JPH06301239A - Carbon black graft polymer composition, its production and use - Google Patents

Abstract

PURPOSE:To improve dispersibility in various materials and toughness by blending a carbon black graft polymer with thermoplastic elastomer. CONSTITUTION:This carbon black graft polymer compsn. consists of a carbon black graft polymer obtd. by allowing 100 pts.wt. carbon black to react with 10-500 pts.wt. polymer having groups reactive with carbon black and thermoplastic elastomer. The carbon black used is required only to have carboxyl and/or hydroxyl groups as functional groups on the surface and any carbon black such as furnace black, channel black, acetylene black or lamp black may be used. Commercially available carbon black can be used as it is but the pH is preferably <=8, especially <=6 in the case where the groups of the polymer reactive with carbon black are epoxy or thioepoxy groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a carbon black graft polymer composition, a method for producing the same and uses thereof. More specifically, the present invention improves the affinity of carbon black with various substances, improves the dispersibility in substances such as organic polymers, water, and organic solvents, and at the same time, provides excellent carbon toughness. The present invention relates to a black graft polymer composition, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art Carbon black (hereinafter referred to as CB) is excellent in coloring properties, conductivity, weather resistance, chemical resistance, etc., and therefore it has been used as a coloring agent for electrostatic image developing toner, thermal transfer ink and the like. As a resin, it is widely used for various purposes such as a reinforcing agent and a filler for rubber. However, CB
Since it has a powdery or granular shape, it is rarely used alone, and usually exhibits its characteristics by being uniformly dispersed in a solid base material such as resin or rubber or a liquid such as water or a solvent.

However, since CB has a weaker affinity for other substances such as organic polymers, water and organic solvents as compared with the cohesive force between particles, it should be uniformly mixed or dispersed under normal mixing or dispersing conditions. Was extremely difficult.

In order to solve this problem, a study has been made to improve the dispersibility of CB by coating the surface of CB with various kinds of surfactants and resins to increase the affinity with a solid or liquid base material. Many have been made.

Among them, the carbon black graft polymer obtained by polymerizing the polymerizable monomer in the coexistence of CB has hydrophilicity and / or lipophilicity by appropriately selecting the type of the polymerizable monomer. Since it can be appropriately added, it has been attracting attention in recent years.

The method for producing this carbon black graft polymer is disclosed in Japanese Examined Patent Publications Nos. 42-22047, 44-3826, 45-17248, and 46-26970. The yield of the carbon black graft polymer obtained by the above method was as low as several percent to several dozen percent, and most of them existed in the form of vinyl homopolymer, and the surface treatment efficiency of CB was extremely poor. Therefore, the affinity with other substances was not improved as expected, and the dispersed state was often different depending on the mixing or dispersing conditions.

Further, in JP-A-63-265913 and JP-A-63-270767, a carbon black graft polymer is obtained by reacting CB with a polymer reactive with CB under a specific temperature condition. It was shown that the carbon black graft polymer thus obtained had a high affinity with water and an organic solvent, and exhibited a good dispersibility in these media. However, even if these carbon black graft polymers are used, in order to obtain a more evenly dispersed and excellent modifying effect in various systems, the carbon black graft polymer is not completely satisfactory, and there is room for improvement. It was a thing.

[0008]

Therefore, it is an object of the present invention to provide a novel carbon black graft polymer composition, a method for producing the same, and various uses to which the composition is applied. The present invention also provides a novel carbon black graft polymer composition useful as a colorant for inks, toners for copying, or a modifier for various polymers.
It is an object of the present invention to provide a manufacturing method and use thereof.
The present invention further provides a novel carbon black graft polymer composition having extremely excellent dispersibility and toughness,
It is an object of the present invention to provide a manufacturing method and use thereof.

[0009]

Means and Actions for Solving the Problems In view of the above-mentioned current situation, the present inventors have conducted diligent research to solve the above problems, and as a result, have a reactivity with CB. By adding a thermoplastic elastomer to a carbon black graft polymer (hereinafter referred to as a CB graft polymer) obtained by reacting a polymer having a group, a sufficient shearing force is applied in the production process to obtain the CB. It has been clarified that the graft polymer composition has remarkably excellent dispersibility in various substances. Further, due to the action of the thermoplastic elastomer, the toughness of the CB graft polymer composition itself is remarkably excellent. Therefore, it can be suitably blended with, for example, an electrostatic image developing toner and a thermal transfer ink. Further, the inventors have found that by specifying the conditions during the reaction, the dispersibility of CB can be further enhanced and a CB graft polymer composition excellent in toughness can be easily obtained, thus completing the present invention.

