JP2981362B2 - Resin composition for electrophotographic toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In general, electrophotography in a copying machine or a printer forms an electrostatic latent image on a photoreceptor, develops the latent image using toner, and forms the latent image on a sheet to be fixed such as paper. After the transfer of the toner image onto the sheet, a method of hot-pressing with a hot roll (hot roll fixing method) is performed. In this method, fixing is performed under heating and pressing, so that the method is quick and the heat efficiency is very good, and therefore, the fixing efficiency is very good. However, if this fixing method is used with a conventional toner,
Since the surface of the hot roll and the toner come into contact with each other in a molten state, the toner adheres and transfers to the surface of the hot roll, and the toner re-transfers to the next sheet to be fixed and becomes dirty (offset phenomenon). On the other hand, the copier is oriented to increase the speed, and the contact time with the fixing roll is inevitably shortened, so that a toner which is melted by heating for a short time is required.
Further, from the viewpoint of energy saving and safety, there is a demand for a toner which melts at as low a temperature as possible and has good fluidity at the time of melting. To obtain toner with good fluidity,
Although there is a method of reducing the molecular weight of the resin, lowering the molecular weight is not preferable because the cohesive force of the resin becomes insufficient and an offset phenomenon is likely to occur. Further, if an attempt is made to reduce the size of the toner particles in order to cope with high resolution, there is a problem in that the generation of unnecessary fine powder as toner during the fine pulverization in the toner production process increases, and the yield of toner production deteriorates.

Japanese Patent Application Laid-Open No. 49-101031 discloses a toner composition which does not cause an offset phenomenon even at a relatively high fixing temperature by using a crosslinked polymer as a binder resin to widen the fixing temperature range. A technique for obtaining a product is disclosed. Japanese Patent Publication No. 55-6895 discloses a polymer having a weight average molecular weight / number average molecular weight of 3.5 to 40 and a number average molecular weight of 2,000 to 30,000 used as a binder resin. A technique for obtaining a toner composition having good properties is disclosed. However, the toner obtained by these techniques is difficult to use in high-speed copying machines and small-sized copying machines in which the amount of heat from the heat fixing roll is not sufficiently transmitted. That is, when a polymer having a large weight average molecular weight or a crosslinked polymer is used for the purpose of preventing the offset phenomenon, the viscosity of the binder resin is increased and the fixability is deteriorated. Conversely, if the binder resin is made to have a low viscosity by using a material having a small weight average molecular weight or a material that is not cross-linked, the image thermally fixed on the paper is destroyed by bending or rubbing the paper, and However, there is a problem in that the toner that has been deposited on the toner drops off to cause a defect in the image, and the image quality is impaired due to the offset phenomenon.

Another solution is disclosed in Japanese Patent Application Laid-Open No. 48-750.
No. 33 uses a block copolymer composed of a hard resin block (a polymer portion having a high glass transition temperature (hereinafter abbreviated as Tg)) and a soft resin block (a polymer portion having a low Tg). Excellent toners are disclosed.
However, when a toner using such a block copolymer is used in a hot-roll fixing type copying machine or the like, an offset phenomenon occurs, and the kneading and pulverizing methods which are the current general manufacturing methods cause pulverization. Is extremely difficult, resulting in an extremely low productivity, which is not preferable. Also, JP-A-55-880
No. 71, JP-A-55-88073 and JP-A-55-90958
Japanese Patent Application Publication No. JP-A-2005-17764 discloses a styrene-based polymer, an ABA-type block copolymer of polystyrene-polybutadiene-polystyrene, a release agent (for example, polybutene, polybutadiene, chlorinated paraffin, polyethylene, polypropylene, etc.), a magnetic powder and carbon black. A technique for melt-kneading, pulverizing, and classifying the modifier to obtain a magnetic toner having excellent offset resistance and fixing properties has been disclosed.
It is difficult to uniformly disperse the ABA block copolymer, release agent, charge control agent, etc. in the styrenic polymer by short-time melt-kneading. It was confirmed that it was easy to do.
Also, when the polystyrene-polybutadiene-polystyrene ABA type block copolymer is used in a large amount,
After kneading, normal pulverization using a jet mill or the like cannot be performed, and freezing or cooling pulverization is required.

