JPH06130721A - Resin composition for electrophotographic toner - Google Patents

Abstract

PURPOSE:To obtain a resin composition for electrophotographic toner capable of increasing the speed of a hot roll and fixing at a low temp. in the toner for an electrophotographic system copying machine or printer. CONSTITUTION:The resin composition for electrophotographic toner is made of an ethylenic polymer (X) and an ethylenic polymer (Y), which are produced by using 0.01-10 pts.wt. of a material having >=3 peroxy groups in the molecule and/or a material respectively having >=1 unsaturated functional group and peroxy group in the molecule with 100 pts.wt. two functional ethylenic unsaturated monomer and have 2-99 Mw/Mb (Mw is weight average molecular weight, Mb is weight average molecular weight between bridged points) and <=50,000 Mw. As a result, fixing property, offset property, toner strength and blocking property, etc., are well-balanced and particularly excellent effect in offset property and toner strength is attained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for electrophotographic toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like. More specifically, the present invention relates to a resin composition for electrophotographic toner, which is compatible with high-speed machines, has a good balance of fixing and offset properties, and has excellent durability.

[0002]

2. Description of the Related Art Generally, in electrophotography in a copying machine or a printer, an electrostatic latent image is formed on a photoconductor, and then the latent image is developed with toner, and then the image is fixed on a fixing sheet such as paper. After the toner image is transferred onto the sheet, a method of heating and pressure bonding with a heat roll (heat roll fixing method) is used. In this method, fixing is performed under heat and pressure, so that the method is quick and the thermal efficiency is very good, and therefore the fixing efficiency is very good. However, when using this fixing method with conventional toner,
Since the surface of the heat roll and the toner are in contact with each other in a molten state, the toner adheres to and transfers to the surface of the heat roll, and this phenomenon is re-transferred to the next sheet to be fixed and stained (offset phenomenon). On the other hand, copiers are oriented toward higher speeds, and the contact time with the fixing roll is inevitably shortened, and there is a demand for toner that melts by heating for a short time.
Further, from the viewpoint of energy saving or safety, there is a demand for a toner that melts at a temperature as low as possible and has good fluidity when melted. To obtain a toner with good fluidity,
There is a method of reducing the molecular weight of the resin, but by lowering it, the cohesive force of the resin becomes insufficient, and the offset phenomenon easily occurs, which is not preferable. Further, if attempts are made to reduce the toner particles in order to cope with high resolution, there is a problem that the generation of unnecessary fine powder as a toner increases during the fine pulverization in the toner manufacturing process, which deteriorates the yield of toner manufacturing.

Japanese Patent Application Laid-Open No. 49-101031 discloses a toner composition in which a cross-linked polymer is used as a binder resin to widen the fixing temperature range so that an offset phenomenon does not occur even at a relatively high fixing temperature. Techniques for obtaining things are disclosed. Further, JP-B-55-6895 discloses that a polymer having a weight-average molecular weight / number-average molecular weight of 3.5 to 40 and a number-average molecular weight of 2,000 to 30,000 is used as a binder resin. A technique for obtaining a toner composition having good properties is disclosed. However, the toner obtained by these techniques is difficult to use in a high speed copying machine or a small copying machine in which the amount of heat from the heat fixing roll is difficult to be sufficiently transmitted. That is, when a polymer having a large weight average molecular weight or a polymer obtained by crosslinking is used for the purpose of preventing the offset phenomenon, the viscosity of the binder resin increases and the fixability deteriorates. On the contrary, if the binder resin has a low viscosity by using one having a small weight average molecular weight or one not cross-linked, the image thermally fixed on the paper is destroyed by bending or rubbing of the paper, There is a problem that the toner adhering to the toner drops off and a defect occurs in the image, and the offset phenomenon deteriorates the image quality.

Another solution is disclosed in Japanese Patent Laid-Open No. 48-750.
A block copolymer comprising a hard resin block (a polymer portion having a high glass transition temperature (hereinafter, abbreviated as Tg)) and a soft resin block (a polymer portion having a low Tg) was used in JP-A-33. Excellent toners are disclosed.
However, when the toner using such a block copolymer is used in a heat roll fixing type copying machine or the like, an offset phenomenon occurs, and it is crushed by the kneading and crushing methods which are the current general manufacturing methods. Is extremely difficult and causes an extreme decrease in productivity, which is not preferable. In addition, JP-A-55-880
71, JP-A-55-88073 and JP-A-55-90958
In the publication, a styrene polymer, an ABA type block copolymer of polystyrene-polybutadiene-polystyrene, a release agent (for example, polybutene, polybutadiene, chlorinated paraffin, polyethylene, polypropylene, etc.), magnetic powder and carbon black, and charging A technique for obtaining a magnetic toner excellent in offset resistance and fixability by melt-kneading, pulverizing, and classifying an adjusting agent is disclosed.
It is difficult to uniformly disperse the ABA type block copolymer, mold release agent, charge control agent, etc. in the styrene polymer by melt kneading for a short time, and the photoconductor becomes dirty due to filming due to the poor dispersion. It was confirmed that it was easy to do.
In addition, if a large amount of polystyrene-polybutadiene-polystyrene ABA type block copolymer is used,
After kneading, it cannot be pulverized normally by a jet mill or the like, and freezing or cooling pulverization is required.