That is, the above-mentioned problems are caused by polymers 10 to 50 having a group reactive with CB per 100 parts by weight of CB.
This is achieved by a CB graft polymer composition comprising a CB graft polymer obtained by reacting 0 part by weight and a thermoplastic elastomer.

The present invention also includes a CB graft polymer 10
It is a CB graft polymer composition in which a thermoplastic elastomer is blended in an amount of 5 to 200 parts by weight with respect to 0 parts by weight.

[0012] Further, the above-mentioned problems are caused by 100 parts by weight of CB and CB.
And 10 to 500 parts by weight of a polymer having a reactive group in the presence of a thermoplastic elastomer at a temperature of 50 to 350 ° C. under stirring and mixing, also by a method for producing a CB graft polymer composition. To be achieved.

Further, the above-mentioned problems are caused by polymers 10 to 500 having a group reactive with CB based on 100 parts by weight of CB.
A CB graft polymer composition, characterized in that, with respect to 100 parts by weight of a CB graft polymer obtained by reacting 1 part by weight, a thermoplastic elastomer is stirred and mixed at a ratio of 5 to 200 parts by weight under a temperature condition of 50 to 350 ° C. It is also achieved by the manufacturing method of.

The present invention also provides a toner for developing an electrostatic charge image and a thermal transfer ink, which contain the above-mentioned CB graft polymer composition.

Hereinafter, the present invention will be described in more detail based on the embodiments. The "thermoplastic elastomer" (hereinafter referred to as TPE) used in the present invention is a polymer material which exhibits the properties of a vulcanized rubber at normal temperature and is plasticized at high temperature and can be molded by a plastic processing machine. Which is composed of a constraining component (hard segment) that forms a constraining phase that prevents plastic deformation as a cross-linking point of the three-dimensional mesh and a rubber component (soft segment) that forms an elastic phase that exhibits entropic elasticity as a mesh chain. For example, various types such as polyolefin type, polystyrene type, polyvinyl chloride type, polyester type, polyurethane type and polyamide type can be used.

Of these, styrene type T is particularly preferable.
It is PE (SBC). Among TPEs, SBC is excellent in flexibility and elasticity and has the most rubber-like property. SB
C is a block copolymer having polystyrene in the hard segment, polybutadiene or polyisoprene in the soft segment, and a polyolefin, and styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) by a rubber block, SEB with hydrogenated SBS
Three types, S and SEPS, are known. Further, among such SBCs, those having a styrene content of about 5 to 60% by weight and a molecular weight of about 10,000 to 1,000,000 are particularly desirable.

On the other hand, the CB used in the present invention has a carboxyl group and / or a functional group on its surface.
Alternatively, any one having a hydroxyl group may be used, and for example, any type of furnace black, channel black, acetylene black, lamp black, etc. can be used, and a normal commercial product can be used as it is, but it does not react with the CB. When the reactive group of the polymer having properties is an epoxy group or a thioepoxy group, the reactivity becomes low when the pH of CB is high.
The range of 6 or less is preferable. CB
The test method of pH is according to JIS K 6211.

Examples of the polymer having a group reactive with CB (hereinafter referred to as polymer A) include, for example, aziridine group, oxazoline group, N-hydroxyalkylamide group, epoxy group and Polymers such as vinyl polymers, polyesters and polyethers having at least one reactive group selected from thioepoxy groups in the molecule can be used. The group capable of reacting with the functional group present on the CB surface is not necessarily limited to the reactive groups exemplified above, but a polymer having a group other than these reactive groups may be used. When used, it requires a step of pre-treating CB prior to stirring and mixing.

As a method for obtaining such a polymer A,
For example, (1) the polymerizable monomer having the reactive group in the molecule (hereinafter referred to as the monomer a) may be replaced with another polymerizable monomer (hereinafter referred to as the monomer b), if necessary. (2) a compound having a reactive group in the molecule (hereinafter, referred to as compound c) in the molecule, and a polymer having a group capable of reacting with the compound c (hereinafter, referred to as a polymer). A polymer having a reactive group other than the reactive group in the molecule (hereinafter referred to as polymer e). .) And converting it into a polymer A having the reactive group by a known method.