In order to improve the fixing characteristics, Japanese Patent Application Laid-Open
Based on the idea that star-shaped branched polystyrene as disclosed in JP 2-67302 is superior in melt flowability to linear polystyrene of the same molecular weight, a branched functional There is disclosed a technique for producing a polymer and using the polymer as a high molecular weight component to obtain a toner having improved offset resistance. In addition,
No. 2-48657 discloses that a high-molecular-weight polymer is produced by a suspension polymerization method using a polyfunctional initiator, and further a low-molecular-weight polymer is produced in the presence of this polymer. By toner using a mixture of polymer and low molecular weight polymer,
A technique for improving the offset resistance has been disclosed. JP-A-2-48675 discloses that a low molecular weight polymer obtained by a solution polymerization method is dissolved in a polymerizable monomer for a high molecular weight polymer and polymerized using a polyfunctional (trifunctional or higher) initiator. There is also disclosed a technique for producing a toner resin.

Various techniques have been disclosed as described above. In general, when a suspension polymerization method is used, a polymer is produced by using a crosslinking agent such as divinylbenzene, diethylene glycol dimethacrylate, or trimethylolpropane dimethacrylate. Although a high molecular weight resin can be obtained relatively easily, it is necessary to use a dispersant or a dispersing aid in combination. Since the dispersant easily absorbs moisture and adversely affects the electric properties, particularly the charge stability, it is necessary to remove these as much as possible after producing the polymer. However, removing the dispersant from the polymer by washing or the like requires a large amount of washing water, and the treatment of wastewater after washing is also difficult. Further, although these techniques have a great effect in a conventional copying machine in which the offset property becomes a problem, a low heat fixing copying machine cannot obtain sufficient low-temperature fixing property and offset resistance. This is because a high-molecular weight polymer having a large weight average molecular weight is used to improve the strength and offset resistance of the toner, so that the resin for the toner has a high viscosity, the melt fluidity of the toner is reduced, and the low calorie copying machine is used. It is presumed that this was inappropriate. However, when a material having a small weight average molecular weight is used, the melt fluidity can be improved, but the offset resistance or the strength of the toner is insufficient, and the problem that the toner is broken or the image quality is impaired due to the application of the toner over a long period of time occurs. I was Accordingly, the present inventors have disclosed that, as disclosed in Japanese Patent Application No. 3-501873, 0.1 to 4.0 parts by weight of divinylbenzene is used, the Z-average molecular weight / number-average molecular weight (Mz / Mn) is 6 or more, and Average molecular weight of 50,000
The following ethylene polymers were used to improve the resin strength. However, although the amount of divinylbenzene used was small, Mw was low.
/ Mb is large, that is, the number of crosslinking points is large, so that the side chains are not sufficiently elongated, the entanglement density of the molecular chains is insufficient, and there is no significant difference from the conventional ethylene-based polymer. I was

So far, the present inventors have disclosed USP 4,963,45.
In JP-A No. 6 and other publications, a resin obtained by a solution polymerization method has been developed as an electrophotographic toner resin having good electric properties, particularly, good charge stability. Solvents obtained by the solution polymerization method remove the solvent after the polymerization is completed. At this time, low volatile components such as unreacted polymerizable monomers and decomposition products of the initiator can be distilled off. A stable and homogeneous resin is obtained, which is optimal as a resin composition for electrophotographic toner. However, the production of a high-molecular-weight resin by the solution polymerization method has a problem that the Weissenberg effect (the resin is wound around a stirring rod) occurs and production is difficult. The present inventors have developed a method in US Pat. No. 5,084,368 in which a bulk polymerization method is used in combination with a solution polymerization method to further increase the molecular weight. However, there is a limit to the high molecular weight that can be produced, and it has not been possible to completely overcome the offset resistance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for an electrophotographic toner which can be fixed with a low heat quantity suitable for a high-speed and low heat fixing copying machine and has excellent strength. .

