JP3435734B2 - Carrier for electrostatic image development and two-component developer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carrier for developing an electrostatic charge image used in an electrophotographic copying machine and a two-component developer using the carrier.

[0002]

2. Description of the Related Art Conventionally, in a two-component developer comprising a positively chargeable toner and a negatively chargeable resin-coated carrier, a resin coating the carrier is a copolymer of vinylidene fluoride and tetrafluoroethylene or a fluoroalkyl. Fluororesin-based materials such as methacrylate copolymers, or
A silicone resin type has been proposed. (For example, JP-A-61-217068, JP-A-62-24268,
(See Japanese Patent Laid-Open No. 2-96770, etc.)

[0003]

However, each of these resin-coated carriers has advantages and disadvantages. For example, a fluororesin-based carrier has good chargeability, but has drawbacks in charge stability and adhesion to a core material. It is known that the silicone resin type has poor adhesion to the core material and has a drawback of being gradually peeled off. Therefore, the copied image is not stable and gradually stains on a white background (hereinafter referred to as fog). However, they all have drawbacks such as lack of durability.

[0004]

The present invention has been studied to solve the problems of the prior art as described above, and as a result, a carrier whose surface was coated with a resin composition containing a specific copolymer compound was obtained. The inventors have found that they exhibit excellent properties that improve the above-mentioned drawbacks, and have reached the present invention. That is, the object of the present invention is that the chargeability is good and stable, the adhesion between the coating resin and the core material is good, and the durability is excellent.
It is to provide a carrier with a good balance of each characteristic.

Further, by using the carrier having such excellent characteristics, it is possible to obtain a clear copy image with a high image density and very little fog. Further, the transfer efficiency of the toner is extremely high and the abrasion resistance is high. An object is to provide an excellent two-component developer. Therefore, the object of the present invention is to provide a copolymer containing a repeating unit represented by the following general formula [I] and a repeating unit derived from a high molecular weight monomer having one polymerizable vinyl group or vinylidene group at one end. This is easily achieved by a carrier for developing an electrostatic charge image, which is characterized in that at least a part of a core material is coated with a resin composition containing a polymer.

[0006]

[Chemical 7]

(R ¹ is a hydrogen atom or a methyl group, and Xa is an ionic residue having a cation group or an anion group.) Preferred repeating units derived from a high molecular weight monomer are those represented by the following general formula: Examples thereof include the repeating unit represented by [II] and / or the repeating unit represented by the following general formula [III].

[0008]

[Chemical 8]

(In the formula, R ² is a divalent aliphatic hydrocarbon group,
R ³ is a hydrogen atom or a methyl group, n is an integer of 2 to 200, and m is an integer of 1 to 8. )

[0010]

[Chemical 9]

(In the formula, R ⁴ is an alkyl group or an aralkyl group, R ⁵ is a divalent aliphatic hydrocarbon group, and R ⁶ is

[0012]

[Chemical 10]

[0013] or a -CO-, R ⁸ is an alkyl group, a hydrogen atom or a halogen atom, a a = 1 to 4 integer, b = 1 to 10 integer, in R ⁶ of

[0014]

[Chemical 11]

A urethane bond is formed adjacent to --O--, R ⁷ is a hydrogen atom or a methyl group, and p is 2 to 200.
Is. ) Also, preferred are those derived from the above-mentioned copolymer, and a high molecular weight monomer having a repeating unit represented by the following general formula [IV] and one polymerizable vinyl group or vinylidene group at one end. Examples thereof include a composition containing a copolymer containing a repeating unit.

[0016]

[Chemical 12]

(R ⁹ is a hydrogen atom or a methyl group, and Xb is a perfluoroalkyl group-containing group.) The present invention is described in detail below. Derived from a high molecular weight monomer (hereinafter, simply referred to as "macromonomer") having a repeating unit represented by the above general formula [I] and one polymerizable vinyl group or vinylidene group at one end, which is used in the present invention. Containing a repeating unit (hereinafter, referred to as “copolymer P”)
Is usually obtained by copolymerizing a vinyl monomer represented by the following general formula [V] and a macromonomer in the presence of a usual radical initiator.

[0018]

[Chemical 13]

The vinyl monomer represented by the general formula [V] will be described in detail below. In the general formula [V], R ¹ represents a hydrogen atom or a methyl group, Xa represents an ionic residue having a cation group or an anion group, and particularly an ionic residue having a quaternary ammonium salt or a metal salt. Is preferred. The vinyl monomer represented by the general formula [V] is a conventionally known radically polymerizable monomer. The vinyl monomer is not particularly limited as long as it is a vinyl monomer having an anionic or cationic ionic residue, or a vinyl monomer that can easily introduce an ionic group after polymerization. .

Examples of the vinyl monomer having a cationic group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylamino (meth) acrylate and dibutylamino. Examples include quaternized products of nitrogen-containing monomers such as ethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminovinyl sulfide, diethylaminoethyl vinyl ether, vinylbenzyl-N, N'-dimethylamine, vinylpyridine and vinylquinoline. To be

The above-mentioned quaternization reaction is carried out by a known method.
It can be carried out by acting a quaternizing agent on the tertiary amino group. Examples of the quaternizing agent include inorganic acids such as hydrogen chloride, hydrogen bromide and sulfuric acid, benzyl chloride, benzyl bromide,
Examples thereof include methyl chloride and methyl bromide.
The quaternization reaction may be carried out at any stage before or after the copolymerization.

Examples of the vinyl monomer having an anionic group include (meth) acrylic acid and α-chloro (meth).
Acrylic acid, vinyl sulfonic acid, sulfonated styrene,
2-acrylamido-2-methylpropanesulfonic acid,
Sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 3-sulfoethyl (meth) acrylate, 3-sulfopropyl (meth) acrylate,
Allyl sulfonic acid, 1-phenyl vinyl sulfonic acid, acid phosphooxyethyl (meth) acrylate, 3-
Chloro-2-amidophosphooxypropyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, and other vinyl monomers having a carboxyl group, a sulfonic acid group, a phosphoric acid group, or an alkali metal salt or ammonium thereof. Examples thereof include salts, organic amine salts such as dimethylamine, triethylamine and triethanolamine, and tetrabutylphosphonium salts.

When a metal salt or an organic salt is used as the vinyl monomer represented by the general formula [V], the corresponding monomer may be directly subjected to polymerization, but it may be neutralized after the polymerization. Good. As a monomer having an ionic residue,
Particularly preferred monomer is dimethylaminoethyl (meth)
These are quaternary ammonium salts of dialkylamino (meth) acrylates such as acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, and metal salts of (meth) acrylic acid.

The macromonomer means a polymer compound having a polymerizable vinyl group at one end of a polymer portion (also referred to as polymer chain portion). The polymer chain portion is a polymer of various monomers such as vinyl monomers and has a number average molecular weight in the range of 1,500 to 20,000, preferably 3,000 to 15, Those in the range of 000 are good. When the number average molecular weight of the polymer chain portion of the macromonomer is too small, the compatibility between the antistatic component having the polymer chain portion and the binder resin decreases, and a sufficient antistatic effect cannot be obtained. On the other hand, if it is too large, it is necessary to use a large amount of the vinyl monomer [V] in order to obtain the desired antistatic property and water repellency. As a result, the cost is increased, which is not preferable.

As the vinyl-based monomer constituting the polymer portion of the macromonomer, acrylic acid, methacrylic acid or alkyl esters thereof having 1 to 10 carbon atoms, styrene, α-methylstyrene, o -, M
-, Or p-vinyltoluene, a mixture thereof, a halogenated styrene, and a vinyl compound such as α- or β-vinylnaphthalene. Of these, alkyl esters such as acrylic acid or methacrylic acid, especially methyl methacrylate are preferable.