The monomer a that can be used in the above method (1) is

[Chemical 1]

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[Chemical 18]

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[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

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[Chemical 31]

[Chemical 32]

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[Chemical Formula 39]

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[Chemical formula 45]

[Chemical formula 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

[Chemical 52]

[Chemical 53]

[Chemical 54] Aziridine group-containing polymerizable monomers represented by:

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
-Oxazoline group-containing polymerizable monomers such as isopropenyl-4,5-dimethyl-2-oxazoline;

N-hydroxymethylacrylamide, N
-Hydroxyethylacrylamide, N-hydroxybutylacrylamide, N-hydroxyisobutylacrylamide, N-hydroxy-2-ethylhexylacrylamide, N-hydroxycyclohexylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-hydroxybutyl N-hydroxyalkylamide group-containing polymerizable monomers such as methacrylamide, N-hydroxyisobutylmethacrylamide, N-hydroxy-2-ethylhexylmethacrylamide, and N-hydroxycyclohexylmethacrylamide;

[0023]

[Chemical 55]

[Chemical 56]

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[Chemical 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

[Chemical 64]

[Chemical 65]

[Chemical formula 66]

[Chemical formula 67] (However, R ¹ in these formulas represents hydrogen or a methyl group, n is 0 or an integer of 1 to 20.) Epoxy group-containing polymerizable monomers represented by the formulas;

[0024]

[Chemical 68]

[Chemical 69]

[Chemical 70]

[Chemical 71]

[Chemical 72]

[Chemical formula 73]

[Chemical 74]

[Chemical 75]

[Chemical 76]

[Chemical 77]

[Chemical 78]

[Chemical 79]

[Chemical 80] (However, R ¹ and n in these formulas are the same as in the case of the epoxy group-containing polymerizable monomer.) And the like.
One or more selected from these groups can be used.

The monomer b that can be optionally used in the method (1) is not particularly limited as long as it can be copolymerized with the monomer a. For example, styrene, o-methylstyrene, m-methylstyrene. , P-methylstyrene, α-
Styrene monomers such as methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate , Propyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, dodecyl acrylate,
Stearyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate. , Acrylic acid or methacrylic acid-based monomers such as stearyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile,
Acrylamide, methacrylamide, N-vinylpyrrolidone, etc. are mentioned, and these 1 type (s) or 2 or more types can be used.

In order to obtain the polymer A having a reactive group by the method (1), the monomer a and, if necessary, the monomer b together with a conventionally known polymerization method such as a bulk polymerization method or a suspension polymerization method are used. Polymerization may be performed by a conventional method, an emulsion polymerization method, a precipitation polymerization method, a solution polymerization method, or the like.

Compound c which can be used in the method (2)
Examples of the compound include (2-1) a compound having two or more kinds of the reactive groups in the molecule, (2-2) a compound having two or more kinds of the reactive groups in the molecule, (2- 3) Examples thereof include compounds having in the molecule one or more types of the above-mentioned reactive groups and a group other than the above-mentioned reactive groups. Provided that the groups other than the reactive group described in the item (2-3) are aziridine group, oxazoline group, N
-A group other than a hydroxyalkylamide group, an epoxy group and a thioepoxy group, which is capable of reacting with a group contained in the polymer d described later, such as an isocyanate group, an amino group, a carboxyl group, a hydroxyl group,
A vinyl group and a halogen group correspond to this.

The polymer d in the method (2) means the above-mentioned
Examples thereof include vinyl polymers, polyesters and polyethers having a group capable of reacting with the compound c described in (2-1) to (2-3). Examples of the group capable of reacting with the compound c include a hydroxyl group (including a phenolic hydroxyl group), a carboxyl group, a quinone group, an amino group, an epoxy group and the like, and the polymer d having these groups is a radical. It can be easily obtained by known polymerization means such as polymerization and polycondensation.

In order to obtain the polymer A having a reactive group by the method (2), the compound c and the polymer d are reacted with each other under the condition that at least one of the reactive groups remains unreacted. do it.

The polymer e in the method (3) is a group which can be converted into an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group or a thioepoxy group, for example, a vinyl group, a carboxyl group, a chlorohydrin group, a glycol group and the like. Polymers having a in the molecule thereof can be easily made into a polymer A having an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group and / or a thioepoxy group by a conventionally known method.

The molecular weight of the polymer A is not particularly limited, but the number average molecular weight is 500 to 1,000,0 from the viewpoint of remarkable treatment effect on CB and workability during reaction with CB.
It is preferably in the range of 00, more preferably 1,
000-500,000, most preferably 2,000-
It is 100,000.

