JPH0753781B2 - Modified low molecular weight polyolefin and its application - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel graft-modified low-molecular weight polyolefin (hereinafter also simply referred to as modified low-molecular-weight polyolefin) and a synthetic resin processing aid comprising the graft-modified low-molecular weight polyolefin. , A pigment dispersant or a heat-fixing electrophotographic toner forming element.

[Conventional technology]

(1) When heat-processing synthetic resin, processing aids such as a lubricant, a fluidity improver, a release agent, and a slip agent are added as described in JP-B-54-42381 in order to improve processability. However, in recent years, the graft-modified polyolefin wax as described in this publication has come to be used. Such modified polyolefin wax is superior to conventionally used metal soaps esters, amides, and higher alcohols in terms of lubricity, heat stability, transparency, bleed-out properties, etc. However, since compatibility with aromatic and / or polar group-containing resins such as polystyrene, ABS, polyvinyl chloride, polyester, polycarbonate, polyamide, (meth) acrylic acid ester resin, and epoxy resin is still insufficient, There are problems such as the effect of improving the fluidity of these resins during injection molding or columnar molding is not sufficient, and when the addition amount is increased, the mechanical properties of the resin after molding may be significantly reduced. Atsuta

(2) As a method for coloring a synthetic resin such as polystyrene, ABS, polycarbonate, polyester, or polyamide, a dry color method or a color compound method is mainly used, and a master batch method is not so often used. In both the former two methods, a pigment dispersant is used to uniformly disperse the pigment. For example, conventionally, various metal salts of higher fatty acids such as stearic acid, low molecular weight polystyrene, and styrene-acrylic acid ester copolymer oligomers have been used as pigment dispersants for these synthetic resins. However, when a higher fatty acid is used as a pigment dispersant, the higher fatty acid salt bleeds out from the colored polymer, and the dispersibility of the pigment decreases, and the transparency decreases. There is. Further, when a low molecular weight polyolefin is used as the pigment dispersibility, the kneading workability is poor when adjusting the dry color or when kneading the dry color with, for example, a styrene-based polymer, resulting in poor pigment dispersibility. It also has the disadvantage of being inferior. Further, when the conventional dispersant is used, a large amount of pigment cannot be uniformly dispersed in the synthetic resin,
It was impossible to use the master batch method.

On the other hand, as a coloring method for polyolefin resins such as polyethylene and polypropylene and vinyl chloride resins, a master batch method in which a pigment is dispersed at a high concentration in a carrier resin such as polyethylene using a dispersant such as low molecular weight polyethylene or fatty acid metal soap Is often used. However, the conventional master batch cannot raise the pigment concentration so much, and in recent years, the coloring of the polyolefin resin and other synthetic resins tends to have a high dilution ratio and high speed coloring, which makes it difficult to sufficiently cope with the conventional master batch. However, especially in thin-walled and large-sized injection-molded products, the speed of dye / pigment dispersion in the resin to be colored of the master batch is insufficient, and therefore the problem of poor appearance such as color unevenness of the molded products cannot be avoided.

(3) Electrophotographic developer, so-called electrostatic toner (hereinafter, also simply referred to as toner) is an image forming material at the next stage of electrostatic exposure in electrostatic exposure, and carbon black or pigment is contained in resin. Is a charged fine powder in which is dispersed.

Generally, electrostatic toners are dry two-component type toners used with carriers such as iron powder and glass particles, dispersion type wet toners using an organic solvent such as impalafine, and magnetic fine powders are dispersed in itself. Are classified as dry one-component toners.

The image obtained by being developed on the photosensitive plate with the electrostatic toner is transferred to paper, and then the image directly developed on the paper coated with the photosensitive layer is fixed as it is by heat or solvent vapor. Of these, fixing by a heating roller is a contact-type fixing method, so that it has a high heat effect, an image can be surely fixed by a heat source at a relatively low temperature, and it is also suitable for high-speed copying, which is preferable.

However, when an image is fixed by contacting a heating body such as a heating roller, there is a possibility that a part of the electrostatic toner adheres to the heating body and is transferred to a subsequent image portion, so-called offset development occurs. Especially in high-speed copying, raising the temperature of the heating element in order to increase the fixing effect and the fixing speed results in making the offset phenomenon more likely to occur. Therefore, for example, when fixing an image formed with a one-component electrostatic toner with a heating roller, the roller surface is impregnated with silicone oil or the silicone oil is supplied to the roller surface to eliminate the offset phenomenon. However, on the contrary, a problem such as contamination of the roll may occur.

On the other hand, as the thermoplastic resin which is the main material of the electrostatic toner,
Polystyrene, polystyrene, styrene / (meth) acrylic acid ester copolymer and other polysterene resins, polyester resins, ketone resins, maleic acid resins, coumarone resins, phenol resins, epoxy resins, terpene resins, polyvinyl butyral, polybutyl methacrylate, etc. Among them, polystyrene-based resins have good chargeability, have a suitable softening point (90 ° C to 160 ° C), and have good fixability.
Easy to clean the photosensitive plate, less pollution, less hygroscopic,
It is most used because it has characteristics such as good miscibility with carbon black, which is a coloring material, and easy pulverization. However, since the polystyrene resin having such characteristics is likely to cause the offset phenomenon in high-speed copying as described above, it is desired to develop an electrostatic toner which does not cause the offset phenomenon.

As a method of solving the above problems, (i) a method of improving the thermoplastic resin itself which is the main material of the electrostatic toner, and (ii) the thermoplastic resin which is the main material of the electrostatic toner is as it is. Then, a method of adding a release agent for the purpose of not causing the offset phenomenon can be considered.

In order to solve the above problems by the method (ii) above,
A technique of adding polyolefin wax as a release agent to a styrene-based polymer is, for example, Japanese Patent Publications Nos. 52-3304 and 52-3305.
57-52574 and 58-59455. However, even in such a technique, because the compatibility between the polyolefin wax and the styrene resin component is still insufficient, not only the performance as a release agent of the polyolefin wax is not sufficiently exhibited, Toners are likely to aggregate during storage or copying operation, and waxes are more likely to be released than toners, which easily leads to contamination of the photosensitive drum and the like, and further has poor bending resistance of a fixed image after fixing.

As a result of various studies on the above problems of the processing aid of synthetic resin, pigment dispersant for resin and toner, the above problems were solved by using the predetermined graft-modified low molecular weight polyolefin proposed in the present application. By finding out what can be done, each invention of the present application was completed.

That is, by using the graft-modified low molecular weight polyolefin (A) of the present application as a processing aid for synthetic resin,
It was found that the fluidity and releasability during molding can be improved without impairing the mechanical strength of the synthetic resin.

Further, originally, printing, coating, and non-polar resins such as polystyrene resins that are inferior in secondary processability such as adhesion, by blending the graft-modified molecular weight polyolefin of the present invention, Surprisingly, it has been found that the above-mentioned secondary processability can also be significantly improved.

