured by a method of forming a pattern such as a stripe type or a mosaic type.

Also, a color filter having a black matrix is used as a light shielding film in a touch panel that combines an image display device and a position input device. Until now, it was generally formed on the opposite side of the sensor substrate with a cover glass interposed therebetween. However, as the demand for weight reduction of the touch panel increases, the development of a technology for simultaneously forming a light-shielding film and a touch sensor on the same side of the cover glass is in progress to achieve further weight reduction.

For example, in Patent Document 1, as a pigment dispersion for a black matrix containing acidic carbon black, a pigment dispersant, a polyfunctional epoxy compound, and a solvent, the polyfunctional epoxy compound is 0.1 to 50 parts by mass based on 100 parts by mass of the acidic carbon black. A pigment dispersion for a black matrix characterized in that it is contained in parts by mass is disclosed.

Recently, image display devices are intended to be used in various scenes such as mobile applications.

Accompanying the expansion of the use of such an image display device, a more robust black matrix has been demanded.

As a method of making a black matrix more rigid, the method of performing post-baking for a high temperature and a long time may be used.

However, in the conventional pigment dispersion for black matrices, when post-baking was performed for a high temperature and a long time, there existed a problem that a surface resistance value would fall, and there existed room for improvement.

Moreover, as a method of making a black matrix more rigid, forming the black matrix excellent in sealing strength is also examined.

In the conventional pigment dispersion for black matrices, there existed room for further improvement also in sealing strength.

Patent Document 1: International Publication No. 2015/056688 Pamphlet

Then, an object of this invention is to provide the pigment dispersion composition for black matrices which can form the black matrix excellent also in sealing strength without a surface resistance value falling even if it post-baking for a high temperature and a long time.

The inventors of the present invention contain a black colorant, an epoxy resin, an oxazine compound, and an organic solvent, and use a compound having a specific structure as the epoxy resin. It discovered that the pigment dispersion composition for black matrices which can form a black matrix can be obtained, and came to complete this invention.

That is, this invention contains a black coloring agent, an epoxy resin, an oxazine compound, and an organic solvent, The said epoxy resin has an aromatic ring, The pigment dispersion composition for black matrices characterized by the above-mentioned.

In the pigment dispersion composition for black matrices of the present invention, the epoxy resin is preferably at least one selected from the group consisting of the following (Formula 1) to (Formula 7).

Moreover, it is preferable that the ratio of content of the said epoxy resin and content of the said oxazine compound is 10/90-90/10.

In addition, the black colorant preferably includes carbon black.

In addition, it is preferable that the said carbon black is acidic carbon black.

This invention is also the resist composition for black matrices obtained from the pigment dispersion composition for black matrices of this invention.

This invention is also a black matrix formed from the resist composition for black matrices of this invention.

Hereinafter, the pigment dispersion composition for black matrices of this invention, the resist composition for black matrices, and the black matrix formed from it are demonstrated in detail.

<Pigment dispersion composition for black matrix>

The pigment dispersion composition for a black matrix of the present invention contains a black colorant, an epoxy resin, an oxazine compound, and an organic solvent, and the epoxy resin has an aromatic ring.

(black colorant)

The pigment dispersion composition for black matrices of this invention contains a black coloring agent.

It is preferable that carbon black is included as said black coloring agent, and it is more preferable that the said carbon black is acidic carbon black.

As the carbon black, an average primary particle diameter of 20 to 60 nm is preferable, and among these, neutral carbon black having an average primary particle diameter of 20 to 60 nm and/or acidic carbon black having an average primary particle diameter of 20 to 60 nm is more preferable.

When the primary particle diameter of the said black coloring agent is smaller than 20 nm, or when larger than 60 nm, there may be no sufficient light shielding or storage stability may be inferior.

In addition, the said average primary particle diameter is the value of the arithmetic mean diameter by electron microscope observation.

When using the said neutral carbon black and acidic carbon black together, 85/15 - 15/85 are preferable and, as for the mixing ratio (mass ratio) of neutral carbon black and acidic carbon black, 75/25 - 40/60 are more preferable.

When the ratio of the neutral carbon black to the carbon black is more than 85/15, the sealing strength may decrease. .

The above-mentioned acidic carbon black and neutral carbon black are demonstrated.

Carbon black can be roughly divided into acid carbon and neutral carbon according to the structure of the surface. Acidic carbon is a carbonaceous substance originally or artificially oxidized, and exhibits acidity when mixed with distilled water and boiled. On the other hand, it is known that neutral carbon exhibits a neutral or higher pH when mixed and boiled with distilled water.

The neutral carbon black is preferably in a pH range of 8.0 to 10.0, and specifically, Printex 25 (average primary particle diameter 56 nm, pH 9.5) manufactured by Orion Engineered Carbons, and Printex 35 (average primary particle size). Diameter 31 nm, pH 9.5), Printex 65 (average primary particle diameter 21 nm, pH 9.5), Mitsubishi Chemical Corporation MA#20 (average primary particle diameter 40 nm, pH 8.0), MA#40 (average 1 a primary particle diameter of 40 nm, pH 8.0), MA#30 (average primary particle diameter of 30 nm, pH 8.0), etc. are mentioned.

