JPS62148508A - Modified low-molecular weight polyolefin and use thereof - Google Patents

Abstract

PURPOSE:A polyolefin, obtained by grafting a vinyl aromatic carboxylate onto a low-molecular weight polyolefin in a specific proportion, having a specified intrinsic viscosity and improved compatibility with binder resins and suitable for high-speed copying and energy saving copying. CONSTITUTION:A polyolefin, obtained by grafting 3-200pts.wt. vinyl aromatic carboxylate, preferably a compound expressed by the formula (X<1>, Y<1>, Z<1>-Z<3> are bond or substituent group constituted of atoms selected from H, C, O and N; l is an integer of 0-5; m is 0 or 1), e.g. vinyl benzoate, etc., onto 100pts.wt. low-molecular weight polyolefin, e.g. homopolymer or copolymer of ethylene, 1-butene, 4-methy-1-pentene, etc., and having 0.05-0.7dl/g intrinsic viscosity. USE:Used as processing assistants for synthetic resins, pigment dispersing agents for aromatic synthetic resins, forming elements of heat fixing elec trophotographic toners, etc.

Description

Detailed Description of the Invention [Industrial Field of 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 synthesis of the graft-modified low-molecular-weight male polyolefin) for Δ4 fats. It relates to a processing aid, a pigment dispersant, or a forming element of a heat-fixable electrophotographic toner.

[Conventional technology]

(1) During heat processing of synthetic resins, in order to improve the processing 1'L, as described in Japanese Patent Publication No. 54 42381], lubricious lubricants, fluidity improvers J, type Il agents, slip agents, etc. However, in recent years, graft-modified polyolefin waxes such as those described in this publication have come to be used. Such modified polyolefin waxes have better lubricity and lubricity than conventionally used metal soap esters, amides, and higher alcohols.
It is excellent in terms of thermal stability, transparency, bleed-out property, etc., but aromatic and/or Because the compatibility with resins containing scratchable groups is still insufficient, the effect of improving the fluidity during injection molding or cast molding of these resins is insufficient, and when the amount added is increased, molding There were problems such as a significant deterioration in the mechanical properties of the subsequent resin.

(2) Polystyrene, ABS, polycarbonate,
As a method for coloring synthetic resins such as polyester and polyamide, the dry color method or the color compound method is mainly used, and the master hatch method is not often used. Either of the first two methods,
Pigment dispersants are used to distribute pigments uniformly. For example, conventionally, various metal salts of higher fatty acids such as stearic acid, low molecular weight polystyrene, styrene-acrylic acid ester copolymer oligomers, etc. have been used as pigment dispersants for these synthetic resins. However, when a higher fatty acid is used as a pigment dispersant, phenomena such as bleeding of the higher fatty acid salt from the colored polymer, a decrease in the agent content to 11% of the pigment, and a decrease in transparency may occur. The disadvantage is that this occurs. Furthermore, when a low molecular weight polyolefin is used as a pigment dispersant, the kneading workability is poor when preparing a dry color or when kneading the dry color into, for example, a styrene polymer, and as a result, the pigment content Hk, It also has the disadvantage of being inferior in gender. Further, when the conventional dispersant is used, it is impossible to uniformly disperse a large amount of pigment in the synthetic resin, so the master hatch method cannot be used.

On the other hand, as a method for coloring polyolefin resins such as polyethylene and polypropylene, and vinyl chloride resins, pigments are dispersed at high concentrations in polyethylene and other carrier resins using agents such as low molecular weight polyethylene and fatty acid metal soaps. The master hatch method is often used. However, with conventional masterbatches, it is not possible to increase the pigment concentration very high, and in recent years, the coloring of polyolefin-based and other synthetic resins has moved toward high dilution ratios and high-speed coloring, and conventional masterbatches do not allow for high pigment concentration. This is becoming difficult, especially for thin-walled large injection molded products, as the dispersion speed of dyes and pigments into the resin to be colored by the master hatch is insufficient, resulting in problems with poor appearance such as uneven coloring of the molded products. It was inevitable.

(3) So-called electrostatic toner (hereinafter also simply referred to as toner) is an image forming + A material used in the next stage of electrostatic electrophotographic charging and exposure. Face: A charged fine powder in which I'4 is dispersed.

In general, electrostatic toners include dry two-component toners that are used with carriers such as iron powder or glass particles, wet toners that are dispersed using an organic solvent such as isoparaffin, and even fine magnetic powder. It is classified as a dry-component toner.

The image developed on the photosensitive plate with electrostatic toner is transferred to paper, and the image developed directly on the paper coated with the photosensitive layer is fixed as it is with heat or solvent vapor. Among these, fixing using a heated roller is preferable because it is a contact fixing method, has a high thermal effect, can reliably fix images using a heat source at a relatively low temperature, and is also suitable for high-speed copying.

However, when fixing an image by contacting a heating body such as a heating roller, there is a risk that a so-called offset phenomenon may occur in which a portion of the electrostatic toner adheres to the heating body and is transferred to a subsequent image portion.

Particularly in high-speed copying, raising the temperature of the heating element to increase the fixing effect and fixing speed tends to cause the off-cella I phenomenon more easily.

For this reason, for example, when fixing an image formed using a component-based electrostatic toner using a heated roller, the offset phenomenon is eliminated by impregnating the roller surface with silicone oil or supplying silicone oil to the roller surface. However, this results in problems such as staining of the rolls.

On the other hand, the thermoplastic resin that is the main material of electrostatic toner is
Polystyrene resins such as polystyrene, styrene/(meth)acrylic acid ester copolymers, polyester resins, ketone resins, maleic acid resins, coumaron resins, phenolic resins, epoxy resins, terpene resins, polyvinyl butyral, polybutyl methacrylate, etc. Among them, polystyrene resin has good charging properties, has a suitable softening point (90°C to 160'C) and has good fixing properties, is easy to clean the photosensitive plate and causes little contamination, and has low hygroscopicity. It is most commonly used because it has characteristics such as good miscibility with carbon black, which is a colorant, and ease of crushing. However, as described above, polystyrene resins having such characteristics are also susceptible to offset phenomenon during high-speed copying, and therefore it is desired to develop an electrostatic toner that does not cause offset phenomenon.

Methods to solve the above problems include (i) improving the roof plastic resin itself, which is the main material of the electrostatic toner, and (11) using the thermoplastic resin, which is the main material of the electrostatic toner, as it is. There are two methods that can be considered: a method of adding a mold release agent for the purpose of preventing this phenomenon.