[0009]

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

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

In general, a polymer produced using a bifunctional monomer (in the present invention, a bifunctional monomer is an ethylenically unsaturated monomer) has a Mw / Mb of 1, As the amount of the polyfunctional monomer used increases, Mw / Mb
Is greater than 1. If the Mw / Mb of the ethylene polymer (X) in the present invention is smaller than 2, the resin strength of the ethylene polymer (X) is not guaranteed and the copy image is not stable. On the other hand, if Mw / Mb is greater than 99 or Mw exceeds 50,000, although the resin strength is guaranteed, the melt fluidity deteriorates, and fixing with a low calorific value becomes impossible. If the Mw / Mb of the ethylene-based polymer (X) is smaller than 2, a large amount of fine powder is generated in the toner production stage, or the toner is broken or broken during long-term running, resulting in deterioration of image quality. Not preferred. On the other hand, if it is larger than 99, a great amount of energy is consumed in the pulverizing step of toner production, and there is a problem in productivity.

The ethylene polymer (X) according to the present invention comprises:
It is manufactured by the following method. Specifically, depending on the type of the substance to be used, (1) a substance having one or more unsaturated functional groups and one or more peroxy groups in the molecule (hereinafter referred to as a copolymerizable peroxide), for example, t- Examples of using butyl peroxy methacrylate, t-butyl peroxycrotonate, di (t-butyl peroxy) fumarate, t-butyl peroxy allyl carbonate, and the like will be described, but the present invention is not limited thereto.

Since the copolymerizable peroxide has a vinyl group and a peroxy group in the molecule, the structure of the molecule can be controlled by simultaneously polymerizing the functional groups in the monomer as in the conventional polymerization method. Cannot bring out the expected physical properties. Therefore, the polymerization temperature was 10 hours half-life temperature (t _1/2) from 15 to 40 ° C. lower temperature in the peroxy groups copolymerizable peroxide in, in this temperature range the 10-hour half-life temperature (t _1/2 ), The vinyl group in the copolymerizable peroxide is copolymerized with the bifunctional monomer, and then the temperature is reduced by 10 hours and a half for the peroxy group in the copolymerizable peroxide. By raising the temperature to or higher than the initial temperature (t _1/2 ) and polymerizing, the composition of the main chain and the branched chain can be controlled, and the performance such as the offset property in the toner can be improved. Examples of the catalyst that can be used in combination include conventional catalysts such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO),
3,3,5-trimethylcyclohexanone peroxide, acetyl peroxide, dodecyl peroxide, lauroyl peroxide, 2,2′-azobis (2,4-dimethylvaleronitrile), t-butylperoxyisobutylene
And t-butylperoxy-2-ethylhexanoate.

The amount of the copolymerizable peroxide to be used is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the bifunctional ethylene monomer. The amount of copolymerizable peroxide used is
If the amount is less than 0.05 part by weight, the number of branch points is reduced and the improvement in fluidity due to the branched chain is not exhibited. If the amount is more than 10 parts by weight, the number of branch points is too large and the branched chains are entangled and mixed. ) Is poor, resulting in poor toner offset resistance. (2) When a substance having three or more peroxy groups in a molecule (hereinafter, a polyfunctional initiator) is used, when these initiators are used in the same manner as in a conventional polymerization method, one molecule is used. Since it has a plurality of polymerization initiation points, the weight average molecular weight becomes large and a polymer having Mw of 50,000 or less cannot be obtained. Therefore, in the present invention, the concentration of the polyfunctional initiator in the system is adjusted by controlling various factors such as dilution, dropping time, reaction temperature, stirring efficiency, and Mw / Mb is 2
To obtain an ethylene polymer (X) having an Mw of 50,00099 and an Mw of 50,000 or less. Although the production efficiency deteriorates, it can be produced by increasing the degree of dilution and lengthening the dropping time.