It is essential that the macromonomer has one polymerizable vinyl group attached to one end of its polymer portion. When it has no polymerizable vinyl group at all,
In the case where it cannot be copolymerized and has two or more polymerizable vinyl groups, it is not preferable because crosslinking occurs when the [V] is copolymerized. As the polymerizable vinyl group,
Any copolymer can be used as long as it can be copolymerized with [V] used in the present invention. Among them, acrylic group, methacrylic group, styryl group and the like are preferable because they have excellent copolymerizability.

When the polymer portion of the macromonomer is formed by polymerization of a vinyl monomer, it is produced by radical polymerization or anion polymerization. In the case of radical polymerization, persulfate, benzoyl peroxide, di-
Organic peroxides such as t-butyl peroxide, azo compounds such as azobisisobutyronitrile, and other commonly used radical initiators may be used, or a vinyl monomer may be polymerized by thermal polymerization. , Forming the polymer portion of the macromonomer. At that time, a chain transfer agent is used to adjust the number average molecular weight. At this time, by using a compound having a reactive functional group such as a carboxyl group or a hydroxyl group as the chain transfer agent, the polymerizable vinyl group can be quantitatively introduced at the terminal of the polymer portion. That is, the chain transfer agent is bonded to one end of the polymer part to terminate the polymerization, and as a result, a polymer part in which the chain transfer agent having a reactive functional group is bonded to the end of the polymer part is formed. It The macromonomer used in the present invention can be obtained by reacting this polymer portion with a compound having a polymerizable vinyl group.

Examples of the chain transfer agent having a reactive functional group include hydroxyalkyl mercaptans such as hydroxyethyl mercaptan and hydroxypropyl mercaptan, thioglycolic acid and mercaptopropionic acid. Examples of the compound having a polymerizable vinyl group include acrylic acid, methacrylic acid, chlorides thereof, glycidyl acrylate, and glycidyl methacrylate.

When the polymerized portion of the macromonomer is produced by anionic polymerization, an alkyl alkali metal compound represented by n-butyllithium or sec-butyllithium is used as a polymerization initiator. In this case, the number average molecular weight of the polymer portion can be adjusted by the amount of the polymerization initiator used.

In the case of anionic polymerization, a so-called living polymer in which an alkali metal such as lithium is bonded to the terminal of the polymer portion is obtained, so that a halogen compound containing a desired polymerizable vinyl group, for example, acrylic chloride is obtained. The macromonomer used in the present invention can be obtained by reacting with methacryl chloride, chloromethylstyrene, or the like. A preferred macromonomer is a polyester macromonomer whose polymer portion is composed of polyester. As a typical example, the following general formula [V
I], a macromonomer represented by [VII],
These can be used either alone or as a mixture.

[0031]

[Chemical 14]

The polyester macromonomer represented by the general formula [VI] will be described in detail. In the formula, R ² is a divalent aliphatic hydrocarbon group, preferably a branched or linear aliphatic hydrocarbon group having 3 to 8 carbon atoms. Specifically, it corresponds to the aliphatic hydrocarbon group of the polyester obtained by ring-opening polymerization of the lactone compound described below, and a preferred specific example is:

[0033]

[Chemical 15]

And the like. R ³ is a hydrogen atom or a methyl group, m is an integer of 1 to 8, and preferably an ethylene group, a propylene group, a butylene group or the like. N, which represents the degree of polymerization of the polyester structure, is usually 2 to 200, but is preferably 2 to 100 and more preferably 2 to 50 from the viewpoint of affinity when mixed with another resin.

Among the polyester macromonomers of the general formula [VI], the following are preferred.

[0036]

[Chemical 16]

The polyester macromonomer [VI] is usually produced as follows. That is,

[0038]

[Chemical 17]

(R ³ and m have the same meanings as defined in the above general formula [VI]) are used as an initiator.

[0040]

[Chemical 18]

(R ² is synonymous with the above general formula [VI]) is subjected to ring-opening polymerization to obtain a polyester macromonomer represented by the general formula [VI]. The above-mentioned initiator is preferably hydroxyethyl acrylate,
Examples thereof include hydroxymethacrylate, hydroxypropylmethacrylate and hydroxybutylmethacrylate. As the lactone compound, a lactone having 3 to 8 carbon atoms is preferable, and ε-caprolactone, β-methyl-δ-valerolactone, and β-ethyl-β-valerolactone are particularly preferable.

This reaction is usually carried out in the presence of a catalyst, and as the catalyst, known catalysts used for ring-opening polymerization of lactones such as mineral acids such as sulfuric acid and phosphoric acid, lithium, sodium, potassium and the like can be used. Alkali metals, alkyl metal compounds such as n-butyl lithium, metal alkoxides such as titanium tetrabutoxide, and the like can be used.

This reaction can be carried out without a solvent, but a solvent may be used depending on the case. As the solvent, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride, etc. can be used. The reaction conditions can be suitably carried out at a temperature between 0 ° C. and 200 ° C. with a reaction time of 10 minutes to 30 hours.

The polyester macromonomer represented by the general formula [VII] will be described in detail. R ⁴ in the formula [VII] is
It is preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group. R ⁵ is a divalent aliphatic hydrocarbon group,
Preferably, it is a branched or straight-chain aliphatic hydrocarbon group having 3 to 8 carbon atoms. Specifically, it corresponds to an aliphatic hydrocarbon group of a polyester obtained by ring-opening polymerization of a lactone compound described below, and preferably includes the groups described as preferable specific examples of R ² in the formula [VI].

R ⁶ is

[0046]

[Chemical 19]

It is also --CO--. Here, R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, a is an integer of 1 to 4 and represents the number of R ⁸ bonds to the benzene ring, and b is 1 to It is an integer of 10. R ⁷ is a hydrogen atom or a methyl group, and R ⁶ is-
When it has a CO-NH- group, it is preferably a methyl group.

P, which represents the degree of polymerization of the polyester structure, is usually 2 to 200, but preferably 2 to 100, more preferably 2 to 5 from the viewpoint of freshness when mixed with other resins.
It is 0. The above polyester macromonomer [VII]
Among these, the following are preferred.

[0049]

[Chemical 20]

[0050]

[Chemical 21]

The polyester macromonomer [VII] is usually produced by the following two steps. That is, in the first step, an alcohol compound represented by R ⁴ —OH (R ⁴ is as defined in the above general formula [VII]) is used as an initiator.

[0052]

[Chemical formula 22]

(R ⁵ is synonymous with the above general formula [VII]) is subjected to ring-opening polymerization to obtain the following polyester alcohol.

[0054]

[Chemical formula 23]

The initiator R ⁴ --OH is preferably methanol, n-butanol, n-hexanol,
Examples include n-octanol and 2-ethylhexanol. As the lactone compound, a lactone having 3 to 8 carbon atoms is preferable, and ε-caprolactone, β-methyl-δ-valerolactone, and β-ethyl-δ-valerolactone are particularly preferable.

The conditions of this reaction such as catalyst, solvent and temperature are as follows:
It can be performed in the same manner as the ring-opening polymerization for obtaining the polyester macromer [VI]. Here, the number p of repeating units can be controlled by the molar ratio of the initiator to the lactone compound, and is about 2 to about 200. Next, the second step consists of reacting the produced polyester alcohol with the compound of the general formula [VIII] or the compound of the general formula [IX] shown below.

[0057]

[Chemical formula 24]

However, R ⁷ , R ⁸ , a and b have the same meaning as in the above general formula [VII].

[0059]

[Chemical 25]

(R ⁷ has the same meaning as in the above general formula [VII], and R ¹¹ represents a halogen atom, an alkoxy group having 1 to 8 carbon atoms or an acyloxy group.) The above general formula [VII]
As a specific example of [I], for example,

[0061]

[Chemical formula 26]

And the like. Specific examples of the general formula [IX] include, for example,

[0063]

[Chemical 27]

And the like. The reaction between the polyester alcohol and the compound of the general formula [VIII] is a urethane bond formation reaction, and these may be reacted in an equimolar manner. Although the reaction proceeds even without a catalyst, a tin catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, or dibutyltin mercaptide may be used to accelerate the reaction rate.