Further, in order to improve the fixing property, the method disclosed in
Based on the idea that star-shaped branched polystyrene as in 2-67302 has better melt flowability than straight-chain polystyrene of the same molecular weight, it is branched by a suspension polymerization method using a polyfunctional initiator. A technique for obtaining a toner having improved offset resistance by producing a polymer and using the polymer as a high molecular weight component is disclosed. In addition,
In the 2-48657 publication, a polyfunctional initiator is used to produce a high molecular weight polymer by a suspension polymerization method, and a low molecular weight polymer is further produced in the presence of this polymer. With a toner using a mixture of polymer and low molecular weight polymer,
A technique of improving offset resistance is disclosed. JP-A-2-48675 discloses that a low molecular weight polymer obtained by a solution polymerization method is dissolved in a polymerizable monomer for a high molecular weight polymer and polymerized by using a polyfunctional (trifunctional or higher) initiator. There is also disclosed a technique of producing a resin for toner.

Various techniques have been disclosed as described above. Generally, in the case of the suspension polymerization method, a cross-linking agent such as divinylbenzene, diethylene glycol dimethacrylate or trimethylolpropane dimethacrylate is used at the time of polymer production. Although a high molecular weight resin can be obtained relatively easily, it is necessary to use a dispersant or a dispersion aid together. Since the dispersant easily absorbs moisture and adversely affects the electrical characteristics, particularly the charging stability, it is necessary to remove these after the polymer is produced as much as possible. However, in order to remove the dispersant from the polymer by washing or the like, a large amount of washing water is required, and the waste water after washing is difficult to treat. Further, although these techniques have a great effect in the conventional copying machine in which the offset property becomes a problem, the low heat fixing copying machine cannot obtain sufficient low temperature fixing property and offset resistance. This is because a high molecular weight polymer having a large weight average molecular weight is used in order to improve the strength and offset resistance of the toner, the toner resin has a high viscosity, the melt flowability of the toner is lowered, and a low heat quantity copying machine is used. It is presumed that it was not suitable for. However, when a resin having a small weight average molecular weight is used, the melt fluidity can be improved, but the offset resistance or the strength of the toner is insufficient, which causes problems such as image deterioration due to cracking or spattering of the toner during long-term running. Was there. Therefore, as disclosed in Japanese Patent Application No. 3-501873, the present inventors have used 0.1 to 4.0 parts by weight of divinylbenzene and have a Z-average molecular weight / number-average molecular weight (Mz / Mn) of 6 or more by weight. Average molecular weight 50,000
The following ethylene-based polymers were used to improve the resin strength, but the amount of divinylbenzene used was small, but the Mw
/ Mb becomes large, that is, the number of cross-linking points is large, the side chains are not sufficiently extended, and the entanglement density of the molecular chains is insufficient, which is not much different from the conventional ethylene polymer. Was there.

Further, so far, the present inventors have proposed USP 4,963,45.
In the publication No. 6, etc., a resin by a solution polymerization method has been developed as a resin for an electrophotographic toner, which has excellent electric characteristics, particularly, charging stability. The resin by the solution polymerization method removes the solvent after the completion of the polymerization, but at this time, low-volatile components such as unreacted polymerizable monomers and decomposed products of the initiator can be distilled off, so that the electricity with very few impurities can be removed. A stable and homogeneous resin is obtained, which is the most suitable resin composition for electrophotographic toner. However, the production of a high molecular weight resin by the solution polymerization method has a problem that the Weisenberg effect (the resin is wrapped around the stirring rod) occurs and the production is difficult. The present inventors have developed a method in US Pat. No. 5,084,368 in which a bulk polymerization method is used in combination with a solution polymerization method to obtain a higher molecular weight. However, there is a limit to the high molecular weight that can be produced, and it has not been possible to completely overcome the offset resistance.

[0008]

SUMMARY OF THE INVENTION The present invention is to obtain a resin composition for an electrophotographic toner, which is capable of fixing with a low heat quantity suitable for a high speed, low heat quantity fixing copying machine and which is excellent in strength. .

[0009]

[Means for Solving the Problems] In order to solve the above problems, the present inventors have found that a substance and / or a molecule having a bifunctional ethylenically unsaturated monomer and three or more peroxy groups in the molecule. As a result of examining a polymer produced by using a substance having at least one unsaturated functional group and one or more peroxy group therein, and further a compound that can be used in combination with the polymer, the fixability,
The present invention has been completed by finding that a resin composition for toner excellent in offset resistance and toner strength (crushability) can be obtained. That is, the present invention relates to 100 parts by weight of a bifunctional ethylenically unsaturated monomer, a substance having three or more peroxy groups in the molecule, and / or an unsaturated functional group and a peroxy group in the molecule, respectively. Mw / M of polymer prepared using 0.01 to 10 parts by weight of a substance having one or more
An electrophotographic photograph composed of an ethylene polymer (X) and an ethylene high polymer (Y) having b (Mw is a weight average molecular weight, Mb is a weight average molecular weight between crosslinking points) of 2 to 99 and Mw of 50,000 or less. A resin composition for toner.

The weight average molecular weight (Mb) between cross-linking points of the ethylene polymer (X) used in the present invention is approximately represented by the formula (1) with the branching parameter (λ). Mb = 1 / λ (1) Further, the branching parameter (λ) is the branching point density (ρ) in the main chain.
_B ) The molecular weight (M _o ) of the bifunctional monomer is represented by the formula (2), and λ = ρ _B / M _o ··· (2) where the branching point density (ρ _B ) is _{ρ B = (- C) [} 1+ (1 / β) ln (1-β)] ·· (3) C = (K 2 / γK 1) (N B / N L) ·· (4) β = ( n _L + n _B ) / (N _L + N _B ) ·· (5) Expression (3), Expression (4), and Expression (5). However, n
_L is a bifunctional monomer, n _B is the number of moles of each polyfunctional monomer after reaction, _NL is a bifunctional monomer, and N _B is each reaction of a polyfunctional monomer. The previous number of moles. Also,
k ₁ is the reaction rate constant of the first functional group, k ₂ is the reaction rate constant of the second functional group, and γ is the reactivity ratio between the bifunctional monomer and the polyfunctional monomer. From the equations (1) and (2), there is a relationship of Mb = M _o / ρ _B (6). Therefore, Mb can be determined by obtaining the branching parameter (λ) or the branching point density (ρ _B ). The value of Mb in the present invention was determined by the equation (1) after obtaining the branching parameter (λ) by the GPC-LALLS method.

