JP3512129B2 - Colorant composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a colorant composition containing carbon black as a coloring component. In particular, the present invention relates to a toner for developing an electrostatic charge image for developing an electrostatic latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like. The present invention further relates to water-soluble and oil-soluble ink compositions for writing instruments such as ballpoint pens and ink jet printers. The present invention also relates to a photocurable black resin composition such as a UV paint, a UV ink and a black matrix forming agent for a color filter.

[0002]

[Prior art]

(1) Colorant composition Carbon black is excellent not only in colorability but also in various properties such as conductivity, weather resistance and chemical resistance.
It is blended in a liquid or solid matrix such as a photo- or thermosetting resin composition and a water-soluble or oil-soluble solvent and used as a colorant composition in various applications. However, carbon black has a weak affinity for other substances, such as organic polymers, water, and organic solvents, as compared with the cohesive force between particles, so that carbon black can be uniformly mixed or dispersed in these matrices. It was extremely difficult and was a cause of deterioration of product characteristics. The colorant composition as used herein means any base material such as paper, cloth,
Various films, final products or the like made of metal or other materials, when coated, spread or coated, etc., when viewed macroscopically or microscopically, carbon black is dispersed in the finally solidified matrix. It includes all those forming a coating film or an impregnated layer, and specifically includes, for example, electrostatic image developing toner, water-soluble ink,
Oil-soluble ink, ink for inkjet printer, UV
Paints, UV inks, black matrix forming agents for color filters, thermal transfer inks, thermal transfer ink ribbon coating agents, magnetic recording medium back coating agents, electrophotographic liquid developers, and other coating compositions including coating materials. and so on.

(2) Toner for developing electrostatic image A representative of such colorant compositions is toner for developing electrostatic image.

In electrophotography, an electric latent image is formed on a photoconductor formed of an optical conductor material such as selenium, zinc oxide or cadmium sulfide, and the latent image is developed with a powder developer to be applied to paper or the like. It is transferred and fixed.

Conventionally, a toner used for developing an electrostatic image is generally prepared by melt-kneading a colorant and other additives such as a charge control agent, an offset preventing agent, a lubricant, etc. in a thermoplastic resin and then dispersing them. The solidified product was finely pulverized and classified to produce colored fine particles having a desired particle size.

Various methods for producing a toner by an emulsion polymerization method or a suspension polymerization method have been proposed (for example, Japanese Patent Publication No. 36-10231, Japanese Patent Publication No. 43-10799, US Pat. No. 3,959,153, and US Pat. 3634251
issue). These methods are methods in which a colorant such as carbon black and other additives are added to a polymerizable monomer, and emulsion or suspension polymerization is performed to synthesize a toner containing the colorant at once. The toner obtained by this method has a spherical shape and is excellent in fluidity.

By the way, in such a toner, carbon black is often used as a colorant. However, carbon black is excellent in coloring property, weather resistance, chemical resistance and the like, on the other hand, compared with cohesive force between particles. Due to its weak affinity with other substances, it does not disperse uniformly in the binder resin under ordinary kneading or dispersing conditions, which increases the variations in the electrical resistance and charging friction of the toner particles. There remains a technical problem in obtaining a toner capable of forming an image.

In order to solve this problem, the surface of carbon black is coated with various kinds of surfactants or resins to enhance the affinity with a solid or liquid base material so that carbon black is uniformly mixed or Many methods of dispersion are being studied.

Among them, the carbon black graft polymer obtained by polymerizing the polymerizable monomer in the presence of carbon black is hydrophilic and / or lipophilic by appropriately selecting the type of the polymerizable monomer. Since it can be changed appropriately, it has attracted attention in recent years.

As a method for producing this carbon black graft polymer, for example, Japanese Examined Patent Publication No. 42-22047.
No. 44/3826/45/17284
No. 3,570,040, the yield of the carbon black graft polymer obtained by these methods is as low as several% to several dozen%, and most of them are present in the form of vinyl homopolymer. The surface treatment efficiency of was extremely poor.

Further, Japanese Patent Publication No. 6-27269 discloses 50 to 25 carbon black and a polymer having 1 to 2 epoxy groups, thioepoxy groups and the like in one molecule.
A method for producing a carbon black graft polymer by stirring and mixing under a temperature condition of 0 ° C. is disclosed, and JP-A-6-148927 discloses an emulsification method in the presence of such a carbon black graft polymer. Alternatively, it has been proposed to use colored fine particles obtained by suspension polymerization as a toner. According to this method, epoxy groups, thioepoxy groups, etc. existing in the molecule of the polymer react extremely efficiently with the surface functional groups of carbon black, and a carbon black graft polymer having excellent dispersibility in various substances can be obtained. The toner also exhibited relatively excellent characteristics as a toner.

However, such a carbon black graft polymer has a problem that the carbon content in the carbon black graft polymer cannot be increased, and therefore it is difficult to make the particle size sufficiently small, and the electrical insulation is low. Had the problem. Therefore, the toner for developing an electrostatic charge image containing such a carbon black graft polymer can satisfy the low temperature fixability of toner particles and the characteristics of small particle size, which are required in terms of speeding up. There wasn't. That is, since the amount of the polymer component in the carbon black graft polymer is relatively large, even if the binder resin is sufficiently improved in accordance with the requirement of low temperature fixability,
Depending on the polymer component in the carbon black graft polymer, the effect cannot be obtained as expected. Further, it is difficult to cope with the tendency toward smaller particle size of the toner particles, which is required from the viewpoint of higher resolution, and the charging stability has not been sufficiently satisfactory.

Further, in general, an electrostatic image developing toner is required to have offset resistance to a heat fixing roller, abrasion resistance of a fixed image, filming resistance to a photoreceptor, and the like.
In particular, when a low-molecular weight binder resin is used for low-temperature fixing, such a characteristic becomes a problem. Conventionally, in order to improve these points, low molecular weight polyethylene, liquid paraffin, silicone oil, or the like has been added, but none of them has achieved sufficient properties.

(3) Ink composition An ink composition is another typical example of the colorant composition containing such carbon black. The use of the photocurable resin as a matrix in the ink composition will be described in (4).

For example, as the ink for a ballpoint pen, the viscosity of an aqueous ballpoint pen ink having a solvent of water or a water-soluble solvent and having a viscosity of 10 centipoises or less and an oily solvent such as mineral oil, polyhydric alcohol, fatty acid or cellosolve 1
Ink for oil-based ballpoint pens of about 2,000 to 20,000 centipoise is generally used.

Although various dyes and pigments are used as the coloring component in these ink compositions, those using carbon black as the coloring agent have a lightness of color when spread on a substrate. It is good and has little discoloration over time, which is important for recording applications requiring storage stability.

However, as described above, carbon black has poor dispersibility in both water-soluble and oil-soluble solvents as compared with other dyes or pigments, and due to the lowered dispersibility, clogging of writing instruments, such as fading, occurs. Cause
There is also a problem that the ink itself is inferior in long-term storage stability. For this reason, various dispersion stabilizers such as polyoxyethylene alkyl ether derivatives and various polymer surfactants have been added, but sufficient effects have not been obtained yet.

Further, in such an ink composition,
Performance such as bleeding when spread on a base material such as paper or rubbing resistance after fixing is required. For this purpose, a composition obtained by adding silicone oil or the like is also known. It has not reached the desired effect.

Further, as an ink composition using carbon black, an ink for ink jet printer is known. This is disclosed in, for example, JP-A-2-21214.
As shown in No. 9, carbon black as dielectric particles is dispersed in an electrically insulating dispersion medium,
By applying a voltage, the viscosity of the ink is changed to control the ejection of the ink to form an image. However, the ink composition containing carbon black as the disperse phase has a problem that the disperse phase particles are precipitated and the dispersion stability is poor. In addition, as a known major problem of ink for inkjet pudding, there is a problem that this ink easily causes bleeding and paper that is generally used in the office cannot be used. Therefore, various additives should be added. Has been tried, but it has not been sufficiently effective.

(4) Photocurable Black Resin Composition As another typical example of such a carbon black-containing composition, there is a photocurable black resin composition.

The method for curing paints and inks by irradiation with ultraviolet rays began in 1968 by Bayer AG in Germany as a method for promoting the curing of unsaturated polyester resin paints for woodwork paints, and in 1969 in the United States. Acrylic UV curable resin was developed for printing ink by Sun Chemical Co., Ltd. and Inmont Co. Ltd.
In the year, a practical test of UV curable ink was developed.

Since then, along with social conditions, energy conservation,
As a paint and ink suitable for saving resources, UV curable paint and UV curable ink have been actively developed.
It still has many problems left over.

Photopolymerization accelerators, chain transfer agents, stabilizers, adhesion promoters and the like are used in this type of paint and ink depending on the application.

Amines are used as the photopolymerization accelerator, and mercaptan and the like are used as the chain transfer agent.

The system becomes particularly unstable when a small amount of a metal ion or a reducing substance is contained in the pigment-blended system, such as when a large amount of a photoinitiator is added or when a polymerization accelerator is added. However, there is a problem that it is necessary to add a polymerization inhibitor such as hydroquinone.