In order to solve the above problem by the method (11) above, a technique of adding polyolefin wax to a styrene polymer as a mold release agent was proposed, for example, in Japanese Patent Publications No. 52-3304 and No. 52-3304.
2-3305, 57-52574, 58-594
55, etc. However, even with this technology, the compatibility between the polyolefin wax and the styrene resin component is still insufficient, so not only is the polyolefin wax's performance as a mold release agent not fully demonstrated, but it also deteriorates during storage. Another drawback is that toner tends to build up during copying, wax is more likely to be liberated than 1-toner, which can easily lead to contamination of photosensitive drums, etc., and the fixed image after fixing has poor bending resistance.

As a result of various studies on the above-mentioned problems with processing aids for synthetic resins, pigment dispersants for resins, and toners, we have found that the above-mentioned problems can be solved by using the specified graft-modified low-molecular-weight polyolefin proposed in this application. I discovered what I could do and was able to complete each invention for one book.

That is, we have found that by using the graft-modified low molecular weight polyolefin holes of the present application as a processing aid for synthetic resins, it is possible to improve the fluidity and moldability during molding without impairing the mechanical strength of the synthetic resin. .

In addition, by blending the graft-modified low molecular weight polyolefin of the present invention with non-polar resins such as polyolefin resins and polystyrene resins, which are inherently inferior in secondary processability such as printing, painting, and adhesion. It has surprisingly been found that the above-mentioned secondary processability can also be significantly improved.

In addition, by using it as a pigment dispersant for synthetic resins,
It has been found that it is excellent in kneading workability with pigments and as a pigment dispersant, and also has excellent performance in that it does not deteriorate the properties of the resin to be colored. In other words, synthetic resins such as polystyrene, ABS, polycarbonate, polyester, and polyamide, which were traditionally difficult to form into masterbatches, can now be made into masterbatches with excellent pigment dispersant properties. It has been found that it is possible to increase the concentration without causing appearance defects such as color unevenness even in the production of masterbatches.

Furthermore, regarding the 1-ner, it has been found that by using the modified low-molecular-weight polyolefin as a mold release M, an electrostatic 1-ner that is less likely to cause an offset phenomenon can be obtained.

It has also been found that by using the modified low-molecular-weight polyolefin as a thermoplastic resin that is the main material (binder) of an electrostatic toner, an electrostatic toner that is less likely to cause an offset phenomenon can be obtained. That is, it has been found that the modified low molecular weight polyolefin has excellent performance both as a release agent and as a main material (binder) for electrostatic toners.

[Summary of the invention]

The present invention is made by grafting aromatic vinyl carboxylate (BL) to 100 parts by weight of a low molecular weight polyolefin (a) in a range of 3 to 200 parts by weight, and has an intrinsic viscosity of 0.0.
Graft-modified low-molecular-weight polyolefin (c) having a molecular weight in the range of 5 to 0.141/g is defined as a material invention, and processing aids for synthetic resins, pigment dispersants, and heat-fixing electronics comprising said graft-modified low-molecular-weight polyolefin (c) Each of the elements forming the photographic toner is an application invention. Each invention will be described in detail below.

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

The graft-modified low molecular weight polyolefin (c) of the present invention is obtained by grafting a predetermined amount of aromatic vinyl carboxylate (bl) onto a low molecular weight polyolefin ial.

The low molecular weight polyolefin ta+, which is a raw material used in the graft reaction, preferably has an intrinsic viscosity [measured at 135°C in a decalin solvent] of 0.04 to 1.2 d1/
g, more preferably from 0.05 to 1.g. It is in the range of Odl/H.

Here, the low molecular weight polyolefins include ethylene, propylene, -butene, and 1-hexane.

It is a homopolymer of α-olefin such as 4-methyl-1-pentene or 1-decene, or a copolymer of two or more α-olefins, and the intrinsic viscosity is usually within the above-mentioned 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, and the presence of a metal compound catalyst to reduce ethylene or one or more of the above α-olefins other than ethylene. Polyethylene wax or low molecular weight ethylene/α-olefin copolymer obtained by medium/low pressure (co)merization with
Polypropylene wax, poly-1-butene wax,
Poly 4-methyl-1-pentene wax, propylene
4-nonal-1-pentene compound wax, hexene-
Examples include 1,4-methyl-1-pentene copolymer wax. Note that the low molecular weight polyolefin herein also includes oxides of low molecular weight polyolefins. 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.

(However, in the formula, Xi, Yl, and Z1 to Z3 are H
, C, O, and N, l is an integer of 0 to 5, and m is O or 1. ) Specifically, as Xl, ■-1C113-1CIl+
C112-1110-1112N- and the like,
Specifically, Yl is -CIl = CIl-1-
C1h -1-CIl2-CIl2-1-CmiC-1-
Nil -ell 2-1 Physically, H-1C113-
1Callv- and the like.

Specifically, vinyl benzoate, vinyl cinnamate, α-phenyl vinyl cinnamate, β-phenyl vinyl cinnamate,
Vinyl phenylacetate, vinyl benzyl acetate, vinyl phenylpropiolate, vinyl anilinoacetate, vinyl γ-phenylcrotonate, vinyl phenylpyruvate, vinyl phenoxyacetate, among which vinyl benzoate,
Vinyl cinnamate is preferred. These may be used in combination of two or more types.

1 m of aromatic carboxylic acid vinyl (BL) grafted to low molecular weight polyolefin + a+ is 3 to 200 parts by weight per 100 parts by weight of low molecular weight polyolefin (a+). Preferably, it is used as a processing aid for synthetic resins or as a pigment dispersant. When used, the amount is 3 to 150 parts by weight, and when used as a forming element of a heat-fixable electrophotographic toner, the amount is 5 to 200 parts by weight.The modified low molecular weight polyolefin is used as a processing aid for synthetic resins. In some cases, when the grafting proportion is less than 3 parts by weight, A
The compatibility with polar polymers such as BS, polycarbonate, and polyester deteriorates, and when the graft-modified low molecular weight polyolefin is blended, although a certain degree of lubricity and mold release effects can be obtained, the mechanical strength of the molded product decreases. Therefore, it is not desirable. Furthermore, non-polar polymers such as polyolefins and polystyrene are not preferred because the secondary effect of improving secondary processability such as paintability and printability is lost.

On the other hand, if the graft ratio is greater than 200 parts by weight, even if the graft-modified low molecular weight polyolefin is blended,
The lubricating effect and mold release effect of the compounded synthetic resin are no longer improved. Furthermore, when used as a pigment dispersant, if the graft ffi is less than the above essential range, the mechanical strength of the colored molded product will decrease for the same reason as above for polar polymers such as ABS, polycarbonate, and polyester. At the same time, sufficient affinity with pigments cannot be obtained, and extrusion processability during masterbatch production deteriorates.