The reaction between the polyester alcohol and the compound of the general formula [IX] is a condensation reaction or a transesterification reaction, and these may be reacted in an equimolar manner. When a condensation reaction is adopted, since a hydrogen halide is by-produced, a deoxidizing agent such as an amine may be used for the tertiary.
It may be carried out under an inert gas stream. When the transesterification reaction is adopted, known transesterification catalysts such as mineral acids such as hydrochloric acid and sulfuric acid, metal salts such as zinc, calcium and magnesium, metal alkoxides such as titanium tetrabutoxide may be used.

A catalyst may be used in these reactions. As the solvent, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride, etc. can be used. The reaction conditions can be suitably carried out at a temperature between 0 ° C. and 200 ° C. with a reaction time of 30 minutes to 50 hours. Copolymerization of the vinyl monomer represented by the general formula [V] and the macromonomer can be easily carried out by an ordinary radical polymerization method. As the radical polymerization initiator, an azo compound, a peroxide or the like is usually added in an amount of 0.1 to 1
0 wt% is added, reaction temperature is 0 to 200 ° C, reaction time is 1
It can be suitably polymerized in 24 hours. In addition, a chain transfer agent such as alkyl mercaptan can be used to adjust the degree of polymerization. As the polymerization method, any polymerization method generally used in radical polymerization, such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, may be adopted.

The weight ratio of the vinyl-based monomer [V] to the macromonomer is usually 10:90 or 90: 1.
It is in the range of 0, preferably 20:80 to 80:20. If the ratio of the vinyl-based monomer [V] is too small, the performance is hard to be expressed, and if the ratio of the macromonomer is too small, the affinity with other resins is deteriorated, which is not preferable.

In the copolymerization of the vinyl monomer [V] and the macromonomer, another radical-polymerizable vinyl monomer may be present and copolymerized. Examples of the radically polymerizable vinyl monomer include styrene, α-methylstyrene, methyl methacrylate, methyl acrylate,
Examples thereof include butyl methacrylate, butyl acrylate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl chloride and the like. In this case, the same ordinary radical polymerization method as described above can be easily performed.

In this case, the weight ratio of the vinyl monomer [V] to the macromer and the radical-polymerizable vinyl monomer other than 10 may be 10 to 90:90 to 10 to 0 to 80, but the performance is exhibited. And from the viewpoint of the affinity of other resins, 20-80: 80-
The range of 20 to 60 is more preferable. The obtained copolymer P uses a mixed solvent of methyl ethyl ketone / methanol (7/3), and has an intrinsic viscosity ηinh of 0.02 or more measured under the conditions of a concentration of 0.5 g / dl and a temperature of 25 ° C. Is preferred. If the intrinsic viscosity of the copolymer is too low, the advantage of having a high molecular weight is lost, and the copolymer is likely to bleed out from the resin substrate, resulting in poor performance.

The copolymer P is a copolymer containing a repeating unit represented by the general formula [IV] and a repeating unit derived from a macromonomer (hereinafter, referred to as "copolymer Q") as the case may be. Combined. The copolymer Q is usually obtained by copolymerizing a vinyl monomer represented by the following general formula [X] and a macromonomer in the presence of a usual radical initiator.

[0071]

[Chemical 28]

In the general formula [X], R ⁹ represents a hydrogen atom or a methyl group, and Xb preferably represents a perfluoroalkyl group-containing group having 4 to 20 carbon atoms. The vinyl monomer represented by the general formula [X] is a conventionally known radical-polymerizable perfluoroalkyl group-containing vinyl monomer.

Examples of the perfluoroalkyl group-containing vinyl monomer include the following polyfluoroalkyl group-containing (meth) acrylate derivatives.

[0074]

[Chemical 29]

Examples of perfluoroalkyl group-containing vinyl monomers include the following polyfluoroalkyl group-containing vinyl ether derivatives.

[0076]

[Chemical 30]

Furthermore, a perfluoroalkyl group-containing group
As the vinyl monomer, for example, the following polyfluoro
Rukyl group-substituted (α-methyl) styrene derivative, CHF =
CF ₂, CHCI = CFCl, CHF = CF₂, CF₂
= C (CF₃)₂, CF₃CH = CH₂, C₃F₇CH
= CH₂And other fluorine-containing vinyl monomers.

[0078]

[Chemical 31]

In the present invention, a particularly preferable perfluoroalkyl group-containing vinyl monomer is the following perfluoroalkyl (meth) acrylate. In the formula below, q
Represents an integer of 6 to 10.

[0080]

[Chemical 32]

As the macromonomer used for producing the copolymer Q, the same macromonomers as those used for the copolymer P can be used. A preferred macromonomer is a polyester-based macromonomer, particularly a general formula [VI] VII] is a polyester macromonomer.

Copolymerization of the vinyl monomer represented by the general formula [X] and the macromonomer can be easily carried out by an ordinary radical polymerization method. As the radical polymerization initiator, an azo compound, a peroxide or the like is usually added in an amount of 0.1 to 10% by weight, a reaction temperature of 0 to 200 ° C., and a reaction time of 1 to 2
It can be suitably polymerized in 4 hours. In addition, a chain transfer agent such as alkyl mercaptan can be used to adjust the degree of polymerization. As the polymerization method, any polymerization method generally used in radical polymerization, such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, may be adopted.

The weight ratio of the vinyl-based monomer [X] to the macromonomer is usually 10:90 or 90: 1.
It is in the range of 0, preferably 20:80 to 80:20. If the ratio of the vinyl-based monomer [X] is too small, the performance becomes difficult to develop, and if the ratio of the macromonomer is too small, the affinity with other resins is deteriorated, which is not preferable.

In the copolymerization of the vinyl monomer [X] and the macromonomer, another radical-polymerizable vinyl monomer may be present and copolymerized. Examples of the radically polymerizable vinyl monomer include styrene, α-methylstyrene, methyl methacrylate, methyl acrylate,
Examples thereof include butyl methacrylate, butyl acrylate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl chloride and the like. In this case, the same ordinary radical polymerization method as described above can be easily performed.

In this case, the weight ratio of the vinyl monomer [X] to the macromer and the radically polymerizable vinyl monomer other than 10 may be 10 to 90:90 to 10 to 0 to 80, but the performance is exhibited. And from the viewpoint of the affinity of other resins, 20-80: 80-
The range of 20 to 60 is more preferable. Copolymer Q is dissolved in a mixed solvent of methyl ethyl ketone / methanol (7/3) to a concentration of 0.5 g / dl, and the intrinsic viscosity ηinh measured at 25 ° C. is preferably 0.02 or more. ninh
If is too low, the advantage of having a higher molecular weight is lost, and bleeding out tends to occur.

The copolymer P used in the present invention is kneaded with various binder resins to reduce the electric resistance of the resin and exhibit excellent charging characteristics as a surface member.
When the copolymer P is applied to the support member, the copolymer P of the present invention is added to 100 parts by weight of the thermoplastic, urethane-curable, or ultraviolet-curable binder resin described below. When the resin composition mixed with 200 parts by weight is applied as a solution, a coating film in which both are uniformly compatible or dispersed is obtained, and a coating film having excellent strength and adhesiveness can be obtained.

When the copolymer Q is used in combination, the copolymer P
It is preferable to mix 0.1 to 20 parts by weight, and especially 0.5 to 10 parts by weight of the copolymer Q with 100 parts by weight.
When the copolymer P, the copolymer Q and the binder resin are used, the content of each component is 10 to 90% by weight of the copolymer P, 0.1 to 10% by weight of the copolymer Q and 5 to 9% of the binder resin.
0% by weight is preferred.