The coating system using titanium oxide has good curability due to reflection and scattering on the surface of the pigment, and in particular, anatase titanium oxide is excited by ultraviolet irradiation to cure titanium oxide and hardens, but carbon black is used. In the conventional coating system, carbon traps radicals, so that curing is extremely deteriorated.

In the enamel process, there is no great difference from the conventional thermosetting type such as a dispersion method and a classifier.
It is also necessary to disperse with a sand mill, caddy mill, etc.
In addition, pigments that are easily aggregated and have poor dispersibility, or those with high viscosity are dispersed with a three-roll roll, etc.Due to poor wetting of the pigment during dispersion and work, use a dispersant, etc., and perform sufficient premixing. There is a need to.

Due to the high reactivity of the resin, there is a problem that it is necessary to pay attention to the cooling of the disperser so that a large share is not applied during dispersion.

Further, the color filter is formed by providing fine areas colored in two or more kinds of color layers as pixels on a solid-state image pickup element or a transparent substrate. Such a colored thin film has been conventionally produced by a dyeing method, a printing method, an inkjet method, or the like, and when a high-definition image is required, the dyeing method is generally used.

However, these conventional methods have the following problems. The color filter by the dyeing method is preliminarily printed on the substrate with natural photosensitive resin such as gelatin,
It is created by forming an image with a dyeing base material such as amine-modified polyvinyl alcohol or amine-modified acrylic resin, and then dyeing it with a dye such as an acid dye. However, it is necessary to form multiple colors on the same substrate. It is necessary to carry out dye-proof processing every time it is dyed, and the process is very complicated and long.

In addition, since the dyes and resins used are generally weak in light resistance, heat resistance, and moisture resistance, color filters made using these dyes are naturally unavoidable, so that there is a problem in reliability in light resistance, heat resistance, and moisture resistance. was there. In addition to the dyeing method,
There are printing methods, pigment dispersion methods, and electrodeposition methods for producing color filters, but they all have problems in pigment dispersibility.

For example, a color filter by a printing method is prepared by using an ink in which a pigment is dispersed in a thermosetting or photocurable resin, printing it on a substrate, and then curing it by heat or light. It is difficult to form a high-definition image, and the surface smoothness of the obtained image is often problematic. It can be said that this is because the colorant is internally added to the photosensitive resin in advance, but in general, the photopolymerization initiator requires ultraviolet light to generate radicals,
In the above-described system in which a coloring material is internally added in advance, ultraviolet light is absorbed by the coloring material, radicals cannot be sufficiently generated, and it is often difficult to form a satisfactory image.

In a photocurable resin composition using carbon black as a colorant, in order to solve the above-mentioned problem of photocuring delay, JP-A-50-59431 discloses a carbon black as a coloring component. It has been proposed to use a graft carbon black obtained by grafting a vinyl-based monomer on the surface of. In such a grafted carbon black, a vinyl monomer is grafted to cover the surface of the carbon black with a quinone group, a polymerization inhibiting functional group such as a phenolic hydroxyl group, and is expected to improve photocurability. It is possible. However, when a vinyl monomer is grafted onto carbon black as disclosed in the above-mentioned document, the yield of the graft polymer is low and the surface treatment efficiency of carbon black is extremely poor, so that the photocurability is improved. Was not at a satisfactory level.

Further, JP-A-6-214385 has at least one reactive group selected from the group consisting of aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group and thioepoxy group in the molecule. There has been proposed a photocurable black resin composition containing a compound, particularly a carbon black graft polymer obtained by reacting a compound having a polyalkylene skeleton, with carbon black as a coloring component. In this carbon black graft polymer, relatively good grafting efficiency can be obtained due to the presence of the reactive group, and the polymerization-inhibiting functional group existing on the surface of the carbon black is coated, and it is expected that sufficient photocurability is improved. Met. However, in order to obtain a sufficient polymerization inhibition suppressing effect, it is necessary to contain a certain amount of a polymer component, and therefore a decrease in the carbon content in the carbon black graft polymer is unavoidable, and a high carbon content is required. However, it has not been able to adequately support high-performance applications. Even when such a composition is used, for example, when the black matrix of the color filter as described above is formed, ink bleeding or color mixing in the coloring step cannot be sufficiently avoided and there is room for improvement. was there.

[0035]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel colorant composition in which carbon black is well dispersed and blended.

Another object of the present invention is to provide a novel toner for developing an electrostatic image. Another object of the present invention is to meet the demands for high speed and high resolution, and is excellent in various properties such as moisture resistance, offset resistance, fixed image rubbing resistance, filming resistance, and charging stability. To provide a toner for developing an electrostatic image.

Another object of the present invention is to provide a novel ink composition. Another object of the present invention is bleeding,
An object of the present invention is to provide an ink composition which is excellent in rubbing resistance after fixing and is also excellent in storage stability for a long period of time without causing scratches and the like.

Another object of the present invention is to provide a novel photocurable black resin composition. Another object of the present invention is to have a high carbon content and be applicable to high-performance applications,
Another object of the present invention is to provide a photocurable black resin composition free from ink bleeding and color mixing.

[0039]

[Means for Solving the Problems]
It is achieved by the following (1) to (18).

(1) A polymer having a polysiloxane structure in at least a part and having a reactive group for the surface functional group of carbon black is grafted to carbon black in a liquid or solid matrix. A colorant composition comprising a carbon black graft polymer.

(2) The colorant composition as described in (1) above, wherein the polymer contains a main chain having a carbon-carbon bond.

(3) The polymer has a polysiloxane-containing structural unit represented by the general formula (I).
The colorant composition according to.

[0043]

[Chemical 3]

(In the formula, A represents —COO— or a phenylene group, R ¹ represents a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 6 carbon atoms, R ^{3 to} R ¹³ are the same or different and each represents an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and a is optional. , B and c are the same or different integers of 0 to 10, and d is an integer of 0 to 200, respectively. (4) The average particle size of the carbon black graft polymer is within the range of 0.001 to 0.5 μm (1)
~ The colorant composition according to any one of (4).

(5) Any one of the above (1) to (5), wherein the carbon black graft polymer is obtained by grafting 1 to 1000 parts by weight of the polymer portion with respect to 100 parts by weight of carbon black. The described colorant composition.

(6) The colorant composition according to any one of (1) to (6) above, wherein the carbon black is an acidic carbon black having a pH of less than 6.

(7) The polymer has an epoxy group in the molecule,
The colorant composition according to any one of (1) to (7), which has at least one reactive group selected from the group consisting of a thioepoxy group, an aziridine group and an oxazoline group.

(8) Carbon black obtained by grafting carbon black with a binder resin component and a polymer having a polysiloxane structure at least in part and having a reactive group for the surface functional groups of carbon black. A toner for developing an electrostatic charge image, which comprises a graft polymer.

(9) The toner for developing an electrostatic charge image according to the above (8), wherein the polymer contains a main chain having a carbon-carbon bond.

(10) The toner for developing an electrostatic charge image as described in (8) or (9) above, wherein the polymer has a polysiloxane-containing structural unit represented by the general formula (I).

[0051]

[Chemical 4]

(In the formula, A represents —COO— or a phenylene group, R ¹ represents a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 6 carbon atoms, R ^{3 to} R ¹³ are the same or different and each represents an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and a is optional. , B and c are the same or different integers of 0 to 10, and d is an integer of 0 to 200, respectively. (11) The toner for developing an electrostatic image according to any one of (8) to (10), wherein the carbon black graft polymer has an average particle size within a range of 0.001 to 0.5 μm.

(12) Any one of the above (8) to (11), wherein the carbon black graft polymer is obtained by grafting 1 to 1000 parts by weight of the polymer portion with respect to 100 parts by weight of carbon black. The toner for developing an electrostatic image as described above.

(13) The toner for developing an electrostatic charge image according to any one of (8) to (12) above, wherein the carbon black is an acidic carbon black having a pH of less than 6.

(14) The polymer has at least one reactive group selected from the group consisting of an epoxy group, a thioepoxy group, an aziridine group and an oxazoline group in the molecule (8) to (13). The toner for developing an electrostatic charge image according to any one of 1.

(15) With respect to 100 parts by weight of the binder resin component, the above carbon black graft polymers 1 to 100
The above (8) to (1), in which parts by weight are added.
4. The toner for developing an electrostatic charge image according to any one of 4).

(16) The toner for developing an electrostatic charge image is
The above (8) to (1) obtained by suspension polymerization of a polymerizable monomer that forms a binder resin component by polymerization in the presence of the carbon black graft polymer.
5. The toner for developing an electrostatic charge image according to any one of 5).

(17) An ink composition, wherein the matrix in the colorant composition described in any one of (1) to (7) above is a liquid matrix composed of a water-soluble or oil-soluble solvent.

(18) A photocurable black resin composition in which the matrix in the colorant composition described in any one of (1) to (7) above is a liquid matrix composed of a photocurable resin composition. .

[0060]

The term "carbon black graft polymer" as used herein refers to fine particles in which a polymer portion is grafted to a carbon black portion. The carbon black graft polymer is obtained by grafting a polymer on primary particles of carbon black or several aggregates. Furthermore, the term “grafting” as used herein means done (Jean).
-By the irreversible addition of a polymer to a substrate such as carbon black, as defined by Baptiste Donnet et al. In their book "Carbon Black" (published on May 1, 1978 by Kodansha Ltd.). is there.

