JP2024020840A - Surface-modified carbon black, carbon black dispersion, and black resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide carbon black with superior dispersibility and dispersion stability.

SOLUTION: The present invention provides surface-modified carbon black in which polymers of double bond-containing polymerizable monomers exist on a portion or the entirety of the carbon black surface, wherein the polymers of double bond-containing polymerizable monomers contain calixarene compounds.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a surface-modified carbon black, a carbon black dispersion, a black resist composition, and a method for producing surface-modified carbon black.

Currently, carbon black is widely used as a coloring pigment and light-shielding material in fields such as printing inks, paints, and plastic molding materials. In order to improve the colorability and light absorption performance of these products, it is necessary to uniformly disperse carbon black in a solvent or resin. For example, in carbon black dispersions for forming black matrices of color filters used in liquid crystal display elements, sensors, etc., improvements in the dispersibility and dispersion stability of carbon black are required for the purpose of further improving brightness. However, since carbon black generally has poor dispersibility, improvements in dispersibility through surface treatment have been studied.

As a surface treatment of carbon black for the purpose of improving dispersibility, surface modification with an alkyl group type surface treatment agent having an amino group has been studied (for example, Patent Document 1). However, surface modification using the above-mentioned surface treatment agent does not provide sufficient surface modification density to improve dispersibility, and therefore the improvement in dispersibility is insufficient.

For the purpose of improving the surface modification density, a method of reacting the carboxyl group on the surface of carbon black with an amine surface treatment agent has also been studied (for example, Patent Document 2). However, this method requires chlorination of the carboxyl groups on the surface of carbon black, which makes the process complicated, and residual chlorine causes migration, which can cause failures in liquid crystal display elements, cameras, etc. there is a possibility.

On the other hand, it has also been considered to improve the surface modification density by surface-treating carbon black in a reaction solvent (for example, Patent Document 3). However, with this method, the residual sulfur derived from the sulfonating agent may cause migration similar to chlorine, and the length of the solvent affinity group is not long enough, so the brightness of cutting-edge liquid crystal display elements and sensors etc. The dispersibility that satisfies this has not yet been achieved.

Japanese Patent Application Publication No. 11-256067 Japanese Patent Application Publication No. 2004-346219 Japanese Patent Application Publication No. 10-2110112

As described above, as the definition of liquid crystal display elements becomes higher and the sensitivity of sensors and the like becomes higher, carbon black and its dispersion having better dispersibility and dispersion stability are required.
An object of the present invention is to provide carbon black and a dispersion thereof having excellent dispersibility and dispersion stability.

As a result of intensive studies to solve the above problems, the present inventors have achieved excellent dispersibility and dispersion stability by reacting a mixture containing carbon black, a calixarene compound, and a double bond-containing polymerizable monomer. The present invention was completed based on the discovery that surface-modified carbon black having the following properties can be obtained.

That is, the present invention provides a method in which a polymer of a double bond-containing polymerization-reactive monomer is present on part or all of the surface of carbon black, and the polymer of the double-bond-containing polymerization-reactivity monomer contains a calixarene compound. Related to surface modified carbon black.
The present invention also relates to a carbon black dispersion containing the above surface-modified carbon black.
The present invention also relates to a black resist composition containing the above surface-modified carbon black.
The present invention also provides a method for preparing a mixture containing (A) carbon black, (B) a calixarene compound, (C) a double bond-containing polymerization-reactive monomer, (D) a solvent, and (E) a polymerization initiator, The present invention relates to a method for producing surface-modified carbon black, which comprises the step of polymerizing the double bond-containing polymerization-reactive monomer (C).

According to the present invention, carbon black and its dispersion having excellent dispersibility and dispersion stability can be provided.

An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.
As used herein, "(meth)acrylate" means one or both of acrylate and methacrylate.

1. Surface Modified Carbon Black The surface modified carbon black according to one embodiment of the present invention has a polymer of a double bond-containing polymerization-reactive monomer present on a part or all of the surface of the carbon black, and a double bond-containing polymerization reaction. It is characterized in that the polymer of the monomer contains a calixarene compound. This allows carbon black to have excellent dispersibility and dispersion stability. The constituent components will be explained below.

[(a) Carbon black]
Carbon black is not particularly limited, and various types such as commercially available oil furnace black, gas furnace black, thermal black, acetylene black, channel black, etc. can be used. Further, carbon black that has been subjected to the usual ozone treatment, plasma treatment, or liquid phase oxidation treatment may be used. One type of carbon black may be used alone, or two or more types may be used in combination.

The blending amount of carbon black is 40% by mass or more and 94.9% by mass or less based on the total mass of the polymer of (a) carbon black, (b) calixarene compound, and (c) double bond-containing polymerization-reactive monomer. The content is preferably in the range of 60% by mass or more and 89.5% by mass or less.