The acidic carbon black is preferably in the range of pH 2.0 to 4.0, specifically, Raven 1080 (average primary particle diameter 28 nm, pH 2.4) manufactured by Columbia Chemicals, Raven 1100 (average primary particle diameter 32 nm, pH 2.9). ), MA-8 (average primary particle diameter 24 nm, pH 3.0) manufactured by Mitsubishi Chemical, MA-100 (average primary particle diameter 22 nm, pH 3.5), Special Black 250 manufactured by Orion Engineered Carbons Company (average) Primary particle diameter 56 nm, pH 3.0), Special Black 350 (average primary particle diameter 31 nm, pH 3.0), Special Black 550 (average primary particle diameter 25 nm, pH 4.0), etc. are mentioned.

As said black colorant, it is preferable that it is special black 250 from a viewpoint of providing pigment dispersibility and a surface resistance value suitably.

In addition, the pH can be measured at 25° C. by adding 1 g of carbon black to 20 ml of distilled water (pH 7.0) from which carbonic acid has been removed, mixing with a magnetic stirrer to prepare an aqueous suspension, and using a glass electrode (German industrial product standard DIN DIN ISO 787/9).

As content of the said black coloring agent, 3-70 mass % is preferable as a mass fraction with respect to the total solid of the pigment dispersion composition for black matrices of this invention, and 10-50 mass % is more preferable.

When content of the said black coloring agent is less than 3 mass %, light-shielding property at the time of forming a black matrix may become low, and when it exceeds 70 mass %, pigment dispersion may become difficult.

(epoxy resin)

The pigment dispersion composition for black matrices of this invention contains an epoxy resin. The said epoxy resin has an aromatic ring.

By containing the epoxy resin and an oxazine compound to be described later, the oxazine compound is polymerized by high temperature during post-baking to become a high molecular weight, so even if movement of the black colorant occurs in the coating film softened by high temperature, the oxazine compound When the polymer becomes a spacer, the black colorants do not contact each other. Therefore, in the resist composition for black matrices of this invention, it is estimated that a high surface resistance value can be ensured by not forming an electroconductive structure structure. In addition, since the oxazine compound described later acts as a curing agent for the epoxy resin, it is estimated that a stronger cured product can be produced as compared to the case where the epoxy resin or the oxazine compound described later is used alone.

However, the present invention does not need to be interpreted as being limited to this mechanism of action.

Examples of the epoxy resin include Eporite 4000, Eporite 3002 (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol DLC-101, Denacol DLC-202, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146, Denacol EX-147 (all made by Nagase Kamtex), GAN, GOT, NC2000-L, NC3000, NC3000-L, NC3000-H, NC3000-FH-75M, NC3100, CER3000-L, XD1000 , NC7000L, NC7300L, EPPN-201, EPPN-501H, EPPN-501HY, EPPN502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, RE303S-L, RE310S (all made by Japan Explosives) , jER157S70, jER828, jER1002, jER1032H60, jER1750, jER1007, YX8100-BH30, E1256, E4250, E4275 (all made by Mitsubishi Chemical), Epicron EXA-9583, Epicron N695, HP4032, HP5000, HP7200L (all manufactured by DIC) VG3101 (manufactured by Mitsui Chemical Corporation), Potot YH-434L (manufactured by Toto Chemical Corporation), VG3101L (manufactured by Air Water Corporation), and the like.

The epoxy resin is preferably at least one selected from the group consisting of the following (Formula 1) to (Formula 7).

The following (Formula 2) and (Formula 3) are more preferable from a viewpoint of forming the black matrix especially excellent in a surface resistance value and sealing strength among the said epoxy resin.

As for content of the said epoxy resin, 4.0 mass % or more is preferable as a mass fraction with respect to the total solid of the pigment dispersion composition for black matrices of this invention, 5.0 mass % or more is more preferable, 6.0 mass % or more is still more preferable. Moreover, as for content of the said epoxy resin, 12.0 mass % or less is preferable as a mass fraction with respect to the total solid of the pigment dispersion composition for black matrices of this invention, 10.0 mass % or less is more preferable, 9.0 mass % or less is still more preferable.

It is preferable that it is 10/90-90/10, and, as for the ratio of content of the said epoxy resin and content of the oxazine compound mentioned later, it is more preferable that it is 15/85-85/15.

By setting it as such a ratio, a surface resistance value and sealing strength can be provided suitably.

In addition, content of the said epoxy resin and content of an oxazine compound are content represented by the mass fraction with respect to the total solid of the pigment dispersion composition for black matrices of this invention.

(oxazine compound)

The pigment dispersion composition for black matrices of this invention contains an oxazine compound.

The oxazine compound is preferably a compound represented by the following general formulas (8) and/or (9).

[In the general formula (8), R ¹ and R ² represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ¹ is a divalent linking group.