The above-mentioned thermoplastic resin is not particularly limited as long as it is soluble in a solvent, and may be appropriately selected depending on the type of resin base material to which the copolymer composition of the present invention is applied. Specific examples of the thermoplastic resin include polyvinyl chloride, polyester, polyamide, polyacrylic acid ester, polyurethane and the like. In the case of a copolymer composition that requires higher strength and chemical resistance as coating film performance, the use of a thermosetting resin as a binder resin is effective. That is, the copolymer composition of the present invention is mixed with polyols generally used in the urethane industry, and further,
After mixing with a curing agent containing an isocyanate compound, coating on a resin substrate, curing, and drying, a highly durable coating film with more excellent abrasion resistance can be formed. At this time, a solvent generally used in the urethane industry and additives such as a curing catalyst may be used.

Further, in the case of a copolymer composition which requires quick drying and high hardness as coating film performance, it is effective to use an ultraviolet curable resin as a binder resin. That is, a known ultraviolet-curable resin composition is blended with the copolymer composition of the present invention, applied to a resin substrate, and then cured with ultraviolet rays according to a conventional method to form a coating film having good surface properties in a short time. Can be formed. The ultraviolet curable resin is not particularly limited, and examples thereof include monofunctional monomers such as butyl acrylate, tetrahydrofurfuryl acrylate and vinylpyrrolidone, and polyfunctional oligomers such as polyurethane acrylate and polyester acrylate.

The coating material for the carrier core material may be used in the form of a composition obtained by blending the above copolymer compound with other resin. More specifically, for example,
Vinylidene fluoride, vinylidene fluoride-blend with fluororesin such as ethylene tetrafluoride copolymer, silicone resin, acrylic resin, polyester resin, polycarbonate resin, epoxy resin, phenoxy resin, polyamide resin, polyimide resin, urea resin, Blends with other resins such as alkyd resin, phenol resin, vinylidene chloride copolymer resin, vinyl chloride resin, polysulfone resin, polyether resin, polybutadiene resin, polystyrene resin, silica powder, charge control agent, surfactant, lubricant And the like. The amount of these blend materials used is preferably 50% or less of the copolymer. In order to prevent dehydrochlorination of the copolymer, stabilizers such as vinyl chloride and vinylidene chloride which are usually used for stabilization can be used. As such a stabilizer,
For example, a metal soap, an epoxy compound, a phosphorous acid ester, a polyol, etc. are illustrated.

The film formation on the carrier core material is carried out in substantially the same manner as in the usual method. For example, a mixture containing a copolymer compound used in the present invention is dissolved or dispersed in an organic solvent to prepare a coating solution having a solid content concentration of 0.1 to 30% by weight, more preferably 1 to 5% by weight, and a dipping method. The core material is coated and dried by a dry spray method, a fluid spray method using a flow coater, or the like. If necessary, heat treatment may be performed at a temperature up to 100 ° C. after forming the film.

Any organic solvent can be used as long as it can dissolve the copolymer compound. For example, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents: ethyl acetate, cellosolve acetate, acetic acid ester solvents such as n-butyl acetate: tetrahydrofuran, cyclic ethers such as dioxane Examples include aromatic hydrocarbons such as toluene and xylene: halogenated hydrocarbons such as tetrachloroethylene, trichloroethylene, and methylene chloride.

These solvents may be used alone or in admixture of two or more. Further, these solvents can be used as long as they have a boiling point of about 50 to 150 ° C., but from the viewpoint of dissolution treatment, drying treatment after coating, etc., 60
It is more preferably about 120 ° C.

As the core material of the carrier used in the present invention, all known core materials can be used and are not particularly limited. Specifically, ferrite, magnetite, and other metals exhibiting ferromagnetism such as iron, cobalt, and nickel; alloys or compounds containing these metals; not including ferromagnetic metals, but exhibiting ferromagnetism by heat treatment Examples of suitable alloys include, for example, so-called Whistler alloys such as Mn-Cu-Al and Mn-Cu-Sn, and metal oxides such as CrO ₂ . The particle size of such a carrier is usually about 20 to 1000 μm, more preferably about 30 to 500 μm.

The thickness of the coating layer of the carrier is
The thickness is preferably about 0.05 to 5 μm, and 0.3 to
More preferably, it is about 3 μm. If the layer is too thin, the durability is insufficient and the charging stability tends to be poor. If the thickness of the coating layer is too thick, there is substantially no problem in terms of performance, but it has reached the maximum value in terms of performance, and the copolymer is consumed in large amounts, which is not economical.

The carrier of the present invention is used as an electrostatic image developer in combination with a known toner, particularly a positively chargeable toner. Such a toner is obtained by dispersing a colorant in a binder resin. Examples of the binder resin include styrenes such as styrene, valachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, and meta. Α-methylene fatty acid monocarboxylic acid esters such as methyl acrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile; 2 -Vinyl pyridines such as vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ethers such as vinyl methyl ketone, vinyl ethyl ketone and methyl isopropenyl ketone. Nylketones; unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene, and their halides; homopolymers of monomers such as halogenated unsaturated hydrocarbons such as chloroprene, and copolymers of two or more of these. Examples include polymers, and mixtures of two or more of these homopolymers and copolymers. Alternatively, a non-vinyl resin such as a rosin-modified phenol formalin resin, an oil-modified epoxy resin, a polyester resin, a polyurethane resin, a polyimide resin, a cellulose resin, or a polyether resin, a mixture of these non-vinyl resins and the above vinyl-based resin, and the like can also be given. To be

Examples of colorants used in the toner include carbon black, nigrosine, aniline blue, chalco oil blue, chrome yellow, ultramarine blue, methylene blue, rose bengal and phthalocyanine blue.

The above-mentioned toner may be used, if desired, by further containing or mixing known additives such as a charge control agent, waxes, silica, zinc stearate and the like. The carrier of the present invention and such a toner are usually mixed in a ratio of about 0.3 to 20 parts by weight with respect to 100 parts by weight of the former and used for developing an electrostatic image such as a magnetic brush method or a cascade method. To be done.

[0099]

EFFECT OF THE INVENTION The carrier coating layer made of the specific resin composition used in the present invention has excellent wear resistance and good adhesion to the core material. Rapidly rises and gives the carrier high chargeability. Further, since the charging stability is excellent, a clear copy image with very little fog can be obtained.

[0100]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following, "part" means "part by weight".

Reference Example A Synthesis of Polyester Macromonomer 22.8 parts of ε-caprolactone was added to a reactor equipped with a stirring blade and a reflux condenser, and heated to 140 ° C. 2-
Hydroxyethyl methacrylate 26 parts, tin octylate 0.03 g, and hydroquinone monomethyl ether 0.
02 parts was added in 10 minutes, and the mixture was heated and reacted at 140 ° C. for 6 hours. This product had a hydroxyl value of 55.4 KOHmg / g and an acid value of 0.07 KOHmg / g. 1 H-NMR was measured, and it was confirmed that a polyester macromonomer having the following structure was obtained.

[0102]

[Chemical 33]

Reference Example B Synthesis of Polyester Macromonomer A flask equipped with a stirring blade, a dropping funnel and a gas inlet was sufficiently replaced with dry nitrogen, and then 13 parts of 2-hydroxyl methacrylate and 0.4 part of metallic sodium were charged. The metal sodium was dissolved by stirring. Next, this flask was immersed in an oil bath at 40 ° C., and 100 parts of β-methyl-δ-valerolactone was added dropwise from a dropping funnel while stirring. After 1 hour, stirring was stopped, the contents of the flask were taken out, and dissolved in 745 parts of chloroform. This solution was put into 500 parts of deionized water, washed, and the chloroform layer was branched. After repeating this washing once again, the solvent was distilled off from the chloroform solution under reduced pressure to obtain a colorless and transparent polyester macromonomer. This product has a hydroxyl value of 58.1 KOHmg / g and an acid value of 0.04K.
It was OH mg / g. IR spectrum and H- of the product
The NMR was measured to confirm that the following macromonomer was obtained.