Furthermore, if the amount exceeds the required range, the three rolls will become extremely sticky during the preparation of the master patch, resulting in poor workability.

Furthermore, when used as a toner forming element for electrophotography,
First, when used as a mold release agent, if the amount of grafting is less than the above-mentioned essential range, the compatibility between the modified low molecular weight polyolefin 8 and a binder resin such as a styrene resin will be poor, and it will be difficult to improve the compatibility. As a result, the effects of improved mold releasability, agglomeration resistance, drum contamination resistance, bending resistance, etc. become smaller, while if the graft i exceeds the above upper limit, binding of modified polyolefin wax 8 and styrene resin etc. If the compatibility with the agent resin becomes too large, it becomes difficult for the modified low molecular weight polyolefin (c) in the toner to be liberated on the surface of the melt during fixing, and the effect as a mold release agent becomes poor.

In addition, when the modified low molecular weight polyolefin 8 is used as a binder, if the graph hffl exceeds the upper limit, adhesion to the heat fixing roller will occur when it is used as a toner raw material, and the amount of grafting will fall below the above lower limit. If the colorant is rotated, the colorant will not be dispersed properly and its fixability to paper will be insufficient, which is not preferable.

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

When the intrinsic viscosity of the graft-modified low molecular weight polyolefin (c) is smaller than 0.05, even if it is blended into a synthetic resin, the blend will have excellent properties and release properties, but The appearance shrinkage rate of the molded product becomes poor. Furthermore, it tends to bleed out onto the surface of the molded product, causing stickiness on the surface of the molded product. Furthermore, even when used as a pigment dispersant, a sufficient dispersion effect cannot be obtained due to the low melt viscosity, resulting in uneven coloring.

Furthermore, the intrinsic viscosity of the modified low molecular weight polyolefin is 0.
．． If it exceeds 1 Lil/g, even if it is blended into a synthetic resin, no improvement in the lubricity and mold release effects of the blend will be observed, and no improvement in moldability will be observed. Furthermore, even when used as a pigment dispersant, the melt viscosity is too high, making it difficult to prepare a master hatch, resulting in a lack of compatibility as a dispersant.

Furthermore, when used as a toner forming element for heat-fixable electrophotography, first, when used as a mold release agent, if the intrinsic viscosity of the modified low molecular weight polyolefin is below the above-mentioned lower limit, the release agent component has a 7g melt viscosity. If the release agent becomes too low, a sufficient release agent effect cannot be obtained, and the agglomeration of the )-ner and contamination of the photoreceptor are likely to occur. Furthermore, if the intrinsic viscosity of the modified low molecular weight polyolefin exceeds the above upper limit, even if it is similarly used as a Tonato raw material, it will lack compatibility with the styrene polymers described below, and the melt viscosity will be too high. Therefore, the mold release agent no longer exhibits sufficient effect.

Furthermore, when using graft-modified low-molecular-weight polyolefin holes as a binder, if the intrinsic viscosity is below the above lower limit, problems may occur in the storage stability of the toner and the staining of the photoreceptor even if it is used as a raw material for a toner composition. Not only that, but the melt viscosity is too low, resulting in a toner that cannot produce clear images. On the other hand, if the intrinsic viscosity of the modified low molecular weight polyolefin (c) exceeds the above upper limit, even when used as a toner raw material,
Sufficient fixability to paper cannot be obtained. The intrinsic viscosity of the modified low molecular weight polyolefin (c) can be easily controlled by controlling the intrinsic viscosity of the raw material low molecular weight polyolefin (Ill), the grafting amount of vinyl aromatic acid, reaction conditions, etc.

Monomers other than vinyl aromatic acid (BL) may be grafted to the graft-modified low molecular weight polyolefin (c) of the present invention together with vinyl aromatic acid. Examples of such monomers include methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-chloroethyl acrylate, Phenyl acrylate, methyl α-chloroacrylate, 2-hydroxyethyl acrylate, diethylaminoethyl acrylate, diethylene glycol ethoxylate acrylate, 2-ethoxy acrylate, 1,4-butanediol diacrylate, 2,2.2-1 -lifluoroethyl acrylate,
Acrylic acid esters such as 2-acryloyloxyethyl acid phosphate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylate dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, ester methacrylate,
Dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, 2,2.2-trifluoroethyl methacrylate, 2-methacryloyloxydiethyl acid phosphate, etc. Methacrylic acid ester, monoethyl maleate, diethyl maleate, monopropyl maleate, dipropyl maleate, motuputyl maleate, dibutyl maleate, di2-ethylhexyl maleate, monoethyl fumarate, diethyl fumarate,
Dibutyl fumarate, 2-ethylhexyl fumarate, monoethyl itaconate, diethyl maleate-1.
Unsaturated dibasic acid esters such as monoethyl itaconate, di-2-ethylhexyl itaconate, monoethyl citraconate, diethyl citraconate, dibutyl citraconate, di-2-ethylhexyl citraconate-1, styrene, α- Examples include methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, N-methylolacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylbutyral, vinylacecool, acrylic acid, and methacrylic acid. The graph of these monomers t-(ff
It is preferable that i is 50 mol% or less of the total amount of graft monomers.

The graft-modified low-molecular-weight polyolefin of the present invention can be prepared by conventionally known methods such as those disclosed in Japanese Patent Publication No. 54-42381,
JP-A-59-219370, JP-A-58-639
It can be manufactured according to the method described in Japanese Patent No. 47.

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

The radical initiators used in the above reaction include organic peroxides and peresters such as hensyl peroxide, dichlorohendyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5
-dimethyl-2,5-di(peroxide benzoate)
Hexyne-3,1,4-bis(tert-butylperoxyisopropyl)henzen, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2 , 5-di(tert-butylperoxy)hexane, tert-butylphenyl acetate, ter
tert-butyl perisobutyrate, tert-butylperu 5ec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, other azo compounds such as azobis-isobutyronitrile, dimethyl There is azoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-butyl peroxide, 2,5-dimethyl-2,5-di(L
er t-butylperoxy)hexyne-3,2゜5-
Dimethyl-2,5-di(tert-butylperoxy)
Dialkyl peroxides such as hexane, 1,4-bis(tart-butylperoxyisopropyl)hembin are preferred. The temperature during the reaction is usually 130 to 350
°C1 is preferably in the range of 135 to 300 °C.