By carrying out an irreversible addition reaction, the polymer portion can be chemically bonded to the surface portion of the carbon black particles, whereby both of the above can be reliably bonded. Addition reactions that can be used for "grafting" include electrophilic addition reactions, radical addition reactions, nucleophilic addition reactions, and cycloaddition reactions.

Carbon black is usually several nm to several hundreds 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 size of several microns or more. This strong cohesive force
It is considered that this is due to the π-π interaction between the aromatic rings of carbon black. Due to this π-π interaction, carbon black exhibits high conductivity. In addition, the cohesive force between carbon blacks is significantly higher than the affinity between carbon blacks and other media, and it is very difficult to disperse carbon blacks in media in the submicron range. On the other hand, in the carbon black graft polymer, the polymer portion effectively enters between the carbon black particles, and the cohesive force between the carbon blacks can be weakened. Further, when the polymer portion has an affinity with the matrix of the colorant composition, for example, the binder resin in the toner for developing an electrostatic image, or the polymerizable monomer that becomes the binder resin by polymerization, carbon black is used. The graft polymer can be submicron dispersed in a matrix or medium. However, even if the polymer portion has a high affinity with the medium, if the polymer portion is not effectively grafted to the carbon black portion, its properties will not be stable and will cause variations. It becomes easy, and when it is attempted to obtain a certain level of affinity, the content of the carbon black portion in the carbon black graft polymer becomes low.

As a result of intensive studies, the present inventors have found that a carbon black graft polymer having a polymer portion containing a polysiloxane structure has more excellent dispersibility than conventional carbon black graft polymers. . That is, it can be said that the carbon black graft polymer according to the present invention reacts the carbon black and the polymer more effectively than the conventional carbon black graft polymer. Therefore, as compared with the conventional carbon black graft polymer, the carbon content in the carbon black graft polymer can be increased, the particle size can be reduced, and the electrical insulating property is high.

Therefore, in the toner for electrostatic charge development containing such a carbon black graft polymer, not only the dispersibility of carbon black becomes good, but also the particle size can be reduced with a high carbon content. Further, low temperature fixing is possible by fully exhibiting the characteristics of the binder resin of the toner, and the charging stability is also good. In addition, due to the fact that the polymer component in the carbon black graft polymer according to the present invention has a polysiloxane structure, the offset resistance, the rub resistance of the fixed image, the filming resistance, and the moisture resistance can be improved. Various characteristics will be improved.

Similarly, in the ink composition containing such a carbon black graft polymer, the dispersibility of the carbon black is good, and the long-term storage stability is excellent without causing blurring. In addition to the above, the polymer component in the carbon black graft polymer does not cause bleeding and the like due to the fact that the polymer component in the carbon black graft polymer has a polysiloxane structure, and the rubbing resistance after fixing is excellent.

Similarly, in the photocurable black resin composition containing such a carbon black graft polymer, not only the dispersibility of carbon black becomes good, but also a sufficient polymerization inhibition suppressing effect is obtained. And the photocurability is improved, and further, the carbon content in the carbon black graft polymer is increased, and as a result, the carbon content in the composition can be made high to be applied to high-performance applications. Due to the fact that the polymer component in the polymer has a polysiloxane structure, there is no risk of problems such as ink bleeding and color mixing in the coloring step when used for forming a black matrix of a color filter.

Hereinafter, the present invention will be described in more detail based on the embodiments. (1) Colorant Composition The colorant composition of the present invention comprises a liquid or solid matrix having at least a part of a polysiloxane structure and a reactive group for a surface functional group of carbon black. A colorant composition comprising a carbon black graft polymer obtained by grafting a polymer onto carbon black.

As the matrix, that is, the dispersion medium, in the colorant composition of the present invention, various ones suitable for the specific use of the colorant composition are used. For example, thermoplastic resin, light or thermosetting resin composition. Substances, water-soluble or oil-soluble solvents, and the like.

(2) Toner for Developing Electrostatic Image Also, the colorant composition of the present invention includes a great many aspects as described above. Hereinafter, the toner for developing electrostatic image will be taken as an example. The toner for developing an electrostatic image of the present invention to be described is a polymer containing at least a binder resin component and a polysiloxane structure in at least a part thereof and having a reactive group for the surface functional group of carbon black. It contains a carbon black graft polymer obtained by grafting on black.

The carbon black graft polymer compounded in the toner for developing an electrostatic image according to the present invention needs to contain a polysiloxane structure in its polymer portion, and particularly has a polysiloxane structure in its side chain. Those that are preferable. If the polymer portion does not contain a polysiloxane structure, it is difficult to obtain good dispersibility in the binder resin, the problem that the carbon content cannot be increased, and it is difficult to reduce the particle size. In addition, there is a problem in that improvement in various properties such as offset resistance, fixed image rubbing resistance, filming resistance, and moisture resistance cannot be expected.

Here, the polysiloxane structure means a polydimethylsiloxane group, a polydimethylsiloxane group substituted with a partial alkyl group, a polydimethylsiloxane group substituted with a partial aryl group, a polyorgano group such as tris (trialkylsiloxy) silylpropyl group. It is a portion containing siloxane.

The polymer portion of the present invention preferably contains a polysiloxane structure represented by the general formula (1) as a structural unit of the polysiloxane structure.

[0073]

[Chemical 5]

(In the formula, A represents —COO— or a phenylene group, R ¹ represents a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 6 carbon atoms, R ^{3 to} R ¹³ are the same or different and each represents an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and a is a natural number. And b and c are the same or different and are 0
The integer of 10 is shown, d shows the integer of 0-200, respectively. Further, the average particle size of the carbon black graft polymer is 0.001 to 0.5 μm, and particularly 0.005 to 0.2 μm.
It is preferably within the range of m. Average particle size 0.0
Carbon black graft polymer of less than 01 μm
Since carbon black as a raw material cannot be easily obtained, it has little industrial significance. If the average particle size exceeds 0.5 μm, sufficient dispersibility may not be obtained, and it may not be possible to sufficiently cope with the reduction in the particle size of the toner.

In the carbon black graft polymer according to the present invention, the ratio of the carbon black portion and the polymer portion containing the polysiloxane structure is 1 to 1000 parts by weight, particularly 5 to 500 parts by weight, relative to 100 parts by weight of the former. Preferably there is. When the latter is less than 1 part by weight, the obtained carbon black graft polymers aggregate with each other,
There may occur a problem that sufficient dispersibility cannot be obtained in the binder resin or the polymerizable monomer forming the binder resin by polymerization. If the latter exceeds 1000 parts by weight, the polymer portion reacts with the carbon black portion more than necessary, which is not economical.

The carbon black graft polymer can be easily and inexpensively obtained by reacting carbon black with a polymer having a reactive group for carbon black and a polysiloxane structure. The reaction efficiency is increased by directly reacting the polymer with carbon black. When a monomer mixture that gives the polymer is polymerized in the presence of carbon black and an attempt is made to carry out a reaction with carbon black at the same time, the reaction efficiency may be lowered.

This polymer is preferably obtained by polymerizing a vinyl monomer and contains a main chain having a carbon-carbon bond. When the polymer has a main chain having a carbon-carbon bond, the affinity between the polymer and carbon black is large, so that the reaction with carbon black effectively occurs.

The carbon black reactive group contained in the polymer is preferably at least one reactive group selected from the group consisting of an epoxy group, a thioepoxy group, an aziridine group and an oxazoline group. The reactive groups for carbon black are not necessarily limited to these, but when a polymer having a group other than these reactive groups is used, the type of carbon black that can be used may be limited. The reason why the polymer preferably has the above-mentioned reactive group is that regardless of the type and state of the carbon black that can be used, the carbon black and the polymer undergo an addition reaction with a very high reaction efficiency even under mild conditions. To do. The carbon black preferably has a functional group such as a carboxyl group or a hydroxy group on its surface, and particularly preferably has a carboxyl group. Further, as the carbon black, it is preferable to use carbon black having a pH of less than 6, particularly pH 1 to 5. Those obtained by oxidizing neutral or basic carbon black can also be suitably used as the carbon black of the present invention. When the carbon black does not have a functional group such as a carboxyl group or has a pH of 6 or higher, the reaction with the polymer may not be effectively performed.

On the other hand, the average particle size of carbon black grafted with such a polymer is 0.0005 to 0.4 μm.
m, particularly preferably in the range of 0.001 to 0.2 μm. Since carbon black having an average particle size of less than 0.0005 μm cannot be easily obtained, it has little industrial significance. If the average particle size exceeds 0.4 μm, the resulting carbon black graft polymer may not be able to have sufficient dispersibility, and the carbon black graft polymer should have the desired particle size as described above. I can't.

In producing the carbon black graft polymer according to the present invention, it is preferable to react carbon black having a carboxyl group with a polymer having a reactive group for the carboxyl group and a polysiloxane structure. Examples of the reactive group for the carboxyl group include an epoxy group, a thioepoxy group, an aziridine group and an oxazoline group, and at least one of them can be selected. Carbon black having a carboxyl group is easily available as acidic carbon black. The carboxyl group undergoes an irreversible addition reaction with a high yield by a thermal reaction with an epoxy group, a thioepoxy group, an aziridine group or an oxazoline group. By this addition reaction, a carbon black graft polymer suitable for the present invention is obtained.