The shape of carbon black is not particularly limited and can be selected depending on the purpose, such as for improving conductivity, for ink (for light shielding), for coloring fibers, for resin masterbatch, etc.
Commercially available carbon blacks include, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, manufactured by Mitsubishi Chemical Corporation. #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000 , #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc. Printex 3, Printex 3 OP, Printex 30, Printex 30 OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex manufactured by Evonik Degussa Japan Co., Ltd. x85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U , Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBla ck4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch manufactured by Cabot Japan Co., Ltd. ch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN VEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RA Examples include VEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000, and the like.

[(b) Calixarene compound]
The calixarene compound is contained in a polymer of a double bond-containing polymerizable monomer described later. The fact that the polymer contains a calixarene compound can be confirmed by gel permeation chromatography (GPC) or gas chromatography mass spectrometry (GC-MS).
The calixarene compound is preferably a compound represented by the following formula (1).

（式中Ｒ_１は水素原子、炭素数１～１２のアルキル基又はアリール基である。Ｒ_２及びＲ_３はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アリール基、又はアラルキル基である。ｎは３～６の整数である。）

(In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. .n is an integer from 3 to 6.)

Specifically, R ₁ in the above formula (1) is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group. , octyl, nonyl, decyl, undecyl, and other alkyl groups; phenyl, naphthyl, anthryl, and other aryl groups. Among these, R ₁ is preferably an alkyl group or aryl group having 1 to 11 carbon atoms, and more preferably a linear alkyl group having 2 to 9 carbon atoms or a phenyl group.
When R ₁ has a substituent, examples of the substituent include an alkyl group, an alkoxy group, an aryl group, and an aralkyl group. Specific examples include the group exemplified by R ₂ described below.

R ₂ and R ₃ in the above formula (1) are each a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and cyclohexyl group. The number of carbon atoms is preferably 1 to 9, for example.
Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, and cyclohexyloxy group. The number of carbon atoms is preferably 1 to 9, for example.

Examples of the aryl group include those having 6 to 14 carbon atoms forming a ring. The aryl group may have a substituent such as the above-mentioned alkyl group, alkoxy group, or hydroxy group. Specific examples include phenyl group, hydroxyphenyl group, dihydroxyphenyl group, hydroxyalkoxyphenyl group, alkoxyphenyl group, tolyl group, xylyl group, naphthyl group, hydroxynaphthyl group, and dihydroxynaphthyl group.

An aralkyl group means an alkyl group in which one or more hydrogen atoms of the alkyl group (C _n H _2n+1 ) are substituted with an aryl group. The aryl group may have a substituent such as the above-mentioned alkyl group, alkoxy group, or hydroxy group. Specifically, phenylmethyl group, hydroxyphenylmethyl group, dihydroxyphenylmethyl group, tolylmethyl group, xylylmethyl group, naphthylmethyl group, hydroxynaphthylmethyl group, dihydroxynaphthylmethyl group, phenylethyl group, hydroxyphenylethyl group, dihydroxyphenyl group. Examples include ethyl group, tolylethyl group, xylylethyl group, naphthylethyl group, hydroxynaphthylethyl group, and dihydroxynaphthylethyl group. The number of carbon atoms is preferably 7 to 15, for example.

In one embodiment, R ₂ and R ₃ in the above formula (1) are preferably hydrogen atoms.

The compound represented by the above formula (1) is a resorcin derivative represented by the following formula (2) (Resorcin is a common name, the accepted common name is resorcinol, and the IUPAC name is 1,3-dihydroxybenzene.) It can be synthesized from and aldehyde compounds.

（式中Ｒ_２及びＲ_３は、上記式（１）のＲ_２及びＲ_３と同一である。）

(In the formula, R ₂ and R ₃ are the same as R ₂ and R ₃ in the above formula (1).)

In one embodiment, both R ₂ and R ₃ of the compound represented by the above formula (2) are preferably hydrogen atoms.
In one embodiment, the aldehyde compound preferably has an alkyl group that may have a substituent or an aryl group that may have a substituent, and the aldehyde compound preferably has an alkyl group having 1 to 12 carbon atoms or an aryl group that may have a substituent. An aldehyde compound having an aryl group is more preferred, and an aliphatic aldehyde compound having an alkyl group having 3 to 10 carbon atoms or an aldehyde compound having a phenyl group is even more preferred.

The calixarene compounds may be used alone or in combination of two or more. Calixarene compounds can be obtained as commercial products or by known synthetic methods.
The blending amount of the calixarene compound is in the range of 0.1% by mass or more and 20% by mass or less based on the total mass of (a) carbon black, (b) calixarene compound, and (c) double bond-containing polymerizable reactive monomer. It is preferable that it is, and it is more preferable that it is the range of 0.5 mass % or more and 10 mass % or less.