Further, by using as a pigment dispersant for synthetic resin,
It has been found that the composition has excellent kneading workability with a pigment and a pigment dispersant, and also has excellent performance of not deteriorating various properties of a resin to be colored. That is, even in synthetic resins such as polystyrene, ABS, polycarbonate, polyester, polyamide, which have been conventionally difficult to master-batching, master-batching with excellent pigment dispersant properties is possible, and further master-batching of polyolefin or polyvinyl chloride. It has been found that even in the case of high density, high density can be achieved without causing appearance defects such as color unevenness.

Further, regarding the toner, it was found that the use of the modified low-molecular weight polyolefin (A) as a release agent makes it possible to obtain an electrostatic toner which hardly causes the offset phenomenon.
It was also found that the modified low molecular weight polyolefin is used as a thermoplastic resin which is a main material (binder) of an electrostatic toner to obtain an electrostatic toner which hardly causes an offset phenomenon. That is, it has been found that the modified low molecular weight polyolefin has excellent performance both as a releasing agent for the electrostatic toner and as a main material (binder).

[Outline of the present invention]

The present invention comprises 100 parts by weight of a low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g and an aromatic vinyl carboxylate (b) grafted in the range of 3 to 200 parts by weight. A graft-modified low-molecular weight polyolefin (A) in the range of 0.05 to 0.7 dl / g is used as a substance invention, and a processing aid for synthetic resin, a pigment dispersant, and a heat-fixing electrophotography, which comprises the graft-modified low-molecular weight polyolefin (A). Each of the forming elements of the toner for use is a use invention. Hereinafter, each invention will be described in detail.

[Graft-modified low molecular weight polyolefin and its production method]

The graft-modified low molecular weight polyolefin (A) of the present invention is obtained by grafting a predetermined amount of aromatic vinyl carboxylate (b) onto the low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g.

The low molecular weight polyolefin (a) used as a raw material for the graft reaction has an intrinsic viscosity [measured in decalin solvent at 135 ° C] in the range of 0.04 to 1.2 dl / g, and more preferably 0.05 to 1.0. It is in the range of dl / g.

Here, the low molecular weight polyolefin includes ethylene, propylene, 1-butene, 1-hexane, and 4-methyl-1.
A homopolymer of α-olefin such as pentene or 1-decene, or a copolymer of two or more α-olefins having an intrinsic viscosity within the above range. For example,
Polyethylene wax obtained by thermal decomposition of high-pressure polyethylene, high-pressure polymerized polyethylene wax obtained by radical polymerization of ethylene at high pressure, ethylene or at least one of α-olefins other than ethylene as a transition metal compound catalyst. Polyethylene wax or low molecular weight ethylene / α-olefin copolymer, polypropylene wax, poly-1-butene wax, poly-4-methyl-1 obtained by medium / low pressure (co) polymerization in the presence
-Pentene wax, propylene-4-methyl-1-pentene copolymer wax, hexene-1-4-methyl-1
Examples thereof include pentene copolymer waxes. The low molecular weight polyolefin mentioned here includes an oxide of low molecular weight polyolefin. The oxygen content in this case is usually within 10% by weight.

The aromatic vinyl carboxylate (b) to be grafted onto the low molecular weight polyolefin is represented by the following general formula.

(In the formula, X ¹ , Y ¹ , and Z ^{1 to} Z ³ are a bond or a substituent composed of an atom selected from the group of H, C, O and N, and l is 0 to 5 And m is 0 or 1.) X ¹ is specifically H-, CH _3- , CH ₃ -CH _2- , or HO.
-, H ₂ N-, and the like, and as Y ¹ , specifically, -C
_{H = CH -, - CH 2} -, - CH 2 -CH 2 -, - C≡C -, - NH-
_{CH 2 -, - CH 2 -CH} = CH-, —O—CH ₂ — and the like. Further, specifically as ^{Z 1 ~Z 3, H-, CH} 3 -, C 6 H 5 - , and the like.

Specifically, vinyl benzoate, vinyl cinnamate, α-vinyl vinyl cinnamate, β-vinyl vinyl cinnamate,
Vinyl phenylacetate, vinyl benzyl acetate, vinyl phenylpropionate, vinyl anilinoacetate, vinyl γ-phenylcrotonate, vinyl phenylpyrupinate, vinyl phenoxyacetate, among others, vinyl benzoate,
Vinyl cinnamate is preferred. You may use these in mixture of 2 or more types.

The graft amount of the aromatic vinyl carboxylate (b) to the low molecular weight polyolefin (a) is 3 to 200 parts by weight based on 100 parts by weight of the low molecular weight polyolefin (a). It is preferably 3 to 150 parts by weight when used as a processing aid for a synthetic resin or a pigment dispersant, and 5 when used as a forming element of a heat fixing type electrophotographic toner.
Or 200 parts by weight. When the modified low molecular weight polyolefin is used as a processing aid for synthetic resins, if the graft ratio is less than 3 parts by weight, the compatibility with polar polymers such as ABS, polycarbonate and polyester becomes poor, and the graft modified low molecular weight When the polyolefin is blended, the sliding effect and the releasing effect are obtained to some extent, but the mechanical strength of the molded article is lowered, which is not preferable. In addition, it is not preferable for non-polar polymers such as polyolefin and polystyrene because the secondary effect of improving secondary processability such as paintability and printability is lost.

On the other hand, when the graft ratio is more than 200 parts by weight, even if the graft-modified low molecular weight polyolefin is blended, the lubricating effect and the releasing effect of the blended synthetic resin are not improved. Further, when used as a pigment dispersant, if the graft amount is less than the above-mentioned essential range, the mechanical strength of the colored molded product is reduced for the same reason as described above for polar polymers such as ABS, polycarbonate and polyester. At the same time, a sufficient affinity with the pigment cannot be obtained, and the extrudability during the production of the master batch decreases. On the other hand, if the amount exceeds the essential range, the stickiness of the three rolls during the production of the master batch becomes severe and the workability becomes poor.

Further, when used as a toner forming element for electrophotography,
First, when used as a release agent, if the graft amount is less than the above desaturation range, the modified low-molecular weight polyolefin (A) has poor compatibility with the binder resin such as styrene resin, and the compatibility is low. While the effects of releasability, cohesion resistance, drum stain resistance, bending resistance, etc., which are improved with the improvement, become smaller, when the grafting amount exceeds the above upper limit, the modified polyolefin wax (A) and the styrene type The compatibility with a binder resin such as a resin becomes too large, and it becomes difficult for the modified low molecular weight polyolefin (A) in the toner to be released on the surface of the melt during fixing, and the effect as a release agent is obtained. Get inferior.

Further, when the modified low molecular weight polyolefin (A) is used as a binder, if the graft amount exceeds the upper limit, a sticking phenomenon to a heat fixing roller occurs when this is used as a toner raw material, and the graft amount is above the upper limit. If it is less than 1, the colorant is poorly dispersed and the fixability to paper is insufficient, which is not preferable.