The reaction between carbon black and the polymer is preferably carried out in an organic solvent. If the addition reaction is not carried out in an organic solvent, the resulting carbon black graft polymer may not have sufficient dispersibility.

Examples of the organic solvent include liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, and partially hydrogenated hydrocarbons such as triphenyl. Silicone oils such as polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, fluorosilicone oils; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorobiphenyl, chlorodiphenylmethane; Daifloyl (Daikin Industrial Co., Ltd.), Dem Nam (Daikin Industry Co., Ltd.)
Fluoride such as; ethyl benzoate, octyl benzoate,
Examples thereof include ester compounds such as dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, ethyl (meth) actylate, butyl (meth) acrylate, and dodecyl (meth) acrylate.

As a method for producing a carbon black graft polymer, carbon black and a polymer containing a reactive group for carbon black and a polysiloxane structure are 40 to 300 ° C., preferably 70 to 250 ° C.
A method of stirring and mixing under the temperature of 0.5 to 10 hours, preferably 2 to 5 hours can be mentioned. If the reaction temperature is lower than 40 ° C, the reaction may not proceed, which is not preferable.
If it exceeds 300 ° C., the polymer component may deteriorate, which is not preferable.

As the reaction procedure, carbon black,
The polymer and, if necessary, an organic solvent and the like may be charged into a reaction apparatus and mixed with heating.

As the reaction apparatus, a kneading machine such as a stirring tank used for ordinary stirring and a ball mill, mixer, kneader used for kneading can be used.

A method for obtaining a polymer containing a reactive group for carbon black and a polysiloxane structure is represented by, for example, a monomer (a) having a reactive group for carbon black and a general formula (II). Examples thereof include a method of polymerizing a monomer mixture containing a silicon-based macromer (b). The monomer mixture may contain other monomer (c), if necessary.

[0087]

[Chemical 6]

(In the formula, B represents —COO— or a phenylene group, R ¹⁴ represents a hydrogen atom or a methyl group,
R ¹⁵ is an alkylene group having 1 to 6 carbon atoms, R ^{16 to} R ²⁶ are the same or different and each represents an aryl group, an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 10 carbon atoms, and e and f Are the same or different and each represents an integer of 0 to 10, and g represents an integer of 0 to 200. ) Examples of the monomer (a) include epoxy group-containing polymerizable monomers represented by the following chemical formulas.

[0089]

[Chemical 7]

[0090]

[Chemical 8]

(However, in these formulas, R represents hydrogen or a methyl group, and n is 0 or an integer of 1 to 20.) The monomer (a) is, for example, represented by the following chemical formula. A thioepoxy group-containing monomer can also be mentioned.

[0092]

[Chemical 9]

[0093]

[Chemical 10]

(However, in these formulas, R and n are the same as the above epoxy group-containing polymerizable monomer.) Examples of the monomer (a) include an aziridine group represented by the following chemical formula. A polymerizable monomer can be mentioned.

[0095]

[Chemical 11]

[0096]

[Chemical 12]

[0097]

[Chemical 13]

[0098]

[Chemical 14]

[0099]

[Chemical 15]

[0100]

[Chemical 16]

Further, as the monomer (a), 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-
Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2
-Vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4
-Methyl-2-oxazoline, 2-isopropenyl-5
-Methyl-2-oxazoline, 2-isopropenyl-4
-Ethyl-2-oxazoline, 2-isopropenyl-5
-Ethyl-2-oxazoline, 2-isopropenyl-
Examples thereof include oxazoline group-containing monomers such as 4,5-dimethyl-2-oxazoline.

The monomer (a) is at least one selected from the group consisting of each epoxy group-containing polymerizable monomer, each thioepoxy group-containing polymerizable monomer and each aziridine group-containing polymerizable monomer described above. Different types can be used.

As the silicone macromer (b),
For example, (meth) acryloyl group-containing polydimethylsiloxane, styryl group-containing polydimethylsiloxane (meth)
Polymerizable polysiloxanes such as acryloyl group-containing partially octyl-substituted polydimethylsiloxane, styryl group-containing partially octyl-substituted polydimethylsiloxasan, styryl group-containing partially phenyl-substituted polydimethylsiloxane, and tris (trimethylsiloxy) silylpropyl (meth) acrylate Among these, 1 type (s) or 2 or more types can be used.

The monomer (c) is not particularly limited as long as it can be copolymerized with the monomer (a) and the silicone macromer (b), and examples thereof include styrene, o-methylstyrene and m-methyl. Styrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-
Styrene-based monomers such as butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-
(Meth) acrylic acid-based monomers such as butyl (meth) acrylate, isobutyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; ethylene, propylene, butylene, vinyl chloride, Vinyl acetate,
(Meth) acrylonitrile, (meth) acrylamide,
Examples thereof include N-vinylpyrrolidone, and one or more of these can be used. By using the monomer (C), the proportion of the main chain having a carbon-carbon bond in the polymer can be increased.

The monomer mixture contains 0.1 to 0.1 parts of the monomer (a).
50% by weight of the silicon-based macromer (b) 1
0 to 99.9% by weight, and 0 to the monomer (c).
It is preferable to contain 89.9% by weight (however,
The sum of the monomers (a), (b) and (c) is 100% by weight.

When the proportion of the monomer (a) is less than 0.1% by weight, the reaction with carbon black may not be carried out effectively. When the proportion of the monomer (a) exceeds 50% by weight, gelation often occurs during the reaction with carbon black, and a carbon black graft polymer suitable for the present invention may not be obtained. Therefore, the preferable ratio of the monomer (a) is 1 to 20% by weight.

The proportion of the silicone macromer (b) in the monomer mixture is preferably 10 to 99.9% by weight, particularly preferably 50 to 95% by weight. 10% by weight of silicone macromer (b)
If it is less than the above range, the resulting carbon black graft polymer may not have desired dispersibility. on the other hand,
The proportion of silicone macromer (b) is 99.9% by weight
If it exceeds, the reaction with carbon black may not be carried out effectively.

The ratio of the monomer (c) in the monomer mixture is preferably 0 to 89.9% by weight, and 4 to 4
It is particularly preferably 9% by weight. When the proportion of the monomer (c) exceeds 89.9% by weight, the resulting carbon black graft polymer may not have desired dispersibility.

As a polymerization method for obtaining the polymer, 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, the solution polymerization method using a radical catalyst is preferable.

As the radical catalyst, any radical catalyst generally used for the polymerization of vinyl monomers can be used. Typical examples include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile); benzoyl peroxide, di-tert-butylperoxide. Oxide, ter
Examples thereof include peroxide compounds such as t-butyl peroctoate and tert-butyl peroxy-2-ethylhexanoate, which are usually 0.2 to 10 parts by weight, preferably 100 parts by weight of the monomer. Is used in the range of 0.5 to 5 parts by weight.

Polymerization is carried out by dissolving the monomer mixture and the radical catalyst in a solvent, and the reaction temperature is usually 40 to 200 ° C., preferably about 60 to 150 ° C. for 1 to 15 hours, preferably about 2 to 10 hours. Done.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as isopropyl alcohol and butanol; methyl isobutyl ketone,
Ketones such as methyl ethyl ketone; esters such as ethyl acetate, isobutyl acetate, amyl acetate and 2-ethylhexyl acetate; cell solves such as methyl cellosolve and ethyl cellosolve can be used.

After the completion of the polymerization, the obtained solution of the polymer containing a polysiloxane structure having a reactive group can be used as it is for the reaction with carbon black, or the solvent of the solution can be distilled off. Can also be taken out and used.

As another method for obtaining the above-mentioned polymer, for example, a compound having a reactive group for carbon black is reacted with a precursor polymer having a group capable of reacting with the compound, and the reactive group is added to the precursor polymer. The method of introducing during coalescence can be mentioned.

Examples of the above-mentioned compound include a compound having two or more kinds of the above-mentioned reactive groups for carbon black in the molecule, a compound having two or more kinds of the above-mentioned reactive groups for carbon black in the molecule, Examples thereof include compounds having in the molecule one or more types of the above-mentioned reactive groups for carbon black and a functional group other than the above-mentioned reactive groups.

However, the above-mentioned functional group is a group other than an epoxy group, a thioepoxy group, an aziridine group, an oxazoline group and an oxazoline group, and is one which the above-mentioned precursor polymer can react with. Examples of the reactive group of the precursor polymer include an isocyanate group,
Examples thereof include amino group, carboxyl group, hydroxyl group, vinyl group and the like.

The molecular weight of the polymer is not particularly limited, but considering the reaction effect on carbon black and workability during reaction with carbon black, the above-mentioned molecular weight is preferably in the range of 1,000 to 1,000,000. It is preferably in the range of 5000 to 100,000.

In the toner for developing an electrostatic charge image of the present invention,
The binder resin component with which the carbon black graft polymer thus obtained is blended is not particularly limited, and polystyrene resins, poly (meth) acrylic resins, styrene conventionally used in this field are used. Various thermoplastic resins such as (meth) acrylic copolymer resin, polyester resin, polyolefin resin, and epoxy resin can be used, but polystyrene resin, poly (meth) acrylic resin, styrene- (meth ) Acrylic copolymer resins, polyester resins and the like are preferable, and particularly styrene- (meth) acrylic acid ester copolymer resins containing 50% by weight or more of styrene.