[0104]

[Chemical 34]

Reference Example C Polyester alcohol synthesis A flask equipped with a stirring blade, a dropping funnel and a gas inlet was sufficiently replaced with dry nitrogen, and then 5.7 parts of 2-ethylhexanol and 0.1 part of metallic sodium were charged. The metal sodium was dissolved by stirring. Then place this flask at 40
Immerse in an oil bath at ℃, β-methyl-δ while stirring
50 parts of valerolactone was added dropwise from a dropping funnel. 1
After a period of time, stop stirring, remove the contents of the flask,
It was dissolved in 745 parts of purified chloroform. This solution was poured into 500 parts of deionized water and washed to separate the chloroform layer. After repeating this washing once again, the solvent was distilled off from the chloroform solution under reduced pressure to obtain a colorless and transparent polyester alcohol. This product has a hydroxyl value of 58.6 KOHmg / g and an acid value of 0.03 KOHm.
It was g / g.

Reference Example D Synthesis of Polyester Macromonomer 20.00 parts of polyester alcohol synthesized in (C) in a reactor equipped with a stirring blade and a reflux condenser, m-isopropenyl-α, α′-dimethylbenzyl isocyanate 4.
25 parts and 0.12 part of dibutyltin dioctoate (1% toluene solution) were charged, heated to 80 ° C., and reacted for 9 hours. The IR spectrum and H-NMR of the product were measured, and it was confirmed that a polyester macromonomer having the following structure was obtained.

[0107]

[Chemical 35]

Reference Example E Synthesis of Polyester Alcohol A polyester alcohol was obtained in the same manner as in Reference Example C, except that β-methyl-δ-valerolactone was changed to ε-caprolactone. The hydroxyl value of this product is 56.78K.
The OH mg / g and the acid value were 0.50 KOH mg / g. Reference Example F Using the polyester alcohol synthesized in (E) of polyester macromonomer,
Reference example D except that the charge amount of -isopropenyl-α-α'-dimethylbenzyl isocyanate was 4.11 parts.
A macromonomer based on caprolactone was synthesized in exactly the same manner as in.

[0109]

[Chemical 36]

Reference Example G Production of high molecular weight monomer 500 g of methyl ethyl ketone (hereinafter referred to as MEK), 1,500 of methyl methacrylate (hereinafter referred to as MMA)
g and 40 g of thioglycolic acid were placed in a 3 liter flask equipped with a stirrer and heated to 50 ° C. under a nitrogen stream. Next, 10 g of azobisisobutyronitrile (hereinafter referred to as AIBN) was added as a polymerization initiator to start the polymerization reaction. Seven and a half hours after the initiation of the polymerization reaction, a small amount of hydroquinone was added to the polymerization system to stop the polymerization reaction. After further adding 500 g of MEK to the reaction solution to dilute it, the mixture was poured into a large excess of hexane to obtain a MMA polymer having thioglycolic acid bonded to the terminal. The polymer was reprecipitated twice with MEK / hexane to purify and then dried. The yield was 420 g. The number average molecular weight of the obtained polymer was 9,200.

Xylene 2 was added to a 500 ml flask.
00 g, 200 g of the above polymer, 6.2 g of glycidyl methacrylate and 2 mg of p-methoxyphenol were charged and the above polymer was dissolved while heating. When the inner temperature of the flask reached 100 ° C., 0.95 g of N, N-dimethyllaurylamine was added, and the temperature was further raised to 130 ° C. and reacted for 5 hours.

After the completion of the reaction, a part of the reaction solution was collected and acid
By base titration, it was confirmed that the -COOH group of thioglycolic acid bonded to the terminal of the above polymer disappeared. Subsequently, MEK was added to dilute the mixture 3-fold, and the mixture was poured into a large excess of hexane to precipitate the MMA-based high molecular weight monomer.
The obtained high molecular weight monomer was purified by reprecipitation twice with a MEK / hexane system, and the yield was 200 g.

Reference Example H Synthesis of Copolymer P 10 g of MMA type high molecular weight monomer synthesized in Reference Example G, 10 g of methacryloyloxyethyltrimethylammonium chloride in a flask equipped with a stirring blade, a reflux condenser and a gas inlet. , Azobisisobutyronitrile (0.2 g) and methyl ethyl ketone (40 g) were charged, and the mixture was stirred under a nitrogen stream for 7
Polymerization was carried out at 0 ° C. for 8 hours. After the polymerization, the reaction solution was put into hexane to precipitate a product, which was dried. The yield was 84%. The intrinsic viscosity ηinh of the obtained copolymer was about 0.
It was 15 dl / g.

Reference Example I Synthesis of Copolymer Q In a flask equipped with a stirring blade, a reflux condenser and a gas inlet,
Charge 10 g of the MMA-based high molecular weight monomer synthesized in Reference Example G, 18 g of perfluorohexyl acrylate, 4.4 g of n-butyl acrylate, 0.3 g of t-butyl peroxyisopropyl carbonate and 32.3 g of butyl acetate, and use a nitrogen stream. Polymerization was carried out at 105 ° C for 7 hours. After the polymerization, the solvent was removed by an evaporator and further dried under reduced pressure at 65 ° C. The intrinsic viscosity of the obtained copolymer was ηinh of 0.13 dl / g.

Example 1 Polyester macromonomer 1 synthesized in Reference Example (A) in a flask equipped with a stirring blade, a reflux condenser and a gas inlet.
0.0 parts, methacryloyloxyethyltrimethylammonium chloride 10.0 parts, azobisisobutyronitrile 0.2 parts, n-dodecyl mercaptan 0.4 parts and isopropyl alcohol 40 parts were charged, and at 70 ° C. under a nitrogen stream. Polymerization was carried out for 7 hours at 95 ° C. for 2 hours.
After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure. Ηinh of the copolymer compound obtained here is 0.
It was 21 dl / g.

100 parts of the copolymer compound obtained by the above method was dissolved in an equal amount of a mixed solvent of tetrahydrofuran and methyl ethyl ketone to prepare a coating solution having a solid content of 4%.
Then, by a fluidized spray method, a spherical ferrite having an average particle diameter of 100 μm was used as a carrier core material and a dry film thickness was 2 μm.
It was applied to give a resin-coated carrier. On the other hand, 100 parts of a copolymer resin of styrene and n-butyl acrylate, 5 parts of carbon black, 2 parts of low molecular weight polypropylene, and 2 parts of a quaternary ammonium salt type charge control agent (trade name P-51 manufactured by Orient Chemical Co., Ltd.). To 100 parts of a toner having an average particle size of 10 μm made of a kneaded and pulverized product, 0.1 part of hydrophobic silica fine powder (manufactured by Degussa Co., trade name R-972) was added and mixed with a Henschel mixer to obtain a silica externally added toner. Obtained. A developer was prepared by mixing 4 parts of the silica externally added toner with 100 parts of the resin-coated carrier. Subsequently, using a commercially available copying machine equipped with an organic photoconductor, a real-life copying durability test was conducted, and image density was measured, and fogging was evaluated and toner transfer rate was evaluated. An image with less fog was obtained. The toner transfer efficiency was also good.

Example 2 In the flask used in Example 1, 10.0 parts of the polyester macromonomer synthesized in Reference Example (B), methacryloyloxyethyltrimethylammonium chloride 10.
0 parts, 0.2 parts of azobisisobutyronitrile and 25 parts of isopropyl alcohol were charged, and 70
Polymerization was carried out at 7 ° C for 7 hours and then at 95 ° C for 2 hours. After polymerization,
Isopropyl alcohol was distilled off and the residue was dried under reduced pressure. ηi
nh was 0.17 dl / g.

A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained by the above method was used, and then evaluated in the same manner as in Example 1. As a result, a clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 3 40.0 parts of the polyester macromonomer synthesized in Reference Example (A) and 1 part of methacrylic acid were placed in the flask used in Example 1.
7.0 parts, 0.6 parts of azobisisobutyronitrile and 85 parts of isopropyl alcohol were charged, and under a nitrogen stream,
Polymerization was carried out at 70 ° C. for 8 hours. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure. ηinh is 0.18d
It was 1 / g.