[Processing aid for synthetic resin]

The graft-modified low molecular weight polyolefin (3) of the present invention is effective as a processing aid for synthetic resins. The processing aid may consist of the graft-modified low molecular weight polyolefin (c) alone, or may consist of other processing aids, 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.
Synthetic resins such as those described in Japanese Patent Publication No. 54-42381 may be used as they are. That is, specifically,
Polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly4-methylpentene-1, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, posttyrene, AB3, etc.
For example, polycarbonate resins obtained from bisphenol A and phosgene, polyester resins such as polyethylene terephthalate and polyethylene terephthalate, polyamide resins, polyphenylene oxide resins, poly(meth)acrylate resins such as polymethyl methacrylate-1, polyvinyl chloride, etc. Examples include thermoplastic resins such as thermoplastic resins, phenolic resins, and epoxy resins.

Furthermore, the lubricant of the present invention can be suitably used for thermoplastic resins.

When the processing aid consisting of graft-modified low molecular weight polyolefin holes of the present invention is blended into a synthetic resin, the blending ratio is usually 0.05 to 3 to 100 plate parts of the synthetic resin.
It is preferably in the range of 0 parts by weight, 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 composition has improved lubricating effect and mold release effect, and has a negative effect on polyolefin resins and polystyrene resins. The effect of improving secondary processability tends to be lost, and if the amount exceeds 30 parts by weight, the molded product will suffer from severe delamination and will lose its balance between mechanical strength and impact strength.

As a method for blending the processing aid of the present invention into a synthetic resin, for example, in the case of a thermoplastic resin, a mixture consisting of a synthetic resin, a graft-modified low molecular weight polyolefin, and optionally its additives is mixed with a Henschel mixer, - Using a blender or ribbon blender directly after mixing, or kneading and granulating with an extruder, etc. - A method of melt-kneading and granulating with a mixer, single or multi-screw extruder, kneader, etc., or molding A method can be adopted.

By using the processing aid of the present invention, it is possible to improve the fluidity, mold releasability, and secondary processability during molding without reducing the mechanical properties of the resin after molding. Furthermore, since it has excellent heat stabilizer properties and bleed-out properties, it has the advantage that it does not cause metal stains during molding or impair the surface properties of molded products.

[Pigment dispersant for synthetic resins]

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

In other words, as a result of careful consideration of the problems mentioned above,
By using the dispersant of the present invention, it is now possible to create a masterbatch with excellent pigment dispersibility even in synthetic resins such as polystyrene, ABS, polycarbonate, polyester, and polyamide, which were previously difficult to create into a masterbatch. Furthermore, it is possible to increase the concentration of polyolefin and polyvinyl chloride masterbatches without causing appearance defects such as color unevenness.

As target resins when used as pigment dispersants, the thermoplastic resins mentioned in the section of processing aids can be mentioned as they are. That is, specifically, polyethylene, polypropylene, polybutene-1, poly4-methylpentene-1
, polyolefin resins such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polystyrene, ABS, etc., styrenic resin, polycarbonate resin obtained from bisphenol A and phosgene, polyester such as polyethylene terephthalate, polybutylene terephthalate, etc. resin, polyamide resin, polyphenylene oxide resin, polyvinyl chloride, etc.

The pigment dispersant of the present invention can be used with any pigment conventionally known for coloring synthetic resins. Specifically, pigments include all pigments such as aluminum, silver, and gold;
Carbonates such as calcium carbonate and barium carbonate; Zn
Oxides such as O1Ti02; Al2O3・nI (20,
Hydroxides such as Fe2O3, Fe2o3 ・n H20; Sulfates such as Ca5Oa, BaSO4; Bi(O
ff) Nitrate such as NO3: chloride such as PdCl2, chromate such as CaCrOa, BaCrO4; chromate, manganate and permanganate such as CoCr204; boric acid such as Cu(BO)2 Salt; Na2U20?・Uranates such as 6H20; Ni3Co(NO2)6 ・Nitrites such as 3H20 Silicates such as 1si02; CuAs03・Cu(OH)
Arsenates and arsenites such as 2; Cu(C2H302)
2 Acetate salts such as Cu(OH)2; (NI+4
)2 Phosphates such as MnO2(P20rt)2; aluminates, molybdates, zincates, stannates, antimonates, tungstateselenides, titanates, iron cyanide salts, phthalates , inorganic pigments such as sulfides such as CaS, ZnS, CdS, natural organic pigments such as cochineal lake, madder lake, naphthol green Y
, Naphthol Green B, and other nitroso pigments; Naphthol Yellow S, Pigment Chlorin 2G, and other nitro pigments; Permanent Red 4R, Hansa Yellow, Brilliant Carmine 6B, Scarlet) 2R and other pigments: Malacaine Green, Rhodamine B, etc. basic flux lakes, acid green lakes, acid flux lakes such as eosin lakes, mordant dye lakes such as alizarin lakes, purpurin lakes, thio-
Examples include organic pigments such as vat dye pigments such as indigo red B and intanthrene orange, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.

When the graft-modified low molecular weight polyolefin (c) of the present invention is used as a pigment dispersant for the aromatic polymer, the blending ratio is usually 25 to 300 parts by weight, preferably 50 to 250 parts by weight, per 100 parts by weight of the pigment. This is within the scope of the department. Furthermore, the pigment dispersant of the present invention can be used for coloring aromatic polymers by any of the dry coloring methods, coloring by color compounding methods, and coloring by masterbatch methods. For example, in coloring by the dry color method or coloring by the color compound method, a mixture consisting of a pigment and the dispersant of the present invention is finely pulverized to prepare a powder or bead-like dry color, which is then mixed into uncolored pellets. Mix together as an aromatic polymer in a tumbler or suitable mixer,
Dry color is uniformly sprinkled on the surface of the resin pellets, and this is colored by passing through an extruder or by kneading the molten resin with a screw in a molding machine, then dispersing the pigment by shearing force, and molding it. In addition, colored pellets obtained by extruding /g FIB colored resin from an extruder and cutting in the above process are color compounds.

[Forming elements of heat-fixable electrophotographic toner] As mentioned above, the modified low molecular weight polyolefin (E) of the present invention is useful both as a release agent and as a binder for toners. A toner using the graft-modified low molecular weight polyolefin of the invention will be described.