Of the reactive groups of the polymer A, an aziridine group, an oxazoline group and an N-hydroxyalkylamide group are most preferable, and the significance of using the polymer A having these reactivity is that the type of CB used and Regardless of the state, CB reacts with the polymer A at a very high grafting efficiency even under mild reaction conditions, and CB excellent in dispersibility in various substances can be obtained. Further, a polymer A having a reactive group having an epoxy group or a thioepoxy group
As described above, when treating CB having a pH of 8 or less, the polymer A must have one or more reactive groups on average, but the amount of the reactive group is large. Since the viscosity increases during the reaction with CB, the workability is deteriorated, and the dispersibility of the obtained CB graft polymer in other substances is deteriorated. It is preferable that the number of the epoxy groups is 1 to 2, more preferably 1 to 2, and most preferably 1 of either the epoxy group or the thioepoxy group.

The CB-grafted polymer composition according to the present invention is obtained by reacting CB with the above-mentioned polymer A, and the polymer A is graft-bonded to CB with extremely high efficiency.
The B graft polymer is further blended with the above-mentioned TPE as a third component.

Such a CB graft polymer composition is obtained by reacting CB with polymer A to form a CB graft polymer, adding TPE to the obtained CB graft polymer, and stirring and mixing under heating. You can Alternatively, from the beginning with CB and polymer A, TP
It can also be obtained by allowing E to exist and stirring and mixing under heating to react CB and the polymer A to form a CB graft polymer and at the same time disperse and blend TPE. However, the latter method in which TPE is allowed to exist during the reaction between CB and the polymer A causes a higher shearing force at the same time as the reaction between the CB and the polymer A, resulting in a CB graft polymer composition having more excellent dispersibility. It is particularly preferable because the product is obtained.

The reaction of CB with the above-mentioned polymer A can be carried out by various methods. For example, a method of reacting CB with the polymer A having a reactive group obtained by the above method (1) or (2) may be used.
The step of carrying out the method (1) or (2) in the presence of B to obtain the polymer A having a reactive group and the reaction step of the polymer and CB may be combined into one. However, in order to obtain a CB graft polymer with high graft efficiency, the former method is preferable. In the reaction, the amount of the polymer A having a reactive group to be used is preferably 10 to 500 parts by weight, more preferably 50 to 300 parts by weight, based on 100 parts by weight of CB. That is, the amount of the polymer A used is CB100.
If it is less than 10 parts by weight based on parts by weight, the dispersibility of the finally obtained CB graft polymer composition in various substances will not be sufficiently improved, while CB10
This is because if the amount of the polymer A used is more than 500 parts by weight with respect to 0 parts by weight, the properties of CB as a colorant, a modifier, etc. may be impaired. Further, the reaction between CB and the polymer A is carried out by reacting the CB and the polymer A at 50 to 350 ° C.
Preferably, it can be performed by stirring and mixing under a temperature condition of 80 to 250 ° C. Further, it can be carried out by stirring and mixing CB and the polymer A having a reactive group in a torque value range of 0.1 to 20 kg · m, preferably 0.3 to 10 kg · m. The temperature condition during the reaction is 35
When the temperature exceeds 0 ° C, the polymer component is deteriorated, which is not preferable. On the other hand, when the temperature is lower than 50 ° C, a sufficient reaction cannot be caused, and the graft ratio of the polymer A to CB is lowered to disperse the CB. It cannot improve the sex.
If the torque value exceeds 50 kg ・ m, polymer A
This is not preferable because it causes inconvenience such as deterioration due to cutting. The reaction between the CB and the polymer A may be a method in which only these two components are reacted, and as described above, in the presence of TPE, other than the polymer A having a reactive group, other Polymer, polymerizable monomer, organic solvent,
The reaction may be carried out in the presence of other substances such as water.

The "carbon black graft polymer" described in the present specification does not strictly mean only CB having a polymer bonded as a graft chain, and CB having a polymer bonded as a graft chain as described above.
And a polymer that could not be directly bonded to CB in the production process. This is because the grafting ratio may not reach 100% in any of the methods described above, and after the manufacturing process, CB to which the polymer is bonded as a graft chain is directly bonded to CB. This is because it is difficult to completely separate the polymer not obtained.

In order to obtain the CB graft polymer composition of the present invention, when TPE is present during the reaction of CB and the polymer A, the stirring and mixing are carried out at 50 to 350 ° C.
It may be carried out preferably under a temperature condition of 80 to 250 ° C. When the stirring and mixing is performed at a temperature of less than 50 ° C,
It may not be possible to cause a sufficient reaction, the graft ratio of the polymer A to CB may be reduced, and the dispersibility of CB may not be improved. Further, TPE may not be sufficiently dispersed and excellent toughness may be obtained. There is a fear that it will not. On the other hand, if it is carried out at a temperature higher than 350 ° C., the polymer component may be denatured, and sufficient shearing may not be applied, resulting in insufficient dispersion of CB.

