JPH10120935A - Electrical resistance-adjusting material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resistance-adjusting material having higher stability of resistance value and capable of readily carrying out control of the resistance value by including a polymer obtained by reacting a polymer which is reactive with carbon black with carbon black. SOLUTION: This adjusting material comprises a carbon black graft polymer obtained by reacting (A) a polymer having reactivity with carbon black with (B) carbon black. The adjusting material is preferably controlled so that electric resistance of a resin-based material becomes 10<2> to 10<15> Ω.cm volume resistivity. The component A is preferably a block type or graft type polymer having a segment capable of reacting with a reactive group capable of reacting with a functional group of the surface of carbon black and a segment different from the segment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electric resistance adjusting material. More specifically, the present invention relates to an electric resistance adjusting material having high resistance value stability and easy resistance value control.

[0002]

2. Description of the Related Art Conventionally, carbon black has been widely used as a conductive material. For example, in addition to using carbon black alone as a conductor, a composite or coating obtained by dispersing and blending carbon black into a resin material, a PTC element of a sheet heating element, an antistatic sheet or coating, Various members such as a conductive belt as a transfer intermediate in a copying machine, a charging roller of a contact charging device, and a conductive layer that covers a core wire of a high-voltage power transmission line and provides an effect of reducing a dielectric breakdown gradient have been made. I have.

Further, the resistance value ranges from a low resistance value of about 10 ⁻² Ω · cm by adding a large amount of Ketjen black or the like as a conductive carbon black to 10 ¹⁵ Ω · cm suitable for antistatic use. Used to a degree.

However, since carbon black generally has a large cohesive force between particles, it is difficult to uniformly disperse carbon black when dispersed in a resin material or the like, and coarse particles which are secondary aggregates of carbon black are generated. Inevitably, the particle size distribution is large. For this reason, the electrical resistance value of the composite or coating film containing carbon black varies widely among individual products, and the stability of the resistance value is lacking. Further, when such a composite or coating film is applied as a heating element or a resistor, a considerably large amount of carbon black must be added to obtain a heating element or a resistor having a low resistance value. In this case, not only does the viscosity significantly increase and the workability deteriorates, but also the mechanical strength of the composite or coating film becomes extremely weak due to poor dispersibility of carbon black.

It is also known to use a grafted carbon black obtained by polymerizing a vinyl polymerizable monomer in the presence of carbon black as an electric resistance adjusting material (for example, Niigata University Research Report No. 15).
No. 1966, pp. 71-81, JP-B-53-423.
No. 8, etc.).

However, the yield of polymer bound to carbon black obtained by these methods is several percent to 10%.
It was as low as a few percent, and mostly existed in the form of vinyl homopolymer, and the surface treatment efficiency of carbon black was extremely low. For this reason, the affinity with other substances was not improved as expected, and the dispersibility of carbon black was still insufficient.

[0007]

Accordingly, an object of the present invention is to provide a novel electric resistance adjusting material. Another object of the present invention is to provide an electric resistance adjusting material having high stability of resistance value and easy control of resistance value.

[0008]

DISCLOSURE OF THE INVENTION The above-mentioned objects are characterized by containing a carbon black graft polymer obtained by reacting a polymer (I) having reactivity with carbon black with carbon black. Achieved by electrical resistance adjusting materials.

The present invention also provides an electric resistance adjusting material characterized in that the electric resistance of the resin material is adjusted so as to have a volume resistivity of 10 ² to 10 ¹⁵ Ω · cm.

The present invention further provides a segment (A) in which the polymer (I) has a reactive group capable of reacting with a functional group on the surface of carbon black, and a segment (B) different from the segment (A). This is a block-type or graft-type polymer having the following. .

In the present invention, the segment (B) preferably comprises:
Polysiloxane structure, poly (meth) acrylic structure,
At least one member selected from the group consisting of a polyether-based structure, a poly (meth) acrylonitrile-based structure, a polyester-based structure, a polyalkylene-based structure, a polyamide-based structure, a polyimide-based structure, a polyurethane-based structure, and a fluorine-based resin structure 1 shows an electric resistance adjusting material having a structure.

[0012]

The "carbon black graft polymer" as used herein refers to fine particles having a polymer portion grafted on a carbon black portion. The carbon black graft polymer is obtained by grafting a polymer to primary particles or several aggregates of carbon black. Further, the term “grafting” as used herein refers to donee (Jean).
Irreversible addition of a polymer to a substrate such as carbon black, as defined by Baptiste Donnet et al. In his book "Carbon Black" (published May 1, 1978 by Kodansha Co., Ltd.). is there.