[(c) Polymer of double bond-containing polymerizable monomer]
The polymer of the double bond-containing polymerizable monomer is present so as to cover all or part of the surface of the carbon black (core-shell structure).
The presence of the polymer on all or part of the surface of the carbon black can be confirmed by weight loss as assessed by thermogravimetry (TGA).
The polymer of the double bond-containing polymerizable monomer may be an oligomer obtained by polymerizing the monomer, or may be a polymer. Here, the term "oligomer" refers to a polymer having a degree of polymerization of about 2 to 100, and the term "polymer" refers to a polymer having a degree of polymerization of more than 100.

Examples of double bond-containing polymerization-reactive monomers include styrene compounds such as styrene, α-methylstyrene, and p-methylstyrene, divinylbenzene, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, and (meth)acrylic acid. Ethyl, butyl (meth)acrylate, glycidyl (meth)acrylate, glycidyl vinyl ether, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, 4-vinylcyclohexene 1,2-epoxide, epoxycyclohexenyl (meth)acrylate, ) acrylate, 2-oxetanylpropyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and the like. Among these, styrene compounds or (meth)acrylates are preferred.
The double bond-containing polymerization-reactive monomers may be used singly or in combination of two or more.

In one embodiment of the present invention, the weight average molecular weight of the polymer of the double bond-containing polymerizable monomer is preferably 300 or more, and preferably 5,000 or less.
In one embodiment of the present invention, the average degree of polymerization of the polymer of (c) the double bond-containing polymerization-reactive monomer is preferably 3 or more, and preferably 50 or less.

In one embodiment of the present invention, the amount of the polymer of the double bond-containing polymerizable monomer is the sum of (a) carbon black, (b) calixarene compound, and (c) double bond-containing polymerizable monomer. It is preferably in the range of 5% by mass or more and 50% by mass or less, and more preferably in the range of 10% by mass or more and 30% by mass or less, based on the mass.

In one embodiment, the surface-modified carbon black may consist essentially only of a polymer of (a) carbon black, (b) a calixarene compound, and (c) a double bond-containing polymerizable monomer.
Here, "substantially consisting only of components (a) to (c)" means that the proportion of components (a) to (c) in the surface-modified carbon black is 90% by mass or more, 95% by mass or more, 99% by mass or more Or it means 100% by mass. Note that when the proportion of components (a) to (c) is 100% by mass, unavoidable impurities may be included.

The surface-modified carbon black of the present invention can be used in fields where light-shielding properties, conductivity, durability, jet blackness, etc. are required, such as gravure ink, offset ink, back coat for magnetic recording media, electrostatic toner, inkjet, and automobile use. It can be suitably used in paints, conductive carbon black, coloring pigments for liquid crystal display elements and sensors, light shielding materials, black resists, paints, plastic molding materials, printing inks, packaging materials, adhesives, negative electrode materials, etc.

2. Method for producing surface-modified carbon black A method for producing surface-modified carbon black according to an embodiment of the present invention includes (A) carbon black, (B) a calixarene compound, (C) a double bond-containing polymerization-reactive monomer, ( D) Preparing a mixture (reaction system) containing a solvent and (E) a polymerization initiator, and (C) polymerizing a double bond-containing polymerizable monomer.

In this embodiment, the dispersibility of carbon black is improved by polymerizing a double bond-containing polymerizable monomer in the presence of a calixarene compound. This is because part or all of the surface of the carbon black was coated with the polymer of the double bond-containing polymerization-reactive monomer. If a calixarene compound is not blended, the effects of the present invention will not be exhibited. It is not clear how calixarene compounds are involved in the polymerization reaction, but calixarene compounds are adsorbed onto the carbon black surface due to chemical bonds or intermolecular interactions, or calixarene compounds are surrounded by carbon black. It is presumed that the presence of the carbon black causes the polymerization reaction of the double bond-containing polymerization-reactive monomer to occur on all or part of the carbon black surface. In addition, since it can be assumed that the calixarene compound represented by formula (1) mediates the reaction of carbon black and the double bond-containing polymerizable monomer as described above, it is assumed that the calixarene compound represented by formula (1) has a kind of catalytic action. It is assumed that this is having an effect.

In this embodiment, the details and blending amounts of (A) carbon black, (B) calixarene compound, and (C) double bond-containing polymerization-reactive monomer are as follows: (a) carbon black, ( The same applies to b) calixarene compounds and (c) double bond-containing polymerizable reactive monomers.

