JPH10324819A - Carbon-black-composited polymer, its production and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel carbon-black-composited polymer having excellent dispersibility in various media in spite of its high carbon black content, excellent electrical insulation properties and sensitivity to light and heat. SOLUTION: There is provided a carbon-black-composited polymer obtained by dispersing carbon black in a block or graft polymer comprising segments (A) having amino, amido and/or nitrile groups and segments (B) having a structure different from that of segment A, wherein in the final state of the carbon- black-composited polymer, segments (A) and/or segments (B) have groups (II) reactive with the matrix being an objective medium to be compounded with the carbon-black-composited polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a carbon black composite polymer, a carbon black composite polymer obtained by the method and its use, and a method for producing a carbon black-containing resin composition. More specifically, the present invention relates to a novel carbon black composite polymer production technique characterized in that a block or graft polymer is complexed with carbon black and that it can react with a matrix of a target medium such as a binder.
The carbon black composite polymer of the present invention includes a resin composition, a coating composition, an ink, a thermal transfer ink, a thermal transfer ink ribbon coating agent, a magnetic recording medium back coating agent, an electrostatic charge developing toner, a paint, a high resistance and Materials requiring light shielding properties, black matrix for liquid crystal color filters, artificial marble, coloring agents such as plastic or rubber molding materials, rubber-like modifiers such as polyolefins and polyesters, fillers and resistance adjusters,
It can be used for a sheet heating element, a lubricant, a traction drive fluid, an electrorheological fluid, a non-linear optical material, and the like, and particularly useful for various thermosetting and photocurable compositions.

[0002]

2. Description of the Related Art Carbon black is colored, conductive,
Because of its excellent weather resistance, chemical resistance and the like, it is widely used for various purposes such as reinforcing agents and fillers for plastics and elastomers. However, carbon black is
Because the shape is powdery or granular, it is rarely used alone, and usually exhibits its properties by being uniformly dispersed in a solid base material such as rubber or resin or a liquid such as water or solvent. . However, carbon black has low affinity for other substances, such as organic polymers, water and organic solvents, as compared with the cohesive force between particles. It was extremely difficult to do. In order to solve this problem, the carbon black surface is coated with various surfactants and resins to improve the dispersibility of the carbon black by increasing the affinity with a solid or liquid base material. Many studies have been made.

[0003] A carbon black graft polymer obtained by polymerizing a polymerizable monomer in the presence of carbon black has a hydrophilicity and / or a lipophilicity which is appropriately determined by appropriately selecting the type of the polymerizable monomer. Attention has been paid to the fact that it can be changed (for example,
22047, JP-B-44-3826, JP-B-45-
17248, JP-B-46-26970). However, the yield of the carbon black graft polymer obtained by these methods is as low as several% to several tens%, most of them are present in the form of vinyl homopolymer, and the surface treatment efficiency of carbon black is extremely low. . For this reason, the affinity with other substances is not improved as expected, and the dispersion state often differs depending on the mixing or dispersion conditions.

[0004] In order to solve this problem, there has been proposed a carbon black graft polymer obtained by reacting a polymer having a reactive group such as an epoxy group or an aziridine group in a molecule with carbon black (Japanese Patent Publication (Kokai) No. Hei 10-26). 2-2
No. 4868, Japanese Patent Publication No. 6-27269), and the carbon black graft polymer had improved dispersibility in various substances.

[0005] However, this carbon black graft polymer is a polymer in which the polymer has a functional group reactive with carbon black, but the polymer chain has only lipophilic or hydrophilic properties. Therefore, it is sufficient to satisfy both conflicting requirements in many cases in terms of grafting efficiency for carbon black and improvement of dispersibility in various target media to be imparted by the grafted polymer chains. It was difficult.

Therefore, a) the carbon content in the carbon black graft polymer cannot be increased, b)
Highly polar media, such as alcohols, cellosolve solvents or the like, or low polar media, such as hydrocarbon solvents or silicone solvents, cannot provide sufficient dispersibility.
c) There was a problem that grafting in an organic solvent was difficult. Therefore, the carbon black graft polymer cannot be used for i) applications where a high carbon black content is desired, such as a black matrix for a liquid crystal color filter. Ii)
It cannot be used for applications requiring high electrical insulation, such as an electrorheological fluid and a sealant for semiconductor devices.

Further, in the conventional carbon black dispersion, for example, a carbon black masterbatch, the final product is thermally unstable due to the fact that it is dispersed only due to the compatibility with the binder, and the high filling ratio is high. Then, there was a problem of insufficient strength.

[0008] A color filter used in a color liquid crystal display device or the like has, as pixels, at least two or more kinds of fine layers colored in color layers, and blocks light between the pixels to display an image. Conventionally, a black matrix is formed to improve the contrast of an image.

Such a black matrix is usually made of a fine pattern of Cr, Ni, A on a glass substrate.
and the like, and is formed by patterning a metal thin film deposited on a substrate by a vapor deposition method, a sputtering method, a vacuum film forming method, or the like by using a photolithography technique.

[0010] However, the black matrix manufactured in this manner has a high production cost due to the complexity of the process, so that there is a problem that the cost of the color filter itself using the black matrix also increases.

Further, when a color filter having a black matrix using a metal thin film of Cr or the like is mounted on a transmission type display, when a strong external light impinges on the filter due to the high reflectance of the metal surface, the reflected light is reduced. There is also a problem that display quality is significantly reduced.

On the other hand, in order to solve the problems of the black matrix using a metal thin film as described above, various methods for forming a black matrix with a resin composition containing a colorant have been proposed.

For example, Japanese Patent Application Laid-Open No. 2-239204 proposes a method in which a light-shielding material such as carbon black is dispersed in a polyimide resin and a black matrix is formed using the light-shielding material. According to this method, there is little external light reflection, and a highly reliable polyimide-based resin having high heat resistance can be obtained, but this method uses a polyimide-based resin composition containing a light-shielding material as a substrate. After coating and drying, a photoresist is further applied, followed by steps of patterning, etching, and resist peeling, which are insufficient in terms of simplification of the process and cost reduction.

Further, a black pigment such as carbon black is blended in the photocurable resin composition, and the photocurable resin composition is applied to a substrate and dried. Attempts have been made to develop a black matrix having a predetermined pattern by development.

However, when the compounding amount of carbon black is increased in order to obtain a sufficient light-shielding property as a black matrix, for example, the amount of carbon black necessary for curing the photo-curable resin is increased.
Since the transmittance of light in the ultraviolet region around 00 nm is extremely reduced, it is extremely difficult to perform photocuring. Further, carbon black captures radicals generated from the photopolymerization initiator by ultraviolet rays. Therefore, photopolymerization was hindered, and it was difficult to form pixels with sufficient economical exposure. When the amount of carbon black added increases, the resulting film becomes conductive, and can no longer be used as a black matrix for liquid crystal displays and the like. In addition, carbon black has a weaker affinity with other substances, such as organic polymers, water and organic solvents, than the cohesive force between particles, and therefore is uniform in the photocurable resin composition as described above. It was extremely difficult to mix or disperse the dyes in the dye, and it was also difficult to obtain a stable and uniform black layer.

In JP-A-4-63870,
As a colorant to be added to the photocurable resin composition, using a set of organic pigments of different colors exhibiting black in combination with carbon black, an increase in the amount of carbon black added to obtain a predetermined light shielding property. It has been proposed to suppress the decrease in transmittance of light in the ultraviolet region required for photo-curing, and to maintain the insulating properties of the film.

However, when an organic pigment is used in combination as described above, the light transmittance in the visible region is increased as compared with the case where only carbon black is used. It has been difficult to form the compound, and the problem of dispersibility of carbon black and the problem of inhibition of photocuring due to radical scavenging by carbon black have not been solved at all.

Meanwhile, with respect to improving the dispersibility of carbon black, studies on coating the surface of carbon black with various surfactants and resins to increase the affinity with a solid or liquid base material are as described above. Application to various photocurable resin compositions is not limited, and many applications have been made conventionally.

For example, (1) a carbon black graft polymer obtained by polymerizing a polymerizable monomer in the presence of carbon black can obtain hydrophilicity and / or hydrophilicity by appropriately selecting the type of polymerizable monomer. In addition, attention has been paid to lipophilicity which can be appropriately changed (for example, Japanese Patent Publication No. 4222047 and Japanese Patent Publication No. 44-3826).
No., JP-B-45-17248, JP-B-46-2697
No. 0).

Further, (2) a carbon black graft polymer obtained by reacting a polymer having a reactive group such as an epoxy group or an aziridine group in a molecule with carbon black has also been proposed (Japanese Patent Publication No. 24868/1990). No. 6-27269).

However, the yield of the carbon black graft polymer obtained by the method (1) is several percent to 1%.
It was as low as 0% and mostly in the form of a vinyl homopolymer, and the surface treatment efficiency of carbon black was extremely low. For this reason, the affinity with other substances is not improved as expected, and the dispersion state often differs depending on the mixing or dispersion conditions.

The carbon black graft polymer of the above (2) has a considerably improved dispersibility in various substances. However, this carbon black graft polymer has a high reactivity with carbon black. Although having a functional group, the polymer chain had only either lipophilic or hydrophilic properties,
In many cases, it is difficult to sufficiently satisfy both conflicting demands in terms of graft efficiency for carbon black and improvement in dispersibility in various target media to be imparted by the grafted polymer chains. there were.

Therefore, a) the carbon content in the carbon black graft polymer cannot be increased, b)
Highly polar media, such as alcohols, cellosolve solvents or the like, or low polar media, such as hydrocarbon solvents or silicone solvents, cannot provide sufficient dispersibility.
c) There was a problem that grafting in an organic solvent was difficult.

JP-A-6-67421 discloses a photocurable resin composition having excellent photosensitivity and dispersion stability suitable for obtaining a black matrix having excellent light-shielding properties and resolution. A composition in which a carbon black graft polymer such as the above (2) is blended as a coloring agent in a conductive resin composition has been proposed. However, as described above, a sufficient light-shielding property cannot be obtained because the carbon content in the carbon black graft polymer cannot be increased, the dispersibility does not reach a satisfactory level, and the sensitivity and photocuring properties are not improved. The strength of the cured film was not sufficient.

Further, when a film such as a black matrix is formed by using such a photocurable resin composition,
After exposure hardening and development, the film is completely cured to improve the adhesion between the substrate and the film.
Heat treatment (after-baking) is performed at a temperature of 0 to 300 ° C. At the time of this heat treatment, it is considered that the dispersion state of carbon black or carbon black graft polymer present in the coating changes. It has been observed that the resistivity of the coating decreases significantly after after-baking. For this reason, it was no longer applicable as a black matrix of a liquid crystal color filter.

[0026]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel carbon black composite polymer, a method for producing the same, and a use thereof.

Another object of the present invention is to provide a binder having a high carbon black content, excellent dispersibility in a binder or other various media, and curing of the medium when added to various light or thermosetting media. It is an object of the present invention to provide a novel carbon black composite polymer which can easily form a high-strength film even at a high addition amount without hindering the addition and which is excellent in various physical properties such as electric insulation, and a method for producing the same.

Another object of the present invention is to provide a novel crosslinking agent for a binder component, which is a black colored material.

Still another object of the present invention is to provide a resin composition,
Rubber composition, coating composition, ink, thermal transfer ink, ink ribbon coating agent for thermal transfer, back coating agent for magnetic recording media, toner for electrostatic charge development, paint, sheet heating element, resistance adjuster, lubricant, An object of the present invention is to provide a useful carbon black composite polymer excellent in dispersibility in various media such as a traction drive fluid, an electrorheological fluid, and a nonlinear optical material.

Still another object of the present invention is to provide a photocurable resin composition useful for forming a black matrix of a color filter.

[0031]

The above objects are achieved by the following (1) to (18).

(1) A block or graft type polymer comprising a segment (A) having an amino group, an amide group and / or a nitrile group and a segment (B) having a different structure from the segment (A), and carbon black Is a carbon black composite polymer obtained by mixing and dispersing the carbon black composite polymer. In the final form of the carbon black composite polymer, the segment (A) and / or (B) is a matrix of a target medium in which the carbon black composite polymer is blended. (II) reactive with
A carbon black composite polymer comprising:

(2) A group (II) in which the segments (A) and / or (B) are reactive with a matrix of a target medium containing the carbon black composite polymer.
The carbon black composite polymer according to the above (1), comprising:

(3) The group (II) is at least one or more selected from the group consisting of an unsaturated double bond group, a carboxyl group and an alkoxysilyl group. The carbon black composite polymer according to 2).

(4) The segment (B) has a polysiloxane structure, a poly (meth) acrylic structure, a polyether structure, a poly (meth) acrylonitrile structure, a polyester structure, a polyalkylene structure, a polyamide structure,
The carbon black composite polymer according to any one of the above (1) to (2), which is at least one kind or two or more kinds selected from the group consisting of a polyimide structure, a polyurethane structure and a fluorine-based resin structure.

(5) The above (1) to (4), wherein the segment (A) is obtained by polymerization of a vinyl monomer composition containing 0.5 mol% or more of aminoalkyl (meth) acrylate. The carbon black composite polymer according to any one of the above.

(6) In the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium, an amino group,
A block or graft polymer having a segment (A) having an amide group and / or a nitrile group and a segment (B) having a higher affinity for the dispersion medium than the segment (A); A method for producing a carbon black composite polymer, which comprises mixing and dispersing black.

(7) In the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium, an amino group,
A segment (A) having an amide group and / or a nitrile group; and a segment (B) having a higher affinity for the dispersion medium than the segment (A), and the segments (A) and / or Or segment (B)
And mixing and dispersing a block or graft polymer containing a group (II) having reactivity with a matrix of a target medium with carbon black.