By performing an irreversible addition reaction, the polymer portion can be chemically bonded to the surface portion of the carbon black particles, whereby the both can be surely 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 hundred n.
It has a particle size of m. However, since carbon black has a large cohesive force between particles, it is usually handled as an aggregate having a particle diameter of several microns or more. In addition, the cohesive force between carbon blacks is remarkably large compared to the affinity between carbon black and another substance, for example, a resin-based material, and it is very difficult to disperse carbon black in a resin-based material or the like at a submicron level. , It is not possible to obtain a stable resistance value. On the other hand, in the carbon black graft polymer, the polymer portion can effectively enter between the carbon black particles, and can reduce the cohesive force between the carbon blacks. Further, when the polymer portion has an affinity for the resin-based material or the like, the carbon black graft polymer can be dispersed in the resin-based material or the like at a submicron level. However, even if the polymer portion has a high affinity for the resin-based material and the like, if the polymer portion is not effectively grafted to the carbon black portion, the characteristics will not be stable, and Variations are likely to occur, it will not be a good electrical resistance adjusting material, and trying to obtain a certain level of affinity will result in a low content of the carbon black portion in the carbon black graft polymer, The conductivity of the black is significantly impaired.

As a result of intensive studies, the present inventors have found that if a carbon black graft polymer obtained by reacting a polymer (I) having reactivity with carbon black with carbon black is used, this carbon black graft polymer can be used. The polymer exhibits a stable electric resistance value from the viewpoint that the polymer is effectively grafted and exhibits good dispersibility in resin materials and the like, and is suitable as an electric resistance adjusting material. This has led to the present invention.

The electric resistance value of the electric resistance adjusting material according to the present invention may be determined, for example, by adjusting the ratio of the ratio of carbon black to the polymer (I) to be grafted in the carbon black graft polymer. Coalescing (I)
By adjusting the number of the reactive groups having, or by changing the type of carbon black, it is possible to easily and satisfactorily control, for example, to have an arbitrary volume resistivity in the range of 10 ² to 10 ¹⁵ Ω · cm. Is possible.

Further, in the electric resistance adjusting material according to the present invention, the polymer (I) has a segment (A) having a reactive group capable of reacting with a functional group on the surface of carbon black;
When a block-type or graft-type polymer having a segment (B) different from the segment (A),
Even when the ratio of the polymer (I) to carbon black is smaller, the obtained carbon black graft polymer exhibits extremely good dispersibility, and the intrinsic conductivity of carbon black is hardly impaired. It is particularly excellent as an electric resistance adjusting material.

Hereinafter, the present invention will be described in more detail based on embodiments.

The carbon black used for producing the carbon black graft polymer according to the electric resistance adjusting material of the present invention is not particularly limited as long as it has a functional group such as a carboxyl group on its surface. Any kind of furnace black, channel black, acetylene black, lamp black and the like can be used, and ordinary commercial products can be used as they are. Further, it is preferable to use carbon black having a pH of less than 7, especially pH 1 to 6, as the carbon black. A carbon black having a carboxyl group can be easily obtained as an acidic carbon black, but a carbon black obtained by oxidizing a neutral or basic carbon black can also be suitably used as a raw material in the present invention. When the carbon black does not have a functional group such as a carboxyl group or has a pH of 7 or more, grafting may not be effectively performed. The test method for the pH of carbon black is JIS
K 6211.

The average particle size of the carbon black is 0.0005 to 0.4 μm, particularly 0.001 to 0.2 μm.
It is preferably within the range of m. Average particle size is 0.0
Since carbon black having a size of less than 005 μm cannot be easily obtained, it has little industrial significance. The average particle size is 0.4
If it exceeds μm, sufficient dispersibility may not be provided to the obtained carbon black graft polymer.

The carbon black graft polymer according to the present invention is obtained by reacting the polymer (I) having reactivity with carbon black with carbon black.

The polymer (I) having reactivity with carbon black may be any polymer having a reactive group having reactivity with the surface functional group of carbon black, for example.
Furthermore, the reactive group is not particularly limited as long as it can react with a functional group present on the surface of carbon black and contribute to grafting of the polymer to carbon black. Available.

Here, in order to make the grafting more reliable and stable, it is desired that the polymer portion be bonded to the carbon black via a covalent bond. Particularly, an ester bond, a thioester bond, an amide bond, At least one bond selected from the group consisting of an amino bond, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond and a sulfonyl bond, and at least one bond selected from the group consisting of an ester bond, a thioester bond and an amide bond Is desired.
Considering these points, the reactive group is an epoxy group,
Desirably, at least one or two or more selected from the group consisting of a thioepoxy group, an aziridine group and an oxazoline group. The reactive group for carbon black is 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 that the polymer preferably has the reactive group is that regardless of the type and state of the carbon black that can be used, the carbon black and the polymer are added with very high grafting efficiency even under mild conditions. To react. In particular, when the carbon black has a carboxyl group as a surface functional group as described above, the carboxyl group performs 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. This is desirable because the above-mentioned covalent bond is formed between the carbon black portion and the polymer portion by the addition reaction.

The method for introducing these reactive groups into the polymer (I) will be described later.

The skeleton structure of the polymer (I) having a reactive group capable of reacting with the functional group on the surface of carbon black used in the present invention is not particularly limited. However, the segment (A) having a reactive group capable of reacting with the functional group on the carbon black surface is different from the segment (A) having substantially no reactive group and more specifically. Is preferably a block type or graft type polymer having a different skeleton structure and a segment (B).