In the toner for developing an electrostatic charge image of the present invention,
The compounding ratio of the binder resin and the carbon black graft polymer depends on the kind of the binder resin used, the characteristics required for the toner, etc., but the binder resin component 1
The amount of the carbon black graft polymer is 1 to 100 parts by weight, more preferably 3 to 60 parts by weight, based on 00 parts by weight.

The method for producing the toner of the present invention is not particularly limited, and various production methods such as a pulverization method, a suspension polymerization method and an emulsion polymerization method may be used. Among them, the suspension polymerization method is preferable. is there.

According to the pulverization method, a toner can be obtained by blending a predetermined amount of carbon black graft polymer with the above-mentioned binder resin, melt-kneading the mixture, and then finely pulverizing it. As described above, since the carbon black graft polymer according to the present invention has a good affinity for the binder resin used, it is uniformly dispersed in the matrix of the binder resin only by kneading under a relatively low shearing force.

On the other hand, according to the suspension polymerization method, the above carbon black graft polymer is blended and dispersed in a polymerizable monomer. Since the carbon black graft polymer has a good affinity for such a polymerizable monomer, it is easily and uniformly dispersed in the polymerizable monomer.

The polymerizable monomer used in the present invention is not particularly limited, but specifically, α,
There are β-ethylenically unsaturated monomers, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p- Styrene monomers such as phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl 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,
Acrylic acid or methacrylic acid type monomers such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinylpyrrolidone and the like. , Or one or more of these are used. Among these, a styrene- (meth) acrylic acid ester mixture containing 50% by weight or more of styrene is most preferable from the viewpoint of the thermal characteristics of the toner for developing an electrostatic image as the final product.

Then, the polymerizable monomer obtained by uniformly dispersing the carbon black graft polymer in this manner is suspended in an aqueous medium to carry out polymerization. The polymerization temperature is 5
A temperature of 0 to 90 ° C, preferably about 60 to 80 ° C is suitable. In this suspension polymerization, it is preferable to carry out the reaction after controlling the particle diameter or while controlling the particle diameter, but it is particularly preferable to carry out the reaction after regulating the particle diameter. The regulation of the particle size is carried out, for example, by using a suspension prepared by dispersing a predetermined component in an aqueous medium in T. K. Stir with a homomixer. Alternatively, it is carried out by passing it through a high-speed stirrer such as a line mixer (for example, Ebara Milder) once or several times.

A crosslinking agent may be added during suspension polymerization. As the cross-linking agent, for example, divinylbenzene, divinylnaphthalene, aromatic divinyl compounds such as derivatives thereof, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butyl. Diethylenically unsaturated carboxylic acid esters such as aminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate,
All divinyl compounds of N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfonic acid and compounds with 3 or more vinyl groups are mentioned.

Further, polybutadiene, polyisoprene,
Unsaturated polyester and chlorosulfonated polyolefin are also effective.

As the stabilizer used in suspension polymerization, polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,
Water-soluble polymers such as sodium polyacrylate and sodium polymethacrylate; surfactants such as anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, etc., and sulfuric acid barium,
Calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, metal oxide powder and the like are used.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and alkylnaphthalene. Examples thereof include sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkylphenyl ether sulfate ester salt, polyoxyethylene alkyl sulfate ester salt and the like.

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine; glycerin fatty acid ester, There are oxyethylene-oxypropylene block polymers and the like.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.

Examples of the zwitterionic surfactant include lauryldimethylamine oxide.

These stabilizers should be used by appropriately adjusting the composition and the amount used so that the resulting toner particles for polymerized electrostatic image development have a particle size of 2 to 20 μm, preferably 3.5 to 15 μm. Kimono. For example, when a water-soluble polymer is used as the stabilizer, the amount is preferably 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer component. In the case of a surfactant, it is suitable to be 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the polymerizable monomer component.

As the polymerization initiator used for the polymerization, oil-soluble peroxide type or azo type initiators usually used for suspension polymerization can be used. As an example, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide,
Orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide,
Peroxide initiators such as t-butyl hydroperoxide and diisopropylbenzene hydroperoxide,
2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2
′ -Azobis-2,3-dimethylbutyronitrile, 2,
2'-azobis- (2-memethylbutyronitrile),
2,2'-azobis-2,3,3-trimethylbutyronitrile, 2,2'-azobis-2-isopropylbutyronitrile, 1,1'-azobis- (cyclohexane-1)
-Carbonitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis-4-cyanovaleric acid, dimethyl -2,2'-azobisisobutyrate and the like. The polymerization initiator is 0.01 to 20% by weight, particularly 0.1
It is preferably used in an amount of 10 to 10% by weight.

In this way, when the polymerizable monomer component is suspension-polymerized to obtain a toner for developing an electrostatic image, other polymer such as polyester may be present in the monomer component. Well, a known additive such as a chain transfer agent for adjusting the degree of polymerization may be appropriately added.

The electrostatic image developing toner thus obtained has an average particle size of 2 to 20 μm, preferably 3.5 to 15 μm.
In m, the particle size distribution exhibits a controlled spherical shape with a coefficient of variation of particle size of 0 to 80%, preferably 1 to 50%.

In the toner for developing an electrostatic charge image of the present invention, additives such as an offset preventive agent, a charge control agent for adjusting the charge and a fluidizing agent which are usually used in a toner for developing an electrostatic charge image are properly mixed. It is also possible to add a magnetic powder to obtain a magnetic toner.

The method of blending these additives is not particularly limited, and any conventionally known method can be adopted. For example, in the suspension polymerization method, a method of preliminarily containing these additives in the monomer when polymerizing the polymerizable monomer in which the carbon black graft polymer is dispersed, and in the pulverization method, melt kneading In the case of a charge control agent or a fluidizing agent, for example, a colored fine particle having a predetermined particle size is obtained by these production methods, and then externally added to make it adhere to the surface of the toner for electrostatic image development. A method or the like can be adopted as appropriate.

Examples of the anti-offset agent include low molecular weight polyolefin wax such as low molecular weight polypropylene and low molecular weight polyethylene, paraffin wax, microcrystalline wax, oxidized wax and silicone oil. It is suitable that the amount of such an offset inhibitor added is 0 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin.

As the magnetic material, for example, powder of ferromagnetic metal such as iron, cobalt and nickel, powder of metal compound such as magnetite, hematite and ferrite can be used. (3) Ink Composition Next, an ink composition which is another embodiment of the colorant composition of the present invention will be described.

The carbon black graft polymer blended in the ink composition according to the present invention has at least a polysiloxane structure which is substantially the same as that described in detail in the description of the toner for developing an electrostatic image. A carbon black graft polymer obtained by grafting a polymer, which is partially contained and has a reactive group for the surface functional group of carbon black, onto carbon black is blended.

The above-mentioned carbon black graft polymer has excellent dispersibility in various water-soluble or oil-soluble solvents, does not cause scratches and the like, and has excellent long-term storage stability. Due to the fact that the polymer component in the black graft polymer has a polysiloxane structure, bleeding does not occur, and it also has excellent rubbing resistance after fixing. Water-based inks for ballpoint pens, oil-based inks for ballpoint pens, etc. The ink may be in the form of various (liquid) inks such as inks for writing instruments and inks for inkjet printers.

When used in an ink composition, when the carbon black graft polymer is obtained, the compounding ratio of the carbon black and the polymer as described above is 1 to 100 parts by weight of the carbon black. About 1000 parts by weight is particularly preferable. When the amount of the polymer is less than 1 part by weight with respect to 100 parts by weight of carbon black, a sufficient effect of modifying the carbon black cannot be obtained, resulting in insufficient dispersibility of carbon black in an ink composition containing the same. There is a great fear, on the other hand, 1000
This is because if the amount is more than parts by weight, the balance of the resulting ink composition may be impaired.

As the ink composition containing such a carbon black graft polymer as a colorant, those having various compositions conventionally used in such fields can be used.

For example, in the case of a water-based ink composition for a ballpoint pen, various water-soluble solvents can be used in addition to water, which is an essential condition, as a water-soluble solvent that serves as a matrix. For example, ethylene glycol, diethylene glycol, triethylene glycol. , Propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycerin and other glycols, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, 2-pyrrolidone and the like can be used alone or in combination of two or more.

If necessary, as a viscosity modifier, natural gum arabic, tragacanth gum, guar gum,
Alginic acid, carrageenan, gelatin, casein, xanthene gum, dextran, semi-synthetic methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium alginate, propylene glycol alginate, synthetic polyvinyl alcohol, polyvinylpyrrolidone, polybityl methyl ether, polyacrylic Sodium acid, carboxyvinyl polymer, polyethylene oxide, vinyl acetate-vinylpyrrolidone copolymer, alkali metal salt of (meth) acrylic resin, (meth) acrylic acid-alkyl (meth) acrylate copolymer, etc. The above can be added.