^{R 3} and R ⁴ in the general formula (9) represent an alkyl group or an aryl group which may have an unsaturated bond, and may be the same as or different from each other. X ² is a divalent linking group.]

R ¹ and R ² , and R ³ and R ⁴ are an alkyl group or an aryl group which may have an unsaturated bond.

The alkyl group may be, for example, linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec- butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc., or an alkyl group which may have an unsaturated bond derived from cashew nut shell liquid (CNSL). can be heard

As said aryl group, a tolyl group, a xylyl group, a phenyl group, a biphenyl group, a naphthyl group, anthracenyl group etc. are mentioned, for example.

X ¹ and X ² are divalent linking groups.

As said divalent linking group, at least one of _{-CH 2} - constituting the alkylene group or a linear or branched alkylene group having 1 to 12 carbon atoms other than the linking group represented by the following formulas (10) to (12) is -O- , -S-, -NH-, a urethane group, a urea group, an amide group, the siloxane bond which may have a substituent, or the divalent coupling group substituted by -CO-, etc. are mentioned.

As an oxazine compound represented by the said General formula (8), from a viewpoint of forming a black matrix with a high surface resistance value, R<^1> and R<^2> are a phenyl group, and X<^1> among the coupling groups represented by the said Formula (10)-(12) Either one is preferable.

Moreover, as an oxazine compound represented by the said General formula (9), from a viewpoint of forming a black matrix with a high surface resistance value, R ³ and R ⁴ are H, and X ² is a methylenedioxy group, or R ³ and R ⁴ are cashew nut It is preferable that the alkyl group which may have an unsaturated bond derived from a shell liquid (CNSL), and X<^2> is an ethylene group.

As a method of obtaining the said oxazine compound, a well-known method can be used, For example, the method of Unexamined-Japanese-Patent No. 2000-178332, Unexamined-Japanese-Patent No. 2003-344996, etc. can be used.

As the content of the oxazine compound, the lower limit is 0.1 as a mass fraction relative to the total solid content of the pigment dispersion composition for a black matrix of the present invention from the viewpoint of appropriately forming a black matrix that does not reduce the surface resistance even after high temperature and long post-baking. It is preferably mass %, the lower limit is more preferably 0.5 mass %, the lower limit is still more preferably 1 mass %, the lower limit is particularly preferably 3 mass %, and the lower limit is most preferably 5 mass %. .

Moreover, as content of the said oxazine compound, it is preferable that an upper limit is 30 mass % as a mass fraction with respect to the total solid of the pigment dispersion composition for black matrices of this invention from a viewpoint of ensuring the optical density derived from the pigment concentration in a black matrix, and an upper limit It is more preferable that it is 25 mass %, and it is still more preferable that the upper limit is 20 mass %, It is especially preferable that the upper limit is 15 mass %.

(organic solvent)

The pigment dispersion composition for black matrices of this invention contains the organic solvent.

As said organic solvent, the organic solvent conventionally used in the field|area of a liquid-crystal black matrix resist can be used suitably.

Specific examples of the organic solvent include ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, and ester-based organic solvents having a boiling point of 100 to 250°C at ^{normal pressure (1.013×10 2 kPa);} aromatic hydrocarbon-based organic solvents, nitrogen-containing organic solvents, and the like.

When the said boiling point contains a large amount of organic solvents over 250 degreeC, when prebaking the coating film formed by apply|coating the resist composition for black matrices obtained from the pigment dispersion composition for black matrices of this invention, the organic solvent does not fully evaporate and a dry coating film It remains inside and the heat resistance of a dry coating film may fall.

In addition, when the organic solvent having a boiling point of less than 100°C is contained in a large amount, it becomes difficult to apply uniformly and uniformly, and a coating film excellent in surface smoothness may not be obtained.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl. ether-based organic solvents such as ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; Ether ester-based organic solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; methyl isobutyl ketone, cyclohexanone , ketone-based organic solvents such as 2-heptanone and δ-butyrolactone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid ester-based organic solvents such as ethyl, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, and n-amyl formate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol; and nitrogen-containing organic solvents such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These can be used individually or in mixture of 2 or more types.

Among the above organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol from the viewpoints of solubility, dispersibility, and applicability, etc. Monoethyl ether acetate, cyclohexanone, 2-heptanone, 2-hydroxyethyl propionate, 3-methyl-3-methoxybutyl propionate, 3-methoxyethyl propionate, 3-ethoxy methyl propionate, formic acid n -amyl etc. are preferable, and it is more preferable that they are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

(pigment dispersant)

It is preferable that the pigment dispersion composition for black matrices of this invention contains a pigment dispersant.

As the pigment dispersant, as a basic group-containing pigment dispersant, an anionic surfactant, a basic group-containing polyester pigment dispersant, a basic group-containing acrylic pigment dispersant, a basic group-containing urethane pigment dispersant, a basic group-containing carbodiimide pigment dispersant, an acidic group A polymer containing pigment dispersant, etc. can be used.