[(D) Solvent]
Examples of the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n- Alcohols such as butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol; Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane; ethylene glycol monomethyl ether, ethylene Alcohol ethers such as glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate , esters such as propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, 2 - Monos such as ethyl oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, etc. Carboxylic acid esters; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Propylene glycols such as glycol monobutyl ether acetate; diethylene glycols such as diethyler glycol monomethyl ether, diethyler glycol monoethyl ether, diethyler glycol dimethyl ether, diethyler glycol diethyl ether, diethyler glycol methyl ethyl ether; Examples include aromatics such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone.
The above solvent is appropriately selected in consideration of the boiling point and raw materials.
The above solvents can be used alone or in combination of two or more.
The amount of the solvent (D) to be blended is preferably in the range of 30 parts by mass or more and 150 parts by mass or less, based on a total of 100 parts by mass of components (A) to (C) and (E).

[(E) Polymerization initiator]
Various polymerization initiators can be used, such as acetyl peroxide, diacyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, and 2-chlorobenzoyl peroxide. , 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, tetralin hydroperoxide, t-butylperoxy-2 -Ethylhexanoate, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl pertriphenylacetate, t-butyl hydroperoxide, t-butyl performate, t-butyl peracetate, t-perbenzoate -butyl, peroxides such as t-butyl per-2-ethylhexanoate, t-butyl perphenylacetate, and t-butyl per-4-methoxyacetate; 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl) diacetate, 2,2'-azobis(2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2' -Azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, 2-(4-methylphenylazo)-2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3, 5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, 4-nitrophenyl Azo compounds such as ethyl azobenzylcyanoacetate, phenyl azodiphenylmethane, phenylazotriphenylmethane, 4-nitrotriphenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, azobisisobutyro Examples include azo compounds such as nitrile, dimethyl azobisisobutyrate, and phenylazotriphenylmethane, and metal chelate compounds such as Mn(acac) ₃ .
If necessary, a chain transfer agent such as lauryl mercaptan, thioglycerol, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a thiol compound having a coupling group such as γ-mercaptopropyltrimethoxysilane may be added to the chain. It may also be used as an additive such as a transfer agent.
The amount of the polymerization initiator (E) to be blended is preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of component (C).

In this embodiment, the double bond-containing polymerizable monomer (C) is polymerized by, for example, mixing and stirring a mixture containing the above-mentioned components while heating. As the method of mixing and stirring, it is preferable to use a known method.

In the production method of this embodiment, the reaction temperature varies depending on each raw material used, but from the viewpoints of reaction rate, solvent selectivity (solvent boiling point), and prevention of gelation, it is preferably carried out at 40° C. or higher and 200° C. or lower. More preferably, the temperature is 70°C or higher and 170°C or lower.
In the production method of the present invention, the reaction time is preferably 4 hours or longer, more preferably 12 hours or longer, from the viewpoints of complete reaction completion, reaction reproducibility, and manufacturing costs. Moreover, it is preferably 32 hours or less, more preferably 24 hours or less.
After the reaction is completed, it is preferable to purify the surface-modified carbon black by washing the obtained solid with water, reprecipitation, and drying.

3. Carbon black dispersion The carbon black dispersion (hereinafter, sometimes simply referred to as "dispersion") according to one embodiment of the present invention is a dispersion containing the above-mentioned surface-modified carbon black and a dispersion medium.
The dispersion medium is not particularly limited as long as it is a liquid in which the surface-modified carbon black of the present invention can be dispersed, but, for example, the solvent used in the method for producing the surface-modified carbon black of the present invention described above is preferred.
Only one type of dispersion medium may be used, or two or more types may be used in combination.

The concentration of surface-modified carbon black in the carbon black dispersion is not particularly limited and can be adjusted as appropriate depending on the use of the carbon black. Usually, the amount is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the dispersion medium.

The method for dispersing surface-modified carbon black in a dispersion medium is not particularly limited, and any known method can be employed. Dispersing machines include, for example, three-roll mills and two-roll mills that finely disperse carbon black particles using shear stress, ball mills, attritors, and sand mills that finely disperse carbon black particles using impact force of media such as glass beads or zirconia beads. , coball mill, basket mill, vibration mill, paint conditioner, etc.; dispers, homogenizers, Clearmix (R), etc. that use rotating blades that generate shear stress, cavitation, collision force, potential core, etc., and carbon black. Examples include kneaders, extruders, jet mills, etc. that finely disperse particles or carbon black particles by collision force or shear force between the vehicle or the wall of the disperser, and ultrasonic dispersion machines that finely disperse particles using ultrasonic waves. It is not limited to this.

The carbon black dispersion according to this embodiment may contain components other than the surface-modified carbon black and dispersion medium described above. Examples include a binder component, a dispersant, a lubricant, an activator, a crosslinking agent, a leveling agent, an antifoaming agent, a solvent, a lubricant, a leveling agent, an antifoaming agent, and a preservative.