(8) a) A segment (A) having an amino group, an amide group and / or a nitrile group, and the segment (A) in the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium. A) a block or graft type precursor polymer having a segment (B) having a higher affinity for the dispersion medium liquid than that of the dispersion medium liquid, and carbon black are mixed and dispersed in advance, and then b) the block or graft type A method for producing a carbon black composite polymer, comprising introducing a group (II) having reactivity with a matrix of a target medium into a precursor polymer.

(9) a) A segment (A) having an amino group, an amide group and / or a nitrile group, and the segment (A) in the presence of a dispersion medium comprising a target medium or a medium having properties close thereto. ) Having a higher affinity for the dispersion medium liquid than the dispersion medium liquid (B),
A precursor polymer having a functional group (III) having substantially no reactivity with the functional group on the surface of carbon black is mixed and dispersed in advance with carbon black. Compound (d) having a reactive group (IV) capable of reacting with the functional group (III) possessed by the union and a group (II) having reactivity with the matrix of the target medium, is a precursor polymer obtained by the above a) A method for producing a carbon black composite polymer, which comprises reacting the compound (C) with a grafted carbon black to introduce the group (II) into a precursor polymer.

(10) A block or graft type having a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having a lower affinity for carbon black than the segment (A). A method for producing a carbon black composite polymer, comprising mixing and dispersing a polymer and carbon black.

(11) a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having a lower affinity for carbon black than the segment (A); (C) mixing and dispersing a block or graft polymer containing a group (II) having reactivity with a matrix of a target medium in (A) and / or a segment (B), and carbon black. A method for producing a black composite polymer.

(12) a) A block or graft having a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having a lower affinity for carbon black than the segment (A). Mixing and dispersing a precursor polymer of the type and carbon black, and then b) introducing a group (II) having reactivity with the matrix of the target medium into the block or graft type precursor polymer. Of producing a carbon black composite polymer.

(13) A black thermosetting resin composition obtained by blending the carbon black composite polymer according to any one of the above (1) to (5) into a thermosetting resin composition.

(14) A black photocurable resin composition comprising the carbon black composite polymer according to any one of the above (1) to (5) mixed with a photocurable resin composition.

(15) The black photocurable resin composition according to the above (15), wherein the molecular weight of the segment (B) of the carbon black composite polymer is 500 or more.

(16) The black photocurable resin composition according to the above (14) or (15), wherein an alkali-soluble resin is blended into the photocurable resin composition.

(17) A black matrix for a color filter, formed by the black photocurable resin composition according to any one of (14) to (16).

(18) A resistance adjuster containing the carbon black composite polymer according to any one of the above (1) to (5).

[0050]

The "carbon black composite polymer" as used herein refers to fine particles in which a polymer portion is bonded to a carbon black portion by ionic interaction.

Carbon black is usually several nm to several hundred n.
It has a particle size of m. However, since carbon black has a large cohesive force between particles, it is usually handled as an aggregate having a particle diameter of several microns or more. Further, the cohesive force between carbon blacks is remarkably large compared to the affinity between carbon black and another medium, and it is very difficult to disperse carbon black in a medium at a submicron level.
On the other hand, in the carbon black composite polymer, the polymer portion can effectively enter between the carbon black particles, and the cohesive force between the carbon blacks can be reduced. further,
When the polymer portion is compatible with the medium, the carbon black graft polymer can be dispersed in the medium at submicron levels. However, even if the polymer portion has a high affinity for the medium, if the polymer portion is not effectively grafted to the carbon black portion, its properties will not be stable and will vary. If a certain level of affinity is to be obtained, the content of the carbon black portion in the carbon black graft polymer will be low, and the application will be restricted.

The inventors of the present invention have intensively worked to obtain a carbon black graft polymer having desired properties by grafting a polymer portion to carbon black via a covalent bond. However, while the carbon black graft polymer obtained in this way can exhibit excellent properties, the functional group having reactivity with carbon black is oxazoline,
Aziridine, isocyanate, etc. had to be considered for safety, and the epoxy group had difficulties in the process, such as high heating temperature during grafting, so there is room for industrial improvement. was there.

As a result of intensive studies, the present inventors have found that a carbon black composite polymer in which a polymer portion is bonded to carbon black by ionic interaction has a higher reactivity than a covalent bond as described above. It is possible to obtain a carbon black composite polymer with high safety without paying attention to the temperature, and by disposing the polymer portion to have an appropriate structure as described later, the dispersibility of carbon black can be obtained by ionic bonding. Have been found to be able to sufficiently improve the various characteristics of.

In the present invention, a block type or graft type polymer is used as the polymer forming the polymer portion. This is because the polymer portion can be more effectively combined with carbon black and the various types of media can be used. This is because excellent dispersibility can be exhibited.

For example, as a polymer forming a polymer portion, a segment (B) having a high affinity for a target medium
And a segment (A) having a lower affinity for the target medium than the segment (B), and only an amino group, an amide group and / or an amino group capable of binding to carbon black by ionic interaction. Alternatively, a molecule is designed so as to have a nitrile group, and mixed and dispersed in a dispersion medium liquid composed of a target medium or a medium having properties (polarity) close to the target medium.

FIG. 1 shows a block type or an amino group, an amide group and / or a nitrile group described above in carbon black in a dispersion medium composed of a target medium or a medium having properties close to the target medium. It is a figure which shows typically the state in the carbon black surface vicinity at the time of mixing and dispersing a graft type polymer. Since the polymer is composed of the segment (A) having an amino group, an amide group and / or a nitrile group and the segment (B) having an affinity for a target medium as described above, it is not shown in the reaction system. As described above, since the segment (B) is oriented so as to extend completely into the dispersion medium, the segment (A) necessarily surrounds the surface of the carbon black particles, and the carbon black and the polymer become Since a field suitable for compounding is provided by ionic bonding, effective compounding is achieved.

In the carbon black composite polymer thus obtained, the graft chain bonded to the surface of the carbon black particles is oriented such that the segment (B) having a high affinity for the target medium is exposed to the outside.
It shows a high affinity for the target medium, and the carbon black composite polymer can be dispersed in the medium in submicron units.

Alternatively, based on the same concept, a segment (A) having an amino group, an amide group and / or a nitrile group may be compared with the segment (A) having substantially no amino group and having a higher carbon black content than the segment (A). A block or graft type weight having a segment (B) having a low affinity (in other words, a segment (A) having a high affinity for carbon black and a segment (B) having a high affinity for a target medium). The coalescence may be compounded with carbon black.

In the reaction system, since the segment (A) of the polymer is oriented to the carbon black side, the amino group, amide group and / or nitrile group present in the segment (A) are replaced with carboxyl groups on the carbon black surface. And more effectively by ionic interaction.
In the carbon black composite polymer thus obtained, the graft chains bonded to the surface are oriented so that the segment (B) having a high affinity for the target medium is exposed to the outside. Show,
The carbon black composite polymer can be dispersed in a medium in sub-micron units. In this case, unlike the above-mentioned case, it is necessary to carry out grafting in a dispersion medium composed of a medium having an affinity for the segment (B), a target medium or a medium having properties close thereto. However, it is possible to melt-knead only the polymer and carbon black, or to react them in a dispersion medium having almost the same affinity for both the segment (A) and the segment (B). For more reliable and efficient compounding, it is desirable to carry out the compounding in a dispersion medium having an affinity for the segment (B).

As described above, the carbon black composite polymer formed by using a block type or graft type polymer as the polymer forming the polymer portion has the polymer portion more effectively compounded and has a more excellent dispersibility. Compared to conventional carbon black graft polymer, it can be dispersed well in various media and can increase the carbon content in the carbon black composite polymer, alleviating the polymerization inhibition effect of carbon black itself , Electrical insulation can be increased, and compounding is easy even in an organic solvent.

If a block-type or graft-type polymer is used as the polymer forming the polymer portion to form a carbon black composite polymer, aspects such as improvement in dispersibility, mitigation of polymerization inhibition effect, and improvement in electrical insulation can be obtained. Although improved, for example, when such a carbon black composite polymer is blended into a photo-curable resin composition to form a black photo-curable resin composition, the carbon black composite polymer having such a structure also has It cannot substantially participate in the curing reaction such as polymerization or photocrosslinking, and in order to obtain sufficient photocuring properties, it is necessary to blend a large amount of the photocurable compound with respect to the blending amount of the carbon black composite polymer. In particular, the upper limit is imposed on the amount of the carbon black composite polymer, making it difficult to obtain a sufficient light-shielding property with a thin film. Similarly, in a mode in which the medium in which the carbon black composite polymer is disposed becomes a cured product by photopolymerization, thermal polymerization, heat crosslinking reaction, or the like, the carbon black composite polymer has reactivity with respect to the medium serving as the matrix. It is desirable to obtain good curing characteristics and dispersion stability of carbon black.

Therefore, in a preferred embodiment of the present invention, the block type or graft type polymer forming the polymer portion of the carbon black composite polymer is:
The carbon black composite polymer has a functional group (II) having a reactivity with a matrix of a target medium such as a binder, for example, an unsaturated double bond. This functional group (II) reacts with the matrix of the target medium, and eventually, the carbon black and the polymer are bonded by ionic interaction, and furthermore, the polymer is covalently bonded to the matrix of the target medium, so that the high functionality is obtained. Not only can a composition having a high resistance value and a high mechanical strength be obtained, but also a composition having a small change in resistance value and a small change in strength can be obtained.

In addition, a functional group (II) such as an unsaturated double bond is introduced into the segment oriented outward, that is, the segment (B), without being subjected to bonding by ionic interaction with the carbon black surface. Then, when the obtained carbon black composite polymer is blended into a photocurable resin composition or the like, the curing reaction of the composition proceeds more favorably,
Although a thin film can provide sufficient light-shielding properties, and is extremely excellent in terms of film strength and carbon black dispersion stability, such a functional group (II) is introduced into the segment (A). Even if it was, the results could be expected to be considerably better than those having no functional group (II). It is a matter of course that both the segment (A) and the segment (B) may have such a functional group (II).

It has been found that the carbon black composite polymer having such a functional group (II) according to the present invention has an effect somewhat similar to a silane coupling agent and the like, unlike a mere carbon black dispersion. did.

When a carbon black composite polymer is formed using a block type or graft type polymer as the polymer forming the polymer portion, the chain length of the outwardly oriented segment (B) is longer than a certain length. For example, when the molecular weight of the segment (B) is about 1000 or more, when the carbon black composite polymer is blended in the target medium, the segment (B) of the carbon black composite polymer in the matrix of the target medium has a wedge-like shape. Since it exists in a form, it exhibits a more stable dispersion state. Therefore, even when the target medium is a photocurable resin composition or the like, depending on the composition system, reaction conditions, or the like, even if the target medium does not have the functional group (II) as described above. It was also found that excellent characteristics could be exhibited without any difference in film strength and the like. Therefore, in another preferred embodiment of the present invention, the segment (B) of the block type or graft type polymer has a relatively long chain length.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail based on embodiments.

The carbon black used for producing the carbon black composite polymer of the present invention is not particularly limited as long as it has a functional group such as a carboxyl group or a hydroxy group on its surface. Any kind of black, acetylene black, lamp black and the like can be used, and ordinary commercial products can be used as they are, but those having a carboxyl group are preferred. Further, it is preferable to use carbon black having a pH of less than 7, particularly 1 to 5 as the carbon black. A carbon black having a carboxyl group can be easily obtained as an acidic carbon black, but a carbon black obtained by oxidizing a neutral or basic carbon black can also be suitably used as a raw material in the present invention. When the carbon black does not have a functional group such as a carboxyl group or has a pH of 7 or more, grafting may not be effectively performed. The test method for the pH of carbon black is based on JIS K 6211.

The carbon black has an average particle size of 0.0005 to 0.5 μm, particularly 0.001 to 0.2 μm.
It is preferably within the range of m. Average particle size is 0.0
Since carbon black having a size of less than 005 μm cannot be easily obtained, it has little industrial significance. In addition, the average particle size is 0.5
If it exceeds μm, sufficient dispersibility may not be imparted to the obtained carbon black composite polymer.

On the other hand, such a polymer that is complexed with carbon black by ionic bonding to form a polymer portion is composed of a segment (A) having an amino group, an amide group and / or a nitrile group, and an affinity for the medium. Or a graft type comprising a segment (B) having

Further, in a preferred embodiment of the present invention, the segments (A) and / or (B)
It is a polymer having a group (II) reactive with the matrix of the target medium in which the carbon black composite polymer is blended. The group (II) having reactivity with the matrix of the target medium is more preferably present in the segment (B), but may be present only in the segment (A) or in both. It may be.
This is because the group (II) reactive with the matrix of the target medium is in the segment (A) and the segment (B)
However, the dispersibility of the carbon black composite polymer obtained is not inferior at all because the segment (B) has an affinity for the medium even in the case where it is not present. This is because the matrix can react with the matrix.

Here, in the final form of the carbon black composite polymer according to the present invention, a block or graft polymer having a desired structure as described above (here,
The amino group, the amide group and / or the nitrile group of the segment (A) are in a state of being ionically bonded to the functional group on the carbon black surface. ), And in the production step of mixing and dispersing the polymer portion in the carbon black, the polymer does not necessarily have to have the desired structure as described above.