It is also possible to add a water-soluble or water-soluble resin, an anionic or nonionic surfactant as a dispersion stabilizer, but the carbon black graft polymer according to the present invention has excellent dispersion stability. Therefore, it does not need to be added.

In addition, if necessary, a preservative, a fungicide,
Other known additives may be blended, and dye-based and pigment-based other colorants may be added as auxiliary colorants.

The blending ratio of such a water-soluble ink composition is not particularly limited, but the blending amount of the above-mentioned carbon black graft polymer depends on the type of solvent used and the color tone. However, the carbon black graft polymer is preferably about 0.1 to 20% by weight of the water-soluble ink composition. That is, if the blending amount of the carbon black graft polymer is less than 1% by weight, the degree of blackening may decrease, while if it exceeds 20% by weight, a predetermined fluidity as an aqueous ink is obtained. This is because there is a risk that it will disappear. The viscosity (25 ° C.) of the aqueous ink composition is generally 1 to 1
It is suitable to set it to about 0 cp.

Further, for example, in the case of an oil-based ink composition for ballpoint pens, the oil-soluble solvent that serves as a matrix is
Benzyl alcohol, high-boiling alcohols such as phenoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, glycols such as glycerin, ethylene glycol monomethyl ether,
Cellosolves such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and fatty acids such as oleic acid. Etc. can be used alone or in combination of two or more.

Further, if necessary, conventional oil-based ink compositions such as ketone resin, sulfamide resin, maleic acid resin, ester gum, xylene resin, alkyd resin, phenol resin, rosin, polyvinylpyrrolidone and polyvinyl butyral are commonly used. Resin component is viscosity adjustment,
For the purpose of imparting adhesion, water resistance, dispersion stability, etc., one kind or a combination of two or more kinds can be blended, but the carbon black graft polymer according to the present invention has excellent dispersion stability, Also, since the carbon black graft polymer itself has a polymer component, it is not necessary to add it.

In addition, as in the case of the water-soluble ink composition, if necessary, a preservative, a fungicide, and other known additives may be blended, and a dye-based agent and an auxiliary colorant may be added. It is also possible to add other pigment-based colorants.

The blending ratio of such an oil-soluble ink composition is not particularly limited, but the blending amount of the carbon black graft polymer as described above depends on the type of solvent used and the color tone. However, the carbon black graft polymer is preferably about 15 to 40% by weight of the oil-soluble ink composition. That is, if the content of the carbon black graft polymer is less than 15% by weight, coloring as an oil-soluble ink may be deteriorated, while if it exceeds 40% by weight, a predetermined fluidity as an oil-based ink may be obtained. Is not obtained, and the writing performance may be deteriorated. The viscosity (25 ° C.) of the aqueous ink composition is generally 1000 to 2
It is suitable to be about 0000 cp.

In the case of an ink for an ink jet printer, the dispersion medium to be the matrix is not particularly limited as long as it is an electrically insulating oil, and any known one can be used. For example, polydimethylsiloxane. Silicone oil such as partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, fluorosilicone oil; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene,
Hydrocarbons such as diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane and partially hydrogenated triphenyl; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorobiphenyl, chlorodiphenylmethane; Daifloyl ( Fluoride such as Daikin Industry Co., Ltd., Demnum (manufactured by Daikin Industry Co., Ltd.); ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, ethyl (meth) actylate, ( Examples thereof include ester compounds such as butyl (meth) acrylate and dodecyl (meth) acrylate. Among these, one kind or a combination of two or more kinds can be used. Considering the viscosity of the prepared electrorheological fluid composition in the state where no electric field is applied, it is desirable that the dispersion medium has a viscosity of 50 cp or less.

In addition, known additives may be blended as necessary, and dye-based and pigment-based other colorants may be added as auxiliary colorants.

The blending ratio of such an ink composition for an ink jet printer is not particularly limited and can be appropriately selected so as to obtain a sufficient electrorheological effect.

(4) Curable Black Resin Composition Next, a photocurable black resin composition which is another embodiment of the colorant composition of the present invention will be described.

The photocurable resin composition of the present invention has at least a part of a polysiloxane structure which is substantially the same as that described in detail in the description of the toner for developing an electrostatic charge image. A carbon black graft polymer obtained by grafting a polymer having a reactive group for a surface functional group of carbon black on carbon black is blended. Therefore, the polymerization-inhibiting functional groups such as quinone group and phenolic hydroxyl group existing on the surface of carbon black are coated, and the photocuring delay of the photocurable resin composition is suppressed. Further, the obtained carbon black graft polymer has excellent dispersibility in various photocurable resin compositions and further has good lubricity, and therefore has an appropriate viscosity when dispersed in the photocurable resin composition. Thus, it can be suitably used as a coloring agent in UV paints, UV inks, photopolymerizable compositions for color filters, and the like. Further, as described above, since the carbon content in the carbon black graft polymer becomes large, the carbon content in the composition can be increased as a result to be applied to highly functional applications, and the polymer component in the carbon black graft polymer can be used. Since it has a polysiloxane structure, there is no possibility of problems such as ink bleeding or color mixing in the composite coloring step when used for forming a black matrix of a color filter.

When used in the photocurable black resin composition, the compounding ratio of the carbon black and the above-mentioned polymer in obtaining the carbon black graft polymer is 100% by weight of carbon black. It is particularly preferable that the combined amount be about 1 to 200 parts by weight. When the amount of the polymer is less than 1 part by weight based on 100 parts by weight of carbon black, a sufficient effect of modifying the carbon black cannot be obtained, and the photocuring delay of the photocurable black resin composition obtained by adding the polymer is delayed. And the possibility of insufficient dispersibility of carbon black in the photocurable black resin composition is high, while
This is because if the amount exceeds 200 parts by weight, the carbon black content of the photocurable black resin composition obtained is low, and there is a possibility that sufficient light-shielding properties may not be obtained.

As the photocurable resin composition containing such a carbon black graft polymer as a coloring agent, various compositions similar to those conventionally used in such fields can be used. It may contain polymerizable monomers, oligomers and / or prepolymers. The photocurable resin composition may be either lipophilic and / or hydrophilic, and by making the properties of the carbon black graft polymer described above correspond to the properties of the photocurable resin composition, Good dispersibility of carbon black is obtained.

As the monomer, 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 triacrylate 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, tetrahydroxymethacrylate, 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 acryloxydimethacrylate, 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) acrylic amide and itaconic acid can be used.

Examples of the oligomer or prepolymer include polyesters and unsaturated polyester resins obtained by substituting an active hydrogen atom of a polyol with an acryloyl group or a methacryloyl group, a drying oil-modified alkyd resin, an unsaturated acid such as acrylic acid or methacrylic acid. Adduct of vinyl copolymer having carboxylic acid as a copolymerization component with glycidyl acrylate, acrylic monomer having an epoxy group such as glycidyl methacrylate, vinyl copolymer having an acrylic monomer having an epoxy group as a copolymerization component An acryl-based monomer having an isocyanate group at the terminal such as an adduct of a polymer and an unsaturated carboxylic acid, tolylene diisocyanate, hexamethylene diisocyanate, or an adduct of 2 mol of tolylene diisocyanate and 1 mol of ethylene glycol. With scale Or the like can be mentioned things.

If necessary, a photosensitizer may be added to the photocurable resin composition. As the photosensitizer, various conventionally known compounds can be used alone or in combination of two or more, and examples thereof include thioxanthone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, xanthone, dimethylxanthone, benzophenone, anthracene. , 2,2-diethoxyacetophenone, benzyl dimethyl ketal, benzyl, diphenyl disulfide, anthraquinone, 1-chloroanthraquinone, 2-ethylanthraquinone, 2
-T-butyl anthraquinone, methyl anthraquinone,
1-chloromethylnaphthalene, N, N'-tetraethyl-4,4'-diaminobenzophenone, dibenzosparone, 1,1-dichloroacetophenone and the like can be mentioned.

If necessary, the photocurable resin composition may contain an organic high molecular polymer compatible with the photopolymerizable compound as a film-forming component. As such organic polymer, polyacrylic acid ester or its partial hydrolyzate, polymethacrylic acid ester or its partial hydrolyzate, polyvinyl acetate or its hydrolyzate, polystyrene, polyvinyl butyral, polychloroprene , Polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylpyrrolidone, a copolymer of styrene and maleic anhydride, or a half ester. Further, within a range that does not impair the 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; aliphatic carbonization such as n-hexane and n-heptane. Suitable organic solvents such as hydrogens, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, nitriles such as acetonitrile and dodecyl nitrile, carbon disulfide, sulfur derivatives such as thiophene may be added. Further, a polymerization inhibitor such as hydroquinone or p-benzoquinone can be added as necessary to prevent overreaction in photocuring. Furthermore, other known additives, for example, thickeners, thixotropic agents, leveling materials,
It is also optional to add a defoaming agent, an adhesion-imparting agent or the like.

The photopolymerizable black resin composition of the present invention comprises the above-described carbon black graft polymer blended in the photopolymerizable resin composition. The blending amount in the composition depends on the kind of the photopolymerizable resin composition used, but the carbon black graft polymer is 1 to 50% by weight, more preferably 5 to 35% by weight of the photopolymerizable resin composition. It is desirable that it be included. That is, if the blending amount of the carbon black graft polymer is less than 1% by weight, the degree of blackening may decrease, while if it exceeds 50% by weight, the strength of the coating film may decrease. This is because.