Even when a polyfunctional initiator is used, it has a 10-hour half-life temperature (t _1/2 ) in a temperature range around the polymerization temperature as in the case of the above-mentioned copolymerizable peroxide. Any suitable catalyst may be used in combination. The amount of the multifunctional initiator used is 2
0.01 to 10 based on 100 parts by weight of the functional ethylene monomer
Parts by weight are desirable. If the amount of the polyfunctional initiator used is less than 0.01 part by weight, the molecular weight increases and no improvement in melt fluidity is exhibited.If the amount is more than 10 parts by weight, the number of branch points is too large, and the branched chains are entangled with each other, and ethylene-based heavy The compatibility with the resin used in combination with (X) is deteriorated, and the toner has poor fixing / offset properties, which is not preferable. Particularly preferred polyfunctional initiators include 4
Those having two peroxy groups are preferred.

Specific examples of the substance name of the polyfunctional initiator include:
Tri-t-butyl pertrimellitic acid, tri-t-amyl pertrimellitic acid, tri-t-hexyl pertrimellitic acid, tri-t-permellitic acid
t-1,1,3,3-tetramethylbutyl ester, tri-t-cumyl pertrimellitic acid ester, tri-t- (p-isopropyl) cumyl pertrimellitic acid ester, tri-t-butyl pertrimesate Esters, tri-t-amyl pertrimesate, tri-t-pertrimesate
Hexyl ester, pertrimesic acid-t-1,1,3,3-tetramethylbutyl ester, pertrimesic acid tri-t-
Cumyl ester, pertrimesic acid tri-t-tri-t-
(P-isopropyl) cumyl ester, 2,2-bis (4,4-
Di-t-butylperoxycyclohexyl) propane,
2,2-bis (4,4-di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4, 4-di-α
-Cumylpa-oxycyclohexyl) propane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) butane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) butane, etc. Is mentioned.

The ethylene-based high polymer (Y) has a Mw of 200,0
An ethylene polymer having a Mw / Mn of 3 or more and an Mw / Mn of 5 or more is more preferable. It is preferable to use an ethylenically unsaturated monomer and / or a polyfunctional monomer as a raw material monomer and to be produced by a polymerization method such as solution polymerization, suspension polymerization or emulsion polymerization. Ethylene polymer (Y)
When Mw is less than 100,000, sufficient offset resistance cannot be obtained, which is not preferable. If Mw / Mn is less than 3, sufficient offset properties and toner strength cannot be achieved, which is not preferable. The ethylenic polymer (Y) was obtained by polymerizing the above polyfunctional initiator or a conventionally known initiator with the following ethylenically unsaturated monomer and / or polyfunctional monomer. And particularly those having a weight average molecular weight of 100,000 or more obtained by a solution polymerization method. The mixing ratio with the ethylene polymer (X) is such that the ethylene polymer (X) is 15% of the total amount of the binder resin.
If the amount is less than about 10% by weight, the resulting toner has insufficient melt fluidity, resulting in poor fixing. On the other hand, if it exceeds 85% by weight, the strength of the toner is improved and the offset resistance is deteriorated, which is not preferable.

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

The polyfunctional monomers mentioned above include 2,2-bis (4-acryloxypolyethoxyphenyl) propane,
1,3-butylene glycol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene Glycol diacrylate,
Acrylic acid units such as polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, polypropylene glycol diacrylate, N, N'-methylenebisacrylamide, pentaerythritol triacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate, etc. Monomer, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane , Aluminum methacrylate, zinc methacrylate, calcium methacrylate, methacrylic acid monomers such as magnesium methacrylate, diallyl phthalate, triallyl cyanurate, and others
Triallyl isocyanurate, triallyl trimellitate, ethylene glycol diglycidyl ether acrylate, divinylbenzene and the like can be mentioned.

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

[0021]

(R ¹ -NHCO) ₂ R ² (wherein R ¹ each independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ² represents a carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group) or a general formula

[0022]

(R ³ —CONH) ₂ R ⁴ (wherein, R ³ independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ⁴ represents a carbon atom having 1 to 10 carbon atoms. As a specific method of adding the amide compound (indicating a hydrogen group), (1) the amide compound is added when the solvent is removed from a solution of a mixture of the ethylene polymer (X) and the ethylene polymer (Y). In this case, the amide compound is added to an apparatus for removing the solvent in the form of a powder or dissolved in a solvent, and after stirring,
Remove the solvent. (2) When adding at the time of melt-kneading in the production of a toner, a mixture of an ethylene-based polymer (X) and an ethylene-based high polymer (Y), a constituent material required as a toner, and the amide compound are simultaneously mixed. And melt kneading.