That is, for example, a carbon black composite polymer in which a matrix of a target medium and a block or graft polymer having a reactive group (II), which is the first preferred embodiment, is composited is obtained. In this case, as described below, (1) a segment (A) having an amino group, an amide group and / or a nitrile group
And a segment (A) and / or a segment (B) having a group (II) which is a block or graft type composed of a segment (B) having an affinity for the medium and which can react with the matrix of the target medium. In addition to the method of first forming a coalescence and mixing and dispersing it in carbon black, (2) a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having an affinity for a medium A) a block or graft-type precursor polymer consisting of) and carbon black are mixed and dispersed in advance, and then a group (II) reactive with the matrix of the target medium is introduced into the precursor polymer. (3) converting the group (II) having reactivity with the matrix of the target medium into a group having substantially no reactivity with carbon black (with a protecting group; By doing so, the polymer is introduced into a block or graft polymer composed of the segment (A) and the segment (B), and after mixing and dispersing the polymer and carbon black, the protecting group is removed to obtain the desired purpose. The carbon black composite polymer according to the present invention can also be produced by a method that exposes the group (II) reactive with the matrix of the medium.

As the block or graft type polymer, those having a simple structure such as an AB type block copolymer shown in FIG. 2A and an AB type graft copolymer shown in FIG. 2B can be used. Without limitation, the BAB type block copolymer shown in FIG. 2 (c) or a more advanced alternating block copolymer, and a plurality of B segments shown in FIG. 2 (d) are grafted to the A segment. Various types such as a comb-shaped graft copolymer and a star-shaped graft copolymer shown in FIG. In the drawing, Y represents a reactive group (II) capable of reacting with the matrix of the target medium. FIG. 2 (f) shows a state in which these various block or graft polymers are bonded to the surface of the carbon black particles (CB) by ionic interaction. The block or graft type polymer has any form as long as at least one segment (B) can be oriented with a certain degree of freedom outward from the surface of the carbon black particles in a state of being bound by ionic interaction. May be
Further, for example, even if the segment (A) has a plurality of types of segments (same as the segment (B)), the segment (A) and the segment (B) have different properties, for example, A different type of segment (hereinafter referred to as segment (C)) which has an intermediate property of the above, or has a function of increasing or decreasing "fluctuation" (mobility) of the graft chain in the medium, elongating the graft chain. ) May be arranged between the segment (A) and the segment (B). Here, the segment (C) may or may not have an amino group. However, it is generally considered that it is preferable that the segment does not have an amino group from the viewpoint of increasing the grafting efficiency. Can be Further, in some cases, it is possible to introduce a reactive group or the like capable of mutually cross-linking the (C) segment. Although the (C) segment is referred to for the sake of explanation, the (C) segment can be roughly classified into either the segment (A) or the segment (B) as described above.

FIG. 2 shows an embodiment in which the reactive group (II) represented by the symbol Y is present only in the segment (B), but as described above, the reactive group (II) It may be present only in (A) or both.

In a first preferred embodiment of the present invention, the polymer is introduced into a block or graft polymer.
The group (II) having reactivity with the matrix of the target medium can be appropriately selected depending on the type of the target medium, and examples thereof include an unsaturated double bond group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thioepoxy group, Examples include an aziridine group, an N-hydroxyacrylamide group, an oxazoline group, an isocyanate group, a silanol group, and a thiol group. That is, when the target medium is a radical polymerizable curable resin as a matrix, the group (II) includes an unsaturated double bond group. Specific examples include a case where a carbon black composite polymer having an unsaturated double bond group is added to a photocurable resin composition or the like, and a case where an unsaturated polyester is thermally cured. In the case of an unsaturated polyester-based curable resin, a carboxyl group and the like are mentioned. If the matrix is silicon based on the sol-gel method, an alkoxysilyl group may be mentioned.

In the present invention, the unsaturated double bond group is
For example, it refers to a vinyl group, an acryloyl group, a methacryloyl group, and the like, and an alkoxysilyl group means -Si (OR
¹⁾ (R ¹ is a hydrogen atom, an alkyl group or an optionally substituted at least one group selected from the group consisting of acyl group, when R ¹ are a plurality in one molecule, the plurality R ¹ May be the same or different.)
Represents a group represented by

Certain functional groups may not react with the binder component in certain curable compositions, in which case the carbon black composite polymer exists as a mere dispersion.
For example, a hydroxyl group is a non-reactive functional group in a photocurable composition, but in a phenolic resin curable composition, it forms a group (II) by performing a covalent bond with a matrix together with a melamine crosslinking agent. Can play a role. Therefore, the group (II) may be appropriately selected so as to react with the binder system.

Here, the matrix of the binder or the target medium referred to in the present specification will be described. In recent years, one of the methods used in reactive processing and the like is an example in which polymers having functional groups are reacted with each other. Based on the same idea, a polymer having reactivity with the group (II) is used. Is a binder or a matrix of a target medium as referred to in the specification of the present application. For example, taking the example of an acrylic photocurable composition,
Although the binder of this composition is divided into a non-crosslinked portion and a cured portion, the system can clearly be a curable composition because the polyfunctional acrylate involves a polymerization reaction by a photoinitiator or direct light. . At this time, it is considered that the reaction with the polyfunctional acrylate reacts with the binder or the matrix of the target medium. For example, in the case of an elastomer cured product, in the case of a polyurethane elastomer, a) a bifunctional polyol isocyanate is reacted with an isocyanate to form a prepolymer, and b) a bifunctional chain extender for improving the molecular weight is added ( Elastomer intermediate product), c) Cross-linking is completed using a trifunctional or higher polyfunctional compound or the like. In this case also, it can be said that as long as it has a group (II) that can react with the trifunctional or higher polyfunctional compound in step c), it has reacted with the polyurethane binder or the matrix of the target medium. As in these examples, a polyfunctional crosslinking agent or vulcanizing agent can also be a binder component or a matrix of a target medium. Therefore, in the present specification, a crosslinking agent, a vulcanizing agent, and the like are also regarded as a binder component or a matrix.

The method of introducing the reactive group (II) into the polymer will be described later.

In a first embodiment of the present invention, an amino group,
The segment (A) having an amide group and / or a nitrile group needs to have a low affinity for the target medium on the segment chain structure. In addition, since the low affinity here is a relative one by comparison with the other segment (B), the segment (A) may have various types depending on the type of the target medium or the configuration of the segment (B). And cannot be specified unambiguously. However, from another perspective,
It is desirable that the segment (A) has a high affinity for carbon black because it exhibits better orientation to carbon black. From this point, the segment (A) has a main chain mainly containing a carbon-carbon bond, and more preferably contains an aromatic ring such as a benzene ring, a naphthalene ring or an indene ring in the main chain. And a reactive group as described above in the molecule, while the segment (B) is
A skeleton structure having fewer carbon-carbon bonds than the segment (A), particularly having less aromatic rings, such as a polysiloxane structure;
Alternatively, it is desirable to include many bonds other than carbon-carbon bonds such as ether bonds and ester bonds.

However, if the segment (A) is substantially composed only of a highly condensed polycyclic structure, the rigidity of the segment (A) becomes extremely high, and the carbon black is grafted onto the carbon black surface. Since there is a possibility that it is difficult to approach the segment (A), it is desirable to have an appropriate linear structure.

As described above, the chain structure of the segment (A) can be appropriately selected according to the chain structure of the segment (B) selected from the viewpoint of dispersibility to be imparted to carbon black. , For example, a styrene monomer,
(Various vinyl polymers, polyesters, polyethers, etc. (having the above reactive group) by homo- or copolymerization of (meth) acrylic monomers, alkylene monomers, etc.
Among them, a vinyl polymer, particularly a vinyl monomer component having an aromatic ring, may be used as a polymer chain.
Since it is a vinyl-based polymer containing at least 60 mol%, more preferably at least 60 mol%, and having a reactive group, the combination with various segments (B) selected according to the target medium becomes possible. desirable.

In consideration of economical efficiency and the like, particularly, a homo- or copolymer having a styrene monomer and a (meth) acrylic monomer as a main component, particularly a styrene monomer component of 50 mol% or more, Is preferably a polymer chain containing 60 mol% or more (having the above reactive group).

However, in the first embodiment, the segment (A) having an amino group, an amide group and / or a nitrile group has a more sufficient affinity for the target medium than the segment (B) on the segment chain structure. If it is low, the segment (A) does not necessarily have to have a high affinity for carbon black, and there is a substantial difference in the affinity between the segment (A) and the segment (B) for carbon black. However, even if it has no affinity than the segment (B), it can be used satisfactorily. In some cases, the segment (B)
It is also possible for the side to have, for example, a styrene-based structure.

On the other hand, the segment (B) has, for example, a polysiloxane-based structure, a poly (meth)
An appropriate one is selected from polymer chains having an acrylic structure, a polyether structure such as a polyalkylene glycol, a polyester structure, a polyalkylene structure, a polyamide structure, a polyimide structure, a polyurethane structure, a fluororesin structure, or the like. For example, a polysiloxane-based structural chain has the purpose of improving dispersibility in a low-polarity medium, and further has excellent water repellency, mold release properties, heat resistance, weather resistance, flexibility, low viscosity, For the purpose of imparting no low-temperature brittleness, the (meth) acrylic chain is introduced with various (meth) acrylic ester monomer components to form a broad hydrophilic-
For the purpose of imparting hydrophobicity (for example, a hydroxyalkyl (meth) acrylate is introduced to increase the hydrophilicity), and the polyalkylene glycol chain has hydrophilicity,
For the purpose of imparting properties such as lubricity, flexibility and antistatic,
Each can be adopted.

Hereinafter, in order to facilitate understanding of the present invention, the segment (A) has an amino group, an amide group and / or a nitrile group, and the segment (B) has a group (A) having reactivity with the matrix of the target medium. The present invention will be described mainly with respect to an embodiment having an unsaturated double bond group as II).

In the following description, the above (1)
I.e., a method in which a block or graft polymer having a desired structure in which an unsaturated double bond as a group (II) is introduced into a segment (B) is bonded to carbon black by ionic interaction. As described above, since the steps of conjugation and introduction of the unsaturated double bond only precede and follow, the other points are almost the same as those of the above method (1) and the method (2). There is,
It will be understood that the method of the above (1) and the method of the above (3) are almost the same, only requiring the deprotection group reaction step after the grafting.

In this embodiment, the segment (B) of the block or graft type polymer needs to have an unsaturated double bond in a part thereof. This unsaturated double bond may be in the form of being present in the main chain of the segment (B). However, it is difficult to synthesize the block or graft polymer according to the present invention. For example, it is desirable that the form be present in the side chain bonded to the main chain of the segment (B).

A block or graft type having such a segment (A) having an amino group, an amide group and / or a nitrile group and a segment (B) having an unsaturated double bond as a reactive group (II). The method for obtaining the polymer is not particularly limited, and the polymer can be produced by appropriately combining a known technique for polymerizing various block or graft polymers with a technique for producing a reactive polymer.

As a method for obtaining a graft-type polymer,
For example, a method of polymerizing a polymer to be a main chain by solution polymerization, emulsion polymerization, bulk polymerization or suspension polymerization of a polymerization initiator and a polymerizable monomer in the presence of a high molecular weight product to be a graft chain It has been known. However, if the high molecular weight polymer does not have a radical polymerizable functional group, the resulting graft copolymer contains a large amount of non-grafted polymer, and has a disadvantage that graft efficiency is low. I have. Therefore, it is preferable to use a radical polymerizable polymer as the polymer. Such a radical polymerizable polymer is generally referred to as a “macromonomer” and is a polymer having a radical polymerizable group at one end, such as a (meth) acryloyl group or a styryl group. It is obtained by reacting a polymer having a carboxyl group at one end with a radical polymerizable monomer having a glycidyl group in an organic solvent (for example, Japanese Patent Publication No. A method is disclosed in which a prepolymer obtained by radical polymerization of a radical polymerizable monomer in the presence of mercaptoacetic acid and glycidyl methacrylate are reacted in the presence of a dimethyllaurylamine catalyst.)

The radical polymerizable polymer as a component forming the main chain of the segment (B) is as follows:
It is necessary to design the molecule to have an active site (functional group) for introducing a side chain or an extended chain having an unsaturated double bond later, which will be described later.

Therefore, for example, in order to obtain the graft copolymer according to the present invention, first, the above-mentioned radical polymerizable high molecular weight polymer (b) as a component for forming the main chain of the segment (B) is used. A polymerizable monomer (a ₁ ) having an amino group in the molecule and / or a polymerizable monomer (a ₂ ) having an amide group in the molecule (hereinafter referred to as polymerizable monomer (a ₁ ) and the polymerizable monomer (a ₂ ) may be collectively referred to as a polymerizable monomer (a).), And other polymerization that forms the skeleton of the segment (A) that is optionally blended. (A) having an amino group, an amide group and / or a nitrile group by polymerizing a water-soluble monomer (c)
And a graft polymer as a precursor comprising a main skeleton portion of the segment (B) and a reactive group for an active site provided in the main skeleton portion of the segment (B) and an unsaturated double bond. A compound (d) having
What is necessary is just to make it react with the said precursor and introduce an unsaturated double bond to the segment (B).

In the polymer portion of the carbon black composite polymer according to the present invention, as exemplified here, the segment (B) is a group (II) having reactivity with the matrix of the target medium such as an unsaturated double bond. ) Is also advantageous from the following points. That is, in the conventional carbon black graft polymer,
When a macromonomer is used as a component constituting the segment (B), when the purity of the macromonomer is low, that is, when the ratio of those having a radical polymerizable group at one end is 1
If it is not 00%, even after the graft polymer is synthesized and grafted onto carbon black, the defective monomer of the macromonomer is mixed as a simple segment (polymer) in the correctly synthesized carbon black composite polymer. As a result, when the obtained product is blended with a target medium such as a binder, the mere segment is
It is assumed that it remains without any contribution in the final binder. However, in the case where the segment (B) has a group (II) having reactivity with the matrix of the target medium, such a mere segment mixed also reacts with the matrix of the target medium and is incorporated into the final binder. It does not impair the curing properties.