[■Binder resin when using modified low molecular weight polyolefin (a) as a mold release agent]

Examples of binder (thermoplastic) resins such as styrene polymers used in the toner of the present invention include JP-A-50-27
Styrenic resins such as those described in No. 546, that is, polymers consisting only of styrene monomers or copolymers of styrene monomers and other vinyl monomers, can be used as they are. That is, monomers other than styrene for forming the copolymer include styrenic monomers such as α-methylstyrene, p-methylstyrene, p-chlorostyrene, and vinylnaphthalene, such as ethylene, propylene, butylene, and isobutylene. ethylenically unsaturated monoolefins such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl halides such as vinyl acetate,
Vinyl propionate, rest? Vinyl esters such as vinyl acid and vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-ethyl acrylate, dodecyl acrylate, and 2-chloro-ethyl acrylate phenyl acrylate. , esters of α-methylene aliphatic monocarboxylic acids such as methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate;
Acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isoprobenikel ketone, etc., such as N-vinyl bicol, N- Examples include N-vinyl compounds such as vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and one or more of these can be copolymerized with a styrene monomer. Suitable styrenic polymers have a number average molecular weight of about 2,000 or more, particularly preferably from 3,000 to 30,000, and have a styrene content of at least about 25% by weight, based on the total weight of the styrenic polymer. It is preferable that

Examples of other thermoplastic resins include polyester resins, ketone resins, maleic acid resins, coumaron resins, phenolic resins, epoxy resins, terpene resins, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, Examples include ethylene-vinyl acetate copolymer.

Among the above, styrene polymers and polyester trees are preferred.

[Resin that may be added in addition to when modified low molecular weight polyolefin 8 is used as a binder] The thermoplastic resin that is the main material of the electrostatic I-ner does not necessarily contain the entire amount of the graft modified low molecular weight polyolefin (HA). ), but it does not need to be 20% by weight or more, preferably 50% by weight of the thermoplastic resin.
If the modified low molecular weight polyolefin (A) accounts for the above, an electrostatic toner with improved offset phenomenon can be obtained.
Examples of the thermoplastic resin for electrostatic toner used in combination with the thermoplastic resin include the various thermoplastic resins exemplified above as the binder.

[■Coloring agent (B)]

The colorants used in the electrostatic toner according to the present invention include carbon black, phthalocyanine blue, aniline blue, alcohol blue, chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine B lake, cardin. 6B, quinacridone derivatives, or one or more pigments or dyes. If necessary, azine nigrosine, isothurin, azo,
Oil-soluble dyes such as anthoniquinone-based, triphenylmethane-based, xanthine-based, and phthalocyanine-based dyes may be used in combination.

[■Other ingredients]

The toner according to the present invention may contain other components in addition to the above-mentioned holes and the component (13) or the above-mentioned thermoplastic resin within a range that does not impair the effects of the present invention.

Other toner additives may be included, such as charge control agents, plasticizers, and the like. These additions (■) are in arbitrary amounts.

[■How to adjust toner]

When the electrostatic toner according to the present invention is used as a two-component electrostatic toner, the graft-modified low molecular weight polyolefin is mixed with the colorant CB) and, if necessary, the thermoplastic resin exemplified above, using a known method such as ball milling, After mixing with an attritor, etc., knead with a heated twin roll, heated knee gourd, extruder, etc., cool and solidify, coarsely crush with a hammer mill, cod mill, etc., and then use a jet mill, vibration mill, or add water and use a ball mill, an attritor, etc. The electrostatic toner is finely pulverized with an average particle size of about 5 to 35 μm, and used as an electrostatic toner. When a two-component electrostatic toner is used as a developing material, a carrier is used in combination. As the carrier, known carriers can be used, such as silica sand, glass beads, iron balls, or magnetic material powders of iron, nickel, cobalt, etc. with a diameter of 200 to 700 mm. In a two-component electrostatic toner, when the modified low molecular weight polyolefin (8) is used as a mold release agent, the amount of the modified low molecular weight polyolefin (8) is 1 to 1 to 100 parts by weight of the thermoplastic resin including the binder resin. It is added in an amount of 20 parts by weight, preferably 2 to 10 parts by weight. Furthermore, when the modified low molecular weight polyolefin (c) is used as a binder,
The amount of modified low molecular weight polyolefin (c) is 20 parts by weight per 100 parts by weight of (a) and other thermoplastic resins.
It is added in an amount of at least 50 parts by weight, preferably at least 50 parts by weight.

Further, when the electrostatic toner of the present invention is used as a one-component electrostatic toner, the modified low molecular weight polyolefin (c),
(coloring agent), the above-mentioned thermoplastic resin and magnetic material powder can be adjusted as necessary in the same manner as the above-mentioned two-component electrostatic toner. - As the magnetic material powder added to component-based electrostatic toner, fine magnetite powder of 1μ or less is usually used, but powders of metals such as cobalt, iron, nickel, alloys thereof, oxides, ferrite, and mixtures thereof, etc. can also be used. - The amount of each component in the component-based electrostatic toner is usually 100 ffiffiffi parts of the total amount of the thermoplastic resin including the modified low molecular weight polyolefin (8) and the magnetic material, and the magnetic material is blended at a ratio of 40 to 70 parts by weight. good. If the amount of magnetic material is too large, the electrical resistance of the electrostatic toner decreases, the charge retention of the electrostatic toner deteriorates, and the image may be distorted. Furthermore, electrostatic l
・The softening point of the toner may become high, making it difficult to properly fix it. On the other hand, if the amount of magnetic material is too small, the electrostatic toner function will be lost, the required charging ability will not be obtained, and the toner will be more likely to scatter. In the case of the -component electrostatic toner, the amount of the modified low molecular weight polyolefin added to the total resin is the same as in the case of the two-component electrostatic toner. Further, a known charge control agent may be added to the one-component electrostatic toner or the two-component electrostatic toner, if necessary.

[■Effects of invention]

Regardless of 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 will not peel off from heating rolls, etc., not only at conventional temperatures but also at high temperatures. It is ideal for high-speed copying because offset phenomenon does not easily occur even if the fixing speed is increased by increasing the temperature of the heating roll or the like. Furthermore, since it has excellent fixing properties to paper, it provides excellent performance even when the heating roll is kept at a low temperature, making it ideal for energy-saving copying. Furthermore, it has low aggregation, excellent development properties, and excellent bending resistance after fixing.

Furthermore, when the graft-modified low-molecular-weight polyolefin according to the present invention is used as a mold release agent, this modified low-molecular-weight polyolefin not only has excellent compatibility with binder resins such as styrene polymers, but also has various additives, For example, it has excellent compatibility or affinity with pigments, bundle amount, charge control, and plasticizers.