4. Black Resist Composition A black resist composition according to one embodiment of the present invention contains the surface-modified carbon black of the present invention.
In this embodiment, since the surface-modified carbon black of the present invention has excellent dispersibility and dispersion stability, a glossy and even coating film (cured product) can be formed.
The black resist composition of the present embodiment only needs to contain the surface-modified carbon black of the present invention, and other components are not particularly limited. Moreover, the black resist composition of this embodiment can be manufactured by a known method. For example, Japanese Patent Application Publication No. 2015-227406 can be referred to.

The black resist composition of the present embodiment contains known constituent members such as the surface-modified carbon black of the present invention, an alkali-soluble resin, a solvent, a polymerizable compound, and a photopolymerization initiator.
The alkali-soluble resin is a resin that is soluble in an alkaline solution that is a developer used when patterning a resist.
Examples of alkali-soluble resins include novolak resins obtained by condensing aromatic hydroxy compound derivatives such as phenol, cresol, xylenol, resorcinol, phloroglycinol, and hydroquinone with aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde; Polymers or copolymers of vinylphenol compound derivatives such as vinylphenol, m-vinylphenol, p-vinylphenol, and α-methylvinylphenol; (meth)acrylics such as acrylic acid, methacrylic acid, and hydroxyethyl (meth)acrylate. Acid-based polymers or copolymers; polyvinyl alcohol; modified products in which radioactive ray-sensitive groups such as quinonediazide groups, naphthoquinone azide groups, aromatic azide groups, and aromatic cinnamoyl groups are introduced through some of the hydroxyl groups of these various resins. Resin; Urethane resin containing acidic groups such as carboxylic acid and sulfonic acid in the molecule; Resin having a fluorene skeleton, epoxy (meth)acrylate, and acid anhydride polycondensate, and the like.
These alkali-soluble resins may be used alone or in combination of two or more.

Examples of the solvent for the black resist composition include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, and butyrolactone; methanol, ethanol, n-propyl alcohol, and - Alcohols such as propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane; Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate , esters such as ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, 2- Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxy Monocarboxylic acid esters such as butyl propionate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Propylene glycols such as monoethyl ether acetate and propylene glycol monobutyl ether acetate; diethyler glycol monomethyl ether, diethyler glycol monoethyl ether, diethyler glycol dimethyl ether, diethyler glycol diethyl ether, diethyler glycol methyl ethyl Diethylene glycols such as ether; halogenated hydrocarbons such as trichloroethylene, chlorofluorocarbon solvents, HCFC, HFC; fully fluorinated solvents such as perfluorooctane; aromatics such as toluene and xylene; dimethylacetamide, dimethylformamide, Examples include polar solvents such as N-methylacetamide and N-methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

The polymerizable compound is a compound having a photopolymerizable functional group that can be polymerized or crosslinked by irradiation with active energy rays such as ultraviolet rays.
Examples of the above polymerizable compounds include unsaturated carboxylic acids such as (meth)acrylic acid, esters of monohydroxy compounds and unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic compounds. Esters obtained by esterification reactions between polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyhydric carboxylic acids, and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. , a polymerizable compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound, a polymerizable compound having an acid group, and the like.
The polymerizable compounds may be used alone or in combination of two or more.

Examples of the ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolethane tri(meth)acrylate. meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa Examples include (meth)acrylic acid esters such as (meth)acrylate and glycerol (meth)acrylate.
Also included are itaconic acid esters in which the (meth)acrylic acid portion of these acrylates is replaced with itaconic acid, crotonic acid esters in which crotonic acid is replaced, or maleic esters in which the (meth)acrylic acid portion is replaced with maleic acid.

Examples of the ester of the aromatic polyhydroxy compound and unsaturated carboxylic acid include hydroquinone di(meth)acrylate, resorcin di(meth)acrylate, and pyrogallol tri(meth)acrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyhydric carboxylic acid, and a polyhydric hydroxy compound may be a single substance or a mixture. Such esters include, for example, esters obtained from (meth)acrylic acid, phthalic acid and ethylene glycol, esters obtained from (meth)acrylic acid, maleic acid and diethylene glycol, (meth)acrylic acid, terephthalic acid and penta Examples include esters obtained from erythritol, esters obtained from (meth)acrylic acid, adipic acid, butanediol, and glycerin.

Examples of the polymerizable compound having a urethane skeleton obtained by reacting the polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; fatty acids such as cyclohexane diisocyanate and isophorone diisocyanate; Cyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; and (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 3-hydroxy[1,1,1-tri(meth)acryloyloxymethyl]propane. Examples include reactants with hydroxy compounds having an acryloyl group.