Generally, a polymer produced by using a bifunctional monomer (the bifunctional monomer in the present invention is an ethylenically unsaturated monomer) has an Mw / Mb of 1, Mw / Mb as the amount of multifunctional monomer used increases
Is greater than 1. When Mw / Mb of the ethylene polymer (X) in the present invention is less than 2, the resin strength of the ethylene polymer (X) is not guaranteed and the copy image is not stable. If Mw / Mb is larger than 99 or Mw exceeds 50,000, the resin strength is guaranteed but the melt fluidity deteriorates, and fixing with a low heat quantity cannot be performed. Further, when the Mw / Mb of the ethylene polymer (X) is less than 2, a large amount of fine powder is generated in the toner manufacturing stage, or the toner is cracked or sprinkled during long-term running, thereby impairing the image quality. Not preferable. On the other hand, if it is larger than 99, a great amount of energy is consumed in the pulverization step of toner production, and there is a problem in productivity.

The ethylene polymer (X) according to the present invention is
It is manufactured by the method described below. Specifically, depending on the type of substance used, (1) a substance having one or more unsaturated functional groups and one or more peroxy groups in the molecule (hereinafter referred to as a copolymerizable peroxide), for example, t- Examples of using butylperoxymethacrylate, t-butylperoxycrotonate, di (t-butylperoxy) fumarate, t-butylperoxyallylcarbonate, etc. are shown, but not limited thereto.

Since the copolymerizable peroxide has a vinyl group and a peroxy group in the molecule, it is possible to control the structure of the molecule by simultaneously polymerizing the functional groups in the monomer as in the conventional polymerization method. Without the expected physical properties. Therefore, the polymerization temperature was 10 hours half-life temperature (t _1/2) from 15 to 40 ° C. lower temperature in the peroxy groups copolymerizable peroxide in, in this temperature range the 10-hour half-life temperature (t _1/2 ) Is used together to copolymerize the vinyl group in the copolymerizable peroxide with the bifunctional monomer, and then the temperature is reduced by half for 10 hours of the peroxy group in the copolymerizable peroxide. By elevating the polymerization temperature to (T _1/2 ) or more and polymerizing it, the composition of the main chain and the branched chain can be controlled and the performance such as offset property in the toner can be improved. Further, as a catalyst which can be used in combination, conventionally used catalysts such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO),
3,3,5-Trimethylcyclohexanone peroxide, acetyl peroxide, dodecyl peroxide, lauroyl peroxide, 2,2'-azobis (2,4-dimethylvaleronitrile), t-butylperoxyisobutyrate
And t-butylperoxy-2-ethylhexanoate.

The amount of the copolymerizable peroxide used is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the bifunctional ethylene monomer. The amount of copolymerizable peroxide used
If it is less than 0.05 parts by weight, the number of branching points will be small and the improvement of fluidity due to the branched chain will not be exhibited. If it is more than 10 parts by weight, the number of branching points will be too large and the branched chains will be entangled with each other, and the ethylene-based high polymer (Y ) And poor offset resistance as a toner, which is not preferable. (2) When a substance having three or more peroxy groups in the molecule (hereinafter referred to as a polyfunctional initiator) is used, if these initiators are used in one molecule as in the conventional polymerization method, Since it has a plurality of polymerization initiation points, the weight average molecular weight becomes large and a polymer having Mw of 50,000 or less cannot be obtained. Therefore, in the present invention, the concentration of the polyfunctional initiator in the system is adjusted by controlling various factors such as the degree of dilution, the dropping time, the reaction temperature, the stirring efficiency, and the Mw / Mb is 2
It is to obtain an ethylene polymer (X) having a Mw of 50,000 or less and a Mw of 50,000 or less. Although the production efficiency is poor, it can be produced by increasing the degree of dilution and extending the dropping time.

Even when a polyfunctional initiator is used, it has a 10-hour half-life temperature (t _1/2 ) in the temperature range around the polymerization temperature, as in the case of the above-mentioned copolymerizable peroxide. You may use together a catalyst. The amount of multifunctional initiator used is 2
0.01 to 10 per 100 parts by weight of functional ethylene monomer
Parts by weight are desirable. If the amount of the polyfunctional initiator used is less than 0.01 part by weight, the molecular weight becomes large and the melt flowability is not improved.If it is more than 10 parts by weight, the number of branching points is too large and the branched chains are entangled with each other, resulting in an ethylene-based heavy chain. It is not preferable because the compatibility with the resin used in combination with the combination (X) becomes poor and the toner has poor fixing and offset properties. Further, as a particularly preferable polyfunctional initiator, 4
Those having two peroxy groups are preferred.