Also, when TPE is added to the preformed CB graft polymer and mixed by stirring to obtain a carbon black graft polymer composition, the stirring and mixing after formation is 50 to 350 ° C., preferably 80. ~
It is desirable to carry out under a temperature condition of 250 ° C.

Further, the blending amount of TPE in the CB graft polymer composition of the present invention is 5 to 200 parts by weight, preferably 10 to 50 parts by weight per 100 parts by weight of CB graft polymer. If the blending amount of TPE is less than 5 parts by weight with respect to 100 parts by weight of the CB graft polymer, the dispersibility of the CB graft polymer will not be sufficiently improved by blending TPE, and high toughness may not be obtained. On the other hand, if the amount exceeds 200 parts by weight, the properties of CB as a colorant, a modifier, etc. may be impaired.

In the present invention, the composition, type and combination of TPE blended in the polymer (A) to be grafted to CB and the CB graft polymer obtained thereby can be arbitrarily selected. It is possible to impart various characteristics to CB according to the above. The CB graft polymer composition of the present invention obtained as described above has improved affinity with various substances. For example, dispersibility in substances such as organic polymers, water, organic solvents and CB grafting. Since the polymer composition itself has remarkably excellent toughness, it can be suitably used as, for example, a colorant in a thermal transfer ink, a toner for developing an electrostatic image or a modifier for various polymers.

The toner for developing an electrostatic image according to the present invention is
It comprises the CB graft polymer composition obtained by the above procedure. The method for producing the toner for developing an electrostatic image is not particularly limited as long as it contains the CB graft polymer composition obtained by the above procedure as a colorant component, and a pulverization method, a suspension polymerization method and an emulsification method. Various manufacturing methods such as a polymerization method can be used.

According to the grinding method, the CB obtained by the above procedure is
The graft polymer composition can be finely pulverized to be used as it is as a toner for developing an electrostatic image, but a polymer not corresponding to the polymer (A) as a fixing resin, particularly a styrene type, a (meth) acrylic acid type, A toner for developing an electrostatic image is preferably obtained by adding a CB graft polymer composition to a thermoplastic polymer such as a polyolefin-based polymer, melt-kneading the mixture, and then finely pulverizing the toner to develop an electrostatic image. Since the CB graft polymer composition has a good affinity for the polymer as the fixing resin used, it can be uniformly dispersed in the matrix of the polymer only by kneading under a relatively low shearing force.

According to the suspension polymerization method, the CB graft polymer composition obtained by the above procedure is prepared by using a polymerizable monomer, particularly a styrene-based monomer, a (meth) acrylic acid-based monomer,
A toner for developing an electrostatic charge image can be obtained by adding and mixing an α, β-ethylenically unsaturated monomer such as a polyolefin-based monomer, suspending it in an aqueous medium, and polymerizing it. Since the CB graft polymer composition has a good affinity for the polymerizable monomer, it can be easily and uniformly dispersed in the polymerizable monomer.

The content of the CB graft polymer composition in such an electrostatic image developing toner is not particularly limited and can be appropriately changed according to the purpose of use, but it is usually in the electrostatic image developing toner. It is desired to adjust the content of the CB graft polymer composition so that the CB component is about 1 to 20% by weight, more preferably about 3 to 10% by weight.

Further, the toner for developing an electrostatic image according to the present invention may be appropriately blended with additives usually used in ordinary toners such as a charge control agent, an offset preventing agent and a fluidizing agent. Further, when it is used as a one-component developer, magnetic fine particles are added as is well known. The average particle size of the electrostatic developing toner is not particularly limited, but is 1 to 25.
μm, and more preferably about 3 to 20 μm.

As described above, in the toner for electrostatic development according to the present invention, by using the CB graft polymer composition, CB is dispersed very uniformly in the matrix of the binder resin in each toner particle. Therefore, the charge distribution of the toner particles is uniform, a stable image without contamination can be formed, and an image with clear contours and extremely rich contrast can be obtained. Further, since the CB graft polymer composition contains TPE having high toughness, this toner is also excellent in terms of fixing property.