Examples of the polymerizable monomer (a ₁ ) having an amino group in the molecule include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N -Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dimethylaminohexyl (Meth) acrylate, aminoalkyl (meth) acrylates such as N, N-diethylaminohexyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) Acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylamino-butyl (meth) acrylamide, N, N-diethylamino-butyl (meth) acrylamide, N, N-
Dimethylaminohexyl (meth) acrylamide, N,
Aminoalkyl (meth) acrylamides such as N-diethylaminohexyl (meth) acrylamide, N, N
-Dimethylaminoethyl vinyl ether, N, N-diethylaminoethyl vinyl ether, N, N-dipropylaminoethyl vinyl ether, N, N-dibutylaminoethyl vinyl ether, N, N-dimethylaminopropyl vinyl ether, N, N-diethylaminopropyl vinyl ether, N, N-dipropylaminopropyl vinyl ether, N, N-dimethylaminobutyl vinyl ether, N, N-diethylaminobutyl vinyl ether,
N, N-dipropylaminobutyl vinyl ether, N,
N-dibutylaminobutyl vinyl ether, N, N-dimethylaminopentyl vinyl ether, N, N-diethylaminopentyl vinyl ether, N, N-dipropylaminopentyl vinyl ether, N, N-dimethylaminohexyl vinyl ether, N, N-diethylaminohexyl vinyl ether Aminoalkyl vinyl ethers such as N, N-dipropylaminohexyl vinyl ether, N, N-dibutylaminohexyl vinyl ether, N, N-dimethylaminooctyl vinyl ether, N, N-diethylaminooctyl vinyl ether, 2-vinylpyridine, 4-vinylpyridine , 5-ethyl-2-
Vinylpyridines such as vinylpyridine, vinylimidazoles such as 1-vinylimidazole and 1-vinyl-2-methylimidazole, vinylquinolines such as 2-vinylquinoline, vinylpiperidines such as N-methyl-3-vinylpiperidine And the like, but are not limited to these. Of these, aminoalkyl (meth) acrylates, and alkyl (meth) acrylates having a tertiary amino group are particularly preferred.

As the polymerizable monomer (a ₂ ) having an amide group, a monomer represented by the following general formula (i) represented by vinylpyrrolidone:

[0096]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group, and n is 2 to 4), acrylamide, methacrylamide, N, N-dimethylacrylamide, and the following general formula (ii) ) Monomer,

[0098]

Embedded image

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are a hydrogen atom or a C ₁ -C ₁₂ alkyl group, which may be the same or different. ) Or N-methylolacrylamide, N
-Butoxymethylacrylamide, diacetoneacrylamide and the like can be exemplified, but of course, the present invention is not limited thereto. Of these, vinylpyrrolidone is particularly preferred.

Polymerizable monomer having a nitrile group (a ₃ )
Examples include, for example, acrylonitrile, methacrylonitrile, and the like, but are not limited thereto. Of these, acrylonitrile is particularly preferred.

The polymerizable monomer (c) that can be used as necessary to form the desired skeleton of the segment (A) as described above includes the monomer (a) and the polymerizable monomer described below. The radical polymerizable high molecular weight polymer (b) as a component forming the segment (B) is not particularly limited as long as it can be copolymerized, and depends on the molecular structure of the segment (A) to be obtained. , For example, styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene,
p-tert-butylstyrene, p-phenylstyrene, o
Styrene monomers such as chlorostyrene, m-chlorostyrene and p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic acid Stearyl, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2 methacrylic acid
Acrylic or methacrylic monomers such as ethylhexyl and stearyl methacrylate; one or more monomers such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate can be used as appropriate.

When the segment (A) has an amino group, the polymerizable monomer (a ₁ ) is added in an amount of 0.1%.
It is desirable to contain 5 mol% or more in order to form a good composite with carbon black, particularly 1 to 50 mol%, and further, aminoalkyl (meth) as a polymerizable monomer (a ₁ ).
0.5% by mole or more of acrylate, more preferably 1 to
It is desirable to contain 50 mol%.

In the case where the segment (A) has an amide group, the carbon black may contain 0.5 mol% or more, especially 1 to 50 mol% of the polymerizable monomer (a ₂ ). It is desirable to perform good compounding with. Here, specific examples of the structure of the segment (A) having an amide group include, for example, the following.

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

Of course, the present invention is not limited to these, and a COOH group,
A group (II) having a reactivity with the matrix of the target medium such as a double bond group may be introduced. In addition, (4) of the structural examples exemplified above is particularly desirable.

Also, when the segment (A) has a nitrile group, the polymerizable monomer (a ₃ ) may contain 0.5 mol% or more, especially 1 to 50 mol%. It is desirable for good composite formation with carbon black.

Further, as the segment (A), not only those having any one of amino group, amide group or nitrile group as described above, but also those having any two or three of these groups It is of course possible to have everything.

On the other hand, as the radical polymerizable high molecular weight polymer (b) for constituting the main chain of the component of the segment (B), a desired polymer chain such as a polysiloxane structure, a poly (meth) acrylic structure, Any material having a reactive group at one end of a polymer chain, such as a polyether-based structure such as an alkylene glycol, a polyester-based structure, a polyalkylene-based structure, a polyamide structure, a polyimide structure, a polyurethane structure, and a fluororesin-based structure may be used.

For example, when the segment (B) has a polysiloxane structure, the polysiloxane structure may be a polydimethylsiloxane group, a polydimethylsiloxane group partially substituted with an alkyl group, or a polydimethylsiloxane group partially substituted with an aryl group. Examples thereof include those containing a polyorganosiloxane such as a dimethylsiloxane group and a tris (trialkylsiloxy) silylpropyl group.

Accordingly, examples of the radical polymerizable high molecular weight polymer (b ₁ ) having a polysiloxane structure include (meth) acryloyl group-containing polydimethylsiloxane and styryl group-containing polydimethylsiloxane (meth) acryloyl group-containing partial octyl substitution. Polymerizable polysiloxanes such as polydimethylsiloxane, styryl group-containing partially octyl-substituted polydimethylsiloxasan, styryl group-containing partially phenyl-substituted polydimethylsiloxane, and tris (trimethylsiloxy) silylpropyl (meth) acrylate are exemplified. Or one or more of them can be used, and the following are particularly desirable.

[0114]

Embedded image

(Wherein, B represents —COO— or a phenylene group, R ¹ represents a hydrogen atom or a methyl group,
R ² represents an alkylene group having 1 to 6 carbon atoms, and R ^{3 to} R ¹³ represent the same or different and represent an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, respectively. Are the same or different and represent an integer of 0 to 10, and n represents an integer of 0 to 200. Similarly, when the segment (B) has a polymeth (acryl) -based structure, the radical polymerizable high molecular weight (b ₂ ) may be, for example, one shown below.

[0116]

Embedded image

(Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom or a methyl group, and R 3 has 1 carbon atom)
Represents an alkyl group of -25, X is an arbitrary connecting chain,
Y represents an initiator terminal or an H atom, and n represents an integer of 0 to 500. )

[0118]

Embedded image

(Wherein, R ¹ , R ² and R ⁴ are the same or different and each represent a hydrogen atom or a methyl group, and R ³ , R ⁵
Are the same or different and represent an alkyl group having 1 to 25 carbon atoms, X is an arbitrary connecting chain, and Y is an initiator terminal or H
Atoms, m and n are the same or different and are each 0 to 500;
Indicates an integer. )

[0120]

Embedded image

(Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom or a methyl group, and R ³ has 1 carbon atom)
Represents an alkylene group of from 25 to 25; R ⁴ represents an alkyl group having from 1 to 25 carbon atoms; X is an arbitrary connecting chain; Y is an initiator terminal or H atom; Indicates an integer of 500. When the segment (B) has a polyalkylene glycol-based structure, for example, those shown below can be used as the radical polymerizable high molecular weight compound (b ₃ ).

[0122]

Embedded image

(Wherein, R ¹ , R ² , and R ³ are the same or different and each represent a hydrogen atom or a methyl group, and n is from 0 to 0)
Indicates an integer of 500. )

[0124]

Embedded image

(Where R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom or a methyl group, and n and m are the same or different and represent an integer of 0 to 500) Further, when the segment (B) has a polystyrene structure, the radical polymerizable high molecular weight substance (b ₄ )
For example, the following can be used.

[0126]

Embedded image

(Wherein, R ¹ represents a hydrogen atom or a methyl group, X is an arbitrary connecting chain, Y is an initiator terminal or an H atom, Z is a hydrogen atom, a halogen substituent or a group having 1 carbon atom. Alkyl groups of n to 8 and n represents an integer of 0 to 500.) For the linking chain X shown in the above formula group, for example, “chemistry and industry of macromonomers” (supervised by Yuya Yamashita,
(Published by IPC Co., Ltd., September 20, 1989), and any of those shown therein can be used.

In the case of using a fluorine resin structure,

[0129]

Embedded image

[0130]

Embedded image

(Wherein, m represents an integer of 1 to 25), such as a fluorinated (meth) acrylic monomer itself as a segment (B). The segment (B) can be made into a macromonomer which is terminated by a living polymerization method of acrylate or a chain transfer method of radical polymerization.

As a polymerization method for obtaining the graft type precursor polymer as described above, a known polymerization method can be used. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be mentioned. Among them, a solution polymerization method using a radical catalyst is preferable.

As the radical catalyst, any of those usually used for polymerization of vinyl monomers can be used. Representative examples include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, di-tert-butyl. Peroxide, ter
Peroxide-based compounds such as t-butyl peroctoate and tert-butyl peroxy-2-ethylhexanoate, and the like, are usually 0.2 to 10 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the monomer. Is used in the range of 0.5 to 5 parts by weight. In addition, the solvent is appropriately selected depending on the type of the monomer and the radical polymerizable polymer used.

In this way, after obtaining a graft-type precursor polymer comprising the segment (A) having an amino group, an amide group and / or a nitrile group and the main skeleton portion of the segment (B), the segment (B) The method for introducing a side chain or an extended chain having an unsaturated double bond into ()) will be described.

The active site (functional group (III)) provided in the main skeleton of the segment (B) in the precursor polymer is not particularly limited, and various active sites can be used. More specifically, the functional group (III) of the segment (B) may be any group other than a carboxyl group, and examples thereof include an amino group, an imino group, a thiol group, a silanol group, and an isocyanate group. Of these, an alcoholic or phenolic hydroxyl group is particularly preferred. In addition,
In the description of the radical polymerizable polymer, some of the structural formulas exemplified as preferable ones do not specifically show such a functional group (III). It will be understood that if a monomer having these functional groups is used as a part of a monomer used for polymerizing a polymer having a high molecular weight, a desired structure can be easily obtained.

On the other hand, a compound (d) having a reactive group (IV) to the functional group (III) of the segment (B) and an unsaturated double bond (reactive group (II)) in the molecule.
Is not particularly limited, but has an unsaturated double bond (reactive group (II)) at one end and an active site (functional group (III)) in segment (B) at the other end. A compound (heterofunctional compound) having a reactive group (IV) having a reactivity with both terminals and having different reactivity at both ends is preferable. The polymerizable monomer (a) is also a heterofunctional compound, but the compound (d) is at least a different kind of reactive group from the polymerizable monomer (a). It is necessary to have

The reactive group (IV) of the compound (d)
Is not particularly limited as long as it is reactive with the active site (functional group (III)) in segment (B), but is preferably an isocyanate group. When a compound having an isocyanate group as a reactive group is used, an alcoholic or phenolic hydroxyl group, an amino group, an imino group, a thiol group, a silanol group, or the like is used as the functional group (III) of the segment (B). And by selecting appropriate conditions, the functional group (II
Reaction of I) with a reactive group (I) such as an epoxy group, thioepoxy group, aziridine group and oxazoline group introduced into segment (A), and the isocyanate group and a reactive group introduced into segment (A) Without causing a reaction with (I), an isocyanate group is easily reacted with the functional group (III) of the segment (B) and bonded to the unsaturated double bond of the compound (d). It is because it can introduce. In particular, when the functional group (III) of the segment (B) is an alcoholic or phenolic hydroxyl group, a favorable nucleophilic reaction occurs with the isocyanate group and a urethane bond can be formed, which is preferable. .

As the isocyanate group-containing unsaturated compound (d ₁ ) having an isocyanate group as a reactive group at one end and an unsaturated double bond at the other end, particularly preferred as the compound (d), (meth) Partial reaction product of a hydroxyl group-containing (meth) acrylate such as acryloyl isocyanate, isocyanate alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate and a polyisocyanate compound, and a polyol having a (meth) acryl residue and a polyisocyanate compound Examples thereof include isocyanate group-terminated urethane prepolymers obtained by the above method. Among them, (meth) acryloyl isocyanate, isocyanate alkyl (meth) acrylate, and the like having the following structural formula are particularly desirable.

[0139]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group)

[0141]

Embedded image

(Where R ¹ is a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 10 carbon atoms)

[0143]

Embedded image

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 10 carbon atoms.) As the compound (d), an unsaturated compound containing an isocyanate group as described above ( Using d1) to react with a precursor polymer having an alcoholic or phenolic hydroxyl group as a functional group (III) in segment (B) to introduce an unsaturated double bond into segment (B) of the precursor polymer ,
The amount of the compound (d) to be added is such that the isocyanate group is 0.01 to 1 equivalent, more preferably 0.3 to 1.0 equivalent to 1 equivalent of the hydroxyl group of the segment (B) of the precursor polymer.
It is necessary to adjust so that the ratio becomes equivalent. That is, 0.01 equivalent of isocyanate group is equivalent to 1 equivalent of hydroxyl group.
When the ratio is less than the equivalent, an effective amount of unsaturated double bond cannot be introduced into the segment (B). On the other hand, when the ratio of the isocyanate group exceeds 1 equivalent to 1 equivalent of the hydroxyl group, the purification The isocyanate group further reacts with the urethane bond to form an allohanate bond, and a desired structure cannot be obtained, and an unreacted isocyanate group-containing unsaturated compound remains. If the reaction conditions are too high, a polymerization reaction occurs at the unsaturated double bond of the unsaturated compound containing an isocyanate group, causing a problem such as gelation.
Conditions such as 1 to 5 hours at 00 ° C. are desirable. In addition, it is also possible to use a polymerization inhibitor to suppress the above-mentioned polymerization reaction during the reaction. It is possible to use a catalyst for these reactions as long as the subsequent physical properties are not adversely affected.If the grafting reaction becomes prolonged at a high temperature and causes a problem, a commonly used urethane-forming catalyst is used. May be avoided.