Specific substance names of the polyfunctional initiator are as follows:
Pertrimellitic acid tri-t-butyl ester, pertrimellitic acid tri-t-amyl ester, pertrimellitic acid tri-t-hexyl ester, pertrimellitic acid tri-
t-1,1,3,3-tetramethylbutyl ester, pertrimellitic acid tri-t-cumyl ester, pertrimellitic acid tri-t- (p-isopropyl) cumyl ester, pertrimesic acid tri-t-butyl ester Ester, pertrimesic acid tri-t-amyl ester, pertrimesic acid tri-t-
Hexyl ester, pertrimesic acid-t-1,1,3,3-tetramethylbutyl ester, pertrimesic acid tri-t-
Cumyl ester, pertrimesic acid tri-t-tri-t-
(P-Isopropyl) cumyl ester, 2,2-bis (4,4-
Di-t-butylperoxycyclohexyl) propane,
2,2-bis (4,4-di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4, 4-di-α
-Cumylpa-oxycyclohexyl) propane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) butane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) butane Is mentioned.

The ethylene high polymer (Y) has a Mw of 200,0.
An ethylene polymer having a Mw / Mn of 3 or more at 00 or more is used, but an ethylene polymer having a Mw of 200,000 or more and an Mw / Mn of 5 or more is more preferable. It is preferable to use an ethylenically unsaturated monomer and / or a polyfunctional monomer as a raw material monomer, which is produced by a polymerization method such as solution polymerization, suspension polymerization or emulsion polymerization. Ethylene polymer (Y)
If the Mw is less than 100,000, sufficient offset resistance cannot be obtained, which is not preferable. If the Mw / Mn is less than 3, sufficient offset properties and toner strength cannot be achieved, which is not preferable. The ethylene polymer (Y) was obtained by polymerizing the above-mentioned polyfunctional initiator or a conventionally known initiator with the following ethylenically unsaturated monomer and / or polyfunctional monomer. In particular, it has a weight average molecular weight of 100,000 or more obtained by a solution polymerization method. The mixing ratio with the ethylene polymer (X) is such that the ethylene polymer (X) is 15% of the total amount of the binder resin.
If it is less than wt%, the melt fluidity of the obtained toner will be insufficient, resulting in poor fixing. Further, if it exceeds 85% by weight, the strength of the toner is improved and the offset resistance is deteriorated, which is not preferable.

Here, the ethylenically unsaturated monomer means, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate,
Stearyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, 2-chloroethyl acrylate,
Phenyl acrylate, methyl α-chloroacrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, etc. Acrylic esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate,
N-Butyl methacrylate, isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate. , Methacrylic acid esters such as benzyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethylaminomethyl methacrylate ester, and dimethylaminoethyl methacrylate ester; o-methylstyrene, m-methylstyrene , P-methylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
pt-butyl styrene, pn-hexyl styrene,
pn-octyl styrene, pn-nonyl styrene,
pn-decylstyrene, pn-dodecylstyrene,
p-methoxystyrene, p-phenylstyrene, 3,4
-Aromatic vinyl monomers such as dichlorostyrene, α-methylstyrene, p-chlorostyrene and styrene; vinylnaphthalenes; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl chloride, bromide Vinyl, vinyl fluoride, vinyl acetate, vinyl propionate and other vinyl esters; unsaturated dibasic acid dialkyl esters such as dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumarate; acrylonitrile, methacrylonitrile, acrylamide , Acrylic acid or methacrylic acid derivatives such as methacrylamide, N-substituted methacrylamide, methacrylamide propane sulfonic acid; vinyl such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc. - ethers; vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones such as methyl isopropenyl ketone, acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid; monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl fumarate, fumaric acid Unsaturated dicarboxylic acid monoesters such as monoethyl acid acid, monobutyl fumarate, and monooctyl fumarate; N-vinylpyrrole, N-
Examples thereof include N-vinyl compounds such as vinylcarbazole, N-vinylindole, and N-vinylpyrrolidene, and at least one kind of these monomers is used. Among these, acrylic acid esters, methacrylic acid esters, aromatic vinyl monomers, fumaric acid dialkyl esters, acrylic acid, acrylamide, methacrylamide, etc. are particularly preferable.

As the polyfunctional monomer mentioned above, 2,2-bis (4-acryloxypolyethoxyphenyl) propane,
1,3-butylene glycol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene Glycol diacrylate,
Polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, polypropylene glycol diacrylate, N, N'-methylenebisacrylamide, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. Polymer, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 Dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane , Methacrylic acid-based monomers such as aluminum methacrylate, zinc methacrylate, calcium methacrylate, magnesium methacrylate, etc., as well as diallyl phthalate, triallyl cyanurate,
Examples thereof include triallyl isocyanurate, triallyl trimellitate, ethylene glycol diglycidyl ether acrylate, and divinylbenzene.

Further, in the present invention, the ethylene polymer (X) and the ethylene high polymer (Y) are mixed and used as a resin composition for toner. The characteristics of the resin composition for toner are as follows. An amide compound is used to lower the minimum fixing temperature, and a block copolymer or a graft copolymer is used to increase the effect of the polyolefin wax added to improve the anti-offset property (improvement of the dispersibility of the polyolefin wax). Can be used. 1. When an amide compound is used, when a solution of a mixture of an ethylene polymer (X) and an ethylene high polymer (Y) is prepared and the solvent is removed from the solution, or when melt kneading in the production of a toner, a general formula is used. [Chemical Formula 1] (Chemical Formula 3), [Chemical Formula 2]
The amide compound represented by (Chemical Formula 4) is added.