Examples of the amide compound of the general formula [Chemical Formula 1] used in the present invention include N, N'-dilauryl adipamide, N, N'-distearyl adipamide, N, N '
-Distearyl sebacamide, N, N-divehenyladipamide and the like. Examples of the amide compound represented by the general formula [Chemical Formula 2] include, for example, methylenebisstearic acid amide, ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebis12
-Hydroxystearic acid amide, ethylenebisbehenic acid amide, hexamethylenebisstearic acid amide, o
-Phenylene bisstearic acid amide and the like.

Preferred commercial products of these amide compounds include, for example, "Bisamide", "Diamid 200 Bis", "Rubron" (manufactured by Nippon Hydrogen Co., Ltd.) and "Plast Flow" (manufactured by Nitto Chemical Co., Ltd.). Company),
"Alflo-50S", "Alflo 50F", "Alflo V-60" (all manufactured by NOF Corporation), "Amide-6L", "Amide-7S", "Amide-6H"
(Above, manufactured by Kawaken Fine Chemical Co., Ltd.), "Armo Wax EBS" (above, manufactured by Lion Armor), "Hoechst Wax C" (produced by Hoechst Japan), "Nobuco Wax 22-DS" (above, manufactured by Nobuco Chemical Co., Ltd.) ),
"Adovax-280" (above, manufactured by Advance Corporation), "Kaowax-EB" (above, manufactured by Kao Corporation),
"Varicin 285" (all manufactured by Baker Casta Oil Co., Ltd.) and the like can be mentioned. In particular, "Alflo-
50S "," Alflo-50F "," Alflo V-6 "
0 "is preferred. These amide compounds generally have a higher softening point as the number of carbon atoms of the aliphatic hydrocarbon group (R ¹ or R ³ ) and the length of the alkylene chain (R ² or R ⁴ ) increase. -From the viewpoint of blocking properties, those having a softening point in the range of 100 to 150 ° C are preferable. The amide compound is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the mixture of the ethylene polymer (X) and the ethylene polymer (Y). This range has the effect of further lowering the minimum fixing temperature. If the amount is less than 0.5 part by weight, the effect of the addition of the amide compound will not be obtained, and if the amount is more than 10 parts by weight, the glass transition temperature in the toner resin composition will be greatly reduced, As a result, the developability and transferability are reduced, and a good visible image is not formed. In addition, the amide compound adheres to the developing sleeve or the electrostatic image support to form a film, which causes a problem that the function is impaired or the blocking resistance is greatly impaired.

2. The block copolymer or the graft copolymer used for improving the effect of the polyolefin wax added to improve the anti-offset property (improving the dispersibility of the polyolefin wax) includes ethylene hydrocarbons and / or conjugates. 1 of diene hydrocarbons
A block copolymer composed of at least one kind of block and a block of polystyrene or a hydrogenated product thereof, and the graft copolymer is a polypropylene-modified polystyrene graft copolymer, both of which are used alone or in combination. Its role in the toner resin composition is to improve the dispersibility of various additives such as polyolefin wax which is an anti-offset agent.