The intrinsic viscosity [η] [measured at 135 ° C. in a decalin solvent] of the graft-modified low molecular weight polyolefin (A) of the present invention must be in the range of 0.05 to 0.7 dl / g.

When the intrinsic viscosity of the graft-modified low-molecular weight polyolefin (A) is less than 0.05, even if it is blended with a synthetic resin, the lubrication effect and releasability effect of the blend are excellent, but the appearance shrinkage of the molded article is reduced. The rate becomes inferior. Furthermore, bleeding out easily occurs on the surface of the molded product, which causes stickiness on the surface of the molded product. Further, even when it is used as a pigment dispersant, a sufficient melting effect cannot be obtained because of its low melt viscosity, and coloring unevenness occurs.

Further, when the intrinsic viscosity of the modified low molecular weight polyolefin (A) exceeds 0.7 dl / g, even if it is added to a synthetic resin, the improvement of the lubricity effect and the releasability of the composition is recognized. No improvement in moldability is observed. Also,
Even if it is used as a pigment dispersant, it is difficult to prepare a master batch because the melt viscosity is too high, and the suitability as a dispersant becomes insufficient.

Further, when used as a heat-fixing type electrophotographic toner forming element, when used as a release agent, when the intrinsic viscosity of the modified low molecular weight polyolefin (A) is below the above lower limit, the release agent component is melted. The viscosity becomes too low, a sufficient releasing agent effect cannot be obtained, and toner aggregation and photoreceptor contamination are likely to occur. Further, if the intrinsic viscosity of the modified low molecular weight polyolefin (A) exceeds the above upper limit, even if the modified low molecular weight polyolefin (A) is used as a toner raw material in the same manner, the compatibility with a styrene-based polymer, which will be described later, becomes insufficient, and the melt viscosity becomes low. Since it has a high pitch, it does not exhibit a sufficient releasing agent effect. When the graft-modified low molecular weight polyolefin (A) is used as a binder and the intrinsic viscosity is below the above lower limit, the toner may have a long shelf life and may be contaminated with a photoreceptor even when used as a raw material of a toner composition. However, since the melt viscosity is too low, it becomes a toner in which a clear image cannot be obtained. On the other hand, if the intrinsic viscosity of the modified low molecular weight polyolefin (A) exceeds the above upper limit, sufficient fixability on paper cannot be obtained even when used as a toner raw material. The intrinsic viscosity of the modified low molecular weight polyolefin (A) can be easily controlled by controlling the intrinsic viscosity of the low molecular weight polyolefin (a) as a raw material, the graft amount of vinyl aromatic acid, the reaction conditions and the like.

The graft-modified low molecular weight polyolefin (A) of the present invention may be grafted with a monomer other than the vinyl aromatic salt (b) together with the vinyl aromatic salt. Examples of such a monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, and acrylic. Stearyl acid, cyclohexyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, 2-hydroxyethyl acrylate, diethylaminoethyl acrylate, diethylene glycol ethoxylate acrylate, 2-ethoxyacrylate, 1 Acrylic esters such as 2,4-butanediol diacrylate, 2,2,2-trifluoroethyl acrylate, 2-acryloyloxyethyl acid phosphate, methyl methacrylate, ethyl methacrylate , Propyl methacrylate, methacrylate n
-Butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, meta Methacrylic acid esters such as diethylaminoethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2-methacryloyloxyethyl acid phosphate, monoethyl methacrylate Rate, diethylmalate, monopropylmalate, dipropylmalate, monobutylmalate, dibutylmalate, di2-ethylhexylmalate, monoethylfumarate, diethylfumarate, dibutylfumarate, di2 Ethylhexyl fumarate,
Unsaturated dibasic bases such as monoethyl itaconate, diethyl itaconate, monobutyl itaconate, di2-ethylhexyl itaconate, monoethyl citracone, diethyl traconate, dibetyl citracone, di 2-ethylhexyl citracone Acid ester, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, N-methylolacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylbutyral, vinylacetal, acrylic acid, methacrylic acid, etc. Can be mentioned. The graft amount of these monomers is preferably 50 mol% or less of the total graft monomer amount.

The graft-modified low molecular weight polyolefin of the present invention can be prepared by a conventionally known method, for example, Japanese Patent Publication No. 54-42381, JP-A No. 5-42381.
It can be produced according to the methods described in JP-A No. 9-219370 and JP-A No. 58-63947.

That is, for example, a method of reacting the low molecular weight polyolefin and the aromatic vinyl or the like under heating in a solution state or a molten state in which a solvent such as a hydrocarbon solvent or a halogenated hydrocarbon solvent is dissolved is adopted, Here, the reaction can be carried out in the presence of a radical initiator, if necessary.

The radical initiator used in the above reaction is an organic peroxide, an organic perester such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate). ) Hexin-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2 , 5-di (tert-butylperoxy) hexane, tert-butylphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylperpivalate and tert -Butyl perdiethyl acetate, other azo compounds such as There are azobis-isobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-
tert-butyl peroxide, 2,5-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) Dialkyl peroxides such as hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred. The temperature during the reaction is usually in the range of 130 to 350 ° C, preferably 135 to 300 ° C.

[Processing aid for synthetic resin]

The graft-modified low molecular weight polyolefin (A) of the present invention is effective as a processing aid for synthetic resins. The processing aid may be composed of the graft-modified low molecular weight polyolefin (A) alone, or may be composed of other processing aid, various plasticizers and various stabilizers.

There is a wide range of synthetic resins to which the processing aid of the present invention can be applied,
The synthetic resin as described in JP-B-54-42381 can be used as it is. That is, specifically, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and other polyolefin resins, polystyrene, ABS and other styrene resins Polycarbonate resins obtained from bisphenol A and phosgene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyphenylene oxide resins, poly (meth) acrylic acid ester resins such as polymethylmethacrylate, polyvinyl chloride And thermoplastic resins such as phenolic resins and epoxy resins.

In particular, the lubricant of the present invention can be preferably used for thermoplastic resins.

When the processing aid comprising the graft-modified low molecular weight polyolefin (A) of the present invention is added to the synthetic resin, the compounding ratio is usually 0.05 to 30 with respect to 100 parts by weight of the synthetic resin.
It is preferably in the range of parts by weight, and more preferably in the range of 0.1 to 20 parts by weight. When the blending ratio of the graft-modified low-molecular weight polyolefin (A) to 100 parts by weight of the synthetic resin is less than 0.05 parts by weight, the sliding effect and the releasing effect of the composition are improved, and the secondary property for the polyolefin resin and the polystyrene resin is improved. When the amount exceeds 30 parts by weight, delamination of the molded product becomes remarkable and the balance between mechanical strength and impact strength is lost.

As a method of blending the processing aid of the present invention with a synthetic resin, for example, in the case of a thermoplastic resin, a synthetic resin, a mixture of a graft-modified low molecular weight polyolefin and, if necessary, an additive thereof, a Henschel mixer, V-blender, ribbon blender are used directly after mixing, further kneading and granulating with an extruder, etc., melt-kneading with a Banbury mixer, a single-screw extruder or a kneader, etc., and granulating Can be adopted.