[0021]

Embedded image (R ¹ —NHCO) ₂ R ² (In the formula, each R ¹ independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ² is a carbon atom having 1 to 10 carbon atoms. Hydrogen group) or general formula

[0022]

Embedded image (R ³ —CONH) ₂ R ⁴ (In the formula, each R ³ independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ⁴ is a carbon atom having 1 to 10 carbon atoms. As a specific method of adding the amide compound (which represents a hydrogen group), (1) it is added when the solvent is removed from the solution of the mixture of the ethylene polymer (X) and the ethylene high polymer (Y). In this case, the amide compound is added to a device for removing the solvent in a powder form or in a state of being dissolved in a solvent, and after stirring,
Remove the solvent. (2) When added at the time of melt kneading in the production of a toner, after simultaneously mixing a mixture of an ethylene polymer (X) and an ethylene high polymer (Y), constituents required as a toner, and the amide compound , Melt and knead.

Examples of the amide compound of the general formula [Chemical Formula 1] used in the present invention include N, N'-dilauryl adipamide, N, N'-distearyl adipamide, N, N '.
Examples include distearyl sebacic acid amide and N, N-dibehenyl adipamic acid amide. Examples of the amide compound represented by the general formula [Formula 2] include methylenebisstearic acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, and ethylenebis12.
-Hydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, o
-Phenylenebisstearic acid amide and the like can be mentioned.

Preferred commercial products of these amide compounds include, for example, "Bisamide", "Diamid 200bis", "Lubron" (above, manufactured by Nippon Hydrogen Industry Co., Ltd.), "Plastflow" (above, Nitto Kagaku). Company),
"Alflo-50S", "Alflo 50F", "Alfro V-60" (above, NOF Corporation), "Amide-6L", "Amide-7S", "Amide-6H"
(Above, manufactured by Kawaken Fine Chemicals Co., Ltd.), "Armorax EBS" (above, manufactured by Lion Armor Co., Ltd.), "Hoechst Wax C" (manufactured by Hoechst Japan Co., Ltd.), "Nobuco Wax 22-DS" (above, manufactured by Nobuco Chemical Co. ),
"Adva Wax-280" (above, manufactured by Advance), "Kaowax-EB" (above, manufactured by Kao),
Examples thereof include "Valicin 285" (above, manufactured by Baker Casta Oil Co., Ltd.). In particular, "Alfro-
50S "," Alflo-50F "," Alflo V-6 "
0 "is preferable. These amide compounds generally have a higher softening point as the number of carbon atoms of the aliphatic hydrocarbon group (R ¹ or R ³ ) and the length of the alkylene chain (R ² or R ⁴ ) increase, but the low temperature fixability of the toner is low. -From the viewpoint of blocking properties, the softening point is preferably in the range of 100 to 150 ° C. Further, the addition amount of these amide compounds is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the mixture of the ethylene polymer (X) and the ethylene high polymer (Y). Those within this range have the effect of further lowering the minimum fixing temperature. If the addition amount is less than 0.5 parts by weight, the effect of the addition of the amide compound cannot be obtained, and if the addition amount is more than 10 parts by weight, the glass transition temperature in the toner resin composition is significantly lowered. Therefore, the developability and transferability are deteriorated and a good visible image cannot be formed. In addition, the amide compound adheres to the developing sleeve or the electrostatic image support to form a film, which impedes its function or significantly impairs blocking resistance.

2. The block copolymer or graft copolymer used to enhance the effect of the polyolefin wax added to improve the anti-offset resistance (improvement of the dispersibility of the polyolefin wax) is an ethylene hydrocarbon and / or a conjugate. Diene hydrocarbon 1
A block copolymer comprising at least one kind of block and a polystyrene block or a hydrogenated product thereof. The graft copolymer is a polypropylene-modified polystyrene graft copolymer, and both are used alone or in combination. Its role in the toner resin composition is to improve the dispersibility of various additives including polyolefin wax which is an anti-offset agent.

In the present invention, a block copolymer comprising an ethylene hydrocarbon and / or a conjugated diene hydrocarbon block and a polystyrene block or a hydrogenated product thereof is used as an ethylene hydrocarbon, for example, ethylene, propylene, 1- Butene, 2-butene, isobutylene, 1
-Pentene, 2-pentene, 2-methyl-1-butene,
3-methyl-1-butene, 2-methyl-2-butene, 1
-Hexene, 2,3-dimethyl-2-butene and the like, one or more kinds of butadiene, isoprene and the like are used as the conjugated diene hydrocarbon, and the end of the block polymer produced by known living anionic polymerization or living cationic polymerization is used. It is produced by a method of using a reactive group and blocking styrene with the reactive group, but the production method is not particularly limited, and a generally known one can be used. The block copolymer can also be used as a hydrogenated product by a conventional method.

Specific product names include "Clayton", "Califlex TR" (all manufactured by Shell Chemical Co., Ltd.), "Septon" manufactured by Kuraray Co., Ltd., "Tuftec", and "Toughprene". , "Sorprene", "Asaprene" (all manufactured by Asahi Kasei Co., Ltd.), "Lavalon" (manufactured by Mitsubishi Petrochemical Co., Ltd.), "Sumitomo TPE-SB" (manufactured by Sumitomo Chemical Co., Ltd.), "Elastomer" AR "(Aron Kasei Co., Ltd.)
Made), "JSR TR" (made by Japan Synthetic Rubber Co., Ltd.),
Examples include "Denka STR" (manufactured by Denki Kagaku Co., Ltd.), "Europrene SOL-T" (manufactured by Tosoh Corporation), and polypropylene modified polystyrene graft copolymers include "MODIPA" (NOF Corporation )), "VM
X ”(manufactured by Mitsubishi Petrochemical Co., Ltd.) and the like. The amount of the block copolymer or graft copolymer and the polyolefin wax used as the dispersant is 0.5 to 0.5 parts by weight of the dispersant based on 100 parts by weight of the mixture of the ethylene polymer (X) and the ethylene high polymer (Y). 25 parts by weight and polyolefin wax are used in the range of 5 to 35 parts by weight. Dispersant
If the amount is less than 0.5 part by weight, the effect of dispersing the polyolefin wax is reduced, and the uniformity of the toner characteristics becomes a problem. On the other hand, when the amount is more than 25 parts by weight, the domain size of the dispersant itself becomes too large, which is not preferable and also economically unfavorable. Further, the proportion of polystyrene block in the block copolymer is preferably 3 to 90% by weight, particularly preferably 5 to 70% by weight. When the ratio of polystyrene block is less than 3% by weight, the fixing roll and the photoconductor are easily soiled. On the other hand, if it exceeds 90% by weight, the strength of the toner decreases, which is not preferable.