The dry film thickness was 2 μm in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained by the above method was used.
When the resin-coated carrier of 1 was manufactured and subsequently evaluated in the same manner as in Example 1, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 4 30 parts of the copolymer compound used in Example 1 and vinylidene chloride copolymer resin (vinylidene chloride 55 mol%, acrylonitrile 45 mol%; molecular weight distribution 3000 to 1200)
The resin-coated carrier having a dry film thickness of 3 μm was produced by the same treatment as in Example 1 except that a mixture of 70 parts by weight, and a weight average molecular weight of 320,000) was used, and subsequently evaluated in the same manner as in Example 1. However, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 5 Copolymer comprising 50 parts of the copolymer compound used in Example 2, 60 mol% of vinylidene chloride, 25 mol% of methacrylonitrile and 15 mol% of n-butyl acrylate (molecular weight distribution of 2000- A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that a mixture of 200,000 and 50 parts by weight average molecular weight of 20,000) was used.
When evaluated in the same manner as, it was stable and clear all the time.
An image with less fog was obtained. The toner transfer efficiency was also good.

Example 6 A copolymer of 40 parts of the copolymer compound used in Example 3, 46 mol% of vinylidene chloride, 28 mol% of acrylonitrile and 26 mol% of methyl methacrylate (molecular weight distribution 2
A mixture of 60 parts by weight of 30 to 30 million and a weight average molecular weight of 380,000) was dissolved in an equivalent solvent mixture of tetrahydrofuran and toluene and treated in the same manner as in Example 1 to obtain a resin-coated carrier having a dry film thickness of 0.3 μm. When manufactured and subsequently evaluated in the same manner as in Example 1, a stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 7 A mixture of 30 parts of the copolymer compound used in Example 4 and 70 parts of vinylidene chloride copolymer resin was dissolved in a mixed solvent of tetrahydrofuran / methyl ethyl ketone = 1/1 (Vol.). Then, a resin-coated carrier having a dry film thickness of 2 μm was produced by treating in the same manner as in Example 1, and subsequently evaluated in the same manner as in Example 1. As a result, a stable clear image with less fog was obtained from the beginning. Was given. The toner transfer efficiency was also good.

Example 8 Polyester macromonomer 1 synthesized in Reference Example (D) in a flask equipped with a stirring blade, a reflux condenser and a gas inlet.
0.0 parts, methacryloyloxyethyltrimethylammonium chloride 10.0 parts, azobisisobutyronitrile 0.2 parts, n-dodecyl mercaptan 0.4 parts and isopropyl alcohol 40 parts were charged, and at 70 ° C. under a nitrogen stream. Polymerization was carried out for 7 hours at 95 ° C. for 2 hours.
After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure. Ηinh of the copolymer compound obtained here is 0.
It was 15 dl / g. A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained by the above method was used, and subsequently evaluated in the same manner as in Example 1. A stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 9 10.0 parts of the polyester macromonomer synthesized in Reference Example (F), methacryloyloxyethyltrimethylammonium chloride in the flask used in Example 8, 10.
0 parts, 0.2 parts of azobisisobutyronitrile and 25 parts of isopropyl alcohol were charged, and 70
Polymerization was carried out at 7 ° C for 7 hours and then at 95 ° C for 2 hours. After polymerization,
Isopropyl alcohol was distilled off, and the residue was dried under reduced pressure to obtain a copolymer compound. ηinh was 0.15 dl / g. A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained above was used. A clear image with less fog was obtained. The toner transfer efficiency was also good.

Example 10 40.0 parts of the polyester macromonomer synthesized in Reference Example (D) and 1 part of methacrylic acid were placed in the flask used in Example 8.
7.0 parts, 0.6 parts of azobisisobutyronitrile and 85 parts of isopropyl alcohol were charged, and under a nitrogen stream,
Polymerization was carried out at 70 ° C. for 8 hours. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure to obtain a copolymer compound. η
inh was 0.11 dl / g. A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained above was used, and subsequently evaluated in the same manner as in Example 1, and A stable, clear image with less fog was obtained. The toner transfer efficiency was also good.

Example 11 30 parts of the copolymer compound used in Example 8 and a vinylidene chloride copolymer resin (vinylidene chloride 55 mol%, acrylonitrile 45 mol%; molecular weight distribution 3000 to 1200)
The resin-coated carrier having a dry film thickness of 3 μm was produced by the same treatment as in Example 1 except that a mixture of 70 parts by weight, and a weight average molecular weight of 320,000) was used, and subsequently evaluated in the same manner as in Example 1. However, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 12 Copolymer comprising 50 parts of the copolymer compound used in Example 9, 60 mol% of vinylidene chloride, 25 mol% of methacrylonitrile and 15 mol% of n-butyl acrylate (molecular weight distribution of 2000 to A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that a mixture of 200,000 and 50 parts by weight average molecular weight of 20,000) was used.
When evaluated in the same manner as, it was stable and clear all the time.
An image with less fog was obtained. The toner transfer efficiency was also good.

Example 13 A copolymer comprising 40 parts of the copolymer compound used in Example 10, 46 mol% of vinylidene chloride, 28 mol% of acrylonitrile and 26 mol% of methyl methacrylate (molecular weight distribution: 20 to 30 million, weight: A mixture of 60 parts of an average molecular weight of 380,000 was dissolved in an equal amount of a mixed solvent of tetrahydrofuran and toluene and treated in the same manner as in Example 1 to produce a resin-coated carrier having a dry film thickness of 0.3 μm. When evaluated in the same manner as in Example 1, a stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 14

[Table 1] Macromonomer synthesized in Reference Example (H) 40.0 g Methacrylic acid 17.0 g Azobisisobutyronitrile 0.6 g and isopyrupyl alcohol 85 g were charged, and under a nitrogen stream at 70 ° C for 8 hours. Polymerized. After the polymerization, isopropylate alcohol was distilled off and the residue was dried under reduced pressure. ηinh is 0.1
It was 1 dl / g.

20 g of this product was dissolved in 200 g of a 9/1 mixed solvent of methyl ethyl ketone / methanol, 41.6 g of a 5% methanol solution of KOH was added, and the mixture was stirred at room temperature for 1 hour. After the reaction, the solvent was distilled off under reduced pressure to obtain 22 g of a product. In the same manner as in Example 1 except that 100 parts of the copolymer compound obtained by the above method was used,
When a resin-coated carrier having a dry film thickness of 2 μm was produced and subsequently evaluated in the same manner as in Example 1, it was stable throughout.
A clear image with less fog was obtained. The toner transfer efficiency was also good.

Example 15

[Table 2] A flask equipped with a stirring blade, a reflux condenser, and a gas inlet was charged with 10 g of methyl methacrylate, 10 g of methacryloyloxyethyltrimethylammonium chloride, 0.9 g of azobisisobutyronitrile, and 13 g of toluene and n- as a solvent. After adding 7 g of hexane to make a uniform solution, 80
Polymerization was performed at 8 ° C for 8 hours. After the polymerization, the reaction solution was poured into methanol to precipitate the product, which was thoroughly washed with methanol,
Dried. The yield was almost 100%.