The heat-sensitive transfer ink according to the present invention contains the CB graft polymer composition obtained by the above procedure. The thermal transfer ink is a known binder component obtained by using a CB graft polymer composition, for example, a natural or synthetic wax such as carnauba wax, montan wax, paraffin wax, microcrystalline wax, oxidation wax, low molecular weight polyethylene wax, low molecular weight polypropylene wax, or the like. It can be obtained by adding and kneading to a synthetic resin such as polysulfone ether, polycarbonate, polystyrene, silicone resin, acrylic resin or the like. Dispersion of the CB graft polymer composition in the binder component is achieved by adding C to these binder components.
It is very easy because the B graft polymer composition shows extremely good affinity, and it is not necessary to knead it under high shear force using a ball mill, a roll mill, etc., and a stirrer with blades of various shapes, static mixer, melt mixing It suffices to perform mixing under a low shear force using a stirrer such as a machine. In addition,
If a polymer suitable for the binder of the ink is selected as the polymer A, C is added without adding other binder components.
It is also possible to use the B graft polymer composition as it is as a thermal transfer ink.

The content of the CB graft polymer composition in such a heat-sensitive transfer ink is not particularly limited and can be appropriately changed according to the purpose of use, but usually the CB component in the heat-sensitive transfer ink is 5 to 40. It is desired to adjust the content of the CB graft polymer composition so that it is about 10% by weight, and more preferably about 10 to 30% by weight.

As described above, in the thermal transfer ink according to the present invention, by using the CB graft polymer composition, the binder component of the ink and the CB graft polymer composition have extremely high affinity, and CB is the binder component. It is very uniformly dispersed in the matrix. Therefore, it is extremely high when applied to a support typified by PET film, polyimide film, condenser paper, silk fabric, aluminum foil, etc. by a known method such as a hot melt coater, a reverse roll coater, a gravure roll coater. A stable image having a high quality can be formed and the durability is excellent. Especially since the line drawing will be high quality and stable,
It can be suitably used as an ink for printing barcodes.

[0050]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples. In addition, "part" in an example shows a weight part, and "%" shows a weight%, respectively.

Example 1 A flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser and a thermometer was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. A mixture prepared by dissolving 16 parts of benzoyl peroxide in a polymerizable monomer composed of 194.4 parts of styrene and 5.1 parts of glycidyl methacrylate prepared in advance was charged and stirred at high speed to obtain a uniform suspension. And Then, the mixture was heated to 80 ° C. while blowing nitrogen gas, and stirring was continued for 5 hours at this temperature to carry out a polymerization reaction, followed by cooling to obtain a polymer suspension. The polymer suspension was filtered, washed and dried to obtain a polymer having an epoxy group as a reactive group. The molecular weight of this polymer was Mn = 5,500 by GPC measurement. 60 parts of a polymer having an epoxy group as a reactive group and carbon black MA-100R (manufactured by Mitsubishi Kasei Co., Ltd.) 40
Parts and styrene-based TPE (SIS) Quintac 345
0 (manufactured by Nippon Zeon Co., Ltd.) and 20 parts using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 160 ° C., 100 rpm
After kneading and reacting under the condition of
A graft polymer composition (1) was obtained. Table 1 shows the evaluation results of the CB dispersion state of the CB graft polymer (1).

Example 2 A flask equipped with a stirrer, an inert gas introducing tube, a reflux condenser and a thermometer was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. A mixture prepared by dissolving 16 parts of benzoyl peroxide in a polymerizable monomer composed of 196 parts of styrene and 4 parts of isopropenyl oxazoline, which had been prepared in advance, was charged and stirred at high speed to obtain a uniform suspension. Then, the mixture was heated to 80 ° C. while blowing nitrogen gas, and stirring was continued for 5 hours at this temperature to carry out a polymerization reaction, followed by cooling to obtain a polymer suspension. The polymer suspension was filtered, washed and dried to obtain a polymer having an oxazoline group as a reactive group. The molecular weight of this polymer was Mn = 5,800 as measured by GPC. 50 parts of a polymer having an oxazoline group as a reactive group and carbon black MA-100R (manufactured by Mitsubishi Kasei Co., Ltd.) 4
0 parts and styrene type TPE (SEBS) elastomer A
R-740B (manufactured by Aron Kasei Co., Ltd.) 30 parts and a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 160 ° C., 1
After kneading and reacting under a condition of 00 rpm, the mixture was cooled and pulverized to obtain a CB graft polymer composition (2). CB
Table 1 shows the evaluation results of the CB dispersion state of the graft polymer (2).