By using the processing aid of the present invention, it becomes possible to improve the fluidity, mold releasability and secondary workability during molding without deteriorating the mechanical properties of the resin after molding. Further, since it has excellent heat stabilizer and bleed-out property of itself, it has an advantage that metal stains at the time of molding and surface characteristics of the molded product are not impaired.

[Pigment dispersant for synthetic resins]

The graft-modified low molecular weight polyolefin (A) of the present invention is also useful as a pigment dispersant for synthetic resins.

In other words, as a result of earnestly examining the above-mentioned problems,
By using the dispersant of the present invention, polystyrene, which has been conventionally difficult to master-batching, ABS, polycarbonate, polyester, even in synthetic resins such as polyamide, master-batching having excellent pigment dispersibility becomes possible. Further, even in the master batch of polyolefin or polyvinyl chloride, it is possible to increase the concentration without causing an appearance defect such as color unevenness.

When the resin is used as a pigment dispersant, the thermoplastic resin described in the section of the processing aid can be used as it is. That is, specifically, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-
1. Polyolefin resin such as ethylene-propylene copolymer and ethylene-vinyl acetate copolymer, polystyrene, styrene resin such as ABS, for example, polycarbonate resin obtained from bisphenol A and phosgene, polyethylene terephthalate, polybutylene terephthalate, etc. Polyester resin, polyamide resin, polyphenylene oxide resin, polyvinyl chloride and the like.

The pigment dispersant of the present invention can be used for any pigment conventionally known for coloring synthetic resins. Specific examples of the pigment include metals such as aluminum, silver and gold;
Carbonates such as calcium carbonate and barium carbonate; ZnO, TiO ₂
Oxides such as; hydroxides such as Al ₂ O ₃ · nH ₂ O, Fe ₂ O ₃ , Fe ₂ O ₃ · nH ₂ O; sulfates such as CaSO ₄ and BaSO ₄ ; Bi (OH) ₂ NO ₃ Such as nitrates; chlorides such as PdCl ₂ ; chromates such as CaCrO ₄ , BaCrO ₄ ; chromates such as CoCr ₂ O ₄ , manganates and permanganates; boric acid such as Cu (BO) _2. Salt; Na ₂ U ₂ O ₇
・ Uranates such as 6H ₂ O; nitrites such as K ₃ Co (NO ₂ ) ₆・ 3H ₂ O; silicates such as SiO ₂ ; arsenates such as CuAsO ₃・ Cu (OH) ₂ and arsenite Cu (C ₂ H ₃ O ₂ ) ₂・ Cu (OH) ₂
Acetates such as; (NH ₄ ) ₂ MnO ₂ (P ₂ O ₇ ) ₂ and other phosphates;
Aluminate, molybdate, zincate, stannate, antimonate, tungstate selenide, titanate, iron cyanide, phthalate, sulfides such as CaS, ZnS, CdS, etc. Inorganic pigment, cochineal rake, mudder
Natural organic pigments such as lake, naphthol green Y,
Nitroso pigments such as naphthol green B; nitro pigments such as naphthol yellow S and pigment chlorin 2G; azo pigments such as permanent red 4R, Hansa yellow, brilliant carmine 6B, and scarlet 2R; bases such as malacaine green and rhodamine B Acid dyed lakes such as sex dyed rake, acid green rake, eosin and lake hex, mordant lakes such as alizarin lake and purpurin lake, thio / indigo / red B, intern / orange Examples of the organic pigments include phthalocyanine pigments such as dye pigments, phthalocyanine blue, and phthalocyanine green.

When the graft-modified low molecular weight polyolefin (A) of the present invention is used as a pigment dispersant for the aromatic polymer, the compounding ratio is usually 25 to 30 parts by weight, preferably 50 to 250 parts by weight, relative to 100 parts by weight of the pigment. It is a range of parts. Further, the pigment dispersant of the present invention can be used for coloring an aromatic polymer by a dry color method, a color combining method, or a master batch method. For example, in coloring by a dry color method or coloring by a color compound method, a mixture of a pigment and the dispersant of the present invention is finely pulverized to prepare a dry color in the form of powder or beads, which is mixed with an uncolored pellet. As an aromatic polymer, weigh and mix them together in a tumbler or a suitable mixer, evenly sprinkle the dry color on the surface of the resin pellets, and knead the resin melted by the screw through the extruder or by the molding machine. Disperse the pigment by shearing force and color it,
Mold this. In the above process, the molten colored resin is extruded from the extruder and cut, and the colored pellet is a color compound.

[Forming element of heat fixing type electrophotographic toner]

As described above, the graft-modified low molecular weight polyolefin (A) of the present invention is useful as a toner release agent and a binder. Hereinafter, a toner using the graft-modified low molecular weight polyolefin of the present invention will be described.

[Binder Resin When Modified Low Molecular Weight Polyolefin (A) is Used as Release Agent] Examples of the binder (thermoplastic) resin such as a styrene polymer used in the toner according to the present invention include JP-A- −27546
The styrene resin as described in 1), that is, a polymer composed of only a styrene monomer or a copolymer of a styrene monomer and another vinyl monomer can be used as it is. That is, as the monomer other than styrene for forming the copolymer, styrene-based monomers such as α-methylstyrene, p-methylstyrene, p-chlorostyrene and vinylnaphthalene, for example, ethylene, propylene, butylene and isobutylene. Ethylenically unsaturated monoolefins such as vinyl chloride, vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, such as acrylic acid. Methyl, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-chloro-ethyl acrylate phenyl acrylate, α-
Α such as methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate
-Esters of methylene aliphatic monocarboxylic acid, acrylonitrile, methacrylonitrile, acrylamide,
For example, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc., such as vinyl methyl ketone, vinyl hexyl ketone,
Vinyl ketones such as methyl isopropenyl ketone, for example, N-vinylpyrrole, N-vinylcarbazole,
N such as N-vinylindole and N-vinylpyrrolidone
-Vinyl compounds and the like, and one or more of them can be copolymerized with a styrene monomer. Suitable styrenic polymers are about 2000 or more, particularly preferably
It preferably has a number average molecular weight of 3000 to 30,000 and its styrene content is at least about 25% by weight based on the total flow rate of the styrenic polymer.

Other thermoplastic resins include, for example, polyester resins, ketone resins, maleic acid resins, coumarone resins, phenol resins, epoxy resins, terpene resins, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, Examples thereof include ethylene-vinyl acetate copolymer.

Of the above, a styrene polymer or a polyester resin is preferable.