As another method for obtaining a graft polymer which can be used in the present invention, for example, a compound (e) having an amino group, an amide group and / or a nitrile group can be used.
Is reacted with a first precursor polymer having a segment capable of reacting with the compound in the segment (A) and the segment (A) grafted with the segment (B) to react with the amino group,
An amide group and / or a nitrile group is introduced into the first precursor polymer, and the final precursor (the segment (A) having an amino group, an amide group and / or a nitrile group, and the segment (B)) Graft-type precursor polymer comprising a main skeleton portion), and then introducing a side chain or an extended chain having an unsaturated double bond into the segment (B) in the same manner as described above. .

The compound (e) includes, for example, an amino group, an amide group and / or a nitrile group in the molecule.
And compounds having an amino group, an amide group and / or a nitrile group and a functional group other than the amino group in the molecule.

However, the above-mentioned functional group is capable of reacting with the reactive group of the segment (A) of the first precursor polymer. Examples of the reactive group contained in the segment (A) of the first precursor polymer include an isocyanate group, a carboxyl group, a hydroxyl group, and a vinyl group. Must be different.

In the first precursor polymer, an unsaturated double bond was first introduced into the segment (B), and then an amino group, an amide group and / or a nitrile group was introduced into the segment (A). It is also possible to introduce.

As a method for obtaining a block type polymer, for example, an anionic living polymerization method, a cationic living polymerization method, an iniferter method and the like are known. Further, as another method, a segment (A) or a segment (A) is used. When radically polymerizing the monomer of B), thiolcarboxylic acid or 2-acetylthioethylthiol,
A polymer obtained by polymerization in the presence of a compound containing a thioester and a thiol group in a molecule such as 0-acetylthiodecanethiol is treated with an alkali such as sodium hydroxide or ammonia to form a thiol at one end. A method is known in which a polymer having a group is formed, and a monomer component of the other segment is subjected to radical polymerization in the presence of the obtained polymer having a thiol group at one end.

Therefore, in order to obtain the block copolymer according to the present invention, the above-mentioned known method is appropriately modified and, similarly to the case of obtaining the graft copolymer, the polymerizable monomer of the segment (A) is obtained. When a polymerizable monomer (a) having an amino group, an amide group and / or a nitrile group as described above in at least a part thereof is used as a monomer, a polymer (A) is added to the segment (A) during the polymerization of the block copolymer. An amino group, an amide group and / or a nitrile group may be introduced, or such an amino group, an amide group and / or a nitrile group may be introduced into the segment (A) after polymerization of the block copolymer. For the introduction of unsaturated double bonds into the segment (B) in the case of these block copolymers, the same method as in the case of the graft copolymer can be used.

The molecular weight of the thus obtained graft or block type polymer is not particularly limited. However, in consideration of the effect of grafting on carbon black and the workability during the reaction with carbon black, the above molecular weight is determined to be an average molecular weight. It is preferably in the range of 1000 to 1,000,000, more preferably 5000 to 1000
00 range.

The molecular weight of the segment (A) and the segment (B) in the graft or block type polymer is not particularly limited, but depends on the kind of the polymer chain constituting these segments. From the viewpoint of graft efficiency with respect to carbon black, the segment (A) has an average molecular weight of 300 to 1000.
00, more preferably in the range of 5,000 to 50,000, and from the viewpoint of the effect of modifying the dispersibility to be imparted to carbon black, the segment (B) has an average molecular weight in the range of 500 to 100,000, more preferably Is 1000 to 50,000, more preferably 5
It is preferable to be in the range of 000 to 30,000.

In particular, when the segment (B) is a polymer having a relatively long chain length, preferably having a molecular weight of 1,000 or more, more preferably having a molecular weight of 5,000 or more, the carbon black composite polymer of the present invention can It is desirable to be able to exhibit high dispersion stability when blended in a curable resin composition or the like.

Further, the number of amino groups, amide groups and / or nitrile groups in the segment (A) of the graft or block type polymer is not particularly limited, but the average number per molecule of the polymer is 50. -1 and more preferably about 20-1.

The number of unsaturated double bonds contained in the segment (B) or the number of groups (II) capable of reacting with the matrix of the target medium is not particularly limited. 20 to 1, more preferably 10
It is desirable to have about 1 to about 1. Note that the number of groups (II) such as double bonds per one molecule of the polymer is directly related to a medium such as a curable composition in which the obtained carbon black composite polymer is blended (for example, sensitivity, reflection characteristics, etc.). ) Is determined as appropriate. For example, when it is desired to reduce the amount of the photocurable monomer in a black photocurable composition as described below, the sensitivity can be maintained by increasing the number of double bonds of the carbon black composite polymer.

In the first embodiment, the composite of the graft or block type polymer with the carbon black as described above is obtained by dispersing the obtained carbon black composite polymer in the above-mentioned target medium or in a property close thereto. This is carried out in the presence of a dispersion medium solution comprising a medium having That is, the dispersion medium has high affinity or compatibility with the segment (B) of the polymer and low affinity or compatibility with the segment (A).

Accordingly, the dispersion medium to be used is appropriately selected according to the combination of the segment (A) and the segment (B) in the polymer.

For example, the segment (A) in the polymer
Has a polystyrene structure and the segment (B) has a polysiloxane structure, the dispersion medium used may be polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, or partially phenyl-substituted polydimethylsiloxane. And silicone oils such as fluorosilicone oil.

For example, when the segment (A) in the polymer has a polystyrene structure and the segment (B) has a hydrophobic (meth) acrylic structure such as polymethyl methacrylate, it is used. Examples of the dispersion medium include cellosolves such as methyl cellosolve and ethyl cellosolve; methyl acetate, ethyl acetate,
Esters such as butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aprotic polar solvents such as pyrrolidone, N, N-dimethylformamide and dimethyl sulfoxide are preferred.

Also, for example, the segment (A) in the polymer has a polystyrene structure, and the segment (B) has a hydrophilic (meth) acrylic structure such as a methyl methacrylate-hydroxymethyl methacrylate copolymer. In this case, the dispersion medium used includes water, a water-alcohol mixture, alcohols such as methyl alcohol and ethyl alcohol; esters of methyl cellosolve, ethyl cellosolve and butyl cellosolve; ketones such as acetone; pyrrolidone, N, N −
Dimethylformamide, dimethylsulfoxide and the like are preferred.

For example, when the segment (A) in the polymer has a polystyrene-based structure and the segment (B) has, for example, a polyalkylene glycol-based structure, the dispersion medium used may be water. ,
Preferred are a water-alcohol mixture, alcohols such as methyl alcohol and ethyl alcohol; glycols such as ethylene glycol and diethylene glycol; and polyhydric alcohols such as glycerin.

In the grafting of the polymer with the carbon black in the presence of the dispersion medium, other substances such as a polymer and a polymerizable monomer which do not correspond to the polymer may be further present.

This complexation is carried out, for example, at a temperature of 0 to 250 ° C., preferably 10 to 150 ° C., for 0.1 to 5 hours.
The mixing is preferably performed for 0.5 to 3 hours, preferably by stirring and mixing. If the mixing temperature is lower than 0 ° C., there is a possibility that the liquid will not be in a liquid state due to the solvent. On the other hand, if the mixing temperature is higher than 250 ° C., the unsaturated double bond of the segment (B) may disappear. Is not preferred.

As a reaction procedure, the carbon black and the polymer and the dispersion medium are charged into a reactor and mixed under a predetermined temperature condition.

As the reaction apparatus, a stirring tank used for ordinary stirring or a kneading machine such as a ball mill, mixer, kneader or the like used for kneading can be used, and particularly preferably, for accommodating a fluid to be treated therein. , A stirrer rotating inside the vessel, a heating device for heating the fluid to be treated contained inside the vessel, and a wet dispersion process comprising a plurality of granular dispersion media contained inside the vessel Device. Many wet dispersion processing apparatuses or wet pulverization processing apparatuses for performing stirring or pulverization using a stirrer and a granular dispersion medium such as beads in combination are known as known ones. It is used as a device configuration in which a heating device for heating the fluid to be processed is added to the device. If an apparatus having such a configuration is used, carbon black having extremely high efficiency and a sufficiently small particle size (that is, a polymer is composited with carbon black that has been crushed well from a secondary aggregation state). A composite polymer can be obtained.

The proportion of the carbon black and the polymer in such grafting depends on the type of the polymer used, the intended use of the product to be obtained, and the like. Although it is not specified, the polymer 1 to 100 parts by weight carbon black 100 parts by weight
0 parts by weight, more preferably about 2 to 500 parts by weight. That is, if the amount of the polymer is less than 1 part by weight, it may be difficult to sufficiently modify the surface properties of the carbon black. This is because the amount is large, and not only is it not economical, but also there is a possibility that the properties of carbon black originally required may be impaired.

Next, a method for producing the carbon black composite polymer according to the second embodiment will be described.

The production method according to the second aspect includes the production method according to the first aspect described in detail above, the grafting of the polymer portion to carbon black, the segment (A) and / or the polymer segment (A). The procedure is basically the same except that the order of the step of introducing the reactive group (II) such as an unsaturated double bond into the segment (B) is reversed. That is, in the production method according to the second embodiment, in the same manner as described above, the block type comprising the segment (A) having an amino group, an amide group and / or a nitrile group and the main skeleton portion of the segment (B) is used. Alternatively, after obtaining a graft-type precursor polymer, in the presence of a dispersion medium solution consisting of the precursor polymer and a medium having properties similar to the target medium, carbon black is mixed and dispersed, and then carbon black is dispersed. The reactive group (II) as described above is introduced into the precursor polymer bound by ionic interaction.

In this case, the precursor polymer has an amino group, an amide group and / or a nitrile group in the segment (A), and is substantially reactive with the functional group on the surface of carbon black. After the precursor polymer is compounded with carbon black, a functional group (III) of the precursor polymer is formed in the segment (A) and / or the segment (B). (D) having a reactive group (IV) capable of reacting with a polymer and a group (II) having reactivity with the matrix of the target medium is reacted with carbon black obtained by complexing the precursor polymer, Group (II)
(In the first embodiment, the functional group (III) is used to introduce the reactive group (II) into the polymer. Since the functional group (III) is substantially consumed before grafting, the functional group (III) is more active than the surface functional group of carbon black on the amino group of the segment (A) as described above. It is important that the functional group (III) is low even after the grafting of the carbon black and the precursor polymer in the second embodiment.
It is more important that the functional group (III) has substantially no reactivity with the functional group on the surface of the carbon black since it is necessary that the functional group remains substantially without being consumed. ).

For example, when an unsaturated double bond group as a reactive group (II) is introduced only into the segment (B) as exemplified in the description of the method of the first embodiment, an amino group After obtaining a block-type or graft-type precursor polymer comprising a segment (A) having an amide group and / or a nitrile group and a main skeleton portion of the segment (B), the precursor polymer is mixed with carbon black. As described above, an unsaturated double bond may be introduced into the precursor polymer dispersed and then composited with carbon black using the compound (d) or the like.

The complexation of the precursor polymer with the carbon black in the second embodiment is relatively less restrictive than in the first embodiment as described above, and is, for example, 0 to 100 ° C., preferably 0 to 100 ° C. At a temperature of 50 ° C,
It can be performed by stirring and mixing for 0.1 to 10 hours, preferably 0.5 to 2 hours. The conditions for introducing an unsaturated double bond using the compound (d) into the segment (B) of the complexed precursor polymer are not particularly limited.
For example, at 10 to 100 ° C. for 0.5 to 5 hours. The other points are almost the same as those in the first embodiment, and thus the description is omitted.

Next, a method for producing the carbon black composite polymer according to the third embodiment will be described.

The manufacturing method according to the third embodiment is basically substantially the same as the manufacturing method according to the first embodiment described above in detail. In the union, a segment (A) having an amino group, an amide group and / or a nitrile group, which is molecularly designed as having a higher affinity for carbon black than a segment (B) having a higher affinity for the target medium, is used. Is grafted onto carbon black.

Therefore, in the grafting reaction system, under a relatively arbitrary dispersion medium (other than a dispersion medium liquid having an extremely high affinity toward the segment (A)) or in the absence of such a dispersion medium. Also, since the segment (A) of the polymer is oriented toward the carbon black, the reactive group (I) present in the segment (A) is effectively compounded by the surface of the carbon black. As a result, a carbon black composite polymer having excellent properties can be obtained.

The (A) segment having an amino group, an amide group and / or a nitrile group in the graft or block type polymer used must have a high affinity for carbon black on the segment chain structure. . In addition, since the high affinity here is a relative one by comparison with the other (B) segment, depending on the configuration of the (B) segment,
(A) The segment can have various configurations and cannot be specified unconditionally. However, the (A) segment has a main chain mainly containing a carbon-carbon bond, and more preferably contains, for example, an aromatic ring such as a benzene ring, a naphthalene ring, and an indene ring in the main chain. And a reactive group (I) as described above in the molecule;
On the other hand, the segment (B) has a smaller number of carbon-carbon bonds than the segment (A), particularly a skeleton structure having less aromatic rings, for example, a polysiloxane structure, or a bond other than a carbon-carbon bond such as an ether bond or an ester bond. Is desirably included.