The polymerizable compound having an acid group is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride. A polyfunctional polymerizable compound having an acid group is preferred. The aliphatic polyhydroxy compound used for preparing the polyfunctional polymerizable compound is preferably pentaerythritol or dipentaerythritol.
The acid value of the polyfunctional polymerizable compound is preferably in the range of 0.1 to 40, more preferably in the range of 5 to 30, since it provides good developability, curability, etc. When using two or more types of polyfunctional polymerizable compounds having an acid group together, or when using a polyfunctional polymerizable compound having an acid group and a polyfunctional polymerizable compound not having an acid group together, a mixture of polymerizable compounds is used. It is preferable that the acid value of is within the above range.

Specific examples of the polymerizable compound having an acid group include a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and a succinic acid ester of dipentaerythritol pentaacrylate as a main component, and the mixture is Aronix TO -1382 (manufactured by Toagosei Co., Ltd.).

Examples of polymerizable compounds other than those mentioned above include (meth)acrylamides such as ethylene bis(meth)acrylamide; allyl esters such as diallyl phthalate; and compounds having a vinyl group such as divinyl phthalate.

The content of the polymerizable compound is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 70% by mass, and more preferably in the range of 20 to 50% by mass based on the total solid content of the resist composition. It is more preferable that

A photopolymerization initiator refers to a compound that generates radicals by bond cleavage and/or reaction upon exposure to light. By containing a photopolymerization initiator, curing of exposed areas is promoted and sensitivity can be improved.

The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used. Examples of photopolymerization initiators include benzyl ketal photopolymerization initiators, α-hydroxyketone photopolymerization initiators, α-aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime ester photopolymerization initiators. Examples include acridine-based photopolymerization initiators, titanocene-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, and benzoic acid ester-based photopolymerization initiators. It will be done.

The photopolymerization initiators may be used alone or in combination of two or more.
The amount of the photopolymerization initiator is preferably 0.1 parts by mass or more, more preferably 5 parts by mass, based on 100 parts by mass of the alkali-soluble resin, since good sensitivity and desired patterns can be obtained. It is more than part by mass. Moreover, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

As for the coating method, any known and publicly used coating method can be used, such as slit coater, slit & spin coater, spin coater, roll coater, electrostatic coating, bar coater, gravure coater, die coater, knife. Methods include coater, inkjet, dipping coating, spray coating, shower coating, screen printing, gravure printing, offset printing, and reverse coating.
After coating, a cured film of the black resist composition is obtained by drying. The cured film is suitable for, for example, a black matrix used in display devices.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
Note that the embodiments of the present invention are not limited to the following examples.

[Synthesis of calixarene compounds]
(Synthesis example 1)
In a 500 ml four-necked flask equipped with a cooling tube, 37.5 g of resorcinol (0.34 mol: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 1,3-dihydroxybenzene) and 53.0 g of decylaldehyde (0.34 mol: manufactured by Kao Chemical) were added. , aliphatic aldehyde having 10 carbon atoms), 94.0 g of butanol, and 3.8 g of 95% sulfuric acid were stirred and reacted under reflux at 80° C. for 4 hours using a mantle heater. After the reaction, ethyl acetate and water were added and washing was performed five times. After the solvent was distilled off under reduced pressure from the remaining resin solution, vacuum drying was performed to obtain 79.5 g of resorcincalixarene powder (a-1) as a pale red powder.

(Synthesis example 2)
76.8 g of resorcincalixarene powder (a-2) was obtained in the same manner as in Synthesis Example 1 except that decylaldehyde was changed to hexylaldehyde (0.34 mol: Kao Chemical, aliphatic aldehyde with 6 carbon atoms). .

(Synthesis example 3)
76.1 g of resorcincalixarene powder (a-3) was obtained in the same manner as in Synthesis Example 1 except that decylaldehyde was changed to propionaldehyde (0.34 mol: Kao Chemical Co., Ltd., aliphatic aldehyde with 3 carbon atoms). .

(Synthesis example 4)
77.3 g of resorcincalixarene powder (a-4) was added in the same manner as in Synthesis Example 1 except that decylaldehyde was changed to benzaldehyde (0.34 mol: Fuji Film Wako Pure Chemical Industries, Ltd., aromatic aldehyde with 7 carbon atoms). Obtained.