Further, among the photopolymerizable black resin compositions of the present invention, those used for color filters and the like are as follows:
The alkali-soluble resin is preferably used, but in such an embodiment, it is desired that the resin contains an alkali-soluble resin.

(5) Other Colorant Compositions The colorant compositions include coating compositions such as paints. The binder used in the coating composition is a thermoplastic resin, a thermosetting resin, or a reactive resin capable of forming a coating film by coating on various substrates, and one or a mixture of two or more thereof depending on the application. Is used.

The thermoplastic resin has an average molecular weight of 1,0.
About 100 to 1,000,000 are preferably used, and specific examples thereof include vinyl chloride polymers and vinyl chloride.
Vinyl chloride resin such as vinylidene chloride copolymer; vinyl ester resin such as vinyl acetate polymer, vinyl acetate / ethylene copolymer, vinyl acetate / methyl methacrylate copolymer; (meth) acrylic ester (copolymer ) Polymers,
(Meth) acrylic ester / styrene copolymer and other (meth) acrylic ester resin copolymers, styrene / butadiene / acrylonitrile copolymer and other styrene resins; poly (ε-caprolactam), adipic acid and hexa Polyamide resins such as condensation products with methylenediamine; polyester resins such as condensation products of terephthalic acid and ethylene glycol, condensation products of adipic acid and ethylene glycol; polyethylene, chlorinated polyethylene, carboxyl modified polyethylene, polyisobutylene, Examples thereof include polyolefin resins such as polybutadiene; cellulose derivatives such as cellulose acetate, cellulose propionate and nitrocellulose; and butyral resins. As these resins, commercially available products may be used as they are, or those synthesized by an ordinary known method may be used.

The thermosetting resin or reactive resin can form a crosslinked structure due to addition reaction, condensation reaction, etc. by heating, active energy ray irradiation, drying or other means during or after the film formation process. Specifically, for example, novolac resin; phenol resin such as resol resin; amino resin such as urea resin, melamine resin, benzoguanamine resin; various alkyd resins; unsaturated polyester resin curable acrylic resin; isocyanate Examples thereof include urethane-modified resins such as group-containing polyesters and isocyanate group-containing polyethers; polyamine resins; epoxy resins.

The above binder should be selected according to the adhesion and wettability to the substrate to be coated, the hardness, flexibility, chemical resistance, stain resistance, weather resistance, etc. required for the coating. In consideration of the intended use of the coating composition, either alone or 2
A combination of two or more species can be used.

The coating composition of the present invention can be obtained by a method of dispersing the carbon black graft polymer in various binders. The ratio of the binder to the carbon black graft polymer used in the coating composition is not particularly limited, but 100 parts by weight of the binder is used in order to sufficiently exhibit the characteristics of the coating composition and not impair the performance as a coating. 5 to 300 parts by weight,
Preferably, 10 to 200 parts by weight of carbon black graft polymer is blended.

The coating composition according to the present invention may appropriately contain, in addition to the above-mentioned components, well-known additives conventionally used in coating compositions, as long as the effects are not impaired.
Examples of such additives include metal soap, dispersion aids such as surfactants, film formation aids, antistatic agents, defoamers, inorganic pigments such as silica, talc, calcium carbonate and titanium oxide. To be

The colorant composition is also used in heat-sensitive transfer ink. The heat-sensitive transfer ink according to the present invention comprises the above-mentioned carbon black graft polymer dispersed in a binder component. The binder component of the thermal transfer ink is a known natural or synthetic wax such as carnauba wax, montan wax, paraffin wax, microcrystalline wax, oxide wax, low molecular weight polyethylene wax; polysulfone ether, polycarbonate, polystyrene, silicone resin, acrylic resin. Examples thereof include synthetic resins such as resins. As the dispersion method, for example, there is a method of simply kneading the carbon black graft polymer and the binder component, a method of mixing these two components in an appropriate organic solvent, etc. A well dispersed thermal transfer ink is obtained. The amount of the carbon black graft polymer in the thermal transfer ink is not particularly limited, but is usually 5 to 80% by weight, preferably 20 to 60% by weight. In addition to the above components, known additives may be added if necessary.

The heat-sensitive transfer ink relating to the present invention is PET.
It can be applied to a support typified by film, polyimide film, capacitor paper, silk fabric, aluminum foil, etc. by a known method such as hot melt coater, reverse roll coater, gravure roll coater, etc. An ink sheet can be obtained.

Further, the colorant composition of the present invention includes an ink ribbon coating agent for thermal transfer. Examples of the binder component of the ribbon coating agent include known vinyl chloride polymers, vinyl chloride / vinyl acetate copolymers, acrylic resins, styrene polymers, polyurethane resins, polyester resins and the like. The carbon black graft polymer is added to these binder components and mixed well by stirring to obtain a ribbon coating agent. The content of the colored spherical fine particles in the coating agent is 1 to 40% by weight, preferably 5 to 20% by weight. The ribbon coating agent thus obtained can be applied to a base material using a known means such as a roll coater, an air knife coater, an air doctor coater or a spray coater to form a ribbon coat layer on the back surface thereof.

Another embodiment is a back coat agent for magnetic recording media. As the binder component of the back coat agent, for example, a known vinyl chloride polymer, vinyl chloride / vinyl acetate copolymer, acrylic resin, styrene polymer, polyurethane resin, polyester resin or the like is used. The carbon black graft polymer is added to these binder components, and well mixed by stirring to form a back coat agent. The amount of the carbon black graft polymer compounded in the coating agent is 1 to 40% by weight, preferably 5 to 20% by weight. The back coat agent thus obtained can be applied to a substrate by a known means such as a roll coater, an air knife coater, an air doctor coater or a spray coater to form a back coat layer on the back surface thereof.

As the substrate used for the magnetic recording medium according to the present invention, known polyester, cellulose acetate, polyvinyl chloride, etc. films, sheets and tapes are used.
The magnetic recording layer can be formed by a known method of applying a coating agent containing magnetic powder or a method of depositing a magnetic material.

The colorant composition of the present invention has been described above based on the embodiments. However, the present invention is not limited to these embodiments and may include various kinds of portable devices other than these.

[0178]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In addition, all "parts" in the following Examples and Comparative Examples are by weight unless otherwise specified.

Synthesis Example 1 200 parts by weight of toluene was charged into a flask equipped with a thermometer, a stirring blade and a cooling tube. There, methacryloyl group-containing polydimethylsiloxane (Silaplane FM0721 manufactured by Chisso Corporation, average molecular weight = about 500).
0) Charge 180 parts by weight, 20 parts by weight of glycidyl methacrylate and 10 parts by weight of benzoyl peroxide,
The contents in the flask were stirred to form a uniform solution.

The solution thus obtained was heated to 70 ° C. and a polymerization reaction was carried out for 4 hours. The solvent of the obtained polymer solution was distilled off under reduced pressure to obtain a polymer (1) containing a silicone component having an epoxy group in its molecule. The molecular weight of this polymer was Mn = 15000 by GPC measurement.

Next, 10 parts by weight of a polymer (1) containing a silicone component having an epoxy group in the molecule and carbon black MA-100R (manufactured by Mitsubishi Chemical Corporation) (pH
3.5) 20 parts by weight was mixed with 20 parts by weight of Laboplast mill (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 160 ° C. and 100 rpm for reaction, and then pulverized to obtain a carbon black graft polymer (1). .

Synthesis Example 2 15 parts by weight of polymer (1) containing a silicone component having an epoxy group in the molecule and carbon black MA-10
15 parts by weight of 0R (manufactured by Mitsubishi Chemical Co., Ltd.) (pH 3.5) was kneaded using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 160 ° C. and 100 rpm to react, and then pulverized to carbon Black graft polymer (2)
Got

Comparative Synthesis Example 1 A flask equipped with a thermometer, a stirring blade and a cooling tube was charged with 200 parts by weight of toluene. There styrene 18
0 parts by weight, 20 parts by weight of glycidyl methacrylate and 10 parts by weight of benzoyl peroxide were charged, and the content in the flask was stirred to form a uniform solution.

The solution thus obtained was heated to 70 ° C. and a polymerization reaction was carried out for 4 hours. The solvent of the obtained polymer solution was distilled off under reduced pressure to obtain a comparative polymer (1) having an epoxy group in the molecule. The molecular weight of this polymer is GP
According to C measurement, Mn was 6500.

Next, 20 parts by weight of the obtained comparative polymer (1) and 10 parts by weight of carbon black MA-100R (manufactured by Mitsubishi Chemical Corporation) (pH 3.5) were added to a Labo Plastomill (Toyo Seiki Co., Ltd.). Manufactured at 160 ° C, 100r
After kneading and reacting under the condition of pm, it was pulverized to obtain a carbon black graft polymer (1) for comparison. Comparative Synthesis Example 2 15 parts by weight of polymer (1) for comparison and carbon black M
A-100R (manufactured by Mitsubishi Chemical Corporation) (pH 3.5) 1
0 parts by weight and Labo Plastomill (made by Toyo Seiki Co., Ltd.)
Was mixed at 160 ° C. and 100 rpm for reaction, and then pulverized to obtain a carbon black graft polymer (2) for comparison.