[Resin that may be added in addition to the case where the modified molecular weight polyolefin (A) is used as a binder] The thermoplastic resin which is the main material of the electrostatic toner does not always have the above graft-modified low molecular weight polyolefin (A). It does not need to be present, and if it accounts for 20% by weight or more, preferably 50% by weight or more of the thermoplastic resin, an electrostatic toner with an improved offset phenomenon can be obtained. Mixing with the modified low molecular weight polyolefin (A) Examples of the thermoplastic resin for electrostatic toner used include various thermoplastic resins exemplified above as the binder.

[Colorant (B)] The colorant (B) used in the electrostatic toner according to the present invention includes carbon black, phthalocyanine blue, aniline blue,
It comprises one or more pigments or dyes such as alcohol oil blue, chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine B lake, carmine 6B and quinacridone derivative. If necessary, for the purpose of complementary color and charge control, azine-based nigrosine, isodiurine, azo-based,
You may use together an oil-soluble dye, such as an antoniquinone type | system | group, a triphenyl methane type | system | group, a xanthene type | system | group, and a phthalocyanine type.

[Other Components] The toner according to the present invention may contain other components in addition to the components (A) and (B) or the above-mentioned thermoplastic resin as long as the effects of the present invention are not impaired. . Other toner additives such as charge control and plasticizers may be included. The amount of these added is arbitrary and appropriate.

[Toner Preparation Method] When the electrostatic toner according to the present invention is used as a two-component electrostatic toner, the graft-modified low molecular weight polyolefin (A), the colorant (B) and, if necessary, the above-mentioned thermoplastic After mixing with a resin by a known method such as a ball mill or an attritor, it is kneaded by a heating two rolls, a heating kneader, an extruder or the like, cooled and solidified, and then roughly crushed by a hammer mill, a classifier, etc., and then a jet mill, a vibration mill. Alternatively, water is added and finely pulverized by a ball mill, an attritor or the like, and an electrostatic toner having an average particle size of about 5 to 35 μm is used. When a two-component electrostatic toner is used as a developing material, a carrier is also used. As the carrier, known materials such as silica sand having a diameter of 200 to 700, glass beads, iron balls or magnetic material powders of iron, nickel, cobalt and the like can be used. In the case of using the modified low molecular weight polyolefin (A) as a release agent in a two-component electrostatic toner, the amount of the modified low molecular weight polyolefin (A) is 100 parts by weight of the thermoplastic resin including the binder resin. 1 to 20 parts by weight, preferably 2 to 10 parts by weight are added. When the modified low molecular weight polyolefin (A) is used as a binder, the amount of the modified low molecular weight polyolefin (A) is 20 parts by weight based on 100 parts by weight of the total amount of (A) and the thermoplastic resin to be added. More preferably, 50 parts by weight or more is added.

When the electrostatic toner of the present invention is used as a one-component electrostatic toner, the modified low molecular weight polyolefin (A),
The colorant (B) and, if necessary, the above-mentioned thermoplastic resin and magnetic material powder can be adjusted by a method similar to that for adjusting the two-component electrostatic toner. As the magnetic material powder to be added to the one-component electrostatic toner, magnetite fine powder having a particle size of 1 μm or less is usually used, but powders of metals such as cobalt, iron and nickel, alloys thereof, oxides, ferrite and mixtures thereof. Can also be used. The amount of each component in the one-component electrostatic toner is usually 40 to 70 parts by weight based on 100 parts by weight of the total amount of the thermoplastic resin including the modified low molecular weight polyolefin (A) and the magnetic material. Good. If the amount of the magnetic material is too large, the electric resistance of the electrostatic toner decreases, the charge retention of the electrostatic toner deteriorates, and the image may blur. Further, the softening point of the electrostatic toner becomes high, which may make appropriate fixing difficult. On the other hand, when the amount of the magnetic material is too small, the function as the electrostatic toner is lost, the required charging ability cannot be obtained, and the toner easily scatters. Also in the one-component electrostatic toner, the amount of the modified low molecular weight polyolefin (A) added to all the resins is the same as in the two-component electrostatic toner. If necessary, a known charge control agent may be added to the one-component electrostatic toner or the two-component electrostatic toner.

[Effects of the Invention] Whether the modified low molecular weight polyolefin of the present invention is used as a release agent or a binder, the heat-fixing type electrophotographic developer of the present invention can be heated not only at a conventional temperature but also at a high temperature. Since it is excellent in peelability from a roll or the like, the offset phenomenon does not easily occur even if the heating roll or the like is heated to a high temperature to increase the fixing speed, and therefore it is suitable for high-speed copying. Further, since it is excellent in fixing property to paper, sufficiently excellent performance can be obtained even when the temperature of a heating roll or the like is low, which is also suitable for energy-saving copying. Further, it has low cohesiveness, excellent development characteristics, and excellent bending resistance after fixing.

When the graft modified low molecular weight polyolefin according to the present invention is used as a release agent, the modified low molecular weight polyolefin is not only excellent in compatibility with a binder resin such as a styrene-based polymer, but also various additives, For example, it is also excellent in compatibility or affinity with pigments, dyes, charge control, plasticizers and the like. Therefore, it also has the functions of enhancing the dispersibility in these binder resins, enhancing the physical uniformity of the toner such as charge controllability, and improving the performance as a developer.

〔Example〕

The present invention and their effects will be described in more detail with reference to the following examples.

Example (Preparation of aromatic vinyl carboxylate-modified low molecular weight polyolefin) Preparation example 1 (W-1) 540 g of low molecular weight high density polyethylene having an intrinsic viscosity of 0.32 dl / g
It was charged in a glass reactor of 1.5 and melted at 160 ° C.
Then, 160 g of vinyl benzoate and 13.0 g of di-tert-butyl peroxide (hereinafter abbreviated as DTBPO) are added, and 5
The reaction was carried out by heating for an hour. Then, in the molten state, 5mmHg
The mixture was degassed in vacuum for 1 hour to remove volatile matter, and then cooled. The intrinsic viscosity of the obtained vinyl benzoate-modified low-molecular-weight polyethylene (W-1) was 0.33 dl / g. Also,
30 g of the modified low molecular weight polyethylene was dissolved in 300 ml of para-xylene, and the resulting solution was added to acetone 1 at room temperature with stirring and cooled to room temperature. The precipitated solid part was further washed twice with 500 ml of acetone and dried. The content of vinyl benzoate in the obtained solid part was quantified by ¹ H-NMR. The amount of graft thus obtained was 21 parts by weight to 100 parts by weight of vinyl benzoate-grafted modified low molecular weight polyolefin (ie, 27 parts by weight of vinyl benzoate to 100 parts by weight of polyethylene wax (a)). It was grafted. Preparation Example 2 to 18 (W-2 to 18) Other than changing the raw low molecular weight polyolefin type and charging amount, aromatic vinyl carboxylate type and charging amount, DTBPO amount, and reaction time as shown in Table 1. Various aromatic vinyl carboxylate-modified low molecular weight polyolefins were obtained in the same manner as in Preparation Example 1. In addition, Table 1 also shows the intrinsic viscosity of the obtained modified low-molecular weight polyolefin and the graft amount of aromatic vinyl carboxylate.