[Production and evaluation of surface-modified carbon black and dispersion]
(Example 1)
In a 500 ml four-necked flask equipped with a cooling tube, 0.6 g of resorcincalixarene powder (a-1) and 60 g of carbon black powder (b-1) produced by the furnace method (manufactured by Mitsubishi Chemical: #3350B (primary Particle size: about 20 nm)), 12.0 g of a double bond-containing polymerizable reactive monomer (c-1) (styrene), 0.02 g of benzoyl peroxide, and 108.4 g of toluene were heated in a mantle heater under reflux at 70°C. The reaction was stirred for 4 hours. After the reaction, washing was performed by adding methanol and water to precipitate the solid content and removing the supernatant liquid three times. After the solvent was distilled off under reduced pressure from the remaining solid solution, vacuum drying was performed to obtain 67.3 g of black surface-modified carbon black powder (A-1).
By mixing 20 g of the surface-modified carbon black powder (A-1) obtained above with 180 g of N-methylpyrrolidone as a dispersion medium, and performing a dispersion treatment using an ultrasonic homogenizer (Yamato Scientific Co., Ltd.: LUH300) for 10 minutes. , a carbon black dispersion (B-1) was obtained.

(Example 2)
68.4 g of black surface-modified carbon black powder (A-2) in the same manner as in Example 1 except that resorcincalix arene powder (a-2) was used instead of resorcincalix arene powder (a-1). I got it.
Using the obtained surface-modified carbon black powder (A-2), a carbon black dispersion (B-2) was obtained in the same manner as in Example 1.

(Example 3)
67.4 g of black surface-modified carbon black powder (A-3) in the same manner as in Example 1 except that resorcincalix arene powder (a-3) was used instead of resorcincalix arene powder (a-1). I got it.
Using the obtained surface-modified carbon black powder (A-3), a carbon black dispersion (B-3) was obtained in the same manner as in Example 1.

(Example 4)
68.3 g of black surface-modified carbon black powder (A-4) in the same manner as in Example 1 except that resorcincalixarene powder (a-4) was used instead of resorcincalixarene powder (a-1). I got it.
Using the obtained surface-modified carbon black powder (A-4), a carbon black dispersion (B-4) was obtained in the same manner as in Example 1.

(Example 5)
A black powder was prepared in the same manner as in Example 1, except that the carbon black powder was carbon black powder (b-2) produced by the acetylene method (Fuji Film Wako Pure Chemical Industries, Ltd.: Acetylene black (primary particle size approximately 40 nm)). 66.9 g of surface-modified carbon black powder (A-5) was obtained.
Using the obtained surface-modified carbon black powder (A-5), a carbon black dispersion (B-6) was obtained in the same manner as in Example 1.

(Example 6)
68.0 g of black surface-modified carbon black powder (A-6) was obtained in the same manner as in Example 1, except that methyl methacrylate (c-2) was used as the double bond-containing polymerization-reactive monomer.
Using the obtained surface-modified carbon black powder (A-6), a carbon black dispersion (B-6) was obtained in the same manner as in Example 1.

(Comparative example 1)
68.9 g of black surface-modified carbon black powder (A-7) was obtained in the same manner as in Example 1 except that resorcincalixarene powder (a-1) was not used.
Using the obtained surface-modified carbon black powder (A-7), a carbon black dispersion (B-7) was obtained in the same manner as in Example 1.

(Comparative example 2)
60 g of the same carbon black powder (b-1) as in Example 1, 1800 g of sulfolane, and 5 g of sulfamic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were mixed, and the agglomerated particles were subjected to a stirring reaction at 140°C for 5 hours to obtain carbon black. The surface was treated. After the reaction, the surface-treated carbon black was washed several times with excess solvent, poured into water, and the precipitate was filtered, followed by vacuum drying to obtain surface-treated carbon black powder (A-8).
Using the obtained surface-treated carbon black powder (A-8), a carbon black dispersion (B-8) was obtained in the same manner as in Example 1.

(Evaluation of dispersibility)
For some of the carbon black dispersions prepared in Examples 1 to 6 and Comparative Examples 1 and 2, on the day of preparation, the concentration was adjusted to 0.1 to 0.5 kg/cm using N-methylpyrrolidone as a dispersion medium. It was diluted to ³ . For this carbon black dispersion, the average particle size of the particles in the dispersion was measured using a heterodyne laser Doppler particle size distribution analyzer (manufactured by Microtrac, UPA model 9340). The value of 50% cumulative frequency (Dupa50%) was taken as the average particle diameter.
When the average particle diameter was less than 200 nm, the dispersibility was good (◯), and when the average particle diameter was 200 nm or more, the dispersibility was poor (×). The results are shown in Table 1.

(Evaluation of dispersion stability)
For the carbon black dispersions of each of the above examples, the average particle diameter was measured after 4 weeks had passed from the date of preparation under the same conditions as described above, and changes in the average particle diameter were evaluated.
When the change in average particle size was less than +10%, the dispersion stability was evaluated as good (○), and when the change in the average particle size was +10% or more, the dispersion stability was evaluated as poor (x).
The results are shown in Table 1.