Example 1 Carbon black graft polymer (1) obtained in Synthesis Example 1 was added to a polymerizable monomer component consisting of 80 parts by weight of styrene, 20 parts by weight of n-butyl acrylate and 0.3 parts by weight of divinylbenzene. 45 parts by weight, azobisisobutyronitrile 6
Parts by weight and 3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were placed in a glass container and mixed and dispersed in a paint shaker for 30 minutes to obtain a polymerizable monomer composition (1).

Next, a polyvinyl alcohol (PVA205, Kuraray Co., Ltd.) was placed in the same flask as used in Synthesis Example 1.
897 parts of deionized water having 3 parts dissolved therein were charged. The polymerizable monomer composition (1) prepared in advance was charged therein, and T. K. Homo mixer (made by Tokushu Kika Kogyo Co., Ltd.)
Was stirred at 8000 rpm for 5 minutes to form a uniform suspension. Then, the mixture was heated to 70 ° C. while blowing nitrogen gas, and the suspension polymerization reaction was carried out by continuing stirring at this temperature for 5 hours, followed by cooling. This suspension was filtered, washed and dried to obtain colored spherical fine particles (1).

Example 2 84.24 parts by weight of styrene, n-butyl acrylate 2
30 parts by weight of the carbon black graft polymer (2) obtained in Synthesis Example 2, 6 parts by weight of azobisisobutyronitrile to a polymerizable monomer component consisting of 1.06 parts by weight and 0.316 parts by weight of divinylbenzene, and 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was placed in a glass container and mixed and dispersed in a paint shaker for 30 minutes to obtain a polymerizable monomer composition (2).

Then, polyvinyl alcohol (PVA 205, manufactured by Kuraray Co., Ltd.) was placed in a flask in the same manner as in Example 1.
897 parts by weight of deionized water having 3 parts by weight dissolved therein were charged. The polymerizable monomer composition (2) prepared in advance was charged therein, and T. K. A homogenous suspension was obtained by stirring for 5 minutes at 8000 rpm with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, while blowing nitrogen gas, 70
The mixture was heated to 0 ° C., stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and then cooled. The suspension was filtered, washed and dried to obtain colored spherical fine particles (2).

Comparative Example 1 Example 1 was repeated except that the carbon black graft polymer (1) used in Example 1 was replaced with the comparative carbon black graft polymer (1) obtained in Comparative Synthesis Example 1. Then, the comparative polymerizable monomer composition (1) contained in a glass container is obtained by the same procedure as described above, and the same procedure as in Example 1 is carried out to obtain comparative colored spherical fine particles (1). It was

Comparative Example 2 Example 2 was repeated except that the carbon black graft polymer (2) used in Example 2 was replaced by the carbon black graft polymer (2) for comparison obtained in Comparative Synthesis Example 2. Then, the comparative polymerizable monomer composition (2) contained in a glass container is obtained, and the same operation as in Example 2 is continuously performed to obtain comparative colored spherical fine particles (2). It was

Example 3 Polymerizable monomer composition (1) obtained in Example 1, polymerizable monomer composition (2) obtained in Example 2, and comparison obtained in Comparative Example 1 For the polymerizable monomer composition (1) for use in the composition and the comparative polymerizable monomer composition (2) obtained in Comparative Example 2, the dispersion state of CB in the polymerizable monomer composition was measured in a glass container. The observation was performed on the wall surface. The results are shown in Table 1.

[0193]

[Table 1]

Example 4 0.1 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) based on 100 parts by weight of the colored spherical fine particles obtained in Examples 1 and 2 and Comparative Examples 1 and 2. Parts were adhered to the surface with a Henschel mixer to obtain electrophotographic toner (1) and electrophotographic toner (2) of the present invention, comparative toner (1) and comparative toner (1), respectively.

These toners were evaluated as follows under different environments (H / H; 35 ° C. × 90% RH, N / N; 23).
℃ × 60% RH, L / L; 10 ℃ × 20% RH),
I did.

Triboelectric charge: Iron carrier (Dowa Iron Powder Co., Ltd.)
(Manufactured by: DSP-128) (toner concentration: 5% by weight) and measured by a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd .: Model TB-200). The obtained results are shown in Table 2.

[0197]

[Table 2]

Example 5 To 95 parts by weight of a ferrite carrier, 5 parts by weight of the toner obtained in Example 4 was mixed with stirring, and each of developer (1), developer (2), comparative developer (1) and comparison A developer (2) was obtained.

The following evaluations were carried out.

Image output evaluation: Facsimile test chart No. by the image output of the electrostatic copying machine (Reo Dry 7610 manufactured by Toshiba Corporation). The fine line reproducibility in the image obtained by copying No. 1 (reading condition of the image obtained by copying the facsimile test chart No. 1) was evaluated. The results obtained are shown in Table 3.

[0201]

[Table 3]

Example 6 Using the developers obtained in Example 5 and the same copying machine, images of solid areas were printed, and then the following fixing test was carried out and the offset resistance test was carried out by the following method. The results obtained are shown in Table 4.

Fixability test: The solid portion when rubbing paper with each other is visually inspected.

Offset resistance test: 22 unfixed solid areas
It was judged whether or not the offset phenomenon occurred by passing through a 0 ° C heat roll.

[0205]

[Table 4]

[0206]

INDUSTRIAL APPLICABILITY As described above, the present invention is a polymer having a polysiloxane structure in at least part of a liquid or solid matrix and having a reactive group for the surface functional group of carbon black. Since it is a colorant composition characterized by being blended with a carbon black graft polymer obtained by grafting carbon black onto carbon black, the dispersion stability of carbon black in the composition is good, and various coloring It can exhibit excellent properties as an agent.

The present invention is also prepared by grafting onto a carbon black a binder resin component and a polymer having a polysiloxane structure in at least a part thereof and having a reactive group for a surface functional group of the carbon black. Since the toner for developing an electrostatic charge image is characterized by containing a carbon black graft polymer, not only the dispersibility of carbon black becomes good, but also a high carbon content can be achieved to reduce the particle size. In addition, low-temperature fixing can be achieved by fully exhibiting the characteristics of the binder resin of the toner, and the charging stability is also good. In addition, due to the polymer component in the carbon black graft polymer according to the present invention having a polysiloxane structure,
It is also excellent in various characteristics such as offset resistance, fixed image rubbing resistance, filming resistance, and moisture resistance.

The present invention also provides a carbon black graft polymer obtained by grafting carbon black with a polymer having a polysiloxane structure in at least a part thereof and having a reactive group for a surface functional group of carbon black. Since the ink composition is characterized by containing, it does not cause bleeding or blurring, has excellent rubbing resistance after fixing, and has excellent long-term storage stability.

Furthermore, the present invention provides a carbon black graft polymer obtained by grafting carbon black with a polymer having a polysiloxane structure in at least a part thereof and having a reactive group for a surface functional group of carbon black. Since it is a photocurable black resin composition characterized by containing it, it provides a photocurable black resin composition having a high carbon content, which can be applied to highly functional applications, and does not cause ink bleeding or color mixing. To do.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Kondo 25-12 Kannondai 1-cho, Tsukuba-shi, Ibaraki Nippon Catalyst Co., Ltd. (56) Reference JP-A-5-241378 (JP, A) JP JP-A-6-214385 (JP, A) JP-A-49-22139 (JP, A) JP-A-62-177053 (JP, A) JP-A-49-22137 (JP, A) JP-A-9-59331 (JP , A) JP-A-2-273757 (JP, A) JP-A 64-79278 (JP, A) International Publication 88/003545 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) C09C 1/56 C08L 43/00 C08L 83/10 G03G 9/083

Claims (6)

(57) [Claims] 1. A carbon obtained by grafting a polymer having a polysiloxane structure in at least a part and having a reactive group for a surface functional group of carbon black in a liquid or solid matrix, onto carbon black. A colorant composition comprising a black graft polymer. 2. The colorant composition according to claim 1, wherein the polymer contains a main chain having a carbon-carbon bond. 3. A colorant composition according to claim 1 or 2 polymer has a polysiloxane containing structural unit represented by the general formula (I). [Chemical 1] (However, in the formula, A represents -COO- or a phenylene group, R ¹ represents a hydrogen atom or a methyl group, and R ² represents 1 carbon atom.
The 6 alkylene group, R ³ to R ¹³ are the same or different aryl groups, respectively an alkyl group or an alkoxyl group having 1 to 10 carbon atoms having 1 to 6 carbon atoms, a is an arbitrary natural number, b and c shows the same or different integer of 0-10, d shows the integer of 0-200, respectively. ) 4. A carbon black graft obtained by grafting carbon black with a binder resin component and a polymer having a polysiloxane structure in at least a part thereof and having a reactive group for a surface functional group of carbon black. A toner for developing an electrostatic charge image, which comprises a polymer. 5. An ink composition, wherein the matrix in the colorant composition according to any one of claims 1 to 3 is a liquid matrix composed of a water-soluble or oil-soluble solvent. 6. A photocurable black resin composition, wherein the matrix in the colorant composition according to any one of claims 1 to 3 is a liquid matrix composed of a photocurable resin composition.