Hereinafter, the polymer (I) grafted to carbon black in the present invention will be described, focusing on such a block or graft type polymer.

First, such a block or graft type polymer is preferred for the following reasons.

As described above, even if the polymer (I) to be grafted onto carbon black has a high affinity for a medium such as a resin-based material, the polymer is effectively grafted onto the carbon black portion. Otherwise, the properties will not be stable and will tend to vary, resulting in a low content of carbon black in the carbon black graft polymer if a certain level of affinity is to be obtained. Also.

In this respect, by using a block type or a graft type as the polymer (I) forming the polymer portion, a carbon black graft having more effective grafting and excellent dispersibility in various media can be obtained. A polymer can be used, and as a result, an electric resistance adjusting material stably exhibiting a desired electric resistance value can be obtained. That is, for example, a block-type or graft-type polymer is divided into a segment (B) having a high affinity for a target medium such as a resin material and a segment (A) having a lower affinity for a target medium than this segment (B). And molecular designing such that only the segment (A) has a reactive group contributing to grafting by reacting with the surface functional group of carbon black, The grafting is carried out in a dispersion medium solution having a medium having the same.

FIG. 1 shows that a block type or graft type polymer having a reactive group is reacted with carbon black in a dispersion medium composed of a target medium or a medium having properties close to the target medium. FIG. 3 is a view schematically showing a state in the vicinity of the surface of the carbon black when being made. As described above, the polymer according to the present invention is composed of the segment (A) having a reactive group and the segment (B) having an affinity for a target medium. , The segment (B) is oriented so as to extend into the dispersion medium liquid,
Since the segment (A) necessarily surrounds the surface of the carbon black particles and provides a suitable reaction field for grafting the carbon black and the polymer, effective grafting is performed.

From the same concept, for example, a segment (A) having a reactive group capable of reacting with a functional group on the surface of carbon black and a segment (A) having substantially no reactive group and having the reactive group (In other words, a segment (A) having a high affinity for carbon black and a segment (B) having a high affinity for a target medium).
And the like.) It is also possible to adopt an embodiment in which a block or graft type polymer (having the following formula) is grafted onto carbon black. In the reaction system, this polymer segment (A)
Are oriented to the carbon black side, so that the reactive group present in the segment (A) is effectively grafted to the carbon black surface. Note that, in this embodiment, unlike the first embodiment, grafting is not necessarily performed in a dispersion medium solution composed of a medium having an affinity for the segment (B) or having a property close to the target medium. It is not necessary to carry out the reaction, and it is possible to melt-knead only the polymer and the carbon black, or to cause the reaction in a dispersion medium having almost the same affinity for both the segment (A) and the segment (B). However, in order to perform grafting more reliably and efficiently, it is desirable to carry out the grafting in a dispersion medium having an affinity for the segment (B).

As described above, the carbon black graft polymer obtained by using the block type or graft type polymer has a polymer portion more effectively grafted and has more excellent dispersibility. And the carbon content of the carbon black graft polymer can be increased, and a desired electrical resistance value can be imparted while utilizing the conductivity of carbon black itself.

As the block or graft type polymer, those having a simple structure such as an AB type block copolymer shown in FIG. 2A and an AB type graft copolymer shown in FIG. 2B can be used. Without limitation, the BAB type block copolymer shown in FIG. 2 (c) or a more advanced alternating block copolymer, and a plurality of B segments shown in FIG. 2 (d) are grafted to the A segment. Various types such as a comb-shaped graft copolymer and a star-shaped graft copolymer shown in FIG. X in the figure represents a reactive group. FIG. 2 (f)
Represents a state in which these various block or graft polymers are bonded to the surface of the carbon black particles (CB). In short, at least one segment ( The block or graft type polymer may have any form as long as B) can be oriented with a certain degree of freedom toward the outside of the surface of the carbon black particles. Even if a segment includes a plurality of types of segments (same for the segment (B)), the segment (A) and the segment (B) have different properties, for example, have an intermediate property between them. Alternatively, it increases or decreases the "fluctuation" (mobility) of the graft chain in the medium, which extends the graft chain. Another type of segment subjecting functions such Runado (hereinafter, referred to. (C) segments), and
It may have a form arranged between the segment (A) and the segment (B). Where (C)
Although the segment may or may not have a reactive group, it is generally considered that the segment does not have a reactive group from the viewpoint of increasing graft efficiency. Further, in some cases, it is possible to introduce a reactive group or the like capable of mutually cross-linking the (C) segment. Although the (C) segment is referred to for the sake of explanation, the (C) segment can be roughly classified into either the segment (A) or the segment (B) as described above.