Therefore, it also has the effect of increasing the dispersibility in these binder resins, increasing the physical uniformity of the toner such as charge control properties, and improving the performance as a developer.

〔Example〕

EXAMPLES Each of the present inventions and their effects will be explained in more detail below with reference to Examples.

Examples (T alliance of vinyl aromatic carbonic acid modified low molecular weight polyolefin) Preparation example 1 (Wl) 540 g of low molecular weight high density polyethylene with an intrinsic viscosity of 0.32 dl/g was charged into a 1.5β glass reactor. 1
It was melted at 60°C. Next, 160g of vinyl benzoate
, and di-tert-butyl peroxide (hereinafter referred to as D
13.0 g of TBPO (abbreviated as TBPO) was added thereto, and the mixture was heated and reacted for 5 hours. Thereafter, in the molten state, 5 mm and 11 g of the product was degassed in vacuum for 1 hour to remove volatile components, and then cooled. The intrinsic viscosity of the obtained vinyl benzoate-modified low molecular weight polyethylene (W-1) was 0.33 dl/g. In addition, 30g of the modified low molecular weight polyethylene was added to 30++
Z was dissolved in paraxylene, and the resulting solution was added to acetone 1β at room temperature with stirring, and cooled to room temperature. The precipitated solid portion was further washed twice with 500 mj of acetone and dried.

The obtained solid portion was subjected to 'H-NMR to add vinyl benzoate. In this way, the graph +-1 determined by L was 21 parts by weight per 100 parts by weight of the vinyl benzoate graph l-i low molecular weight polyolefin [i.e., the amount of benzoate per 100 parts by weight of polyethylene wax (a) 27 parts by weight of vinyl acid. ] m′! Examples A 2 to 18 (W-2 to 18) Preparation except that the type and amount of raw material low molecular weight polyolefin, type and amount of vinyl aromatic carboxylate, amount of DTBpo, and reaction time were changed as shown in Table 1. Various vinyl aromatic carboxylic acid-modified low molecular weight polyolefins were obtained in the same manner as in Example 1. Table 1 also shows the intrinsic viscosity of the obtained modified low molecular weight polyolefin and the amount of grafted vinyl aromatic 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 formula of the present invention.

Examples 1-2 and Comparative Examples 1-2 The modified low-molecular-weight polyethylene obtained in Preparation Examples 1-3 and the unmodified low-molecular-weight polyethylene as raw materials were mixed with a commercially available polycarbonate resin (trade name Panlite L-1250, Kijin Kasei) Transverse crack (hereinafter referred to as pc) 0.5 per 100 parts by weight
．． After tri-blending in proportions of 1 and 2 parts by weight, 20
Pelletization was performed using a mmφ extruder (set temperature: 280°C, 50 rpm), and the extrusion amount was determined. Further, the granulated sample was molded into a test piece for a tensile strength test using a Toshiba Machine (horizontally split Is-50 type injection molding machine).

At the same time, a spiral flow test was conducted (resin temperature 280
°C1 mold temperature 50℃, injection pressure 1000kg/c
n! ).

Tensile properties: Measured according to the method of ASTM D 638.

Spiral length: For example, Mod, Plastics, 34. (12)
The length of the spiral obtained under the above setting conditions was measured by the spiral flow test method as described in +P, 111. The larger this value is, the better the fluidity during melting is.

Mold releasability: Depending on the condition when taking out the formed square plate from the metal frame, 5 indicates a condition in which the square plate can be removed from the metal frame without resistance, and a condition in which it cannot be removed without corrective peeling between the square plate and the metal frame with a razor etc. 1, and the middle was divided into 3 categories, and the evaluation was made on a 5-point scale.

Comparative Example 3 The PC used above was tested alone in the same manner 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/oxidized low molecular weight polyethylene 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 ,
Nippon Zeon (horizontally split, polymerization degree 1050, hereinafter referred to as PVC) was evaluated for its performance 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 diocle ester (manufactured by Wako Pure Chemical Industries, Ltd.), 10 parts by weight of epoxidized soybean oil (product name 0-130P, manufactured by Adeka Argus), fatty acid monoglyceride (product name Rikemarker L) -250
, manufactured by Riken Vitamin Co., Ltd.) and 0 parts by weight of the above processing aids.
．． 2 or 0.4 parts by weight in a Henschel mixer, 90
°C and mixed for 3 minutes. This mixture was kneaded with two rolls and its durability was evaluated.

(1) Roll operating conditions Roll diameter = 8 inches Surface temperature: 170-175°C Roll gap 20.5 mm Roll rotation speed: 18 rpm/16 rpm Sample amount
: 150g/1 time (2) Method for evaluating lubricant effect Gelation time A sample was placed between two rolls, and expressed as the time until the sample melted, became a sheet, and was wound around the rolls.

Release from roll: Put the sample into the roll, Roll after mixing for a minute. 5. After stopping and stopping the roll. 10.20.Sheet after 30 minutes The ease of peeling and application was observed.

A: Good removability.

B: Something that is difficult to peel off.

C: Items that cannot be peeled off.

Bloom phenomenon evaluation method: Knead for 10 minutes with two rolls After that, press processing (150 °C) by 1010X10X1 Get a sheet. this sheet for one week at 70°C, 390% R11. After leaving it for a while, the bloom appears. Visually judge the elephant.

A...Bloom phenomenon occurs. Not yet.

B... is the sea for the total area within the range of 1/2 or less It is occurring.

C. The bloom phenomenon is for the total area within the range of 1/2 or more It is occurring.

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 Ratio/Calibration Rule 6 Using the modified low molecular weight polypropylene obtained in Preparation Example 9, commercially available polypropylene (Mitsui Ishiura Kagaku Volip 0.1
-600, hereinafter referred to as PP).

After mixing modified low molecular weight polypropylene at a ratio of 0.5, 1, and 2 parts by weight, respectively, to 100 parts by weight of PP,
Formed plates for tensile strength tests, specular gloss measurements, and printability tests were molded using a V-14-65 injection molding machine (Japan Steel Works, Ltd.). At the same time, spiral flow tests were conducted (cylinder Temperature 210 degrees, mold temperature 40 degrees, injection pressure 1000 kg/c++!).

Measurement of mirror gloss temperature was performed according to ASTM D-523.

The evaluation method for printability was to apply a commercially available water-based ink (
Apply Toyo Ink Manufacturing (Yokosaki, Aquakind) with a doctor blade (1 mil), and check the affinity of the ink on the molded plate at that time! ! A (ink repellency phenomenon does not occur or assimilation) and after drying, the adhesion product was evaluated in the substrate eye test.