A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that 100 parts of the copolymer compound obtained by the above method was used, and then evaluated in the same manner as in Example 1. As a result, a clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 16 30 parts of the copolymer compound used in Example 14 and a vinylidene chloride copolymer resin (55 mol% vinylidene chloride, 45 mol% acrylonitrile; molecular weight distribution 3000 to 1200)
The resin-coated carrier having a dry film thickness of 3 μm was produced by the same treatment as in Example 1 except that a mixture of 70 parts by weight, and a weight average molecular weight of 320,000) was used, and subsequently evaluated in the same manner as in Example 1. However, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 17 Copolymer comprising 50 parts of the copolymer compound used in Example 15, 60 mol% of vinylidene chloride, 25 mol% of methacrylonitrile and 15 mol% of n-butyl acrylate (molecular weight distribution of 2000- A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 1 except that a mixture of 200,000 and 50 parts by weight average molecular weight of 20,000) was used, and subsequently evaluated in the same manner as in Example 1. As a result, a clear and stable image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 18 Copolymer comprising 40 parts of the copolymer compound used in Example 14, 46 mol% of vinylidene chloride, 28 mol% of acrylonitrile and 26 mol% of methyl methacrylate (molecular weight distribution: 20 to 30 million, weight: A mixture of 60 parts of an average molecular weight of 380,000 was dissolved in an equal amount of a mixed solvent of tetrahydrofuran and toluene and treated in the same manner as in Example 1 to produce a resin-coated carrier having a dry film thickness of 0.3 μm. When evaluated in the same manner as in Example 1, a stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 19 Using a mixture of 30 parts of the copolymer compound used in Example 15 and 70 parts of vinylidene chloride copolymer resin, tetrahydrofuran / methyl ethyl ketone = 1/1 (Vol.)
Was dissolved in a mixed solvent of Example 1 and treated in the same manner as in Example 1 to produce a resin-coated carrier having a dry film thickness of 2 μm. Then, evaluation was performed in the same manner as in Example 1, and a stable, clear, fog was observed throughout. An image with less image quality was obtained. The toner transfer efficiency was also good.

Example 20

[Table 3] Polyester macromonomer synthesized in Reference Example (A) in a flask equipped with a stirring blade, a reflux condenser and a gas inlet 10.0 parts methacryloyloxyethyltrimethylammonium chloride 10.0 parts azobisisobutyronitrile 0.2 parts n-dodecyl mercaptan 0.4 parts and isopropyl alcohol 40 parts were charged, and it superposed | polymerized at 70 degreeC for 8 hours under nitrogen stream. After the polymerization, the reaction solution was put into hexane to precipitate a product, which was dried. Yield 8
It was 3%. Η of the copolymer (P-1) obtained here
inh was 0.15 dl / g.

Next,

[Table 4] Polyester macromonomer synthesized in Reference Example (A) 10.02 parts Perfluorohexyl acrylate 17.94 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-1) obtained here was 0.13 dl / g.

90 parts of the copolymer (P-1) obtained above and 10 parts of the copolymer (Q-1) were dissolved in a mixed solvent of tetrahydrofuran and methyl ethyl ketone in an equal amount to obtain a coating having a solid content of 4%. A liquid was prepared. Then, a spherical ferrite having an average particle diameter of 100 μm was applied as a carrier core material by a fluidized spray method so that the dry film thickness was 2 μm, to obtain a resin-coated carrier.

On the other hand, 100 parts of copolymer resin of styrene and n-butyl acrylate, 5 parts of carbon black, 2 parts of low molecular weight polypropylene, quaternary ammonium salt type charge control agent (Orient Chemical Co., Ltd., trade name P-51). Hydrophobic silica fine powder (manufactured by Degussa Co., trade name R-97) per 100 parts of a toner having an average particle diameter of 10 μm, which is composed of 2 parts of kneaded and pulverized product
2) 0.1 part was added and mixed with a Henschel mixer to obtain a silica externally added toner. A developer was prepared by mixing 4 parts of the silica externally added toner with 100 parts of the resin-coated carrier. Subsequently, using a commercially available copying machine equipped with an organic photoconductor, a real-life copying durability test was conducted, and image density was measured, and fogging was evaluated and toner transfer rate was evaluated. An image with less fog was obtained. The toner transfer efficiency was also good.

Example 21

[Table 5] Polyester macromonomer synthesized in Reference Example (B) in the flask used in Example 20 10.0 parts Methacryloyloxyethyl trimethyl ammonium chloride 10.0 parts Azobisisobutyronitrile 0.2 parts and isopropyl alcohol 25 parts were charged and the polymerization was carried out at 70 ° C. for 7 hours and at 95 ° C. for 2 hours under a nitrogen stream. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure to obtain a copolymer (P-2). ηinh is 0.17
It was dl / g.

Next,

[Table 6] Polyester macromonomer synthesized in Reference Example (B) 10.02 parts Perfluorohexyl acrylate 17.94 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-2) obtained here was 0.13 dl / g.

Example 20 except that 85 parts of the copolymer (P-2) obtained above and 15 parts of the copolymer (Q-2) were used.
A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in (1) and subsequently evaluated in the same manner as in Example 20. As a result, a stable and clear image with less fog was obtained throughout. The toner transfer efficiency was also good.

Example 22

[Table 7] The flask used in Example 20 was charged with the polyester macromonomer synthesized in Reference Example (A) 40.0 parts methacrylic acid 17.0 parts azobisisobutyronitrile 0.6 parts and isopropyl alcohol 85 parts. Polymerization was carried out at 70 ° C. for 8 hours under a nitrogen stream. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure to obtain a copolymer (P-3). ηinh was 0.18 dl / g.

Next,

[Table 8] Polyester macromonomer synthesized in Reference Example (A) 10.02 parts Perfluorohexyl acrylate 17.94 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-1) obtained here was 0.13 dl / g.

Example 2 except that 95 parts of the copolymer (P-3) obtained above and 5 parts of the copolymer (Q-1) were used.
A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 0, and subsequently evaluated in the same manner as in Example 20. As a result, a stable, clear image with less fog was obtained throughout. The toner transfer efficiency was also good.

Example 23 28 parts of the copolymer (P-1) and 2 parts of the copolymer (Q-1) used in Example 20 were mixed with vinylidene chloride copolymer resin (vinylidene chloride 55 mol%, acrylonitrile). 45 mol%; molecular weight distribution 3000 to 12,000,000, weight average molecular weight 320,000) A resin-coated carrier having a dry film thickness of 3 μm was produced in the same manner as in Example 20, except that 70% of the mixture was used. When evaluated in the same manner as in Example 20, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 24 45 parts of the copolymer (P-2) used in Example 21 and 5 parts of the copolymer (Q-2) were mixed with 60 mol% of vinylidene chloride, 25 mol% of methacrylonitrile and acryl. N-Butyl acid 1
Copolymer consisting of 5 mol% (molecular weight distribution 2000-20
The resin-coated carrier having a dry film thickness of 2 μm was produced by the same treatment as in Example 20, except that the resin-coated carrier was used in the same manner as in Example 20 except that the resin-coated carrier was used in the same manner as in Example 20. As a result, a clear and stable image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 25 35 parts of the copolymer (P-3) used in Example 22 and 5 parts of the copolymer (Q-1) were mixed with 46 mol% of vinylidene chloride, 28 mol% of acrylonitrile and methyl methacrylate. 26 mol% copolymer (molecular weight distribution 2000-3000
, A weight average molecular weight of 380,000) and a mixture of 60 parts of
It was dissolved in an equal amount of a mixed solvent of tetrahydrofuran and toluene and treated in the same manner as in Example 20 to produce a resin-coated carrier having a dry film thickness of 0.3 μm, and subsequently evaluated in the same manner as in Example 20, A stable and clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 26

[Table 9] Polyester macromonomer synthesized in Reference Example (D) in a flask equipped with a stirring blade, a reflux condenser and a gas inlet 10.0 parts methacryloyloxyethyltrimethylammonium chloride 10.0 parts azobisisobutyronitrile 0.2 parts n-dodecyl mercaptan 0.4 parts and isopropyl alcohol 40 parts were charged, and the mixture was polymerized under a nitrogen stream at 70 ° C for 7 hours and further at 95 ° C for 2 hours. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure. Ηinh of the copolymer (P-4) obtained here
Was 0.15 dl / g.

Next,

[Table 10] Polyester macromonomer synthesized in Reference Example (D) 10.02 parts Perfluorohexyl acrylate 17.94 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-3) obtained here was 0.13 dl / g.