The segment (A) having such a reactive group preferably has a low affinity for the target medium on the segment chain structure. In addition, since the low affinity here is a relative one by comparison with the other segment (B), the segment (A) may have various types depending on the type of the target medium or the configuration of the segment (B). And cannot be specified unambiguously. However, from another point of view, it is desirable that the segment (A) has a high affinity for carbon black, since it exhibits better orientation to carbon black. From this point, the segment (A) has a main chain mainly containing a carbon-carbon bond, and more preferably contains an aromatic ring such as a benzene ring, a naphthalene ring or an indene ring in the main chain. The segment (B) has a carbon-carbon bond smaller than that of the segment (A), particularly a skeletal structure having fewer aromatic rings, such as an ether bond and an ester bond. It is desirable that the bond contains many bonds other than carbon-carbon bonds.

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

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

On the other hand, the segment (B) has, for example, a poly (meth) acrylic structure, a polyalkylene glycol, etc., depending on the affinity for the target medium such as a resin material constituting the matrix of the electric resistance adjusting material. Appropriate ones are selected from polymer chains having a polyether structure, a poly (meth) acrylonitrile structure, a polyester structure, a polyalkylene structure, a polyamide structure, a polyimide structure, a polyurethane structure, a fluorine resin structure, and the like.

A method for obtaining a block or graft type polymer (I) having such a segment (A) having a reactive group and a segment (B) having a high affinity for a target medium is as follows. There is no particular limitation, and various known block or graft-type polymer polymerization techniques,
It can be produced by appropriately combining techniques for producing a reactive polymer.

As a method for obtaining a graft-type polymer,
For example, a method is known in which a polymerization initiator and a polymerizable monomer are solution-polymerized, emulsion-polymerized, bulk-polymerized, or suspension-polymerized to polymerize a main-chain polymer in the presence of a high-molecular-weight polymer that forms a graft chain. Have been. However, if the high molecular weight polymer does not have a radical polymerizable functional group, the resulting graft copolymer contains a large amount of non-grafted polymer, and has a disadvantage that graft efficiency is low. I have. Therefore, it is preferable to use a radical polymerizable polymer as the polymer. Such a radical polymerizable high molecular weight product is generally called a “macromonomer”, and has a radical polymerizable group at one end, for example,
High molecular weight products having (meth) acryloyl group, styryl group, etc., for example, those obtained by reacting a polymer having a carboxyl group at one end with a radical polymerizable monomer having a glycidyl group in an organic solvent. (For example, JP-B-43-11224 discloses that a prepolymer obtained by radical polymerization of a radical polymerizable monomer in an organic solvent in the presence of mercaptoacetic acid and glycidyl methacrylate are treated with a dimethyllaurylamine catalyst. A method obtained by reacting in the presence is disclosed).

Therefore, for example, to obtain the graft copolymer as the polymer (I) used in the present invention,
In the presence of the above-mentioned radical polymerizable high molecular weight compound (b) as a component forming the segment (B), the above-mentioned polymerizable monomer (a) having a reactive group for carbon black in the molecule. In addition, the polymerizable monomer (c) that forms the skeleton of the segment (A), which is blended as required, may be polymerized.

The polymerizable monomer (a) having a reactive group for carbon black in the molecule includes:

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

(Wherein R ¹ in these formulas represents hydrogen or a methyl group, and n is 0 or an integer of 1 to 20). ;

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

(Provided that R ¹ and n in these formulas are the same as in the case of the epoxy group-containing polymerizable monomer), etc .;

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

Aziridine group-containing polymerizable monomers represented by the following formulas: 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- Oxazoline group-containing polymerizable monomers such as 2-oxazoline and 2-isopropenyl-4,5-dimethyl-2-oxazoline; N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N-hydroxybutylacrylamide, N- Hydroxyisobutylacrylamide, N-hydroxy-
2-ethylhexyl acrylamide, N-hydroxycyclohexyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl methacrylamide, N-hydroxybutyl methacrylamide, N-hydroxyisobutyl methacrylamide, N-hydroxy-
N-hydroxyalkylamide group-containing polymerizable monomers such as 2-ethylhexyl methacrylamide and N-hydroxycyclohexyl methacrylamide; and one or more selected from these groups. Can be.

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

On the other hand, as the radical polymerizable high molecular weight polymer (b) for constituting the component of the segment (B), a desired polymer chain, for example, polysiloxane structure, poly (meth) acrylic structure, polyalkylene glycol, etc. Polyether structure, poly (meth) acrylonitrile structure,
As long as it has a reactive group at one end of a polymer chain, such as a polyester-based structure, a polyalkylene-based structure, a polyamide-based structure, a polyimide-based structure, a polyurethane-based structure, and a fluorine-based resin structure, it is sufficient.

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

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

[0129]

Embedded image

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

[0131]

Embedded image

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

[0133]

Embedded image

[0134] ^{(wherein, R 1, R 2, R} 4 are the same or different and represent a hydrogen atom or a methyl group, R ^3,
R ⁵ is the same or different and represents an alkyl group having 1 to 25 carbon atoms; X is an arbitrary connecting chain; Y is an initiator terminal or a H atom;
Indicates an integer of 00. )

[0135]

Embedded image

(Wherein, R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a methyl group, R ₃ represents an alkylene group having 1 to 25 carbon atoms, and R ₄ represents an alkylene group having 1 to 25 carbon atoms.
X is an arbitrary connecting chain, Y is an initiator terminal or H atom, and n and m are the same or different and represent an integer of 0 to 500. When the segment (B) has a polyalkylene glycol-based structure, for example, those shown below can be used as the radical polymerizable high molecular weight compound (b ₃ ).