Comparative Example 7 The same test as in Example 5 was conducted 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 Recommended Production Examples 10 to 11 were mixed with commercially available ABS resin (trade name Styhook 101, manufactured by Asahi Kasei (41, hereinafter referred to as ABS) 10).
After tri-blending at a ratio of 0.5.1 and 2 parts by weight to 0 parts by weight, the mixture was granulated using a 20 mmφ extruder (set temperature 230 degrees, 50 rpm), and the extrusion amount was determined. Further, the granulated sample was tested for fluidity during injection molding, mold releasability, and strength of the molded product in the same manner as in Example 1.

Comparative Example 9 A test similar to Example 7 was conducted using the ABS used above alone. The above results are shown in Table 5.

Examples 9-12 and Comparative Examples 10-12 Preparation Examples 12-1
Using the modified low molecular weight polybutene-1 and modified low molecular weight polyethylene shown in Section 8, the performance as a pigment dispersant for polyethylene terephthalate and low density polyethylene was evaluated. The results are shown in Table 6.

[Performance evaluation method of pigment dispersant]

Melt 100 parts by weight of fine powder of pigment dispersant at 180 degrees,
To this, 11 parts of Phthalocyanine Blue 1.00ff (for polyethylene terephthalate) or 230 parts by weight (for low-density polyethylene) was gradually added while kneading to obtain a spherical kneaded product with a radius of about 2.5 cm.

This kneaded solid material was supplied to a three-roll kneader at 130'C, and the discharge speed was evaluated from the passage time and discharge amount.

Furthermore, this kneaded composition and polyethylene terephthalate (trade name: Mitsui PET, J-125, Mitsui Petrochemical Industries (Yokosabi, hereinafter referred to as PET), or low density polyethylene (trade name: Miralan 24H1, Mitsui DuPont Polychemical (Yokosabi, hereinafter referred to as PET)), (hereinafter referred to as LDPE) at 280°C (
For PET) 5 Orp at 210°C (LDPI?, )]
The mixture was supplied to a 20 mmφ extruder rotating at a speed of m and kneaded to obtain a master hatch.

Extrusion processability was evaluated by visually determining the surface condition of the strand and the uniformity of the strand diameter.

Further, using each master hatch, press processing was performed under conditions of press temperatures of 280'C (PET) and 210C (LDPE) to obtain a master hatch film with a thickness of 0.1 mm.

The pigment dispersant in this masterbatch film is
It was evaluated on a scale of 5 to 5.

5. Number of particles of 50μ or more, 1. oOX10 here/Ca
The following 4, 〃, 1.00 x 10 coco/C praise ~ 7X10” co/c++! 3, //, 7X101 coco/cI!
! ~2.7 X104 pieces/Cbo 2, // , 2.7 X104 pieces/
clI! ~7.00 X 104 co/co! Above 1
, ． 7.0Ox104 pieces/cn1
(The measurements were carried out using an Lvzex 450 image processor manufactured by Toyo Ink Co., Ltd.) The following examples show the effects when the modified low molecular weight polyolefin (c) of the present invention is used as a forming element of a heat-fixable electrophotographic toner. will be explained more specifically. Note that Example 1
3 to 19 and Comparative Examples 13 to 16 are experimental examples showing the effect when the modified low molecular weight polyolefin (c) of the present invention is used as a mold release agent, and Examples 20 to 2
3 and Comparative Examples 17 and 18 are experimental examples showing the effects of using the modified low molecular weight polyolefin 8 of the present invention as a binder.

Example 13 (Preparation of A-ner and copying test) Styrene/n-butyl methacrylate copolymer (manufactured by Sanyo Chemical Industries, Hymer SBM-600) 85 parts by weight, W-14 synthesized in Preparation Example 1, carbon black (
After mixing 9 parts by weight of Diamond Black 5H (manufactured by Mitsubishi Chemical Industries) and 2 parts by weight of alloy dye (BASF'M Zapon Fast Black B) in a ball mill for 24 hours, the kneading port was cooled with a heated roll, and then crushed and classified. Explosive 15μ electrostatic toner. Next, using iron particles with an average particle size of 50 to 80 μm as a carrier, 1 part of electrostatic toner was added to 100 parts by weight of the carrier.
They were mixed in a proportion of 20 parts by weight, developed on a selenium photoreceptor by a conventionally known electrophotographic method, and transferred onto transfer paper to obtain 18 parts by weight.
The image was fixed by heating with a heating roll at 0°C. As a result, even after copying 5,000 times, a copied image was obtained that was as clear as the initial image and free of offset phenomena, contamination, etc., and almost no contamination of the heat roll or photosensitive drum was observed.

Example 14 7 parts by weight of W-8 synthesized in Preparation Example 8, Noimer SB
Example 1 Using 82 parts by weight of M-600, 9 parts by weight of Diamond Black SH, and 2 parts by weight of Zapon Fast Black.
A toner was made from UR in the same manner as above, and a copying test was conducted. As a result, even after 10,000 copies, a copy image that is as clear as the initial one and free from offset phenomena and stains is obtained.
Almost no contamination of the heat roll or photoreceptor drum was observed.

Furthermore, a bending resistance test was conducted. After fixing, the black image area was repeatedly bent 500 times, and the degree of fixation before and after the bending was visually determined by peeling off cellophane tape.

As a result, it was found that there was almost no change after the bending test, and that 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 t-1 in Example 13, and a copying test was conducted.

As a result, even after 5,000 copies, a copied image was obtained that was as clear as the initial image and free of offset phenomena, contamination, etc., and almost no contamination of the heat roll or photoreceptor drum was observed.

Furthermore, changes in toner fluidity with temperature were investigated.

The toner was placed on a petri dish, and its fluidity was visually determined. As a result, it was found that there was almost no difference in fluidity between those held at 50 degrees for 48 hours and those held at room temperature, indicating excellent fluidity even in a 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 copying test was conducted.

As a result, even after 5,000 copies, a copied image was obtained that was as clear as the initial image and free of offset phenomena, contamination, etc., and almost no contamination of the heat roll or photoreceptor 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 copying test was conducted.

As a result, even after 3,000 copies, a copy image was obtained that was as clear as the initial image and free of offset phenomena, stains, etc., and almost no stains on the heat roll or photosensitive drum were observed.

Furthermore, in the same manner as in Example 15, changes in the fluidity of the toner with temperature were investigated. As a result, the toner was heated at 50°C for 48 hours.
Although the fluidity of the samples kept at room temperature was slightly worse than those kept at room temperature, no lumps were formed, suggesting that there were no problems 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 copying test was conducted.