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

Specific product names include "Clayton", "Califlex TR" (both manufactured by Shell Chemical Co., Ltd.), "Septon" (manufactured by Kuraray Co., Ltd.), "TUFTEC" and "TAFPREN". , "Solprene", "Asaprene" (above, manufactured by Asahi Kasei Kogyo Co., Ltd.), "Lavalon" (manufactured by Mitsubishi Yuka Co., Ltd.), "Sumitomo TPE-SB" (manufactured by Sumitomo Chemical Co., Ltd.), "Elastomer" AR ”(Aron Kasei Co., Ltd.)
JSR TR "(manufactured by Nippon Synthetic Rubber Co., Ltd.),
Examples include “Electric STR” (manufactured by Denki Kagaku Co., Ltd.) and “Europrene SOL-T” (manufactured by Tosoh Corporation). As the polypropylene-modified polystyrene graft copolymer, “MODIPA” (manufactured by NOF Corporation) )), "VM
X "(manufactured by Mitsubishi Yuka Corporation) and the like. The amount of the block copolymer or the graft copolymer and the polyolefin wax used as the dispersant is from 0.5 to 0.5 part by weight based on 100 parts by weight of the mixture of the ethylene polymer (X) and the ethylene polymer (Y). 25 parts by weight of polyolefin wax is used in the range of 5 to 35 parts by weight. The dispersant
If the amount is less than 0.5 part by weight, the effect of dispersing the polyolefin wax is reduced, and there is a problem in the uniformity of the toner characteristics. On the other hand, if it is more than 25 parts by weight, the domain size of the dispersant itself becomes too large, which is not preferable, and it is not economically preferable. Further, the ratio of the polystyrene block in the block copolymerization is preferably from 3 to 90% by weight, particularly preferably from 5 to 70% by weight. When the ratio of the polystyrene block is less than 3% by weight, the fixing roll and the photoconductor are easily stained. On the other hand, if it exceeds 90% by weight, the strength of the toner is undesirably reduced.

The polyolefin wax is used in the range of 5 to 35 parts by weight. If the effect of the polyolefin wax is 5 parts by weight or less, it is not necessary to use a dispersant. In short, in a resin composition for a toner that requires at least 5 parts by weight of a polyolefin wax,
0.5 to 25 parts by weight are used. These dispersant and polyolefin wax are used as an ethylene polymer (X)
Or any of the steps of polymerizing the ethylene-based high polymer (Y), removing the solvent from the mixed solution of the ethylene-based polymer (X) and the ethylene-based high polymer (Y), and melt-kneading the resin for toner. May be added. Moreover, you may separate and add in a several process.

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

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

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

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

The binder resin composed of the ethylene-based polymer (X) and the ethylene-based high polymer (Y) is generally used in the resin composition for a toner in an amount of 50 to 95% by weight. If necessary, the binder resin may be, for example, polyvinyl chloride, polyolefin, polyester, polyvinyl butyral, polyurethane, polyamide, rosin, terpene resin, phenol resin, or epoxy resin as long as the effects of the present invention are not impaired. Resins, paraffin wax, polyolefin wax and the like are added. In the resin composition for an electrophotographic toner using the ethylene polymers (X) and (Y) of the present invention, a colorant is usually used. As a coloring agent used, for example, carbon black, acetylene black, lamp black, black pigments such as magnetite,
Graphite, yellow iron oxide, Hansayello-G, quinoline yellow lake, permanent yellow, NCG molybdenum orange, vulcan orange, indanthrene, brilliant orange GK, bengala, brilliant carmine 6
B, Frizarin Lake, Fast Violet B, Cobalt Blue, Alkaline Blue Lake, Phthalocyanine Blue, Metal Complex of Monoazo Dye, Fast Sky Blue, Pigment Green B, Malachite Green Lake, Titanium Oxide, Zinc Hua, etc. . The amount is usually 5 to 300 parts per 100 parts by weight of the binder resin.
Parts by weight. In the resin composition for an electrophotographic toner of the present invention, for example, known charge adjusting agents and pigment dispersants such as nigrosine, quaternary ammonium salts, metal-containing azo dyes, metal salts of fatty acids, and the like are appropriately selected. To obtain a toner by a known method. That is, the binder resin to which the above-mentioned various additives are added is premixed by a Henschel mixer, kneaded in a heated and melted state by a kneader such as a kneader, cooled, finely pulverized by a jet pulverizer, and then classified by a classifier. The particles are usually collected in the range of 8 to 20 μ to obtain a toner.

In order to obtain a magnetic toner, a magnetic powder may be contained. Such magnetic powders include ferromagnetic substances magnetized in a magnetic field, powders of iron, nickel, cobalt, and the like, and alloys of magnetite, ferrite, and the like. 15 to 70 parts by weight are preferred.