[0137]

Embedded image

(Wherein, R ¹ , R ² , and R ³ are the same or different and each represent a hydrogen atom or a methyl group;
Shows an integer of ~ 500. )

[0139]

Embedded image

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

[0141]

Embedded image

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

In the case of using a fluorine resin structure,

[0144]

Embedded image

[0145]

Embedded image

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

As the polymerization method for obtaining such a polymer, a known polymerization method can be used. For example,
Examples include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among them, a solution polymerization method using a radical catalyst is preferable.

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

After the completion of the polymerization, the obtained solution of the polymer 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 to take out the polymer. it can.

As another method for obtaining a graft polymer which can be used in the present invention, for example, a compound having a group reactive with carbon black is provided in the segment (A). In addition, a method of reacting a precursor polymer obtained by grafting the segment (B) to the segment (A) to introduce the reactive group into the precursor polymer can be mentioned.

Examples of the above compounds include compounds having two or more of the above reactive groups for carbon black in the molecule, compounds having two or more of the above reactive groups for carbon black in the molecule, A compound having at least one of the above-mentioned reactive groups for carbon black and a functional group other than the above-mentioned reactive group in a molecule can be exemplified.

However, the above-mentioned functional group is other than an epoxy group, a thioepoxy group, an aziridine group, an oxazoline group and an oxazoline group, and is capable of reacting with the reactive group of the precursor polymer. Things. Examples of the reactive group of the precursor polymer include an isocyanate group, an amino group, a carboxyl group, a hydroxyl group, and a vinyl group.

As a method for obtaining a block type polymer, for example, an anion living polymerization method, a cation living polymerization method, an iniferter method and the like are known, and as another method, a segment (A) or a segment ( B) (in the present invention, the segment (A) is preferably a segment (B) because a reactive group is introduced into the segment (A)).
Alternatively, a polymer obtained by polymerization in the presence of a compound containing a thioester and a thiol group in a molecule such as 2-acetylthioethylthiol, 10-acetylthiodecanethiol, or the like, is polymerized with an alkali such as sodium hydroxide or ammonia. A method is known in which a polymer having a thiol group at one end is treated, and a monomer component of the other segment is subjected to radical polymerization in the presence of the obtained polymer having a thiol group at one end. .

Therefore, in order to obtain the block copolymer as the polymer (I) used in the present invention, the above-mentioned known method is appropriately modified, and as in the case of obtaining the graft copolymer, The polymerizable monomer (a) having a reactive group as described above in at least a part of the polymerizable monomer of the segment (A) is used to polymerize the segment (A) at the time of polymerization of the block copolymer. Or a reactive group may be introduced into the segment (A) after polymerization of the block copolymer.

The molecular weight of the polymer (I) to be grafted onto carbon black thus obtained is not particularly limited, but the grafting effect on carbon black and the workability during the reaction with carbon black are considered. In consideration of the above, the average molecular weight is 1000 to 10
It is preferably in the range of 00000, more preferably in the range of 5,000 to 100,000.

The molecular weight of the segments (A) and (B) in the graft or block type polymer, which is desirable as the polymer (I) to be grafted on carbon black, is also particularly limited. However, it depends on the type of the polymer chains constituting these segments, but from the viewpoint of the grafting efficiency to carbon black, the segment (A) has an average molecular weight of 300 to 100,000, more preferably 500 to 50,000. It is preferable that the average molecular weight is in the range of 500 to 100,000, more preferably 1000, from the viewpoint of the effect of modifying the dispersibility to be imparted to carbon black.
It is preferably in the range of 50,000 to 50,000.

Further, the number of reactive groups contained in the polymer (I) to be grafted on the carbon black is not particularly limited, and the electric resistance value to be imparted to the electric resistance adjusting material to be obtained is not limited. It can be appropriately selected in consideration of, for example, the average molecular weight of 50 to 50 per polymer molecule.
It is desired to have about 1, more preferably about 20 to 1.

The polymer (I) may have a functional group such as an ethylenically unsaturated double bond or a carboxyl group as long as the grafting with carbon black is not inhibited. . When the polymer (I) has a crosslinkable group such as an ethylenically unsaturated double bond, better and stable dispersibility is obtained when the obtained carbon black graft polymer is blended with a resin material or the like. This is because it is expected that the carbon black graft polymer obtained by having a functional group such as a carboxyl group can easily adjust the electric resistance value. If the polymer (I) has a carboxyl group in advance, the reactive group of the polymer (I) and the carboxyl group react during heating and mixing with carbon black. As a result, a desired carbon black graft polymer cannot be obtained. Therefore, it is desirable to employ a method of introducing a carboxyl group into a polymer chain bonded to carbon black after the reaction between carbon black and the polymer (I). It is. For example, a method can be considered in which the polymer (I) is molecularly designed as having a hydroxyl group, and after the reaction with carbon black, the hydroxyl group is treated with an acid anhydride to be half-esterified. In addition, when trying to introduce an ethylenically unsaturated double bond,
Similarly, it is also possible to add a double bond to the polymer chain bonded to the carbon black after the reaction with the carbon black. Further, when the polymer (I) is a graft or block type polymer as described above, such an ethylenically unsaturated double bond, a carboxyl group, or the like may be added to either the segment (A) or the segment (B). However, it is preferable that the segment (B) which is oriented outward in the obtained carbon black graft polymer has at least these functional groups, etc. Desirable to be.