These basic-group containing pigment dispersants may be used independently and may use a combination of 2 or more types. Especially, a basic-group containing polymeric pigment dispersant is preferable at the point which can obtain favorable pigment dispersibility.

As a specific example of the said basic group-containing polymeric pigment dispersant,

(1) polyester having an amino group and/or imino group and a free carboxyl group of a polyamine compound (for example, poly(lower alkyleneamine) such as polyallylamine, polyvinylamine, polyethylenepolyimine, etc.); a reaction product with at least one selected from the group consisting of polyamide and polyesteramide (Japanese Patent Application Laid-Open No. 2001-59906);

(2) A reaction product of a low molecular weight amino compound such as poly(lower) alkyleneimine and methyliminobispropylamine and a polyester having a free carboxyl group (Japanese Patent Application Laid-Open No. 54-37082, Japanese Patent Application Laid-Open No. 01-311177) report),

(3) Polyesters having one hydroxyl group such as alcohols such as methoxypolyethylene glycol or caprolactone polyester in the isocyanate group of the polyisocyanate compound, compounds having 2 to 3 isocyanate-reactive functional groups, and isocyanate-reactive functional groups A reaction product formed by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a tertiary amino group (Japanese Patent Application Laid-Open No. Hei 02-612);

(4) a compound obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group;

(5) a reaction product formed by adding a polyether chain to a low molecular weight amino compound;

(6) a reaction product formed by reacting a compound having an isocyanate group with a compound having an amino group (Japanese Patent Application Laid-Open No. 04-210220);

(7) a reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group (Japanese Patent Application Laid-Open No. 09-87537);

(8) a reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Application Laid-Open No. 09-194585);

(9) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, At least one selected from methacrylic acid esters or acrylic acid esters such as stearyl acrylate and benzyl acrylate, and acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, amino group and polycapro A copolymer of at least one basic group-containing polymerizable monomer such as a monomer having a lactone skeleton and at least one of styrene, a styrene derivative, and other polymerizable monomers (Japanese Patent Application Laid-Open No. Hei 01-164429);

(10) a basic group-containing carbodiimide pigment dispersant (International Publication No. WO04/000950);

(11) a block copolymer comprising a block having a basic group such as a tertiary amino group and a quaternary ammonium base and a block having no functional group (refer to the description of Japanese Patent Application Laid-Open No. 2005-55814);

(12) a pigment dispersant obtained by Michael addition reaction of a polycarbonate compound to polyallylamine (Japanese Patent Application Laid-Open No. 09-194585);

(13) a carbodiimide-based compound having at least one polybutadiene chain and at least one alkaline nitrogen-containing group, respectively (Japanese Patent Application Laid-Open No. 2006-257243);

(14) a carbodiimide-based compound having at least one each of a side chain having an amide group and an alkaline nitrogen-containing group in the molecule (Japanese Patent Application Laid-Open No. 2006-176657);

(15) a polyurethane compound having a structural unit having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized by a quaternizing agent (Japanese Patent Application Laid-Open No. 2009-175613);

(16) A compound obtainable by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in a molecule and an active hydrogen group of a compound having an active hydrogen group in the molecule and a carbazole ring and/or an azobenzene skeleton, In the molecule, the number of carbazole rings and azobenzene skeletons relative to the total of the isocyanate group derived from the isocyanate compound having an isocyanurate ring and the urethane bond and urea bond generated by the reaction of the isocyanate group with the active hydrogen group is 15 to 85% compound (Japanese Patent Application No. 2009-220836).

(17) a graft copolymer in which a polyether or polyester side chain is introduced into an acrylate polymer having an amino group; and the like.

Among the basic group-containing polymeric pigment dispersants, basic group-containing urethane polymeric pigment dispersants, basic group-containing polyester polymeric pigment dispersants, and basic group-containing acrylic polymeric pigment dispersants are more preferable, amino group-containing urethane polymeric pigment dispersants, amino group-containing polyesters A polymeric pigment dispersant and an amino group-containing acrylic polymeric pigment dispersant are still more preferable. Among the basic group-containing polymeric pigment dispersants, a basic group (amino group)-containing polymeric pigment dispersant having at least one selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains is particularly preferable.

As content of the said pigment dispersant, it is preferable that it is 1-200 mass parts with respect to 100 mass parts of said black coloring agents, and it is more preferable that it is 5-100 mass parts.

(pigment derivative)

It is preferable that the pigment dispersion composition for black matrices of this invention contains a pigment dispersant.

Examples of the pigment derivative include a phthalocyanine pigment derivative having an acid group, an anthraquinone pigment derivative having an acid group, and a naphthalene pigment derivative having an acid group.

Among these, a phthalocyanine-based pigment derivative having a sulfonic acid group is preferable from the viewpoint of dispersibility of carbon black.

In the process of micronization or dispersion of the black colorant, a part of the basic skeleton is adsorbed on the surface of the pigment to increase the affinity of the acid group with the organic solvent or pigment dispersant. time) has the effect of improving dispersion stability and the like. Moreover, it is more preferable that the said black coloring agent dispersing aid itself dissolves in an organic solvent or becomes a dispersed state as fine particles, since it can make it adsorb|suck over a wider range than the surface of the said black coloring agent.