Further, in the present invention, a releasing agent as described below may be appropriately used at the time of polymerization or melting and kneading. The release agent referred to here is a substance that functions to reduce friction, improve releasability, or improve fluidity at the time of melting by coming into contact with a fixing roller at the time of fixing. For example, paraffin wax, high-grade (saturated) (Straight chain) fatty acids (C12
50), higher alcohols (8 to 32 carbon atoms), fatty acid metal salts, fatty acid amides, metal soaps, polyhydric alcohols and the like. In the toner, a charge adjuster, a colorant, and a powder fluidity modifier may be mixed (externally added) with the toner particles, if necessary. As this charge adjusting agent,
Examples include metal-containing dyes and nigrosine, and examples of powder fluidity modifiers include colloidal silica and fatty acid metal salts. For the purpose of increasing the amount, fillers such as calcium carbonate and finely divided silica may be added to the toner in the range of 0.5 to 20 parts by weight. Furthermore, preventing aggregation of toner particles,
In order to improve the powder flowability, a powder flow improver such as Teflon fine powder may be blended. As described above, in the method for obtaining the ethylene polymers (X) and (Y) of the present invention, various additives may be dissolved and dispersed in a monomer and polymerized. The electrophotographic toner composition containing the ethylene polymers (X) and (Y) of the present invention as a main component of the binder resin can be applied to all known developing methods. For example, a two-component developing method such as a cascade method, a magnetic brush method, or a microtoning method; a one-component developing method containing a magnetic substance such as a conductive one-component developing method, an insulating one-component developing method, or a jumping developing method; Method and fur brush method;
A non-magnetic one-component developing method in which the toner is conveyed to the developing unit by being held on the toner carrier by electrostatic force can be used.

[0036]

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

[0037]

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

[0038]

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

Detector SHOdex RI SE-31 Column A-80M x 2 + KF-802 Solvent THF (tetrahydrofuran) Discharge rate 1.2 ml / min Sample 0.25% THF solution Production Examples of Binder Resin (1) Ethylene-based polymer (X) or polymer solution thereof obtained as described above, and ethylene-based high polymer (Y)
Were mixed at the ratios shown in each table, and the solvent was removed to obtain a binder resin. 4. Production Examples and Evaluation Results of Toner Examples 1 to 101 and Comparative Examples 1 to 26 100 parts of the binder resin described above and 10 parts of carbon black (MA-100 (manufactured by Mitsubishi Kasei Corporation), 5 parts of polypropylene wax,
After premixing 1 part of a nigrosine dye as a charge control agent with a Henschel mixer, kneading was performed at 170 ° C. using a twin-screw kneader, followed by cooling, coarse pulverization, fine pulverization, and classification by a classifier. ~ 20μ toner was obtained. Using the above toner, the fixing property, the offset property, the image quality stability and the like were evaluated. Fixing properties and offset properties were evaluated using a machine modified so that the roll temperature of a commercial copying machine could be changed arbitrarily. Next, an evaluation method will be described. 70% fixing temperature; 2 cm × 2 cm solid black portion of the image quality toner of - a layer of a load of academic sustaining oscillating rubbing fastness tester (KK Daiei Kagaku Seiki Seisakusho) at 300 g / cm ^2, a sand eraser Weight ratio of toner layer after rubbing 50 times with 70%
The minimum hot roll temperature required to exceed Offset temperature: The temperature at which offset began to occur as the hot roll temperature was raised. Blocking property: 100 g of the toner was tapped in a polybin, kept at 50 ° C. for 50 hours, returned to room temperature, transferred onto paraffin paper, and visually determined according to the following criteria. ◎ No blocking at all. ○ There is some blocking, but there is no practical problem. △ It is quite blocking. × Almost one lump. Toner strength; pulverizability was measured by roughly pulverizing a pulverulent lump in the production of each toner, classifying it using a jet pulverizer, using a pulverization pressure of 2.5 kg / cm ² and a feed amount of 20.
It was carried out by pulverizing under the condition of g / min and measuring the average particle size of the obtained product. Photoreceptor stain; photoreceptor when 100,000 copies are taken
The fixing roll was wiped with cotton, and the cotton was visually judged to determine the degree of dirt. ◎ Not stained at all ○ Slightly black cotton △ Fairly black × Black black Domain size in the binder resin; A transmission electron micrograph was taken of the resin internally added when the mixture was desolvated, and the dispersion particle size of the dispersant in the resin was measured therefrom. Charging stability: The toner particles and the spherical iron oxide powder were mixed in a ratio of 3:97 in a V blender for 30 hours.
The amount of charge after time is calculated by the following formula (absolute value)
The ratio was defined as good when the ratio was within 10%. [(Charge amount after 30 minutes)-(Charge amount after 30 hours)] ÷ (30
Image quality (fog); comparing the 100th and 10,000th white background portions in continuous copying, Judgment was made based on the degree of dirt in the part.良 Good The degree that cannot be confirmed with a magnifying glass of 30 times magnification.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