In the present invention, the grafting of the polymer onto the carbon black as described above is carried out by using the carbon black and the polymer (I) reactive with the carbon black.
Is heated and mixed, for example, at 40 to 300 ° C., preferably at 7 ° C.
It is carried out by stirring and mixing at a temperature of 0 to 250 ° C for 0.5 to 10 hours, preferably 2 to 5 hours. If the reaction temperature is lower than 40 ° C., the grafting may not proceed, which is not preferable. If the temperature exceeds 300 ° C., the polymer component may be deteriorated, which is not preferable.

As described above, when the polymer is a block or graft type polymer, the grafting treatment is preferably carried out on the above-mentioned target medium or a target medium for dispersing the carbon black graft polymer. It is carried out in the presence of a dispersion medium comprising a medium having similar properties. That is, the dispersion medium has high affinity or compatibility with the segment (B) of the polymer and low affinity or compatibility with the segment (A).

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

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

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

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

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

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

As a reaction procedure, the carbon black and the polymer and the dispersion medium may be charged into a reactor and mixed under heating.

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

The mixing ratio of carbon black and the polymer in such grafting depends on the kind of the polymer used, the electric resistance value to be applied to the electric resistance adjusting material to be obtained, and the like. Although it cannot be specified unconditionally because it depends on
The amount of the polymer is preferably 1 to 1000 parts by weight, more preferably about 2 to 500 parts by weight with respect to parts by weight.
That is, if the amount of the polymer is less than 1 part by weight, it may be difficult to sufficiently modify the surface properties such as the dispersibility of the carbon black.
This is because the amount of the polymer bonded to the carbon black increases, which may not only be uneconomical, but also impair the inherently required conductivity of the carbon black.

In the graft or block type polymer described above, the segment (A) having a reactive group capable of reacting with the functional group on the surface of carbon black is separated from the segment (B) having a high affinity for the target medium. When a material having a high molecular affinity for carbon black is used, it may be used under a relatively arbitrary dispersion medium (other than a dispersion medium liquid having an extremely high affinity toward the segment (A)), or as described above. Even in the absence of a suitable dispersing medium, the segment (A) of the polymer is oriented toward the carbon black, so that the reactive groups present in the segment (A) are effectively grafted to the carbon black surface, As in the case, a carbon black graft polymer having excellent properties can be obtained.

The thus obtained carbon black graft polymer of the present invention has an average particle size of 0.00
It is preferably in the range of 1 to 0.5 μm, particularly 0.005 to 0.2 μm. A carbon black graft polymer having an average particle diameter of less than 0.001 μm has little industrial significance because carbon black as a raw material cannot be easily obtained. When the average particle size exceeds 0.5 μm, sufficient dispersibility may not be obtained.

The carbon black graft polymer according to the present invention obtained by the above-described production method has excellent dispersion in various target media such as various resin materials because the polymer portion is more effectively grafted. And have predetermined conductive properties, and may be used alone or in a resin-based material.
A predetermined volume resistivity in the range of 0 ² to 10 ¹⁵ Ω · cm can be exhibited stably. The conductive properties of the carbon black graft polymer itself obtained as described above are determined by the ratio of the carbon black to the polymer (I) and the polymer (I).
It is possible to control to a specific value depending on the type of carbon black and the type of carbon black. Even if the polymers are the same, a desired electric resistance value can be easily and stably obtained only by changing the compounding amount.

When the electric resistance adjusting material is blended with a resin material or the like as described above, the dispersion stability of the carbon black graft polymer according to the present invention with respect to these resin materials is extremely good. In addition, a stable electric resistance value is exhibited even when added, and the mechanical strength and the like are also excellent. The compounding amount cannot be specified unconditionally because it depends on the molding form of the product, for example, whether it is a coating film or a lump, or a desired electric resistance value or electric characteristic, etc. It is possible, but if the amount exceeds 400 parts by weight with respect to 100 parts by weight of the resin-based material, sufficient mechanical strength may not be expected. Is not desirable. .

The resin-based material in which the carbon black graft polymer is blended is not particularly limited, and various materials can be used according to the specific application of the electric resistance adjusting material. , (Meth) acrylic resin, polyether resin, poly (meth) acrylonitrile resin, polyester resin, polyalkylene resin, polyamide resin, polyimide resin, polyurethane resin, fluorine resin, natural rubber, isoprene Rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber,
Chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber and the like are used. In this specification, the term “resin-based material” has a broad meaning including, for example, elastomers and rubbers. Further, the molding form may be an arbitrary form such as a coating film, a film, or a lump according to the application.