0.1-20 mass parts is preferable with respect to 100 mass parts of said black coloring agents, and, as for content of the said pigment derivative, 0.5-10 mass parts is more preferable.

(Method for producing pigment dispersion composition for black matrix)

As a manufacturing method of the pigment dispersion composition for black matrices of this invention, it can obtain by adding the various components mentioned above, and mixing and milling.

The milling method is not particularly limited, and for example, bead mill, ready mill, ultrasonic homogenizer, high pressure homogenizer, paint shaker, ball mill, roll mill, sand mill, sand grinder, dyno mill, dispermat (DISPERMAT), an SC mill, a nanomizer, etc., may be milled by a known method.

<Resist composition for black matrix>

This invention is also the resist composition for black matrices obtained from the pigment dispersion composition for black matrices of this invention.

(Pigment dispersion composition for black matrix)

The resist composition for black matrices of this invention contains the pigment dispersion composition for black matrices of this invention mentioned above.

As content of the said pigment dispersion composition for black matrices, it is preferable on the basis of the total mass of the resist composition for black matrices of this invention that it is 30-80 mass %, and it is more preferable that it is 40-75 mass %.

(Photoinitiator)

It is preferable that the resist composition for black matrices of this invention contains a photoinitiator.

The photopolymerization initiator is not particularly limited as long as it can generate radicals or cations by irradiating active energy rays such as ultraviolet rays or electron beams, for example, 1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]-1-(O-acetyloxime)ethanone, benzophenone, N,N'-tetraethyl-4, 4'-diaminobenzophenone, 4-methoxy-4'-dimethyl Aminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-Hydroxycyclohexylphenylketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naph Toquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1 [4-(methylthio)phenyl]-2-morpholinopropan-1-one Photoinitiators, such as a benzophenone type, such as a thioxanthone type, an anthraquinone type, a triazine type, etc. are mentioned.

The said photoinitiator is used individually or in combination of 2 or more types.

It is preferable that content of the said photoinitiator is 1-20 mass % as a mass fraction with respect to the total solid of the resist composition for black matrices of this invention.

(photopolymerizable compound)

It is preferable that the resist composition for black matrices of this invention contains a photopolymerizable compound.

As said photopolymerizable compound, the monomer which has one or two or more photopolymerizable unsaturated bonds in a molecule|numerator, the oligomer which has a photopolymerizable unsaturated bond, etc. are mentioned.

As a monomer having one photopolymerizable unsaturated bond in the molecule, for example, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Alkoxyalkyl methacrylates or acrylates such as alkyl methacrylate or acrylate, benzyl methacrylate, benzyl acrylate or aralkyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate Aminoalkyl methacrylates or acrylates such as N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, diethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol mono Methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoalkyl ether such as methyl ether, methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether, isobornyl methacrylate, or Acrylate, glycerol methacrylate or acrylate, 2-hydroxyethyl methacrylate or acrylate may be used.

As a monomer having two or more photopolymerizable unsaturated bonds in the molecule, for example, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol Dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate , pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, bisphenol A diacrylate, 1, 4-butanediol Diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol Diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. can be used.

As the oligomer having the photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the monomer can be used.

The said photopolymerizable compound can be used individually or in combination of 2 or more types.

It is preferable that content of the said photopolymerizable compound is 3-50 mass % as a mass fraction with respect to the total solid of the resist composition for black matrices of this invention.

(Alkali-soluble resin)

It is preferable that the resist composition for black matrices of this invention contains alkali-soluble resin.

As said alkali-soluble resin, it acts as a binder with respect to the said black coloring agent, and when manufacturing a black matrix, it is preferable to have solubility with respect to the developing solution used in the developing process, especially alkali developing solution.

A block copolymer may be sufficient as said alkali-soluble resin. By employing the block copolymer, the pigment dispersing ability is improved compared to other copolymers, and solubility in PGMEA or alkaline developer can be imparted.

Among the block copolymers, a block copolymer having a block composed of an ethylenically unsaturated monomer having at least one carboxyl group and a block composed of another copolymerizable ethylenically unsaturated monomer is preferable.

It does not specifically limit as said block copolymer, Conventionally used thing can be used. Among them, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl copolymerizable with an ethylenically unsaturated monomer having a carboxyl group, such as acrylic acid or methacrylic acid, and an ethylenically unsaturated monomer having a carboxyl group Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenyl maleimide, polystyrene macromonomer, polymethyl and a copolymer with at least one ethylenically unsaturated monomer selected from the group of monomers and oligomers such as methacrylate macromonomer and carboepoxy diacrylate.

However, it is preferable not to use N-vinylpyrrolidone and a sulfur element containing monomer.

As said block copolymer, the block resin synthesize|combined by living radical polymerization and anionic polymerization can be employ|adopted.

A part of the block portion of the block copolymer may be composed of a random copolymer.