The polyolefin wax is used in the range of 5 to 35 parts by weight, but when the effect of the polyolefin wax is 5 parts by weight or less, it is not necessary to use a dispersant. In short, in a resin composition for a toner that requires 5 parts by weight or more of a polyolefin wax, the dispersant is
0.5 to 25 parts by weight is used. These dispersants and polyolefin wax are ethylene polymers (X)
Or any step during the polymerization of the ethylene-based high polymer (Y), when removing the solvent from the mixed solution of the ethylene-based polymer (X) and the ethylene-based high polymer (Y), and during the melt-kneading in the production of the resin for toner May be added in. Alternatively, they may be added separately in a plurality of steps.

Further, as the polyolefin wax used in the resin composition for toner containing the ethylene polymer (X) and the ethylene high polymer (Y) of the present invention as the main components, a low molecular weight polyolefin wax is preferable, The low molecular weight polyolefin wax may be either an unmodified polyolefin wax or a modified polyolefin wax in which a modifying component is blocked or grafted with respect to an olefin component. The olefin component of the unmodified polyolefin wax or the modified polyolefin wax can be obtained by homopolymer type obtained from a single olefin monomer or by copolymerizing an olefin monomer with another monomer copolymerizable therewith. Any type of copolymer type may be used. Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, and all other olefin monomers. I can. Further, as the other monomer copolymerizable with the olefin monomer, other olefin monomers, for example, vinyl ethers such as vinyl methyl ether, vinyl esters such as vinyl acetate, vinyl fluoride, etc. Examples thereof include haloolefins, acrylic acid esters or methacrylic acid esters such as methyl acrylate and methyl methacrylate, acrylic acid derivatives such as acrylonitrile, and organic acids such as acrylic acid and methacrylic acid. When the olefin component is a copolymer type, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl methyl ether copolymer, ethylene-propylene-vinyl acetate. It may be of a copolymer type such as a copolymer. When a monomer other than the olefin monomer is used to form the copolymer type, the proportion of the olefin moiety of the olefin monomer in the polyolefin component is preferably 50 mol% or more.

Examples of the modifying component in the modified polyolefin wax include aromatic vinyl monomers such as 1-phenylpropene, styrene, p-ethylstyrene and pn-butylstyrene, methyl acrylate, ethyl acrylate and methacryl. Examples thereof include α-methylene fatty acid monocarboxylic acid ester monomers such as methyl acidate and ethyl methacrylate. When an aromatic vinyl monomer is used as the modifying component, the ratio of the modifying component to the modified polyolefin is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight. When the α-methylene fatty acid monocarboxylic acid ester monomer is used as the modifying component, the ratio of the modifying component to the modified polyolefin is preferably 0.1 to 50 parts by weight, particularly preferably 1 to 40 parts by weight. It is desirable that such unmodified polyolefin wax or modified polyolefin wax itself has a low softening point. For example, the softening point is 80 to 180 when measured by the ring and ball method specified in JIS K2531-1960.
It is desirable that the temperature is 90 ° C, preferably 90 to 160 ° C.

Specific examples of this polyolefin wax include "Viscole 660P" and "Viscole 550".
P "(above, Sanyo Kasei Co., Ltd.)," Polyethylene 6A "
(Manufactured by Allied Chemical Co., Ltd.), "High Wax 400
"P", "High Wax 100P", "High Wax 20"
0P "," High Wax 320P "," High Wax 2 "
20P "," High Wax 2203P "," High Wax 4202P "(Mitsui Petrochemical Co., Ltd.)," Hoechst Wax PE520 "," Hoechst Wax PE13 "
0 ”,“ Hoechst Wax PE190 ”(above, manufactured by Hoechst Japan Ltd.) and the like, as well as polyethylene wax block-copolymerized or graft-copolymerized with methyl methacrylate, block-copolymerized with butyl methacrylate or the like. Examples thereof include polyethylene wax graft-copolymerized and polyethylene wax block-polymerized or graft-copolymerized with styrene. These polyolefins are usually used at the time of melt kneading in the production of toner, but may be added at the time of polymerizing the ethylene polymer or removing the solvent.

As the ethylene-based high polymer (Y), those having an Mw of 100,000 or more and an Mw / Mn of 3.0 or more as described above may be used, but more preferably, the intramolecular one as described above is used. A polymer having a weight average molecular weight of 100,000 or more and a Z average molecular weight of 850,000 or more produced by a solution polymerization method using a compound having 3 or more peroxy groups as an initiator improves the offset resistance. Is preferred.