As specific applications of the electric resistance adjusting material according to the present invention, various conventionally known materials can be considered.
For example, various conductors, PTC elements of planar heating elements, antistatic sheets or coatings, conductive belts as transfer intermediates in copying machines, charging rollers of contact charging devices, etc., and core wires in high voltage power transmission lines For example, a conductive layer having an effect of reducing a dielectric breakdown gradient can be exemplified.

[0176]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following, “parts” as a blending ratio indicates “parts by weight”.

Reference Example 1 75 parts of AA-6 (manufactured by Toagosei Co., Ltd., polymethyl methacrylate macromer), styrene monomer (St) 15
Parts, isopropenyl oxazoline (IPO) 10 parts, and azoisobutyronitrile (AIB) as an initiator.
N) 3 parts were dissolved in 100 parts of propylene glycol monomethyl ether acetate (PGM-Ac) to obtain a polymerizable monomer composition (1).

A separable flask equipped with a stirrer, an N ₂ introduction tube, a thermometer and a dropping funnel was charged with 50 parts of PGM-Ac, and the temperature was raised to 80 ° C.

The above monomer composition (1) was charged into a dropping funnel, dropped at 80 ° C. over 3 hours, polymerized at the same temperature for 2 hours, heated to 120 ° C., and aged for 2 hours. And cooled to obtain a polymer solution (1) (nonvolatile content: 40%).

REFERENCE EXAMPLE 2 The same operation as in Reference Example 1 was carried out except that AA-714 (manufactured by Toagosei Co., Ltd., methyl methacrylate / hydroxyethyl methacrylate copolymer macromer) was used instead of AA-6. Was performed to obtain a polymer solution (2) (nonvolatile content: 40%).

Reference Example 3 To 250 parts of the polymer solution (2) obtained in Reference Example 2,
7. Methacrylyl isocyanate (molecular weight 111.1)
A solution obtained by diluting 9 parts into 13.35 parts of PGM-Ac was dropped at room temperature over 30 minutes to obtain a polymer solution (3) having a double bond (nonvolatile content: 40%).

Comparative Reference Example 1 In Reference Example 1, AA-714 was used instead of AA-6,
The same operation as in Reference Example 1 was carried out except that dimethylaminoethyl methacrylate was used instead of PO, to obtain a comparative polymer solution (1) (nonvolatile content: 40%).

Synthesis Example 1 Carbon black MA-8 (Mitsubishi Chemical Corporation) was placed in a separable flask equipped with a thermometer, a stirring blade, and a cooling tube.
30 parts, polymer solution (1) 2 obtained in Reference Example 1
2.5 parts and 97.5 parts of PGM-Ac were separately charged and dispersed.

Subsequently, 800 parts of beads made of zirconia were charged in the flask. The grafting reaction was performed at 100 ° C. for 2 hours while stirring at a rotation speed of 300 rpm.

Subsequently, the reaction contents and zirconia beads were separated to obtain a dispersion liquid (1) containing the carbon black graft polymer (1).

Synthetic Example 2 The same operation as in Synthetic Example 1 was carried out except for using 30 parts instead of 22.5 parts of polymer solution (1) and 90 parts instead of 97.5 parts of PGM-Ac in Synthetic Example 1. A dispersion (2) containing the carbon black graft polymer (2) was obtained.

Synthesis Example 3 The procedure of Synthesis Example 1 was repeated except that carbon black MA-100R (manufactured by Mitsubishi Chemical Corporation) was used instead of carbon black MA-8 in Synthesis Example 1 to obtain a carbon black graft. A dispersion (3) containing the polymer (3) was obtained.

Synthesis Example 4 In Synthesis Example 1, 22.5 parts of polymer solution (1), PG
Polymer solution (2) instead of 97.5 parts of M-Ac 37.
The same operation as in Synthesis Example 1 was carried out except that 5 parts and 82.5 parts of PGM-Ac were used, to obtain a dispersion liquid (4) containing the carbon black graft polymer (4).

Synthesis Example 5 A dispersion containing a carbon black graft polymer (5) was prepared in the same manner as in Synthesis Example 1 except that the polymer solution (3) was used instead of the polymer solution (1). (5) was obtained.

Comparative Synthetic Example 1 The same operation as in Synthetic Example 1 was performed except that Comparative Polymer Solution (1) was used instead of Polymer Solution (2) in Synthetic Example 4, and Comparative Carbon Black Dispersion (1) was prepared. ) Got.

Example 1 Arrow set 5271 (manufactured by Nippon Shokubai Co., Ltd., acrylic binder solution, non-volatile content of 50.times.) Was added to 100 parts of the carbon black graft polymer dispersion (1) obtained in Synthesis Example 1.
(0% toluene solution), 28 parts were uniformly mixed, coated on a glass plate degreased with acetone using a YA type applicator (a gap of 0.152 mm), air-dried, and after 3 hours, 1
After drying at 10 ° C. for 10 minutes, carbon black content 5
0% by weight of the coating film (1) was obtained.