In the table, Preparation Examples other than Preparation Examples 3, 6, 9, 13, and 14 relate to the graft-modified low molecular weight polyolefin (A) of the present invention.

Examples 1-2 and Comparative Examples 1-2 The modified low molecular weight polyethylene obtained in Preparation Examples 1 to 3 and the raw material unmodified low molecular weight polyethylene were commercially available polycarbonate resins (trade name: Panlite L-1250, Teijin Chemicals ( Co., Ltd., hereinafter referred to as PC) 0.5, 1 and 2 parts by weight with respect to 100 parts by weight of dry blend, and then granulated with a 20 mmφ extruder (set temperature 280 ° C., 50 rpm) to obtain the extrusion amount,
Further, the granulated sample was molded into a test piece for a tensile strength test using an IS-50 type injection molding machine manufactured by Toshiba Machine Co., Ltd. At the same time, a spiral flow test was performed (resin temperature 280 ° C, mold temperature 50 ° C, injection pressure 1000 kg / cm ² ).

Tensile Properties: Measured by the method of ASTM D638.

Spiral length: For example, Mod. Plastics, 34, [12], P.111
In the spiral flow test method as described in
The length of the spiral obtained under the above setting conditions was measured. The larger this value is, the better the fluidity at the time of melting.

Releasability: Depending on the condition when taking out the molded square plate from the metal frame,
The state where the square plate can be taken out of the metal frame without resistance is set to 5, and the state where the square plate and the metal frame cannot be taken out without corrective peeling with a razor etc. is set to 1.
It was carried out by graded evaluation.

Comparative Example 3 The PC used above was tested alone as in Example 1. The above results are shown in Table 2.

Examples 3 to 4 and Comparative Examples 4 to 5 Using the modified and oxidized low molecular weight polyethylenes obtained in Preparation Examples 4 to 5 and the oxidized low molecular weight polyethylene as a raw material, commercially available polyvinyl chloride [trade name ZEON 103 EP-8 , Zeon Co., Ltd., polymerization degree 1050, hereinafter referred to as PVC) was evaluated as a processing aid. However, the performance evaluation method is as follows.

100 parts by weight of the above PVC, 30 parts by weight of adipic acid diocluester (manufactured by Wako Pure Chemical Industries), epoxidized soybean oil (trade name 0
-130P, manufactured by ADEKA ARGUS) 10 parts by weight, 2 parts by weight of aliphatic monoglyceride (trade name Rikemarker L-250, manufactured by Riken Vitamin Co.) and 0.2 or 0.4 parts by weight of the above processing aids in a Henschel mixer at 90 ° C. Mix for 3 minutes. This mixture was kneaded with a two-roll and the lubricity was evaluated.

(1) Roll operating conditions Roll diameter: 8 inches Surface temperature: 170 to 175 ° C Roll gap: 0.5 mm Roll rotation speed: 18 rpm / 16 rpm Sample amount: 150 g / 1 time (2) Lubricant effect evaluation method Gelation time: Between rolls The sample was charged into the sample, and the time required for the sample to be melted into a sheet and wound on a roll was shown.

Releasability with roll: Put the sample on the roll, mix for 2 minutes, stop the roll, and after roll stop 5, 10, 20, 30
The ease of peeling of the sheet after a minute was observed.

A: Good peelability.

B ... Things that are difficult to peel off.

C · · Those that cannot be peeled off.

Bloom phenomenon evaluation method: After kneading with a double roll for 10 minutes, press processing (150 ° C.) is performed to obtain a sheet of 10 × 10 × 1 cm. After allowing this sheet to stand still at 70 ° C. and 90% RH for 1 week, the bloom phenomenon is visually evaluated.

A ... Bloom phenomenon does not occur.

B ・ ・ 〃 occurs in the range of less than 1/2 of the total area of the seat.

C .. Bloom phenomenon occurs in the range of more than 1/2 of the total area of the sheet.

Comparative Example 6 The PVC used above was tested alone as in Example 3. The above results are shown in Table 3.

Examples 5 to 6 and Comparative Example 6 Using the modified low molecular weight polypropylene obtained in Preparation Example 9, commercially available polypropylene (Mitsui Petrochemical Polypro J-
Performance evaluation was performed for 600).

Modified low-molecular-weight polypropylene was mixed at a ratio of 0.5, 1 and 2 parts by weight to 100 parts by weight of PP, respectively, and then used for tensile strength test with a V-14-65 type injection molding machine manufactured by Japan Steel Works Ltd., mirror surface. Molded plates for measuring glossiness and for printability test were molded. Spiral flow test was conducted at the same time (cylinder temperature 210 degrees, mold temperature 40 degrees, injection pressure 1000kg / cm
² ).

The specular gloss temperature was measured according to ASTM D-523.

The printability was evaluated by applying a commercially available water-based ink (Aquaxide, manufactured by Toyo Ink Mfg. Co., Ltd.) to the above-mentioned molded plate with a doctor blade (1 mil), and the affinity of the ink on the molded plate at that time ( It was assimilated whether the ink repellency phenomenon did not occur) and the adhesion after drying were examined by a cross-cut test.

Comparative Example 7 The same test as in Example 5 was carried out using the PP used above alone.

The above results are shown in Table 4.

Examples 7 to 8 The modified low-molecular-weight ethylene / propylene copolymers obtained in Preparation Examples 10 to 11 were mixed with a commercially available ABS resin (trade name: Styfuk 10).
1, Asahi Kasei Corporation, hereinafter referred to as ABS) to 100 parts by weight
0.5 after dry blending at 1 and 2 parts by weight 2
The amount of extrusion was determined by granulating with a 0 mmφ extruder (set temperature 230 ° C., 50 rpm). Further, with respect to the granulated sample, the fluidity at the time of injection molding, the releasability, and the strength test of the molded product were conducted in the same manner as in Example 1.

Comparative Example 9 The same test as in Example 7 was carried out using the ABS used above alone. The above results are shown in Table 5.

Examples 9 to 12 and Comparative Examples 10 to 12 Using the modified low molecular weight polybutene-1 and modified low molecular weight polyethylene obtained in Preparation Examples 12 to 18, performance evaluation as a pigment dispersant for polyethylene terephthalate and low density polyethylene was performed. Ivy. The results are shown in Table 6.

[Performance evaluation method for pigment dispersant]

100 parts by weight of fine powder of pigment dispersant is dissolved at 180 degrees, and 100 parts by weight of phthalocyanine blue (for polyethylene terephthalate) or 230 parts by weight (for low density polyethylene) is gradually added while kneading to a radius of about 2.5. A spherical kneaded product of cm was obtained. This kneaded solid was supplied to a three-roll kneader at 130 ° C., and the discharge speed was evaluated from the passing time and the discharge amount.