The binder resin composed of the ethylene-based polymer (X) and the ethylene-based high polymer (Y) is usually used in the toner resin composition in an amount of 50 to 95% by weight. Further, the binder resin may be, for example, polyvinyl chloride, polyolefin, polyester, polyvinyl butyral, polyurethane, polyamide, rosin, terpene resin, phenol resin, epoxy as long as it does not impair the effects of the present invention. Resin, paraffin wax, polyolefin wax, etc. are added. A colorant is usually used in the resin composition for electrophotographic toner using the ethylene polymers (X) and (Y) of the present invention. Examples of the colorant used include carbon black, acetylene black, lamp black, black pigments such as magnetite,
Yellow lead, yellow iron oxide, Hansa yellow-G, quinoline yellow lake, permanent yellow, NCG molybdenum orange, vulcan orange, indanthrene, brilliant orange GK, red iron oxide, brilliant carmine 6
Known pigments such as B, frisarine lake, fast violet B, cobalt blue, alkali blue lake, phthalocyanine blue, metal complex of monoazo dye, fast sky blue, pigment green B, malachite green lake, titanium oxide, zinc white, etc. . The amount is usually 5 to 300 per 100 parts by weight of the binder resin.
Parts by weight. For the resin composition for electrophotographic toner of the present invention, for example, known charge adjusting agents such as nigrosine, quaternary ammonium salts, metal-containing azo dyes, metal salts of fatty acids, pigment dispersants, and anti-offset agents are appropriately selected. Can be added as a toner by a known method. That is, the binder resin to which the above-mentioned various additives are added is premixed with a Henschel mixer, kneaded in a molten state in a kneader such as a kneader, cooled, finely pulverized with a jet pulverizer, and then classified. The particles are usually classified in 8 to 20 .mu.m to collect the particles to obtain a toner.

In order to obtain a magnetic toner, magnetic powder may be contained. Such magnetic powders include ferromagnetic substances magnetized in a magnetic field, powders of iron, nickel, cobalt, etc., or alloys such as magnetite, ferrite, etc. The ratio of the magnetic powders to the toner weight is 15 to 70 parts by weight is preferred.

Further, in the present invention, a releasing agent as described below may be appropriately used during polymerization or during melting / kneading. The releasing agent as referred to herein is a substance that comes into contact with the fixing roller during fixing to reduce friction, improve releasability, or improve fluidity during melting. For example, paraffin wax, high-grade (saturated) Straight-chain) fatty acids (12 carbon atoms
~ 50), higher alcohols (C8-C32), fatty acid metal salts, fatty acid amides, metal soaps, polyhydric alcohols and the like. In the toner, a charge control agent, a colorant, and a powder fluidity modifier may be mixed (externally added) with the toner particles, if necessary. As this charge control agent,
There are metal-containing dyes, nigrosine and the like, and powder fluidity modifiers include colloidal silica and fatty acid metal salts. Further, for the purpose of increasing the amount, a filler such as calcium carbonate or fine powder silica may be blended in the toner in an amount of 0.5 to 20 parts by weight. Furthermore, by preventing the mutual aggregation of toner particles,
In order to improve the powder fluidity, a powder fluidity improver such as Teflon fine powder may be added. As described above, various additives may be dissolved and dispersed in the monomer and polymerized by the method for obtaining the ethylene polymers (X) and (Y) of the present invention. The electrophotographic toner composition containing the ethylene polymers (X) and (Y) of the present invention as a main constituent of the binder resin can be applied to all known developing methods. For example, a two-component developing method such as a cascade method, a magnetic brush method or a microtoning method; a one-component developing method containing a magnetic material such as a conductive one-component developing method, an insulating one-component developing method or a jumping developing method; Method and fur brush method;
A non-magnetic one-component developing method in which the toner is carried on the toner carrier by electrostatic force and conveyed to the developing section can be used.

[0036]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means parts by weight unless otherwise specified. 1. Production Example of Ethylene Polymer (X) of the Present Invention Polymerization was carried out under the monomers, catalyst composition and reaction conditions as shown in Table 1 to obtain an ethylene polymer (X).

[0037]

[Table 1] 2. Production Example of Ethylene High Polymer (Y) of the Present Invention Polymerization was carried out under the monomers, catalyst composition and reaction conditions shown in Table 2 to obtain an ethylene high polymer (Y).

[0038]

[Table 2] The molecular weights of the ethylene-based polymer (X) and the ethylene-based high polymer (X) obtained by the above-described production examples were standardized on a commercially available monodisperse standard polystyrene, tetrahydrofuran was used as a solvent, and a refractometer was used as a detector. The weight average molecular weight (Mw) was determined by GPC, and the weight average molecular weight between crosslinking points (Mb) was determined by the equation (1) by determining the branching parameter (λ) by the GPC-LALLS method.