As a result, even in the 5,000 copy test, 13 copies were made that were as clear as the initial copy and free of offset phenomena, stains, etc., and there was almost no problem with leta staining on the heat roll and photoreceptor drum.

Furthermore, 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 the degree of fixation before and after folding eggplant l- was extremely high, and it was also found to be unsatisfactory in the folding resistance test.

Example 19 Polyester resin (Mitsubishi Chemical Hymer ES 508
) 48 parts by weight, carbon black (Mitsubishi Chemical MΔ
-100) 2 parts by weight of magnetic powder Titanium Kogyo Mabilo Black B L -500) 48 parts by weight and the market weight of W-22 were mixed in a ball mill for 24 hours, and then heated with a heated roll for 1 hour.
Kneaded for hours, then finely pulverized with a jet mill, heat treated with a spray dryer, and passed through a zigzag classifier with an average particle size of 15 μm.
A magnetic toner was obtained. Using the magnetic toner, it was developed on a selenium photoreceptor by a conventionally known electrophotographic method, transferred onto a transfer paper, and the heating roll temperature was set at 200 degrees.
A durability test of 0 transfers was conducted. As a result, a good copy image was obtained without staining 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 copying test was conducted.

As a result, the sharpness of the image began to decrease around the 4000th time. At the same time, on the surface of the photoreceptor drum and iron powder Keetley,
Partial coverage of polyethylene wax (filming phenomenon) was observed.

Furthermore, when a bending resistance test 1- was carried out in the same manner as in Example 14, significant toner peeling was observed along the bending line, and the results were inferior to those in Example 14.

Comparative Example 14 Next, a toner was prepared in the same manner as in Example 3 except that W-3 was used instead of W-1 in Example 13, and a copying test was conducted. As a result, the peelability from the hot roll was poor, and an offset phenomenon and staining of the copy paper were observed.

Furthermore, in the same manner as in Example 15, the temperature change in the fluidity of the toner was investigated, and when the toner was maintained at 50 degrees, particles of approximately 5 mm square or more were produced, indicating that the fluidity was poor and there was a problem in practical use. The result was that.

Comparative Example 15 A toner was prepared in the same manner as in Example 13 except that W-9 was used instead of W-1, and a copying test was conducted.

As a result, the peelability from the hot roll is significantly poor, and
A large amount of filming was observed on the photoreceptor drum and iron powder carrier.

Comparative Example 16 300 g of the raw material polypropylene used to prepare W-7 in Preparation Example 7 was charged into an autoclave having an internal volume of lβ, and thermally decomposed at 340 degrees for 2.2 hours while passing a small amount of nitrogen. [η] of the obtained polypropylene wax was 0.06 dl/g.

Next, 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 copying test was conducted.

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

Furthermore, when the fluidity temperature of the toner was examined at the same time as Example 15, it was found that the toner after being maintained at 50°C had lumps of approximately 5 mm square or more and had extremely poor fluidity, which was a practical problem. The results suggest that there is.

Example 20 Modified low molecular weight polybutene-1 (W) prepared in Preparation Example 15
-15) An electrostatic toner consisting of 100 parts by weight of carbon black (trade name Diablack SH1 manufactured by Mitsubishi Chemical Industries, Ltd.), 5 parts by weight of alloy dye (manufactured by BASF Corporation and Zapon Fast Black type) was prepared as in Example 13. Next, iron powder with an average particle size of 50 to 80 μm was mixed as a carrier in a ratio of 120 parts by weight of electrostatic toner to 100 parts by weight of the carrier, and the electrostatic toner was printed on a selenium photoreceptor using a conventional electrophotographic method. The image was developed using a method, transferred, and heated and fixed using a heating roll.As a result, even after 2000 copies, a copy image was obtained that was as clear as the initial image and had no offset phenomenon or contamination, and no heat roll or drum contamination was observed. There wasn't.

Example 21 150 parts by weight of W-1 obtained in Preparation Example 1, low molecular weight polystyrene (product: Hymer 5T-95, K from Sanyo Chemical Industries)
50 parts by weight and carbon black 5 used in Example 13
Part by weight and 2 parts by weight of the alloy dye were mixed and ground in the same manner as in Example 20 to obtain an electrostatic toner (including carrier). Next, copying was performed 10,000 times in the same manner as in Example 20, and as a result, a copied image was obtained that was as clear as the initial one and free of offset phenomena, contamination, etc., and no contamination of the hot roll or drum was observed.

Comparative Example 7 Low molecular weight polystyrene (trade name: Hymer 5T-95, Sanyo Chemical Industries K) was used instead of W-15 used in Example 20.
K) An electrostatic toner was obtained in the same manner as in Example 20 except for using. Next, copying was performed 1,000 times in the same manner as in Example 20, and as a result, the release from the heat roll was poor, and the offset phenomenon and staining of the copy paper were tolerable.

Example 22 W-1 used in Example 13: 40 parts by weight, magnetic powder (trade name: Mabilo Black BL-500, Titanium Kogyo KK)
: 50 parts by weight, ethylene/vinyl acetate copolymer (trade name: Evaflex 460, Mitsui DuPont Polychemicals KK), 10ffiffi parts and carbon black (trade name: MΔ-100, Mitsubishi Chemical Industries KK): Double Teibu The mixture was mixed in a ball mill for 24 hours, kneaded for 1 hour in a heating roll, then ground in a Ziets L-mill, heat-treated in a spray dryer, and reduced to an average particle size of 15 μm in a zigzag classifier.
A magnetic toner was obtained. Using the magnetic toner, it was developed on a selenium photoreceptor by a conventionally known electrophotographic method, transferred onto transfer paper, and heated at a heating roll temperature of 200°C.
A durability test of multiple copies was conducted. As a result, a good image was obtained without staining the heating roll or drum.

Example 23 Instead of 40ffi parts of W-1 used in Example 22, a mixture consisting of 25i parts of W-1 and 25 parts of low molecular weight polystyrene used in Example 21 was used as the resin component. A magnetic toner was prepared in the same manner as in Example 22. As a result, even after 2000 copies, a good copy image was obtained without any contamination of the heating roll or drum.

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

Example 24 Example 17 in place of W-1:40 Chongfuja of Example 22
Using 40ii parts of W-4 used in Example 22, a toner was prepared using the same method as in Example 22.
A multiple copying test was conducted. As a result, even after copying, there was no contamination of the heating roll or drum, and good copied images were obtained.

Claims (4)

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