Further, this kneaded composition and polyethylene terebutarate (trade name: Mitsui PET, J-125, Mitsui Petrochemical Industry Co., Ltd.)
Manufactured by PET, or low density polyethylene (trade name: Mirason 24H, manufactured by Mitsui Deyupon Polychemical Co., Ltd., hereinafter referred to as LDPE) at a ratio such that the pigment concentration in the kneaded molded product becomes 1 wt%. 280 ℃ (for PET) [210 ℃ (LD
PE)] was fed to a 20 mmφ extruder rotating at a speed of 50 rpm and kneaded to obtain a master batch.

The extrusion processability was evaluated by visually observing the surface condition of the strand and the uniformity of the strand diameter at this time.

Also, using each master batch, press temperature
By pressing at 280 ° C (PET) and 210 ° C (LDPE), a master batch film having a thickness of 0.1 mm was obtained.

The pigment dispersant in this mashitabatchi film is
The evaluation was made on a scale of 5 (5).

5. 50μ or more particles, 1.00 × 10 ³ particles / cm ³ or less 4. 50μ or more particles, 1.00 × 10 ³ particles / cm ³ to 7 × 10 ³ particles / cm ³ 3. 50μ or more particles, 7 × 10 ³ pcs / cm ³ to 2.7 × 10 ⁴ pcs / cm ³ 2. 50μ or more particles, 2.7 × 10 ⁴ pcs / cm ³ 〜 7.00 × 10 ⁴ pcs / cm ³ or more 1. 50μ or more particles , 7.00 × 10 ⁴ pcs / cm ³ or more (Measurement was performed with an Lvzex450 image processor manufactured by Toyo Ink Co., Ltd.) The effects of using the modified low molecular weight polyolefin (A) of the present invention as a forming element of a heat-fixing type electrophotographic toner will be described in more detail below with reference to examples. Example 13
To 19 and Comparative Examples 13 to 16 are experimental examples showing the effect when the modified low molecular weight polyolefin (A) of the present invention is used as a release agent, and Examples 20 to 23 and Comparative Examples 17 to 18 are It is an experimental example which shows the effect when the modified low molecular weight polyolefin (A) of the present invention is used as a binder.

Example 13 (Preparation of toner and copy test) Styrene / n-butylmethacrylate copolymer (manufactured by Sanyo Kasei Co., Ltd., Hymer SBM-600) 85 parts by weight, W-1 4 parts by weight synthesized in Preparation Example 1, carbon black 9 parts by weight of (Mitsubishi Chemical Industries Diamond Black SH) and 2 parts by weight of a metal-containing dye (BASF's Zavon Farst Black B) were mixed in a ball mill for 24 hours, kneaded with a hot roll, cooled, ground and classified. ~ 15μ electrostatic toner was made. Then average particle size
Iron particles of 50 to 80μ are mixed as a carrier at a ratio of 120 parts by weight of electrostatic toner to 100 parts by weight of a carrier, developed by a conventionally known electrophotographic method on a selenium photoreceptor, and transferred onto a transfer paper. It was heated and fixed with a heating roll of 180 ° C.
As a result, even after 5000 times of copying, a clear copy image was obtained as in the initial stage without any offset phenomenon or contamination, and almost no contamination of the heat roll or the photosensitive drum was observed.

Example 14 7 parts by weight of W-8 synthesized in Preparation Example 8, Heimer SBM-6
A toner was prepared in the same manner as in Example 1 by using 82 parts by weight of 00, 9 parts by weight of diamond black, and 2 parts by weight of savon-first black, and a copy test was conducted. As a result, even after copying 10,000 times, a clear copy image was obtained as in the initial stage, without offset phenomenon and contamination, and the contamination of the heat roll and the photoconductor drum was hardly recognized.

Further, a bending resistance test was conducted. The solid black image area after fixing was repeatedly bent 500 times, and the fixing degree before and after the bending was visually determined by peeling with a cellophane tape. As a result, it was found that there was almost no change after the bending test, and the bending resistance was excellent.

Example 15 A toner was prepared in the same manner as in Example 13 except that W-12 was used instead of W-1 in Example 13, and a copy test was conducted.

As a result, even after 5000 times of copying, a copy image as clear as the initial stage and free from offset phenomenon and contamination can be obtained.
Almost no contamination of the heat roll and the photosensitive drum was observed.

Further, the temperature change of the fluidity of the toner was examined. The toner was placed on a shere and the fluidity was visually determined.
As a result, it was found that the fluidity of the one kept at 50 degrees for 48 hours and that of the one kept at room temperature were almost the same, and the fluidity was excellent even in the high temperature environment.

Example 16 A toner was prepared in the same manner as in Example 13 except that W-17 was used instead of W-1 in Example 13, and a copy test was conducted.

As a result, even after 5000 times of copying, a copy image as clear as the initial stage and free from offset phenomenon and contamination can be obtained.
Almost no contamination of the heat roll and the photosensitive drum was observed.

Example 17 A toner was prepared in the same manner as in Example 13 except that W-4 was used instead of W-1 in Example 13, and a copy test was conducted.

As a result, even after copying 3000 times, a clear copy image without offset phenomenon and stain was obtained as in the initial stage, and almost no stain was observed on the heat roll and the photosensitive drum.

Further, in the same manner as in Example 15, the change in toner fluidity with temperature was examined. As a result, the results obtained by holding the toner at 50 ° C. for 48 hours competed with those at the room temperature and the flowability was slightly deteriorated, but no lumps were formed, suggesting that there is no problem in practical use.

Example 18 A toner was prepared in the same manner as in Example 14 except that W-16 was used instead of W-8 in Example 14, and a copy test was conducted.

As a result, even in the 5000-time copying test, a clear copy image was obtained as in the initial stage without any offset phenomenon or contamination, and almost no contamination of the heat roll or the photosensitive drum was observed.

Further, a bending resistance test was conducted in the same manner as in Example 14. As a result, it was found that the retention rate of fixing degree before and after the bending test was extremely high, and the bending resistance test was also excellent.

Example 19 Polyester resin (SANYO CHEMICAL INDUSTRIAL HIMER ES 508) 48 parts by weight, carbon black (MITSUBISHI KASEI MA-100) 2 parts by weight, magnetic powder'titanium industry MABIROBLACK BL-500) 48
1 part by weight and W-22 parts by weight are mixed in a ball mill for 24 hours, kneaded in a heating roll for 1 hour, then finely pulverized in a jet mill and heat-treated in a spray dryer, and a magnetic toner having an average particle size of 15 μ is obtained in a zigzag classifier. Obtained. Using the magnetic toner, a selenium photoconductor was developed by a conventionally known electrophotographic method, transferred onto a transfer paper, and a durability test of 5000 times of transfer with a heating roll temperature set at 200 ° C. was performed. As a result, a good copy image was obtained without stains on the heating roll.

Comparative Example 13 Next, a toner was prepared in the same manner as in Example 14 except that W-13 was used instead of W-8 in Example 14, and a copy test was conducted.

As a result, the sharpness of the image started to decrease from the 4000th time. At the same time, a polyethylene wax coating (filmmind phenomenon) was partially observed on the surface of the photoconductor drum and the iron powder carrier.