From Table 1, it can be seen that the dispersion containing surface-modified carbon black obtained by polymerizing a double bond-containing polymerizable monomer in the presence of carbon black and a calixarene compound has a difference in molecular structure derived from the aldehyde compound in the calixarene compound. It can be seen that the dispersibility and dispersion stability are excellent regardless of the type of carbon black (Examples 1 to 4) and regardless of the type of carbon black or the double bond-containing polymerization-reactive monomer (Examples 5 to 6).
Furthermore, from Table 1, it is clear that a dispersion containing surface-modified carbon black obtained by polymerizing a double bond-containing polymerizable monomer in the presence of carbon black without the presence of a calixarene compound has both dispersibility and dispersion stability. It can be seen that the sample is also defective (Comparative Example 1). Furthermore, it can be seen that a dispersion in which carbon black was simply treated with a surface treatment agent was also poor in both dispersibility and dispersion stability (Comparative Example 2).

[Preparation and evaluation of black resist composition]
(Example 7)
In a 10 ml screw tube, 3 g of the carbon black dispersion (B-1) obtained in Example 1, 0.07 g of dipentaerythritol hexaacrylate, and an acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton as an alkali-soluble resin ( Solid content 56% by mass, 0.52 g of V259ME (manufactured by Nippon Steel Chemical Co., Ltd.), 0.03 g of photopolymerization initiator Irgacure OXE02 (manufactured by BASF Japan), and 1.39 g of propylene glycol monomethyl ether acetate were added, and stirred with a magnetic stirrer. After stirring for 10 minutes, a black resist composition (C-1) was obtained. The carbon black content in the black resist composition is 6% by mass.

(Examples 8 to 12, Comparative Examples 3 and 4)
A black resist composition (C -2) to (C-8) were prepared.

(Evaluation of film formability of coating film)
The black resist compositions obtained in Examples 7 to 12 and Comparative Examples 3 and 4 were applied onto a 150 mm x 150 mm glass using a spin coater so that the film thickness after drying was 1 μm, This was dried for 1 minute on a hot plate with a surface temperature of 90°C to form a coating film. The film formability of the obtained coating film was evaluated.
A film that was glossy and had no unevenness was rated as having good film formability (〇), and a film that was not glossy or had unevenness was rated as poor film formability (x).
The results are shown in Table 2.

Table 2 shows that the black resist compositions containing the carbon black dispersion of the present invention have excellent film forming properties (Examples 7 to 12).

Claims (12)

A surface-modified carbon black, wherein a polymer of a double bond-containing polymerizable monomer is present on part or all of the surface of the carbon black, and the polymer of the double bond-containing polymerizable monomer contains a calixarene compound. The surface-modified carbon black according to claim 1, wherein the calixarene compound is a compound represented by the following formula (1).

(In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. .n is an integer from 3 to 6.) The surface-modified carbon black according to claim 2, wherein R ₁ is a phenyl group or an alkyl group having 2 to 10 carbon atoms. The double bond-containing polymerization-reactive monomer is styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate. Butyl acid, glycidyl (meth)acrylate and glycidyl vinyl ether, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, 4-vinylcyclohexene 1,2-epoxide, epoxycyclohexenyl (meth)acrylate, 2-oxetanyl The surface-modified carbon black according to any one of claims 1 to 3, which is one or more selected from propyl (meth)acrylate, ethylene glycol di(meth)acrylate, and 1,3-butylene glycol di(meth)acrylate. . The surface-modified carbon black according to claim 4, wherein the double bond-containing polymerization-reactive monomer is one or more selected from styrene compounds, acrylates, and methacrylates. A carbon black dispersion comprising the surface-modified carbon black according to any one of claims 1 to 5 and a dispersion medium. A black resist composition comprising the surface-modified carbon black according to any one of claims 1 to 5. A cured film of the black resist composition according to claim 7. A mixture containing (A) carbon black, (B) a calixarene compound, (C) a double bond-containing polymerization-reactive monomer, (D) a solvent, and (E) a polymerization initiator is prepared, and the (C) A method for producing surface-modified carbon black, comprising the step of polymerizing a bond-containing polymerizable monomer. The manufacturing method according to claim 9, wherein the calixarene compound (B) is a compound represented by the following formula (1).

(In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group. R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group. .n is an integer from 3 to 6.) The manufacturing method according to claim 10, wherein the R ₁ is a phenyl group or an alkyl group having 2 to 10 carbon atoms. The double bond-containing polymerization-reactive monomer (C) is styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, ( Butyl meth)acrylate, glycidyl (meth)acrylate and glycidyl vinyl ether, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, 4-vinylcyclohexene 1,2-epoxide, epoxycyclohexenyl (meth)acrylate, 12. The monomer according to claim 9, wherein the monomer is one or more monomers selected from 2-oxetanylpropyl (meth)acrylate, ethylene glycol di(meth)acrylate, and 1,3-butylene glycol di(meth)acrylate. Production method.