However, if the segment (A) is substantially composed only of a highly condensed polycyclic structure, the rigidity of the segment (A) becomes extremely high, and the carbon black is grafted onto the carbon black surface. (A) It is desirable to have an appropriate linear structure because it may be difficult to approach the segments.

As described above, the chain structure of the (A) segment is selected from the viewpoint of dispersibility to be imparted to carbon black, and the chain structure of the (B) segment, for example, as described above, is a polysiloxane-based. Determined according to the polymer chain having the structure, poly (meth) acrylic structure, polyether structure such as polyalkylene glycol, polyester structure, polyalkylene structure, polyamide structure, polyimide structure, polyurethane structure, etc. Is not particularly limited as long as it has high affinity for carbon black. Generally, a vinyl-based polymer, in particular, a vinyl-based monomer component having an aromatic ring is 50 mol% or more. More preferably, a vinyl polymer containing at least 60 mol% and having a reactive group is desirable. In consideration of economical efficiency, homopolymers or copolymers mainly composed of styrene-based monomers and (meth) acrylic monomers, especially 50% by mole or more, more preferably 60% by mole of styrene-based monomer components % Of the polymer chain (having the above reactive group). When the segment (B) is a polysiloxane-based polymer chain or the like, there are relatively many types of polymer chains that can be used as the segment (A), but the segment (B) is, for example, poly (meth).
In the case of a vinyl-based structure such as an acrylic structure, the polymer chains that can constitute the segment (A) are considerably limited, and include only a polystyrene-based structure and a (meth) acryl-styrene copolymer-based structure.

In the production method according to the third embodiment, the grafting of carbon black and the above-mentioned polymer is carried out unless these components show an extremely high affinity to the segment (A) of the above-mentioned polymer. , In the presence of any dispersion medium,
Alternatively, stirring and mixing without such a dispersion medium,
Alternatively, it is performed by melt-kneading.

The usable dispersing medium depends on the structure of the polymer segment (A), but includes, for example, water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol; Hydrocarbons such as paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, and partially hydrogenated triphenyl; polydimethylsiloxane, partially octyl-substituted polydimethyl Siloxane, partially phenyl-substituted polydimethylsiloxane, silicone oil such as fluorosilicone oil; chlorobenzene, dichlorobenzene, bromobenzene, chlorobiphenyl, chlorodiphenylmeta Halogenated hydrocarbons and the like; ethyl benzoate; Daifloil (manufactured by Daikin Industries, Ltd.), fluoride, etc. DEMNUM (manufactured by Daikin Industries, Ltd.)
Examples thereof include ester compounds such as octyl benzoate, dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, ethyl (meth) actylate, butyl (meth) acrylate, and dodecyl (meth) acrylate.

The other conditions during the compounding treatment are the same as those in the first embodiment, and the characteristics and the like of the obtained carbon black composite polymer are also the same.

Further, the production method according to the fourth aspect of the present invention comprises, similarly to the above-mentioned second aspect, a method of preparing a segment (A) and a segment (B) having an amino group, an amide group and / or a nitrile group. After obtaining a block-type or graft-type precursor polymer consisting of a skeleton portion, this precursor polymer and carbon black are mixed and dispersed, and then a precursor polymer composited with carbon black is obtained.
Introduces a reactive group (II) such as an unsaturated double bond, and similarly to the third embodiment, an amino group or an amide group in a block-type or graft-type polymer (precursor polymer) And / or compounding the carbon black with a segment (A) having a nitrile group, which is molecularly designed as having a higher affinity for carbon black than the segment (B). The various conditions in the method according to the fourth embodiment are substantially the same as those in the manufacturing method according to the third embodiment, but are the same as those in the manufacturing method according to the second embodiment. The reaction temperature conditions at the time of complexation and introduction of the functional group (II) such as an unsaturated double bond are as follows:
The range can be relatively wide as compared with the method in the manufacturing method according to the third aspect.

As described above, in the carbon black composite polymer according to the present invention, the segment (A) of the graft or block type polymer has an amino group, an amide group and / or a nitrile group, and the segment (B) has The present invention has been described mainly on the case where the reactive group (II) has an unsaturated double bond group, but other examples will be described.

For example, when the group (II) is a carboxyl group, the carboxyl group must be introduced into a polymer having an amino group in order to generate a bond by ionic interaction with the carboxyl group on the surface of carbon black in advance. Is
There are difficulties such as a gelling reaction.

Accordingly, a) a polymer in which a hydroxyl group or the like has been previously introduced as a group (III) is reacted with carbon black, and then an acid anhydride or the like is added; A method of introducing a carboxyl group by a half esterification reaction with an acid anhydride, and b)
It is preferable to react the polymer, which has been introduced as a group (IV) blocked with a protective group, with carbon black, and then remove the protective group and introduce a carboxyl group.

The acid anhydride used in the method a) includes phthalic anhydride, succinic anhydride, maleic anhydride,
Dibasic anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, etc. And tetrabasic dianhydrides such as aliphatic or aromatic tetracarboxylic dianhydrides, and one or more of these can be used.

The acid anhydride is used in an amount of 0.1 to 1 equivalent of hydroxyl group in the polymer composited with carbon black.
The reaction is carried out at 50 to 130 ° C. in the presence or absence of a diluent in the presence or absence of a polymerization inhibitor such as hydroquinone or oxygen. it can. In the half esterification reaction between the hydroxyl group and the acid anhydride, general literature such as New Experimental Chemistry 14, “Synthesis and Reaction of Organic Compounds (II)”,
Published by Maruzen Co., Ltd., issued on December 20, 1977, No. 1
A catalyst as described on page 014 can be used. Examples of the catalyst include an acid catalyst, a basic catalyst, and a metal inorganic salt. Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid and the like, or a combination thereof. Basic catalysts include tertiary amines such as triethylamine,
Triethylenediamine, N-pentamethylethylenetriamine, N, N-dimethylbenzylamine, N, N-dimethyluralylamine, N, N, N ', N'-tetramethylpropylenediamine, N-methylmorpholine, N-
Ethylmorpholine, N, N'-methylpiperazine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, 1,8-diazabicyclo- [5,4,0] -7
-Undecene (DBU) and the like or a combination thereof. Examples of the metal inorganic salt include chlorides of metals such as lithium, zirconium, potassium, sodium, tin, zinc, and lead, sodium acetate, and the like, or a combination thereof.

On the other hand, various protecting groups for the carboxyl group in the method b) are known, and for example, a tetrahydropyranyl group and the like can be used. Examples of blocked monomers that yield acrylic or methacrylic acid after removal of the protecting groups include trimethylsilyl methacrylate, trimethylsilyl acrylate, 1-butoxyethyl acrylate,
-Ethoxyethyl acrylate, 2-tetrahydropyranyl acrylate, t-butyl methacrylate and 2
-Tetrahydropyranyl methacrylate and the like.

When the group (II) is a hydroxyl group, the monomers constituting the segments (A) and (B) include, for example, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and acrylic acid Acrylic or hydroxyalkyl methacrylate monomers such as hydroxy 2-ethylhexyl, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxy 2-ethylhexyl methacrylate;
By using a hydroxyalkyl (meth) acrylate such as hydroxyacrylamide or hydroxymethacrylamide for at least a part thereof, the hydroxyl group can be introduced into the polymer.

When the group (II) is an alkoxysilyl group, for example, as a monomer constituting the segment (A), a monomer represented by the following general formula is used at least in part. This makes it possible to introduce an alkoxysilyl group into the polymer.

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

(Provided that R ¹ is a hydrogen atom or a C ₁ -C ₅ optionally substituted alkyl group, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group, ⁴ is a hydrogen atom or an optionally substituted group selected from an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an acyl group; l, m, and n independently represent 0 or 1; A plurality of R ¹ in one molecule may be the same or different from each other.) Specific examples of the alkoxysilyl group-containing monomer represented by the above general formula include γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethy Silane, γ-acryloxypropylmethyldimethoxysilane, methacryloxyethoxypropyltrimethoxysilane, γ-methacryloxypropylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, 1-hexenyltrimethoxysilane, Examples include 1-octenyltrimethoxysilane, vinyloxypropyltrimethoxysilane, 3-vinylphenyltrimethoxysilane, and 3- (vinylbenzylaminopropyl) trimethoxysilane.

In the case where an alkoxysilane group is introduced into the segment (B), for example, a radical polymerizable polymer (b1) having a polysiloxane-based structure as described above may be blocked by an alkoxysilyl group (blocking with a protecting group). Which is preferably used) can be used.

In the embodiment in which the carbon black composite polymer to be obtained does not substantially have the group (II) reactive with the matrix of the target medium as described above, the obtained carbon black composite polymer is A segment (A) having an amino group, an amide group and / or a nitrile group in the presence of a dispersion medium comprising the target medium to be dispersed or a medium having properties close to the target medium; Alternatively, carbon black may be mixed and dispersed with a block or graft polymer having a segment (B) having a high affinity for the dispersion medium. Alternatively, a block or graft polymer having a segment (A) having an amino group, an amide group and / or a nitrile group, and having high affinity for carbon black, and a segment (B); May be mixed and dispersed.

The carbon black composite polymer according to the present invention thus obtained has an average particle diameter of 0.001 to 0.001.
It is preferably 0.5 μm, particularly preferably in the range of 0.005 to 0.2 μm. Carbon black composite polymers having an average particle diameter of less than 0.001 μm have little industrial significance because carbon black as a raw material cannot be easily obtained.
When the average particle size exceeds 0.5 μm, sufficient dispersibility may not be obtained.

In the carbon black composite polymer of the present invention, the ratio of the carbon black portion to the polymer portion is 1 to 1000 parts by weight, especially 5 to 100 parts by weight of the former.
Preferably it is 500 parts by weight. When the latter is less than 1 part by weight, the obtained carbon black composite polymers are aggregated with each other and sufficient dispersibility in the target medium cannot be obtained.
Further, there may be a problem that the electric insulation property and the photopolymerization inhibition property are not improved. On the other hand, when the amount of the latter exceeds 1000 parts by weight, the polymer portion is grafted more than necessary, and there is a possibility that the inherent properties of carbon black, such as colorability and light-shielding properties, cannot be exhibited.

The carbon black composite polymer obtained by the above method has remarkably excellent dispersibility in various substances, for example, organic polymers, water, organic solvents and the like, and generally has high electric insulation. In addition, it has a number of properties.

Particularly, in the embodiment in which the segment (A) and / or the segment (B) has a reactive group (II) such as an unsaturated double bond, the photocurable resin composition and the thermosetting resin composition When added to various media such as, for example, the carbon black composite polymer can contribute to the curing reaction of the medium. Therefore, even if the amount of the carbon black composite polymer is increased, a sufficient curing reaction can be performed in a short time. The hardness and the dispersion stability of carbon black in the resulting cured film or cured product are improved.

In this connection, it has been described above that the carbon black composite polymer of the present invention has an effect similar to that of the silane coupling agent. Explain that the mechanism of action is different.

That is, in a general silane coupling agent, the hydroxyl group (M-OH) on the inorganic surface and the Si—OR group (alkoxysilyl group) of the silane coupling agent are hydrolyzed to form an oxane bond (—MO—O—). While forming Si-), one of the organic functional groups of the silane coupling agent forms a reaction with an organic substance (binder) to form a bridge between the organic substance and the inorganic substance. Here, the Si-OR group (alkoxysilyl group) easily reacts with an inorganic substance having a positive zeta potential, and is disadvantageous for application of a rather negatively charged substance such as carbon black. That is, the transesterification between the carboxyl group and the alkoxysilyl group of the carbon black is carried out by -COO-Si
The bond is very unstable and the reaction is practically difficult.

Furthermore, the ordinary coupling agent has a relatively low molecular weight and thus has no steric stabilizing effect on the dispersion system as compared with the polymer block or graft of the present invention. It is considered that there is also a problem, and instead of using the carbon black composite polymer according to the present invention, even when a silane coupling agent is used in combination when dispersing carbon black in a target medium, the same effect cannot be expected. .

In the carbon black composite polymer of the present invention, if the segment (B) in the composite block or graft type polymer has a relatively long chain length, for example, a molecular weight of 1,000 or more,
When the carbon black composite polymer is blended in the intended dispersion medium, the outwardly oriented segment (B) is present in the matrix of the dispersion medium in a wedge-like form, and its dispersion stability is high. Even if it does not have the reactive group (II) as described above, even if it is added to various media such as a photocurable resin composition and a thermosetting resin composition, the Depending on the conditions and the like, the hardness in the cured film or cured product and the dispersion stability of carbon black can be obtained, which are comparable to those having the reactive group (II) as described above.

Further, for example, when the polymer segment (B) is a polysiloxane-based structural chain, it is excellent in water repellency, release property, heat resistance, weather resistance, flexibility, low viscosity and the like. In the case where the (meth) acrylic chain has a property such as low temperature brittleness, and various (meth) acrylic ester monomer components are introduced, a particularly wide hydrophilic-hydrophobic property is further improved. When it is an alkylene glycol chain, properties such as hydrophilicity, lubricity, flexibility, and antistatic properties are imparted.

Accordingly, the carbon black composite polymer can be used as a coloring agent, a filler or the like for a conventionally known thermoplastic resin or thermosetting resin. When added to a thermoplastic resin, a toner having the above characteristics, a film,
It can be used for fibers and the like. The same characteristics are also obtained when the carbon black composite polymer is added to a thermosetting resin, and a solution to the problem of carbon conventionally can be achieved.