Detector SHODEX RI SE-31 Column A-80M x 2 + KF-802 Solvent THF (tetrahydrofuran) Discharge rate 1.2 ml / min Sample 0.25% THF solution 3. Production Example of Binder Resin (1) Ethylene polymer (X) or polymer solution thereof obtained as described above, and ethylene high polymer (Y)
Were mixed in the proportions shown in each table and the solvent was removed to obtain a binder resin. 4. Toner Production Examples and Evaluation Results Examples 1 to 101 and Comparative Examples 1 to 26 100 parts of the above-mentioned binder resin and carbon black (MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.) 10 parts, polypropylene wax 5 parts,
As a charge control agent, 1 part of Nigrosine dye was pre-mixed with a Henschel mixer, and then kneaded at 170 ° C using a twin-screw kneader, then cooled, coarsely pulverized, finely pulverized, and further classified by a classifier. ~ 20μ toner was obtained. Using the above toner, the fixability, offset property, image quality stability, etc. were evaluated. The fixability and offset property were evaluated using a machine modified so that the roll temperature of a commercial copying machine could be arbitrarily changed. Next, an evaluation method will be shown. 70% fixing temperature; 2cm x 2cm toner layer of solid black part on the image quality is applied with a Gakushin-type friction fastness tester (manufactured by Daiei Kagaku Seiki Co., Ltd.) with a load of 300g / cm ² and sand eraser. The residual weight ratio of the toner layer after rubbing 50 times at 70%
The minimum heat roll temperature required to exceed the temperature was set. Offset temperature: The temperature of the hot roll was raised to the temperature at which offset began to occur. Blocking property: 100 g of the toner was placed in a polybin, tapped, kept at 50 ° C. for 50 hours, returned to room temperature, transferred to a paraffin paper, and visually judged according to the following judgment criteria. ◎ No blocking at all. ○ There is some blocking, but there is no problem in practical use. △ Very blocking. × Almost one lump. Toner strength; crushability is measured by roughly crushing crushable agglomerates in the production of each toner, classifying and using a jet crusher, crushing pressure 2.5 kg / cm ² , feed amount 20
It was pulverized under the condition of g / min and the average particle size of the obtained product was measured. Dirt on photoconductor; photoconductor when 100,000 copies are taken,
The fixing roll was wiped with cotton, and the cotton was visually evaluated to determine the degree of stain. ◎ No stain at all ○ Cotton becomes slightly black △ Very black × Totally black Domain size in the binder resin: The block or graft polymer (dispersant) according to claim 4 is replaced with an ethylene polymer. A transmission electron micrograph of the resin internally added at the time of removing the solvent from the mixture was taken to measure the dispersed particle size of the dispersant in the resin. Charge stability: Toner particles and spherical iron oxide powder are mixed at a ratio of 3:97 in a V blender for 30 hours, and after 30 minutes and 30 minutes.
Ratio of Tobori charge after time (absolute value) in the following formula
It was expressed as, and the ratio within 10% was regarded as good. [(Charge amount after 30 minutes)-(charge amount after 30 hours)] ÷ (30
(Charge amount after minute) ○ ≤ 10% △ 10 to 14% × ＞ 14% Image quality (fog); White areas of 100th sheet and 10,000th sheet in continuous copying are compared. It was judged based on the degree to which the stain on the part was severe. ○ Good level that cannot be confirmed with a magnifying glass having a magnification of 30 times △ Level that can be seen with a magnifying glass having a magnification of 30 times × Tables 3 to 5 show evaluation results that can be visually confirmed.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

According to the method of the present invention, a stable and high-quality image can always be obtained even in a low heat fixing copying machine which cannot be solved by the conventional technique. That is, the toner using the resin composition of the present invention has a low fixing lower limit temperature, a wide non-offset temperature range, and very good image characteristics, and has excellent performance as an electrophotographic toner composition. .

 ─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 4-167351 (32) Priority date Hei 4 (1992) June 25 (33) Country of priority claim Japan (JP) (31) Priority Claim number Japanese patent application No. 4-237295 (32) Priority date Hei 4 (1992) September 4, (33) Priority claiming country Japan (JP) (72) Inventor Kenji Uchiyama 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Katsuo Uramoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tamami Fukui 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chem Within the corporation

Claims (6)

[Claims] 1. A substance having three or more peroxy groups in the molecule and / or one or more unsaturated functional groups and peroxy groups in the molecule per 100 parts by weight of a bifunctional ethylenically unsaturated monomer. Mw / Mb (Mw is weight average molecular weight, Mb is weight average molecular weight between cross-linking points) of the polymer produced by using 0.01 to 10 parts by weight of the substance having
A resin composition for an electrophotographic toner comprising an ethylene polymer (X) having an Mw of 50,000 or less and an ethylene high polymer (Y). 2. The use ratio of the ethylene-based polymer (X) and the ethylene-based high polymer (Y) is 15:85 to 85:15 (weight ratio), and the Mw of the ethylene-based high polymer (Y) is The resin composition for an electrophotographic toner according to claim 1, which has a Mw / Mn of not less than 200,000 and not less than 3.0. 3. The ethylene-based high polymer (Y) has a Mw of 200,
000 or more, and Mw / Mn is 5.0 or more.
The resin composition for electrophotographic toner as described above. 4. When the ethylene-based polymer (X) and the ethylene-based high polymer (Y) are used, when the solvent is removed from the solution of the mixture of them, or during the melt-kneading in the production of a toner, the compound represented by the general formula: (R ¹ —NHCO) ₂ R ² (In the formula, each R ¹ independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ² is 1 to 1 carbon atoms. 10 hydrocarbon groups) or the general formula [Chemical formula 2]
(Formula 2) ## STR2 ## (R ³ -CONH) in ₂ R ⁴ (wherein, R ³ is each independently an alkyl group having an alkyl group or a hydroxyl group having 7 to 24 carbon atoms, R ⁴ is C 1 -C The resin composition for an electrophotographic toner according to claim 1, further comprising an amide compound represented by the formula (1 to 10 represents a hydrocarbon group). 5. An ethylene-based hydrocarbon and / or conjugated diene-based hydrocarbon block and a polystyrene block per 100 parts by weight of a resin mixture of the ethylene-based polymer (X) and the ethylene-based high polymer (Y). At least one block copolymer or hydrogenated product thereof or polypropylene-modified polystyrene graft copolymer is added to 0.5 to 25
2. The resin composition for electrophotographic toner according to claim 1, wherein the resin composition contains 5 to 35 parts by weight of polyolefin wax. 6. A weight average molecular weight of 100,0 produced by solution polymerization of an ethylene high polymer (Y) using a compound having 3 or more peroxy groups in one molecule as an initiator.
The resin composition for electrophotographic toner according to claim 1, which is a polymer having a Z-average molecular weight of at least 00 and at least 850,000.