Further, when a bending resistance test was performed in the same manner as in Example 14, remarkable peeling of toner was observed along the folding line, which was inferior to that in Example 14.

Comparative Example 14 Next, a toner was prepared in the same manner as in Example 13 except that W-1 was used instead of W-1 in Example 13, and a copy test was conducted. As a result, the releasability from the hot roll was poor, and the offset phenomenon and the contamination of the copy paper were observed.

Furthermore, when the temperature change of the fluidity of the toner was examined in the same manner as in Example 15, it was suggested that the toner having a retention of 50 degrees produces a lump of 5 mm square or more, the fluidity is poor, and there is a practical problem. It was a result.

Comparative Example 15 A toner was prepared and a copying test was conducted in the same manner as in Example 13 except that W-9 was used instead of W-2.

As a result, the releasability from the hot roll is extremely poor, and also
A large amount of filming phenomenon was observed on the photoconductor drum and iron powder carrier.

Comparative Example 16 300 g of the raw material polypropylene used to prepare W-7 of Preparation Example 7 was charged into an autoclave having an internal volume of 1, and pyrolysis was carried out at 340 ° C. for 2.2 hours while passing a slight amount of nitrogen.
The obtained polypropylene wax [η] was 0.06 dl / g.

Then, in Example 14, a toner was prepared in the same manner as in Example 14 except that the above polypropylene wax was used instead of W-8, and a copy test was conducted.

As a result, the sharpness of the image started to decrease from the 3500th copy. At the same time, partial coating of polypropylene wax (filming phenomenon) was observed on the surface of the photoconductor drum and the carrier of iron powder.

Furthermore, when the temperature of fluidity of the toner was examined at the same time as in Example 15, those after holding at 50 ° C. produced lumps of about 5 mm square or more, and the fluidity was extremely poor, which was a problem in practical use. The result suggests that

Example 20 Modified low molecular weight polybutene-1 (W- prepared in Preparation Example 15)
15) An electrostatic toner composed of 100 parts by weight, 5 parts by weight of carbon black (trade name: Diamond Black SH, manufactured by Mitsubishi Kasei) and 2 parts by weight of a metal-containing dye (BASF Co., Ltd., Zaboon Fast Black B) was used as Example 13. It was prepared by the same method. Next, carrier 10 with iron powder having an average particle size of 50 to 80 μ is used as a carrier.
Mixing 120 parts by weight of electrostatic toner to 0 parts by weight,
It was developed on a selenium photoreceptor by a conventionally known electrophotographic method, transferred, and heat-fixed with a heating roll. As a result, even after 2000 copies, it was as clear as the initial stage and the offset phenomenon,
A copy image without contamination was obtained, and neither contamination of the hot roll nor drum was observed.

Example 21 50 parts by weight of W-1 obtained in Preparation Example 1, 50 parts by weight of low molecular weight polystyrene (commercial name: Hymer ST-95, Sanyo Kasei KK) and 5 parts by weight of carbon black used in Example 13 and metallurgical content 2 parts by weight of the dye were kneaded and pulverized in the same manner as in Example 20 to obtain an electrostatic toner (including a carrier). Next Example
As a result of copying 1000 times in the same manner as in No. 20, a copy image as clear as the initial stage and free from offset phenomenon and contamination was obtained, and no contamination of the hot roll or drum was observed.

Comparative Example 7 An electrostatic toner was obtained in the same manner as in Example 20 except that low molecular weight polystyrene (trade name: Hymer ST-95, Sanyo Kasei KK) was used instead of W-15 used in Example 20. Next, as a result of copying 1000 times by the same method as in Example 20, the peeling from the hot roll was inferior, the offset phenomenon and the contamination of the copy paper were observed.

Example 22 W-1 used in Example 13: 40 parts by weight, magnetic powder (trade name: Mavirobraque BL-500, Titanium Industry KK): 50 parts by weight, ethylene / vinyl acetate copolymer (trade name: Evaflex 46
0, Mitsui Deupon Polychemical KK) 10 parts by weight and carbon black (Product name MA-100, Mitsubishi Kasei KK): 2
Part by weight is mixed with a ball mill for 24 hours and then mixed with a heating roll.
After kneading for a while, the mixture was finely pulverized with a jet mill and then heat-treated with a spray dryer to obtain a magnetic toner having an average particle diameter of 15 μ by a zigzag classifier. Using the magnetic toner, a selenium photoreceptor was developed by a conventionally known electrophotographic method, transferred onto a transfer paper, and a durability test of 5000 times of copying was performed with the heating roll temperature set at 200 ° C. As a result, good images were obtained without stains on the heating roll and drum.

Example 23 Except that a mixture of W-1: 25 parts by weight and the low molecular weight polystyrene: 25 parts by weight used in Example 21 was used as the resin component instead of W-1: 40 parts by weight used in Example 22. A magnetic toner was prepared in the same manner as in Example 22. As a result 2000
Even in the repeated copying, good copied images were obtained without contamination of the heating roll and the drum.

Comparative Example 18 Example 2 except that 40 parts by weight of the low molecular weight polystyrene used in Comparative Example 17 was used in place of 40 parts by weight of W-1 of Example 22.
A magnetic toner was prepared in the same manner as in 2. As a result, after 1000 times of copying, the heating roll was contaminated and the copied image became unclear.

Example 24 A toner was prepared in the same manner as in Example 22 except that 40 parts by weight of W-4 used in Example 17 was used instead of 40 parts by weight of W-1 of Example 22. I made a copy test 5,000 times. As a result, even after the copying, the heating roll and the drum were not contaminated, and a good copied image was obtained.

Claims (4)

[Claims] 1. An aromatic vinyl vinylate (b) is grafted in an amount of 3 to 200 parts by weight onto 100 parts by weight of a low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g. Graft-modified low molecular weight polyolefin (A) in the range of 0.05 to 0.7 dl / g. 2. An aromatic vinyl carboxylate (b) is grafted to 100 parts by weight of a low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g in the range of 3 to 200 parts by weight, and the intrinsic viscosity is A processing aid for synthetic resins comprising a graft-modified low molecular weight polyophine (A) in the range of 0.05 to 0.7 dl / g. 3. An aromatic vinyl vinylate (b) is grafted to 100 parts by weight of a low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g in the range of 3 to 200 parts by weight, and the intrinsic viscosity is A pigment dispersant for synthetic resins, comprising a graft-modified low molecular weight polyolefin (A) in the range of 0.05 to 0.7 dl / g. 4. A 100 parts by weight of a low molecular weight polyolefin (a) having an intrinsic viscosity of 0.04 to 1.2 dl / g is grafted with an aromatic vinyl carboxylate (b) in an amount of 3 to 200 parts by weight, and has an intrinsic viscosity of A heat-fixing electrophotographic toner forming element comprising a graft-modified low molecular weight polyolefin (A) in the range of 0.05 to 0.7 dl / g.