The carbon black composite polymer of the present invention may be used as a coating composition. It is preferable to add a binder to the coating composition and apply it to various substrates to form a strong film. Such a binder component is, for example, a conventionally known thermoplastic resin, thermosetting resin or reactive resin, and one or a mixture of two or more of them is used depending on the application.

Further, for example, by adding the carbon black composite polymer to a photocurable resin composition,
A black photocurable resin composition can be obtained, and it can be particularly preferably used for a black matrix of a color filter.

The carbon black composite polymer according to the present invention has a high ionic interaction between the surface functional group of carbon black and the amino group of the segment (A) in the block or graft type polymer component. The polymer component is compounded on the surface of carbon black with high efficiency. Therefore, the surface of the carbon black is coated with a polymerization-inhibiting functional group such as a quinone group or a phenolic hydroxyl group, and the photocurable resin composition is inhibited from retarding photocuring. Further, the obtained graft carbon black has an improved affinity for various substances because the segment (B) in the polymer is oriented outward, and has excellent dispersibility in various photocurable resin compositions. In order to have a good lubricating property, when it is dispersed in the photocurable resin composition, it exhibits an appropriate viscosity. In addition, when an unsaturated double bond is present as a reactive group (II) in the polymer portion, more preferably in the segment (B), it contributes to photopolymerization or photocrosslinking reaction, and thus UV paint, UV It can be suitably used as a colorant in inks, photocurable resin compositions for color filters, and the like.

As the photocurable resin composition containing such a carbon black composite polymer as a coloring agent or a light-shielding agent, the same ones as various compositions conventionally used in such fields can be used. Crosslinkable or photopolymerizable monomers, oligomers and / or prepolymers may be included. Further, the photocurable resin composition may be either lipophilic and / or hydrophilic, and the properties of the segment (B) in the block or graft type polymer used in the synthesis of the carbon black composite polymer described above. Is suitable for the properties of the photocurable resin composition, whereby good dispersibility of carbon black can be obtained.

Examples of the monomer include ethylene glycol diacrylate, ethylene glycol methacrylate,
Polyethylene glycol acrylate, polyethylene glycol methacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol acrylate, neopentyl glycol methacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri Methacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, β-hydroxyalkyl acrylate, β-hydroxyalkyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, melamine acrylate, butoxyethyl acrylate , Steari Acrylate, lauryl acrylate, tetrahydroxy acrylate, tetrahydroxy methacrylate, aminoalkyl acrylate, aminoalkyl methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, dipropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, 1,5-pentadiol diacrylate, isobornyl acrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acryloxy dimethacrylate, ethyl carbitol acrylate, methyl triglycol acrylate, 2-hydroxyethyl acryloyl phosphate , N-vinyl-2-pyrrolidone, Kuriruamaido, N- methylol acrylamide, N-n-butoxymethyl acrylamide, N- (1,1-dimethyl -
Ethylenically unsaturated compounds such as (3-oxobutyl) acrylamide and itaconic acid can be used.

Examples of the oligomer or prepolymer include, for example, polyesters in which the active hydrogen atom of a polyol is substituted with an acryloyl group or a methacryloyl group, unsaturated polyester resins, dry oil-modified alkyd resins, and unsaturated acids such as acrylic acid and methacrylic acid. An adduct of a vinyl copolymer having a carboxylic acid as a copolymer component and an acrylic monomer having an epoxy group such as glycidyl acrylate or glycidyl methacrylate, or a vinyl copolymer having an acrylic monomer having an epoxy group as a copolymer component Adduct of polymer with unsaturated carboxylic acid, tolylene diisocyanate, adduct of hexynyl copolymer with unsaturated carboxylic acid, tolylene diisocyanate, hexamethylene diisocyanate, 2 mol of tolylene diisocyanate and ethylene Glycol 1 And the like adduct of acrylic monomer having an isocyanate group at such end of the adducts with Le.

[0212] A photosensitizer can be added to the photocurable resin composition, if necessary. As the photosensitizer, one or a combination of two or more types of conventionally known photosensitizers can be used. , 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl, diphenyldisulfide, anthraquinone, 1-chloroanthraquinone, 2-ethylanthraquinone,
-T-butylanthraquinone, methylanthraquinone,
Examples thereof include 1-chloromethylnaphthalene, N, N'-tetraethyl-4,4'-diaminobenzophenone, dibenzosparone, 1,1-dichloroacetophenone and the like.

[0213] In the photocurable resin composition, an organic polymer which is compatible with the photopolymerizable compound as described above can be added as a film-forming component, if necessary. Examples of such organic high-molecular polymers include polyacrylates or partial hydrolysates thereof, polymethacrylates or partial hydrolysates thereof, polyvinyl acetate or hydrolysates thereof, polystyrene, polyvinyl butyral, and polychloroprene. , Polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinyl pyrrolidone, a copolymer of styrene and maleic anhydride, or a half ester. Further, within the range not impairing photocurability, for example, lower alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol, amides such as dimethylformamide, esters such as methyl acetate, ethyl acetate, and butyl acetate, 2-ethylhexyl Ethers such as ether, dioxane, ethylene glycol and monomethyl ether; furans such as 2-methyltetrahydrofuran and furfural; halogen compounds such as chloroform, methylchloroform and trichloroethylene; and aliphatic carbons such as n-hexane and n-heptane. Appropriate organic solvents such as hydrogens, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and dodecyl nitrile, and sulfur derivatives such as carbon disulfide and thiophene may be added. If necessary, a polymerization inhibitor such as hydroquinone or p-benzoquinone can be added to prevent overreaction in photocuring. Further, other known additives, for example, a thickener, a thixotropic agent, a leveling material,
It is also optional to add an antifoaming agent and an adhesion-imparting agent.

The black photocurable resin composition of the present invention is obtained by blending the above-described carbon black composite polymer into the photocurable resin composition. The blending amount in the composition depends on the type of the photocurable resin composition to be used, but the graft carbon black accounts for 1 to 80% by weight, more preferably 5 to 60% by weight of the photocurable resin composition. It is desirable that it be included. That is, if the compounding amount of the carbon black composite polymer is less than 1% by weight, the degree of blackening may decrease, while if it exceeds 80% by weight, the strength of the coating may decrease. It is.

In the black light-curable resin composition of the present invention, for example, those used for applications such as color filters may be of an alkali-soluble type. And an alkali-soluble resin.

The alkali-developable photocurable composition basically comprises a photopolymerization initiator, a polyfunctional monomer, and a polymer binder having an alkali-soluble group in the molecule. Insolubilize.

Examples of the binder which can be blended with the alkali-soluble photocurable composition containing the carbon black composite polymer and which is suitable for use as the alkali-developable photosensitive layer include the following. Can be mentioned.

Alkali-soluble resins containing styrene such as styrene / acrylic acid copolymer, styrene / methacrylic acid copolymer, styrene / α-methylstyrene / acrylic acid copolymer; benzyl acrylate / acrylic acid copolymer Benzyl acrylate / methacrylic acid copolymer,
A repeating unit derived from at least one compound selected from the group consisting of acrylic acid and methacrylic acid such as benzyl methacrylate / acrylic acid copolymer and benzyl methacrylate / methacrylic acid copolymer; and (B) benzyl acrylate; Alkali-soluble resin having a repeating unit derived from at least one compound selected from the group consisting of benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate and 3-phenylpropyl methacrylate; methyl methacrylate / 2-ethylhexyl methacrylate / (meth) acrylic acid terpolymer, methyl methacrylate / styrene / ethyl acrylate / (meth) acrylic acid quaternary copolymer, methyl methacrylate / ethyl acrylate / Alkali-soluble resin containing methyl methacrylate such as terpolymer of (meth) acrylic acid; alkali-soluble resin containing acrylonitrile such as terpolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid Resin: Half-esterified maleic anhydride alkali-soluble resin such as styrene / maleic acid mono-n-butyl ester copolymer and partially half-esterified polymer of styrene / maleic anhydride copolymer And other combinations of these can be added to the photocurable composition.

The black photocurable resin composition of the present invention can be applied to various substrates such as a glass plate, a plastic sheet or film, paper, synthetic paper, and a silicon wafer by using a bar coater, a spin coater, a roll coater, spray coating, or the like.
After applying by an application method such as dipping, gravure printing, screen printing, or the like, a black film can be formed by irradiating with ultraviolet rays at 10 to 5000 mJ and curing.

Further, when a black matrix in a color filter is formed by using the black photocurable resin composition of the present invention, for example, the following is carried out.

The black photocurable resin composition is applied to a substrate such as a glass plate using a spin coater or the like, and then the coating is applied at 150 ° C. or less, particularly at 80 to 120 ° C., using a hot air drier or a hot plate. Dry (pre-bake) for about 1 to 60 minutes. In addition, it is preferable that the film of the black photocurable resin composition obtained by this method is usually about 1.0 to 3.0 μm. Thereafter, a mask of a predetermined shape such as a dot pattern and a stripe pattern is adhered to the film of the black photocurable resin composition, and the mask is passed through the mask.
For example, 50 to 50 parallel rays from an ultraviolet light source such as a high pressure mercury lamp
After pattern exposure by irradiating 1000 mJ, development is performed to form a pattern such as a black matrix.

The development of the pattern-exposed film is carried out by immersing the film in an appropriate developer at a temperature of about 0 to 100 ° C. to elute and remove the uncured portion of the film. It is. After the development, the formed colored pixels are rinsed with an appropriate cleaning solution, and then heated at about 100 to 300 ° C. for 1 to 120 ° C. using a hot air drier, a hot plate or the like.
It is desirable to heat-treat (after-bake) for about a minute to completely cure the colored pixels.

In the case where the carbon black composite polymer according to the present invention has an unsaturated double bond as the reactive group (II), as described above,
It can be bonded to the resin matrix forming the film via a crosslinked or polymerized chain generated by the action of the unsaturated double bond. Therefore, even after the above-described after-baking, the dispersion state of the carbon black present in the film is stably maintained, and the after-baking does not cause a problem that the electrical resistivity is reduced. .

When a black matrix in a color filter is formed by using the black photocurable resin composition according to the present invention, a black matrix is first formed on a substrate, and then red, green and blue colors are formed. A method of forming a pattern or a method of forming a colored pattern of each of red, green, and blue on a substrate first and then forming a black matrix can be used.

Further, in the carbon black composite polymer according to the present invention, carbon black is micro-dispersed,
It is suitable for various uses as a colorant and dispersed in the liquid phase, that is, the carbon black dispersion as an ink having excellent dispersion stability and good coloring power for oil-based writing, information recording or printing. It can be used as it is or by adding necessary components appropriately.

The carbon black composite polymer dispersion of the present invention can be used for plating, thermal transfer inks, paints and the like. Further, because of having the above characteristics, it can be used for a thermal transfer ink ribbon coating agent, a magnetic recording medium, and the like. Furthermore, as an application in a form in which the resistance is adjusted, for example, an electric resistance adjusting agent, an antistatic agent,
There are a sealant for semiconductor devices, a planar heating element, and the like.

The electric resistance adjusting agent can be used, for example, for forming a conductive layer formed on the surface of a roll base material of a charging roll in an electrophotographic apparatus such as a copying machine, a printer, and a facsimile machine. Formulated carbon black dispersion according to the appropriate binder solution,
This may be applied to the surface of the roll substrate to form a film.

[0228]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 (Methyl methacrylate / hydroxyethyl methacrylate) macromonomer having a methacryloyl group at one end (AA714 Poly, manufactured by Toa Gosei Chemical Industry Co., Ltd.)
(MMA / HEMA), MMA: HEMA = 86: 1
75 parts of 4), 15 parts of styrene, 10 parts of dimethylaminoethyl methacrylate, and 3 parts of azoisobutyronitrile as an initiator, propylene glycol monomethyl ether acetate solvent (hereinafter abbreviated as PGM-Ac) 150 Was dissolved.

The above monomer composition was charged into a separable flask equipped with a stirring blade, an inert gas inlet tube, a reflux condenser, a thermometer and a dropping funnel.
Polymerization reaction was carried out for an hour, and the mixture was further heated at 110 ° C. for 2 hours to carry out polymerization ripening, followed by cooling to obtain a polymer (1) having a tertiary amino group having a nonvolatile content of 40%.

Next, 30 parts of carbon black (MA-8, manufactured by Mitsubishi Chemical Corporation), 22.5 parts of the above polymer (1) solution, were placed in a separable flask equipped with a thermometer, stirring blades, and a cooling tube. 97.5 parts of PGM-Ac were charged, and carbon black was used. Subsequently, 750 parts of zirconia beads were charged into the flask, and the rotation speed was 75.
Dispersion processing was performed at 0 rpm. Then, PGM-Ac50
Then, the zirconia beads were separated to obtain a carbon black dispersion (1).

Synthesis Example 2 8.9 parts of methacryloyl isocyanate (molecular weight 111.1) was added dropwise to the polymer (1) obtained in Synthesis Example 1 at room temperature (25 ° C. ± 5 ° C.) over 30 minutes. Thereafter, stirring was continued for 1 hour to obtain a polymer (2) solution having a double bond having a nonvolatile content of 43.6%.

Next, 30 parts of carbon black (MA-8, manufactured by Mitsubishi Chemical Corporation), 20.6 parts of the above polymer (2) solution, were placed in a separable flask equipped with a thermometer, stirring blades, and a cooling tube. 108.4 parts of PGM-Ac were charged, and carbon black was used. Subsequently, 750 parts of beads made of zirconia were charged into the flask and subjected to a dispersion treatment at a rotation speed of 750 rpm. Then, PGM-
50 parts of Ac were added to separate the zirconia beads to obtain a carbon black dispersion (2) having a double bond.