As said alkali-soluble resin, alkali-soluble cardo resin can also be employ|adopted.

Examples of the alkali-soluble cardo resin include an epoxy (meth) acrylate acid adduct having a fluorene skeleton, which is an addition product of a fluorene epoxy (meth) acrylic acid derivative and dicarboxylic acid anhydride and/or tetracarboxylic dianhydride. .

Moreover, this alkali-soluble resin may have a photopolymerizable functional group.

The acid value of the alkali-soluble resin is preferably 5-300 mgKOH/g, more preferably 5-250 mgKOH/g, still more preferably 10-200 mgKOH/g, and still more preferably 60-150 mgKOH/g, from the viewpoint of developing characteristics. g is particularly preferred.

In addition, in the present specification, the acid value is a value obtained arithmetically based on an ethylenically unsaturated monomer having a carboxyl group and its content as a theoretical acid value.

The weight average molecular weight of the alkali-soluble resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 5,000 to 30,000 from the viewpoint of developing characteristics or solubility in an organic solvent.

In addition, in the present invention, the weight average molecular weight is a weight average molecular weight in terms of polystyrene obtained based on GPC.

As an apparatus for measuring the weight average molecular weight herein, Water2690 (manufactured by Waters) and PLge 5 µm MIXED-D (manufactured by Agilent Technologies) are used as a column.

1-200 mass parts is preferable with respect to 100 mass parts of said black coloring agents, and, as for content of the said alkali-soluble resin, 10-150 mass parts is more preferable.

In this case, if the content of the alkali-soluble resin is less than 1 part by mass, the developing characteristics may be lowered, and if the content of the alkali-soluble resin exceeds 200 parts by mass, the concentration of the black colorant is relatively decreased. In some cases, it may be difficult to achieve the desired color density.

It is preferable that the said alkali-soluble resin does not contain any primary, secondary, and tertiary amino group, and also does not contain a quaternary ammonium group. Furthermore, it is more preferable that it does not have a basic group.

In addition, you may mix|blend alkali-soluble resin which has structures other than a block copolymer in the range which does not impair the effect by this invention.

(organic solvent)

As said organic solvent, the organic solvent described in the pigment dispersion composition for black matrices of this invention mentioned above can be selected suitably and can be used.

As content of the said organic solvent, it is preferable that it is 1-40 mass % on the basis of the total mass of the resist composition for black matrices of this invention, and it is more preferable that it is 5-35 mass %.

(Other additives)

The resist composition for black matrices of this invention can use various additives, such as a thermal-polymerization inhibitor, a ultraviolet absorber, and antioxidant, as needed suitably.

(Method for producing resist composition for black matrix)

As a manufacturing method of the resist composition for black matrices of this invention, it can produce by producing the pigment dispersion composition for black matrices of this invention, adding the remaining materials after that, and stirring and mixing using a stirring apparatus etc., for example.

The stirring and mixing method is not particularly limited, and known methods such as an ultrasonic disperser, a high pressure emulsifier, a bead mill, three rolls, a sand mill, and a kneader can be used.

In addition, when producing the resist composition for black matrices of this invention, you may add the said black coloring agent of the pigment dispersion composition for black matrices of this invention, the said epoxy resin, the said oxazine compound, etc. as needed.

<Black Matrix>

The black matrix of this invention is formed from the resist composition for black matrices of this invention.

The method of forming the black matrix of the present invention is not particularly limited, and for example, the resist composition for a black matrix of the present invention is applied on a transparent substrate and dried to form a coating film, then a photomask is placed on the coating film and the photomask Through this, the black matrix can be formed by image exposure, development, and, if necessary, photocuring.

The method of apply|coating, drying, exposure, and developing the resist composition for black matrices of this invention, etc. can select a well-known method suitably.

Moreover, as said transparent substrate, well-known transparent substrates, such as a glass substrate and a plastic substrate, can be selected suitably and can be used.

As a thickness of the said coating film, 0.2-10 micrometers is preferable as a film thickness after drying, 0.5-6 micrometers is more preferable, 1-4 micrometers is still more preferable.

By setting it as the said thickness range, a predetermined pattern can be developed suitably, and a predetermined|prescribed optical density can be provided suitably.

The black matrix of the present invention is coated on a glass substrate (Corning 1737) and pre-baked at 100° C. for 3 minutes, then exposed with a high-pressure mercury lamp (UV integrated light amount 400 mJ/cm ² ) and post-baked at 230° C. for 30 minutes. the surface resistance value when forming a resist pattern having a thickness of 1μm 5.0 × ¹⁰ 10 Ω / □ or more is preferable, 1.0 × 10 ¹¹ Ω / □ or more, and more preferably, 1.0 × 10 ¹² Ω / □ or higher in addition, this Preferably, 1.0×10 ¹³ Ω/□ or more is particularly preferable, and 1.0×10 ¹⁴ Ω/□ or more is most preferable.

In addition, the said surface resistance value can be measured with main body: microammeter R8340, option: shield box R12702A (all are made by Advance Corporation).