According to the method of the present invention, a stable and high-quality image can always be obtained even with a low-calorie fixing copying machine which cannot be solved by the prior art. That is, the toner using the resin composition of the present invention has a low minimum fixing temperature, a wide non-offset temperature range, extremely good image characteristics, and has excellent performance as a toner composition for electrophotography. .

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 4-167351 (32) Priority date Hei 4 (1992) June 25 (33) Priority claim country Japan (JP) (31) Priority Claim number Japanese Patent Application No. 4-237295 (32) Priority Date Hei 4 (1992) September 4 (33) Priority Country Japan (JP) (72) Inventor Katsuo Uramoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tamami Fukui 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. Yoshio Kanno (56) References JP-A-2-48675 (JP, A) JP-A-2-27459 (JP, A) JP-A-1-161261 (JP, A) JP-A-64-15752 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03G 9/08

Claims (5)

(57) [Claims] 1. A material having three or more peroxy groups in a molecule and / or one or more unsaturated functional groups and one or more peroxy groups in a molecule per 100 parts by weight of a bifunctional ethylenically unsaturated monomer. Mw / Mb (Mw is a weight average molecular weight, Mb is a weight average molecular weight between cross-linking points) of a polymer produced using 0.01 to 10 parts by weight of a substance having
Ethylene polymer (X) having Mw of 50,000 or less and Mw
From 200,000 or more and Mw / Mn of 3.0 or more, comprising an ethylene-based polymer (Y) ,
(X) and the use ratio of the ethylene-based high polymer (Y) is 15:85.
A resin composition for electrophotographic toner having a weight ratio of about 85:15 . 2. An ethylene-based high polymer (Y) having a Mw of 200,
000 or more, and Mw / Mn is 5.0 or more claims 1
The resin composition for an electrophotographic toner according to the above. 3. When the ethylene-based polymer (X) and the ethylene-based high polymer (Y) are used, when the solvent is removed from a solution of a mixture of the two or when the mixture is melt-kneaded in the production of a toner, the general formula [Chem. (1) (R ¹ -NHCO) ₂ R ² (wherein R ¹ each independently represents an alkyl group having 7 to 24 carbon atoms or an alkyl group having a hydroxyl group, and R ² represents 1 to ² carbon atoms) Which represents 10 hydrocarbon groups) or a general formula [Chemical Formula 2]
(Formula 2) ## STR2 ## (R ³ -CONH) in ₂ R ⁴ (wherein, R ³ is each independently an alkyl group having an alkyl group or a hydroxyl group having 7 to 24 carbon atoms, R ⁴ is C 1 -C 2. The resin composition for an electrophotographic toner according to claim 1, further comprising an amide compound represented by the following formula: 4. A block of ethylene hydrocarbon and / or conjugated diene hydrocarbon and a block of polystyrene, based on 100 parts by weight of a resin mixture of an ethylene polymer (X) and an ethylene polymer (Y). A block copolymer or a hydrogenated product thereof, or at least one of a polypropylene-modified polystyrene graft copolymer and 0.5 to 25
The resin composition for an electrophotographic toner according to claim 1, wherein the resin composition contains 5 to 35 parts by weight of a polyolefin wax. 5. A weight-average molecular weight of 100,0 produced by a solution polymerization method using a compound having three or more peroxy groups in one molecule as an initiator.
2. The resin composition for an electrophotographic toner according to claim 1, wherein the polymer is a polymer having a Z average molecular weight of at least 850,000.