The surface resistance value of the obtained coating film (1) was measured with a resistance measuring device (High resta IP / MCT-HT 26 manufactured by Mitsubishi Chemical Corporation).
0) and found to be 7.63 × 10 ⁸ Ω /
It was □.

Example 2 Arrow set 5271 (manufactured by Nippon Shokubai Co., Ltd., acrylic binder solution, non-volatile matter 5) was added to 100 parts by weight of the carbon black graft polymer dispersion (2) obtained in Synthesis Example 2.
Example 1 was prepared by uniformly mixing 24 parts of a 0.0% toluene solution and using a YA type applicator (a gap of 0.152 mm).
The same operation as in was repeated to obtain a coating film (2) having a carbon black content of 50% by weight.

The surface resistance of the obtained coating film (2) was measured in the same manner as in Example 1. The result was 1.88 × 10 ¹⁰ Ω /.
It was □.

Example 3 The procedure of Example 1 was repeated, except that the carbon black graft polymer dispersion (3) obtained in Synthesis Example 3 was used instead of the carbon black graft polymer dispersion (1). The operation was performed to obtain a coating film (3) having a carbon black content of 50% by weight.

The surface resistance of the obtained coating film (3) was measured in the same manner as in Example 1, and found to be 7.95 × 10 ⁵ Ω /.
It was □.

Comparative Example 1 Arrowset 5271 was added to 50 parts of carbon black MA-8 and 50 parts as a binder component, and the same dispersing treatment was carried out by the dispersing apparatus used in Synthesis Example 1 to obtain a mixture. The same operation as in Example 1 was repeated to prepare a black coating film for comparison (1), but the coating film lacked uniformity and became ragged.

Comparative Example 2 Comparative Example 1 was repeated except that carbon black MA-100R was used in place of carbon black MA-8.
By performing the same operation as in the above, a comparative black coating film (2) was prepared. However, as in Comparative Example 1, the coating film lacked uniformity and became a ragged coating film.

Example 4 Using the dispersion (4) containing the carbon black graft polymer (4) obtained in Synthesis Example 4, a 3 μm-thick coating film was formed on a glass substrate under the conditions shown in Table 1. And the change in resistance value was examined. The measurement was performed using a resistance measuring device (manufactured by Mitsubishi Chemical Corporation, High resta IP / MCT-HT 260). Table 1 shows the obtained results.

Comparative Example 3 A film having a thickness of 3 μm was formed on a glass substrate using the comparative carbon black dispersion liquid (1) obtained in Comparative Synthesis Example 1, and heated under the conditions shown in Table 1. The change in the resistance value was examined in the same manner as in Example 4. Table 1 shows the obtained results.

[0201]

[Table 1]

Example 5 A dispersion (5) of the carbon black graft polymer (5) obtained in Synthesis Example 5 was used, and a styrene-acrylic resin (Johncryl 68, manufactured by Johnson Polymer Co., Ltd.) was used as a binder. 46.8 parts of a black graft polymer and 49.2 parts of a binder were prepared, and a coating film having a thickness of 2 μm was formed on a glass substrate. After heating under the conditions shown in Table 2, a resistance measuring device (Mitsubishi Chemical Corporation) Manufactured by
High restaIP / MCT-HT 260). Table 2 shows the obtained results.

[0203]

[Table 2]

As shown in Table 2, no change was observed in the resistance value.

[0205]

As described above, the electric resistance adjusting material of the present invention contains a carbon black graft polymer obtained by reacting the polymer (I) having reactivity with carbon black with carbon black. Therefore, a desired electric resistance value can be stably exhibited.

[Brief description of the drawings]

FIG. 1 schematically shows a state near the surface of carbon black when carbon black is grafted onto a block type or graft type polymer in producing a carbon black graft polymer used for an electric resistance adjusting material of the present invention. FIG.

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

Claims (4)

[Claims] 1. An electric resistance adjusting material comprising a carbon black graft polymer obtained by reacting a polymer (I) having reactivity with carbon black with carbon black. 2. An electric resistance value of the resin material is 10 ² to 1
The electric resistance adjusting material according to claim 1, wherein the electric resistance adjusting material is adjusted to have a volume resistivity of 0 ¹⁵ Ω · cm. 3. A block type wherein the polymer (I) has a segment (A) having a reactive group capable of reacting with a functional group on the surface of carbon black, and a segment (B) different from the segment (A). The electrical resistance adjusting material according to claim 1 or 2, wherein the electrical resistance adjusting material is a graft-type polymer. 4. The segment (B) has a polysiloxane structure, a poly (meth) acrylic structure, a polyether structure, a poly (meth) acrylonitrile structure, a polyester structure, a polyalkylene structure, and a polyamide structure. At least one selected from the group consisting of a polyimide-based structure, a polyurethane-based structure and a fluorine-based resin structure
The electrical resistance adjusting material according to claim 3, which has a kind of structure.