The black matrix of the present invention is coated on a glass substrate (Corning 1737) and pre-baked at 100° C. for 3 minutes, then exposed with a high-pressure mercury lamp (UV integrated light amount 400 mJ/cm ² ) and post-baked at 230° C. for 3 hours. the surface resistance value when forming a resist pattern having a thickness of 1μm 5.0 × 10 ⁹ Ω / □ or more is preferable, 1.0 × ¹⁰ 10 Ω / □ or more, and more preferably, 1.0 × 10 ¹¹ Ω / □ or higher in addition, this Preferably, 5.0×10 ¹² Ω/□ or more is particularly preferable, and 5.0×10 ¹³ Ω/□ or more is most preferable.

The black matrix of the present invention is coated on a glass substrate (Corning 1737) and pre-baked at 100° C. for 3 minutes, then exposed with a high-pressure mercury lamp (UV integrated light amount 400 mJ/cm ² ) and post-baked at 150° C. for 1 hour. When a resist pattern with a thickness of 1 μm is formed, and the resist pattern is bonded to an aluminum pin having a diameter of 5 mm through a sealing agent of 50 mg to prepare a test piece, the sealing strength is ^{preferably 120 N/mm 2} or more, and 150 N/mm 2 or more mm ² or more is more preferable, 180 N/mm ² or more is still more preferable, 200 N/mm ² or more is particularly preferable, and 250 N/mm ² or more is most preferable.

In addition, the sealing strength is measured by stretching the test piece at a rate of 10 mm/min using a load measuring device (LTS-200N/500N, manufactured by Minebea), and measuring the maximum stress when the aluminum fin is peeled from the test piece, and applying a sealing agent By dividing by the area, the sealing strength per unit area (N/mm ² ) can be obtained.

Since the pigment dispersion composition for black matrices of this invention, the resist composition for black matrices, and a black matrix have the characteristics mentioned above, they can use suitably as black matrices, such as an image display apparatus and a touch panel.

ADVANTAGE OF THE INVENTION According to this invention, even if it post-baking for a high temperature and a long time, the surface resistance value does not fall, and the pigment dispersion composition for black matrices which can form the black matrix excellent also in sealing strength can be provided.

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited thereto as long as it does not depart from the gist and scope of application. In addition, unless otherwise specified, "part" and "%" in this Example represent "parts by mass" and "% by mass", respectively.

Various materials used in the following examples and comparative examples are as follows.

<Black Colorant>

(Carbon Black 1)

Acidic carbon black, product name "SPECIAL BLACK 250", average primary particle diameter 56 nm, pH 3.0, manufactured by Orion Engineered Carbons

(Carbon Black 2)

Neutral carbon black, product name "Printex35", average primary particle diameter 31 nm, pH 9.5, manufactured by Orion Engineered Carbons

<Epoxy resin>

(epoxy resin 1)

Product name "EPPN-502H", the epoxy resin of the above (Formula 1), manufactured by Nippon Kayaku Co., Ltd.

(epoxy resin 2)

Product name "VG3101L", the epoxy resin of the above (Formula 2), manufactured by Air Water Corporation

(epoxy resin 3)

Product name "jER1032H60", epoxy resin of the above (Formula 3), manufactured by Mitsubishi Chemical

(epoxy resin 4)

Product name "jER157S70", the epoxy resin of the above (formula 4), R ₁ to _{R 6} are methyl groups, n is 0 or more, manufactured by Mitsubishi Chemical Co., Ltd.)

(epoxy resin 5)

Product name "HP5000", epoxy resin of the above (formula 5), manufactured by DIC

(epoxy resin 6)

Product name "HP7200L", epoxy resin of the above (Formula 6), R ¹ to ^{R 2} are all hydrogen, n is 1 to 20, manufactured by DIC)

(epoxy resin 7)

Product name "EOCN-103S", epoxy resin of the above (Formula 7), manufactured by Nippon Kayaku Co., Ltd.

(epoxy resin 8)

Product name "Denacol EX-411", pentaerythritol polyglycidyl ether, manufactured by Nagase Chemtex

(epoxy resin 9)

Product name "EHPE3150", 1,2-epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corporation

<oxazine compound>

(oxazine compound 1)

In the general formula (9), R ³ and R ⁴ are H, and X ² is an oxazine compound represented by a methylenedioxy group (trade name "JBZ-OP100N", manufactured by JFE Chemicals)

(oxazine compound 2)

In the general formula (8), R ¹ and R ² are a phenyl group, and X ¹ is a linking group represented by the formula (10). An oxazine compound is synthesized by a known method (the method described in Japanese Patent Application Laid-Open No. 2000-178332, etc.) did.