Comparative Synthesis Example 1 64.5 parts of methyl methacrylate, 10.5 parts of hydroxyethyl methacrylate, 15 parts of styrene, 10 parts of dimethylaminoethyl methacrylate, 3 parts of azoisobutyronitrile as an initiator, and PGM-Ac1 as a solvent
50 parts were charged into the same separable flask as used in Synthesis Example 1, and the polymerization reaction was carried out for 4 hours.
After heating for 2 hours at 20 ° C. to effect polymerization aging, the non-volatile
% Of a tertiary amino group was obtained as a comparative polymer (C1).

Then, carbon black (manufactured by Mitsubishi Chemical Corporation, MA-
8) 30 parts, 22.5 parts of the comparative polymer (C1),
97.5 parts of PGM-Ac were charged, and carbon black was used. Subsequently, zirconia beads 75
0 parts were charged in a flask and subjected to a dispersion treatment at a rotation speed of 750 rpm. Thereafter, 50 parts of PGM-Ac was added to separate the zirconia beads to obtain a comparative carbon black dispersion (C1).

Example 1 The carbon black dispersion (1) obtained in Synthesis Example 1 above
To 50 parts were added John Crill 68 (21.25 parts, manufactured by Johnson Polymer Co., Ltd., 62.5 parts of dipentaerythritol hexaacrylate, 9.38 parts of Irgacure 907 (manufactured by Ciba Geigy) as a photoinitiator and uniformly dispersed. Thus, a black photocurable composition (1) was obtained.

The black photocurable composition (1) was applied by a spinner so as to have a dry film thickness of 0.5 μm, and was prebaked on a hot plate at 100 ° C. for 1 minute. The obtained film was exposed to ultraviolet light of 800 mJ / cm ² using a high-pressure mercury lamp to be cured. Then, the surface resistance after exposure to ultraviolet light was measured. Thereafter, after-baking was performed in an oven at 200 ° C., and changes in the surface resistance value with the lapse of time were examined. Table 1 shows the obtained results. The surface resistance was measured using a surface resistance measuring device Hiresta IP / M.
It was measured with a CP-HT260 model.

Example 2 The procedure of Example 1 was repeated, except that the carbon black dispersion (2) was used instead of the carbon black dispersion (1).
The same operation as in Example 1 was repeated to obtain a black photocurable composition (2), and the change in surface resistance was examined by the same method. Table 1 shows the obtained results.

Comparative Example 1 The procedure of Example 1 was repeated, except that the carbon black dispersion (C1) was used in place of the carbon black dispersion (1). The curable composition (C1) was obtained, and the change in the surface resistance was examined by the same method. Table 1 shows the obtained results.

[0240]

[Table 1]

As shown in Table 1, when the polymer in the carbon black dispersion used was a block type polymer having an amino group or a polymer having a double bond, the resistance value was reduced by heating. It turned out to be an excellent film without any.

Synthesis Example 3 30 parts of carbon black, the polymer (1) solution, and 30 parts of carbon black, 22.5 parts of the polymer (1) solution and 97.5 parts of PGM-Ac in Synthesis Example 1 Except that 30 parts and 90 parts of PGM-Ac were used, the same operation as in Synthesis Example 1 was performed to obtain a carbon black dispersion (3).
I got

Example 3 200 parts of carbon black dispersion (1) (30 parts of carbon black, 9 parts of polymer) were added to 182 parts of Alloset 5271 (acrylic binder solution, Nippon Shokubai Co., Ltd., nonvolatile content: 50%). A) a black resin liquid (1),
And 176 parts of Alloset 5271 (manufactured by Nippon Shokubai Co., Ltd., acrylic binder solution, non-volatile content 50%), and a black resin comprising 200 parts of carbon black dispersion (3) (30 parts of carbon black, 12 parts of polymer) Liquid (3) was prepared.

Each of the black resin liquids was applied to a glass substrate using an applicator to form a black film, and after the solvent was volatilized, the surface resistance was measured. As a result, at the same carbon black content of 30 PHR, the black resin liquid (1)
Is of the order of 10 ⁷ Ω / □,
The coating film formed from the black resin liquid (3) showed an order of 10 ⁸ Ω / □.

Synthesis Example 4 50 parts of the macromonomer (AA714, manufactured by Toa Gosei Chemical Industry Co., Ltd.) used in Synthesis Example 1, 15 parts of styrene, 5 parts of dimethylaminoethyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, and As an agent, 3 parts of azoisobutyronitrile was dissolved in 150 parts of PGM-Ac.

The above-mentioned monomer composition was charged into the same separable flask as in Synthesis Example 1, subjected to a polymerization reaction at 80 ° C. for 4 hours, and further subjected to polymerization aging at 110 ° C. for 2 hours.
% Of a polymer (2) having a tertiary amino group.

Next, in the same manner as in Synthesis Example 1, 20 parts of carbon black (MA-8, manufactured by Mitsubishi Chemical Corporation), 22.5 parts of the above polymer (2) solution, and 97.5 parts of PGM-Ac were charged. Black was used. continue,
Subsequently, 750 parts of beads made of zirconia were charged into the flask and subjected to a dispersion treatment at a rotation speed of 750 rpm. Then, P
50 parts of GM-Ac was added to separate the zirconia beads to obtain a carbon black dispersion (4).

Synthesis Example 5 Carbon black dispersion (4) 15 obtained in Synthesis Example 4
0 parts by weight of trimellitic anhydride (molecular weight 192.1
3) 3.59 parts were dissolved.

Next, the above dispersion was charged into a separable flask equipped with a thermometer, a stirring blade, a cooling tube, and a dropping funnel, and the 1,8-diazabicyclo [5,4,
0] and charged over 30 minutes.
The reaction was performed at a temperature of 0 ° C. for 1 hour to obtain a carbon black dispersion (5) containing a carboxyl group.

Examples 4 and 5 To the carbon black dispersions (4) and (5) obtained in Synthesis Examples (4) and (5), dipentaerythritol triacrylate as a photocurable monomer and alkali as a binder were used. Soluble styrene-acrylic resin (Johncryl 68, manufactured by Johnson Polymer Co., Ltd.) was added at the compounding ratio shown in Table 2 to obtain alkali-soluble photocurable compositions (4) and (5).

This solution was applied on a glass substrate to a dry film thickness of 1 μm.
m, and prebaked at 100 ° C. for 1 minute. The resulting dried coating film was developed using a 0.5% NaOH aqueous solution, and the remaining film was visually evaluated. As a result, it was confirmed that the carbon black dispersion (5) was a carbon black composite polymer-containing dispersion having a COOH group. The photocurable composition (5) prepared according to (1) had a clear surface on the glass substrate, whereas the photocurable composition (4) had a slight black residue on the glass substrate. Was.

[0252]

[Table 2]

[0253]

As described above, the present invention provides an amino group,
A carbon obtained by mixing and dispersing a block or graft polymer comprising a segment (A) having an amide group and / or a nitrile group and a segment (B) having a different structure from the segment (A), and carbon black. Since it is a black composite polymer, it has a high content of carbon black while being excellent in dispersibility in various media.

In addition, since the compounding of the carbon black and the polymer portion is performed by the ionic interaction between the amino group, the amide group and / or the nitrile group and the functional group on the surface of the carbon black, a covalent bond is formed. As compared with the case of grafting via, there are fewer safety problems in production, restrictions on reaction conditions, etc., which are industrially more advantageous.

Further, the segment (A) and / or (B) is a group (II) having a reactivity with a matrix of a target medium containing the carbon black composite polymer.
When it has, more excellent dispersion stability is obtained, in addition, when added to various light or thermosetting resin composition, it can contribute to the curing of the resin composition, Even with a high addition amount, a high-strength film can be easily formed, a film having excellent light-shielding properties and blackening degree can be obtained, and further, various properties such as electrical insulation properties are excellent. For this reason, it can be suitably added as a colorant, a filler, a light-shielding agent and the like to various media including the light- or thermosetting resin composition as described above, and particularly, a black matrix formation of a color filter. It can be preferably added to the photocurable resin composition used for the material for application. Further, the group (II) having reactivity with the matrix of the target medium does not necessarily improve the physical properties obtained by reacting with the matrix. For example, in an embodiment used for a resin black matrix for a color filter. In some cases, additional effects may be obtained depending on the mode of use, such as the fact that a COOH group as a group having reactivity with a matrix improves alkali developability.

Further, the film formed from the photocurable resin composition to which the carbon black composite polymer according to the present invention is added can exhibit a high light-shielding property at a sufficiently small film thickness, and has a high film strength and Since it can exhibit high electric resistance, it is particularly suitable for forming a black matrix of a color filter.

[Brief description of the drawings]

FIG. 1 is a view schematically showing a state in the vicinity of a carbon black surface in a method for producing a carbon black composite polymer according to the present invention.

2 (a) to 2 (e) are diagrams schematically showing various structural examples of a block or graft type polymer used in the present invention, and FIG. 2 (f) is a diagram showing these various blocks or grafts. FIG. 4 is a view schematically showing a state in which a polymer of a type is bonded to the surface of carbon black particles (CB).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00 C09D 7/12 C09D 7/12 Z 11/00 11/00 17/00 17/00 G02B 5 / 20 101 G02B 5/20 101

Claims (18)

[Claims] 1. A block or graft polymer comprising a segment (A) having an amino group, an amide group and / or a nitrile group and a segment (B) having a structure different from that of the segment (A), and carbon black. Are mixed and dispersed to obtain a carbon black composite polymer. 2. The method according to claim 1, wherein the segments (A) and / or (B) have a group (II) reactive with a matrix of a target medium in which the carbon black composite polymer is blended. The carbon black composite polymer according to the above. 3. The group (II) is at least one or two or more selected from the group consisting of an unsaturated double bond group, a carboxyl group and an alkoxysilyl group. 3. The carbon black composite polymer according to item 1. 4. The segment (B) has a polysiloxane structure, a poly (meth) acrylic structure, a polyether structure, a poly (meth) acrylonitrile structure, a polyester structure, a polyalkylene structure, a polyamide structure, a polyimide structure, and a polyurethane. The carbon black composite polymer according to any one of claims 1 to 3, wherein the carbon black composite polymer has at least one kind or two or more kinds selected from the group consisting of a structure and a fluorine-based resin structure. 5. The segment (A) according to claim 1, wherein the segment (A) is obtained by polymerization of a vinyl monomer composition containing 0.5 mol% or more of an aminoalkyl (meth) acrylate. The carbon black composite polymer according to one of the above. 6. A segment (A) having an amino group, an amide group and / or a nitrile group in the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium.
And a block or graft polymer having a segment (B) having a higher affinity for the dispersion medium liquid than the segment (A), and carbon black mixed and dispersed. A method for producing a composite polymer. 7. A segment (A) having an amino group, an amide group and / or a nitrile group in the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium.
And a segment (B) having a higher affinity for the dispersion medium liquid than the segment (A), and the segment (A) and / or the segment (B) has a reactivity with a matrix of a target medium. A method for producing a reactive carbon black composite polymer, comprising mixing and dispersing a block or graft polymer comprising a group (II) having the formula (I) and carbon black. 8. A) a segment (A) having an amino group, an amide group and / or a nitrile group in the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium, and the segment (A) A block or graft type precursor polymer having a segment (B) having a higher affinity for the dispersion medium than carbon black, and then b) mixing and dispersing the block or graft type precursor polymer. A method for producing a carbon black composite polymer, comprising introducing a group (II) having reactivity with a matrix of a target medium into the coalesced product. 9. A segment (A) having an amino group, an amide group and / or a nitrile group in the presence of a dispersion medium comprising a target medium or a medium having properties close to the target medium, and the segment (A) A precursor polymer having a functional group (III) having a segment (B) having a higher affinity for the dispersion medium than the functional group on the surface of carbon black and having substantially no reactivity with the carbon black surface; Is mixed and dispersed in advance with carbon black, and then b) has a reactive group (IV) capable of reacting with the functional group (III) of the block or graft type precursor polymer and a reactivity with the matrix of the target medium. Compound (d) having group (II)
Is reacted with the carbon black obtained in the above a) to introduce the group (II) into the precursor polymer, thereby producing a carbon black composite polymer. 10. A block or graft type polymer having a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having a lower affinity for carbon black than the segment (A). A method for producing a carbon black composite polymer, comprising mixing and dispersing the coalesced particles and carbon black. 11. A segment (A) having an amino group, an amide group and / or a nitrile group, a segment (B) having a lower affinity for carbon black than the segment (A), and the segment (A) Carbon black characterized by mixing and dispersing a block or graft type polymer comprising a group (II) reactive with a matrix of a target medium in A) and / or a segment (B), and carbon black. A method for producing a composite polymer. 12. A block or graft type comprising: a) a segment (A) having an amino group, an amide group and / or a nitrile group, and a segment (B) having a lower affinity for carbon black than said segment (A). And the carbon black is mixed and dispersed, and then b) a group (II) having reactivity with a matrix of a target medium is introduced into the block or graft type precursor polymer. A method for producing a carbon black composite polymer. 13. A black thermosetting resin composition obtained by blending the carbon black composite polymer according to claim 1 into a thermosetting resin composition. 14. A black photocurable resin composition comprising the carbon black composite polymer according to claim 1 mixed with a photocurable resin composition. 15. The black photocurable resin composition according to claim 15, wherein the molecular weight of the segment (B) of the carbon black composite polymer is 500 or more. 16. The composition according to claim 14, wherein an alkali-soluble resin is blended in the photocurable resin composition.
Or the black photocurable resin composition according to 15. 17. A black matrix for a color filter, formed from the black photocurable resin composition according to claim 14. Description: 18. A resistance adjuster comprising the carbon black composite polymer according to claim 1.