Comparative Example 1 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved was charged into a flask equipped with a stirrer, an inert gas introduction tube, a reflux condenser tube and a thermometer. A mixture prepared by dissolving 16 parts of benzoyl peroxide in a polymerizable monomer consisting of 194.4 parts of styrene and 5.1 parts of glycidyl methacrylate, which had been prepared in advance, was charged and stirred at high speed to obtain a uniform suspension. And Then, the mixture was heated to 80 ° C. while blowing nitrogen gas, and stirring was continued for 5 hours at this temperature to carry out a polymerization reaction, followed by cooling to obtain a polymer suspension. The polymer suspension was filtered, washed and dried to obtain a polymer having an epoxy group as a reactive group. The molecular weight of this polymer was Mn = 5,500 by GPC measurement. 60 parts of a polymer having an epoxy group as a reactive group and carbon black MA-100R (manufactured by Mitsubishi Kasei Co., Ltd.) 40
Part and kneading with a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 160 ° C. and 100 rpm for reaction, and then cooling and pulverizing for comparison CB graft polymer (a)
Got Table 1 shows the evaluation results of the CB dispersion state of the comparative CB graft polymer (a).

Comparative Example 2 Carbon black MA-100R (Mitsubishi Kasei Kogyo Co., Ltd.)
CB was used as it was, and the dispersion state of CB was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0055]

[Table 1]

Example 3 CB graft polymer composition (1) obtained in Example 1
30 parts, styrene butyl methacrylate copolymer (manufactured by Sanyo Kasei Co., Ltd., Hymer SBM73) 70 parts, low molecular weight polypropylene (manufactured by Sanyo Kasei Co., Ltd., Viscole 550)
P) 3 parts and charge control agent (Hodogaya Chemical Co., Ltd.,
1 part of Aizen Spiron Black TRH) is stirred and mixed in a Henschel mixer, and further 20 minutes at 160 ° C. by a roll mill.
The mixture was kneaded for a minute, cooled, and coarsely pulverized by a continuous vibration mill. Then, after finely pulverizing with a jet mill, classification was carried out to obtain a toner (1) for developing an electrostatic image having a particle size of 3 to 15 μm.
5 parts of this toner (1) for developing an electrostatic image was uniformly mixed with 95 parts of an iron powder carrier having an average particle diameter of 50 to 80 μm to prepare a developer (1). Table 2 shows the results of the image fixing test performed on the developer (1).

Example 4 8,970 parts of deionized water prepared by dissolving 5 parts of sodium dodecylbenzenesulfonate as an anionic surfactant in a reaction vessel equipped with a stirrer, an inert gas introducing tube, a reflux condenser and a thermometer. Was charged. The CB graft polymer composition (2) obtained in Example 2 was added to a polymerizable monomer component composed of 800 parts of styrene, 200 parts of n-butyl acrylate and 0.03 part of divinylbenzene prepared in advance. 500 parts, charge control agent (Hodogaya Chemical Co., Ltd.)
Manufactured by Aizen Spiron Black TRH) 3 parts, azobisisobutyronitrile 30 parts and 2,2'-azobis (2,4-
A mixture containing 30 parts of dimethylvaleronitrile) was charged, and T. K. Homo mixer (made by Tokushu Kika Kogyo Co., Ltd.)
Was stirred at 8,000 rpm for 5 minutes to form a uniform suspension. Then, the mixture was heated to 65 ° C. while blowing nitrogen gas, stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and further heated at 75 ° C. for 1 hour.
A suspension of colored spherical fine particles having a particle diameter of 5%, an average particle diameter of 5.82 μm, and a coefficient of variation of particle diameter of 20.5% was obtained. To the suspension of colored spherical fine particles kept at 75 ° C, methanol 2,09
When 5 parts was added and the mixture was further heated for 1 hour, a block-shaped material formed by fusion of particles was formed. This was filtered and dried at 50 ° C. for 10 hours using a hot air dryer to obtain 1,500 parts of a block-shaped material having a millet-raised shape in a fused state with grain boundaries left. This block-shaped product is a supersonic jet crusher type IDS2 (Nippon Pneumatic Mfg. Co., Ltd.)
(Manufactured by Mfg. Co., Ltd.) at a feed rate of 15 kg / hr to obtain colored fine particles (2). As a result of measuring the obtained colored fine particles (2) with a Coulter counter (aperture 100 μm), the average particle diameter was 5.67 μm, and the variation coefficient of particle diameter was 18.7%. Using the colored fine particles (2) as they were as the toner (2) for developing an electrostatic image, a developer (2) was prepared in the same manner as in Example 3. Table 2 shows the results of the image fixing test performed on the developer (2).