A resin coating having a dry film thickness of 2 μm was prepared in the same manner as in Example 20 except that 85 parts of the copolymer (P-4) obtained above and 15 parts of the copolymer (Q-3) were used. When the carrier was manufactured and subsequently evaluated in the same manner as in Example 20, a stable and clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 27

Table 11: Polyester macromonomer synthesized in Reference Example (F) in the flask used in Example 20 10.0 parts Methacryloyloxyethyl trimethyl ammonium chloride 10.0 parts Azobisisobutyronitrile 0.2 parts and isopropyl alcohol 25 parts were charged and the polymerization was carried out at 70 ° C. for 7 hours and at 95 ° C. for 2 hours under a nitrogen stream. After the polymerization, isopropyl alcohol was distilled off and the residue was dried under reduced pressure to obtain a copolymer (P-5). ηinh is 0.1
It was 5 dl / g.

Next,

[Table 12] Polyester macromonomer synthesized in Reference Example (F) 10.02 parts Perfluorohexyl acrylate 17.94 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-4) obtained here was 0.13 dl / g.

Example 2 was repeated except that 94 parts of the copolymer (P-5) obtained above and 6 parts of the copolymer (Q-4) were used.
A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 0 and subsequently evaluated in the same manner as in Example 20. As a result, a stable and clear image with less fog was obtained from the beginning. The toner transfer efficiency was also good.

Example 28

[Table 13] The flask used in Example 20 was charged with the polyester macromonomer synthesized in Reference Example (D) 40.0 parts, methacrylic acid 17.0 parts, azobisisobutyronitrile 0.6 parts and isopropyl alcohol 85 parts. Polymerization was carried out at 70 ° C. for 8 hours under a nitrogen stream. After polymerization, isopropyl alcohol was distilled off, and the residue was dried under reduced pressure to obtain a copolymer (P-6).
Got ηinh was 0.11 dl / g.

Next,

Table 14 Polyester macromonomer synthesized in Reference Example (A) 10.02 parts Perfluorooctyl acrylate 19.84 parts n-Butyl acrylate 4.41 parts t-Butyl peroxyisopropyl carbonate 0.30 parts and butyl acetate 32 .3 parts were charged, and under nitrogen flow, 1
Polymerization was carried out at 05 ° C for 7 hours. After the polymerization, the solvent was evaporated and further dried under reduced pressure at 65 ° C. Ηinh of the copolymer (Q-5) obtained here was 0.13 dl / g.

A resin coating having a dry film thickness of 2 μm was obtained in the same manner as in Example 20 except that 90 parts of the copolymer (P-6) obtained above and 10 parts of the copolymer (Q-5) were used. When the carrier was manufactured and subsequently evaluated in the same manner as in Example 20, a stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 29 25 parts of the copolymer (P-4) used in Example 26 and 5 parts of the copolymer (Q-3) were mixed with a vinylidene chloride copolymer resin (vinylidene chloride 55 mol%, acrylonitrile). 45 mol%; molecular weight distribution 3,000 to 12,000,000, weight average molecular weight 320,000) The same procedure as in Example 20 except that 70 parts of a mixture was used to produce a resin-coated carrier having a dry film thickness of 3 μm, which was subsequently carried out. The evaluation was carried out in the same manner as in Example 20. As a result, a stable, clear image with less fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 30 46 parts of the copolymer (P-5) used in Example 27 and 4 parts of the copolymer (Q-4) were mixed with 60 mol% of vinylidene chloride, 25 mol% of methacrylonitrile and acryl. N-Butyl acid 1
Copolymer consisting of 5 mol% (molecular weight distribution 2000-20
And a weight average molecular weight of 20,000) was used in the same manner as in Example 20, except that a resin-coated carrier having a dry film thickness of 2 μm was produced, and then evaluated in the same manner as in Example 20. As a result, a stable and clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Example 31 36 parts of the copolymer (P-6) used in Example 28 and 4 parts of the copolymer (Q-5) were mixed with 46 mol% of vinylidene chloride, 28 mol% of acrylonitrile and methyl methacrylate. 26 mol% copolymer (molecular weight distribution 2000-3000
, A weight average molecular weight of 380,000) and a mixture of 60 parts of
A resin-coated carrier having a dry film thickness of 0.3 μm was prepared by dissolving in a mixed solvent of tetrahydrofuran and toluene in the same manner as in Example 20, and subsequently evaluated in the same manner as in Example 20. A stable and clear image with less fog was obtained. The toner transfer efficiency was also good.

Example 32

[Table 15] Methyl methacrylate 10 g Perfluorohexyl acrylate 18 g n-Butyl acrylate 4.4 g t-Butyl peroxyisopropyl carbonate 0.3 g and butyl acetate 32.3 g in a flask equipped with a stirring blade, a reflux condenser and a gas inlet. , And under a nitrogen stream for 10
Polymerization was carried out at 5 ° C for 7 hours. After the polymerization, the solvent was removed by an evaporator and further dried under reduced pressure at 65 ° C. to obtain a copolymer.

A resin-coated carrier having a dry film thickness of 2 μm was produced in the same manner as in Example 20 except that 100 parts of the copolymer obtained above was used, and subsequently evaluated in the same manner as in Example 20. In particular, a clear image with little fog was obtained from beginning to end. The toner transfer efficiency was also good.

Comparative Example 1 A developer was prepared in the same manner as in Example 1 except that a spherical ferrite not coated with a resin was used as a carrier, and a silica externally added toner was used. The image density was decreased as was repeated. In addition, the image was very dirty and dirty from the beginning. Further, the toner transfer efficiency was poor, and a large amount of untransferred toner was repaired.

Comparative Example 2 Commercially available carrier coated with silicone resin (core material is ferrite)
Was evaluated in the same manner as in Comparative Example 1 except that
The image density was almost good, but the image was slightly soiled with some fog. In addition, the amount of untransferred toner collected was slightly large, and the toner transfer efficiency was slightly poor.

─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Hiroaki Yamaoka 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Co., Ltd. (56) Reference JP 4-188159 (JP, A) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/113

Claims (5)

(57) [Claims] 1. A repeating unit represented by the following general formula [I], and a polymerization degree of 2 to by ring-opening polymerization of lactone compound
Having 200 molecular chains, one polymerizable vinyl group at one end
Isolated by the amount the resin composition containing a copolymer comprising repeating units derived from body, electrostatic image developing carrier, characterized in that formed by coating at least a portion of the core that have a. [Chemical 1] (R ¹ is a hydrogen atom or a methyl group, and Xa is an ionic residue having a cation group or an anion group.) 2. The repeating unit derived from the monomer according to claim 1 is a repeating unit represented by the following general formula [II] and / or a repeating unit represented by the following general formula [III]: The carrier for developing an electrostatic charge image according to claim 1, which is characterized in that. [Chemical 2] (In the formula, R ² is a divalent aliphatic hydrocarbon group, R ³ is a hydrogen atom or a methyl group, n is an integer of 2 to 200, and m is 1 to
It is an integer of 8. ) [Chemical 3] (In the formula, R ⁴ is an alkyl group or an aralkyl group, R ⁵ is a divalent aliphatic hydrocarbon group, and R ⁶ is Or —CO—, R ⁸ represents an alkyl group, a hydrogen atom or a halogen atom, a = 1 to an integer of 4, b = 1
Is an integer from 10 to 10 in R ⁶ A urethane bond is formed adjacent to —O—, R ⁷ is a hydrogen atom or a methyl group, and p is 2 to 200. ) 3. The copolymer according to claim 1, a repeating unit represented by the following general formula [IV] , and a lactone compound:
Characterized in that the have a molecular chain having a degree of polymerization of 2 to 200 by ring-opening polymerization, a copolymer comprising repeating units derived from a monomer that having a single polymerizable vinyl group at one end The carrier for developing an electrostatic charge image according to claim 1. [Chemical 6] (R ⁹ is a hydrogen atom or a methyl group, and Xb is a perfluoroalkyl group.) 4. The repeating unit derived from the monomer according to claim 3 is a repeating unit represented by the general formula [II] according to claim 2 and / or a general formula [III] according to claim 2.
A carrier for developing an electrostatic charge image, which is a repeating unit represented by: 5. A two-component developer comprising the carrier for developing an electrostatic charge image according to any one of claims 1 to 4 and a positively chargeable toner.