(oxazine compound 3)

In the general formula (9), R ³ and R ⁴ are an alkyl group which may have an unsaturated bond derived from cashew nut shell liquid (CNSL), and X ² is an oxazine compound represented by an ethylene group (trade name "CR-276", manufactured by Tohoku Chemical Corporation) )

<Organic solvent>

PM (propylene glycol monomethyl ether)

PGMEA (propylene glycol monomethyl ether acetate)

<Photoinitiator>

OXE02 (product name "Irgacure OXE02", 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime)ethanone, manufactured by BASF)

<Photopolymerizable compound>

DPHA (dipentaerythritol hexaacrylate)

<Alkali-soluble resin>

WR-301 (product name "WR-301", cardo-based resin, acid value 100 mgKOH/g, solid content 45%, manufactured by ADEKA)

<Pigment dispersant>

DISPERBYK-167 (solids content 52% by mass, manufactured by Big Chemie)

<Pigment derivative>

BYK-2100 (manufactured by Big Chemie)

<Preparation of the pigment dispersion composition for black matrices>

The above-mentioned black colorant, solution of pigment dispersant (solid content 52% by mass), pigment derivative, epoxy resin 1 to 9, oxazine compounds 1 to 3, and organic solvent were mixed so as to have the composition shown in Table 1, and kneaded overnight with a bead mill to form a black matrix. A pigment dispersion composition for use was prepared.

Using a high-speed stirrer, the black matrix pigment dispersion and other materials (photopolymerizable compound, alkali-soluble resin, photopolymerization initiator, and organic solvent) are uniformly mixed so as to have the composition shown in Table 2, and then filtered with a filter having a pore diameter of 3 μm. Thus, the resist compositions for black matrices of Examples and Comparative Examples were obtained.

<Evaluation test>

(surface resistance value 1)

Each of the pigment dispersion resist compositions for black matrix of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) to a film thickness of 1 μm with a spin coater, pre-baked at 100° C. for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated light quantity) 400 mJ/cm ² ) and post-baking at 230° C. for 30 minutes to prepare a black resist pattern formed only with the beta portion.

The surface resistance value of each produced black resist pattern was measured with a main body: a microammeter R8340, an option: a shield box R12702A (both manufactured by Advance Corporation). The results are shown in Table 2.

(surface resistance value 2)

Each of the pigment dispersion resist compositions for black matrix of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) to a film thickness of 1 μm with a spin coater, pre-baked at 100° C. for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated light quantity) 400 mJ/cm ² ) and post-baking at 230° C. for 3 hours to prepare a black resist pattern formed only with the beta portion.

The surface resistance value of each produced black resist pattern was measured with a main body: a microammeter R8340, an option: a shield box R12702A (both manufactured by Advance Corporation). The results are shown in Table 2.

(Sealing strength)

Each of the pigment dispersion resist compositions for black matrix of Examples and Comparative Examples were coated on a glass substrate (Corning 1737) to a film thickness of 1 μm with a spin coater, pre-baked at 100° C. for 3 minutes, and then exposed with a high-pressure mercury lamp (UV integrated light quantity) 400 mJ/cm ² ) and post-baking at 150° C. for 1 hour to prepare a black resist pattern formed only of the beta part.

Thereafter, the black resist pattern was bonded to an aluminum pin having a diameter of 5 mm through a sealing agent of 50 mg to prepare a test piece.

The produced test piece was tensioned at a rate of 10 mm/min using a load measuring device (LTS-200N/500N, manufactured by Minebea), and the maximum stress (N) when the aluminum fin was peeled off from the test piece was measured, and the sealing agent application area The strength per unit area was divided by the sealing strength (N/mm ² ). The results are shown in Table 2.

From Examples, by using a pigment dispersion composition for black matrix containing an epoxy resin, an oxazine compound, and an organic solvent, and the epoxy resin has an aromatic ring, the surface resistance value does not decrease even after post-baking at high temperatures and for a long time, and sealing It was confirmed that a black matrix excellent in strength could also be formed.

On the other hand, in Comparative Example 1 not using an epoxy resin and Comparative Example 2 not using an oxazine compound, a black matrix having sufficient sealing strength could not be formed, and Comparative Example 3 using an epoxy resin other than a predetermined epoxy resin and In 4, when post-baking for a high temperature and a long time was carried out, it was confirmed that the surface resistance value fell.

ADVANTAGE OF THE INVENTION According to this invention, even if it post-baking for a high temperature and a long time, the surface resistance value does not fall, and the pigment dispersion composition for black matrices which can form the black matrix excellent also in sealing strength can be provided.

Claims (7)

It contains a black colorant, an epoxy resin, an oxazine compound, and an organic solvent,
The epoxy resin having an aromatic ring
A pigment dispersion composition for a black matrix, characterized in that. The pigment dispersion composition for a black matrix according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of the following (Formula 1) to (Formula 7).

The pigment dispersion composition for black matrices of Claim 1 or 2 whose ratio of content of the said epoxy resin and content of the said oxazine compound is 10/90-90/10. The pigment dispersion composition for a black matrix according to any one of claims 1 to 3, wherein the black colorant comprises carbon black. The pigment dispersion composition for a black matrix according to claim 4, wherein the carbon black is acid carbon black. The resist composition for black matrices obtained from the pigment dispersion composition for black matrices in any one of Claims 1-5. The black matrix formed from the resist composition for black matrices of Claim 6.