Comparative Example 3 Comparative CB graft polymer (a) obtained in Comparative Example 1
30 parts, styrene butyl methacrylate copolymer (manufactured by Sanyo Kasei Co., Ltd., Hymer SBM73) 70 parts, low molecular weight polypropylene (manufactured by Sanyo Kasei Co., Ltd., Viscole 550)
P) 3 parts and charge control agent (Hodogaya Chemical Co., Ltd.,
1 part of Aizen Spiron Black TRH) is stirred and mixed in a Henschel mixer, and further 20 minutes at 160 ° C. by a roll mill.
The mixture was kneaded for a minute, cooled, and coarsely pulverized by a continuous vibration mill. Then, after finely pulverizing with a jet mill, classification was carried out to obtain a comparative electrostatic image developing toner (a) having a particle size of 3 to 15 μm. 5 parts of this comparative electrostatic image developing toner (a) was uniformly mixed with 95 parts of an iron powder carrier having an average particle diameter of 50 to 80 μm to prepare a comparative developer (a). Table 2 shows the results of an image fixing test performed on the comparative developer (a).

[0059]

[Table 2]

Example 5 CB graft polymer composition (1) obtained in Example 1
50 parts and 50 parts of carnauba wax were prepared by stirring and mixing at 100 ° C. for 30 minutes to obtain a thermal transfer ink (1). The obtained thermal transfer ink (1) was applied to a thickness of 6
A biaxially stretched PET film having a thickness of μm was coated so that the dry film thickness of the ink layer was 4 μm. The application was performed using a wire bar by heating the ink to a temperature suitable for the ink to bring the ink into a fluid state. The obtained thermal transfer sheet was mounted on a thermal printer and printed on plain paper. The scratch strength of the image was evaluated by rubbing the image surface by applying a load of 150 g to a hemispherical stainless rod having a diameter of 1.5 mm at one end, and evaluating the degree of scratching. The results are shown in Table 3.

Comparative Example 4 Comparative CB graft polymer (a) obtained in Comparative Example 1
It was prepared by stirring and mixing 50 parts and 50 parts of carnauba wax at 100 ° C. for 30 minutes to obtain a thermal transfer ink for comparison (a). Using the obtained thermal transfer ink (1), the scratch strength of the image was evaluated in the same manner as in Example 5. The results are shown in Table 3.

[0062]

[Table 3]

[0063]

As described above, according to the present invention, CB
Is reacted with a polymer (A) having a reactive group to form a CB graft polymer, and TPE is further added to the CB graft polymer, and the reactive group in the polymer (A) is the surface of CB. Since the polymer (A) component is highly efficiently grafted onto the CB surface to exhibit high reactivity with the functional group, the dispersibility of CB is improved, and in addition, the dispersibility of CB is further improved by the action of the thermoplastic elastomer. And the toughness of the composition itself can be improved. Since the composition, type, combination, etc. of the polymer (A) and TPE can be arbitrarily selected, it is possible to impart various characteristics to CB depending on the purpose. Therefore, the CB graft polymer composition of the present invention thus obtained has improved affinity with various substances, and is remarkably excellent in dispersibility in, for example, organic polymers, water, organic solvents,
And since the toughness of the carbon black graft polymer composition itself is remarkably excellent, a toner for developing an electrostatic image,
It can be suitably used as a colorant in thermal transfer inks and a modifier for various polymers. Further, according to the production method of the present invention, a CB graft polymer composition in which various characteristics such as dispersibility and toughness are further enhanced is obtained by adding a polymer (A) having a reactive group and TPE to CB. It can be produced by a simple operation of simply stirring and mixing under a predetermined temperature condition.

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Claims (6)

[Claims] 1. A polymer 10 having a group reactive with carbon black with respect to 100 parts by weight of carbon black.
A carbon black graft polymer composition comprising a carbon black graft polymer obtained by reacting ˜500 parts by weight and a thermoplastic elastomer. 2. A carbon black graft polymer 10
The carbon black graft polymer composition according to claim 1, wherein the thermoplastic elastomer is blended in an amount of 5 to 200 parts by weight with respect to 0 parts by weight. 3. Polymers 10 to 5 having 100 parts by weight of carbon black and a group reactive with carbon black.
50 parts by weight in the presence of the thermoplastic elastomer is 50 to 50 parts by weight.
A method for producing a carbon black graft polymer composition, which comprises stirring and mixing under a temperature condition of 350 ° C. 4. A polymer 10 having a group reactive with carbon black with respect to 100 parts by weight of carbon black.
To 500 parts by weight of the carbon black graft polymer, 100 parts by weight of the carbon black graft polymer, and 5 to 200 parts by weight of the thermoplastic elastomer are stirred and mixed at a temperature of 50 to 350 ° C. under stirring. A method for producing a graft polymer composition. 5. A toner for developing an electrostatic charge image, which comprises the composition according to claim 1 or 2. 6. A thermal transfer ink comprising the composition according to claim 1 or 2.