CA2018371C - Toner - Google Patents
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- Publication number
- CA2018371C CA2018371C CA 2018371 CA2018371A CA2018371C CA 2018371 C CA2018371 C CA 2018371C CA 2018371 CA2018371 CA 2018371 CA 2018371 A CA2018371 A CA 2018371A CA 2018371 C CA2018371 C CA 2018371C
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- Prior art keywords
- toner
- acid
- dispersing agent
- styrene
- toner according
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention as described herein provides a toner comprising a polymeric binder obtainable by suspension polymerisation of a mixture of vinyl monomers including both styrene or a styrene derivative and a (meth) acrylic ester, and an acid vinyl monomer in an amount of 0.5 to 10 wt. % based on the total weight of the vinyl monomers, the polymerisation being carried out using a non-ionic dispersing agent and an azo initiator. The toner of the present invention produces copied images having excellent stability of image quality (life) even after a large number of times of copying.
Description
BACKGROUND OF THE INVENTION
Field of the Invention The present invention relates to a toner which includes a vinyl polymer binder that has been prepared by a particular polymerisation method. The vinyl polymer binder used in the toner of the present invention is prepared by suspension polymerisation using a particular dispersing agent and initiator.
Hitherto, there have been a large number of inventions relating to binder resins for dry toners.
Vinyl polymers used as a binder resin for toners are produced by suspension polymerization, bulk polymerizaton, solution polymerization, emulsion polymerization, etc. Suspension polymerization is preferred because the manufacturing costs are minimized.
However, it is not avoidable for the binder resin to contain the residual decomposition by-products of a dispersing agent and initiator used in the suspension polymerization. Toners using such a resin as a binder are undesirable because toners prepared from them have problems in terms of chargeability, and particularly stability (life) of the image quality.
SUMMARY OF THE INVENTION
The present inventors have studied these problems and found that if the toner is prepared using a vinyl polymer binder obtained by suspension polymerisation of a polymerised vinyl monomer with a non-ionic dispersing agent and an azo initiator, the resultant toner will have superior stability of image quality.
According to the present invention, there is provided a toner comprising a polymeric binder obtained by suspension polymerisation of a mixture of vinyl monomers including both styrene or a styrene derivative and a (meth) acrylic acid ester and an acid vinyl monomer in an amount of 0.5 to 10 wt. ~ based on the total weight of the vinyl monomers, the suspension polymerisation being carried out using a non-ionic dispersing agent and an azo initiator.
Preferably the polymerisable vinyl monomer includes an acid monomer in an amount of 1 to 10 wt. o.
The present invention further resides in the use of an acid vinyl monomer in a process for making a polymeric binder by suspension polymerisation of a mixture of vinyl monomers in the presence of a nonionic dispersing agent and an azo initiator, the vinyl monomer mixture including both styrene or a styrene derivative and a (meth)acrylic acid ester and including the acid monomer in an amount of 0.5 - 10 wt. ~ based on the total weight of the monomers, to provide enhanced stability of the image produced using the polymer in a toner.
Field of the Invention The present invention relates to a toner which includes a vinyl polymer binder that has been prepared by a particular polymerisation method. The vinyl polymer binder used in the toner of the present invention is prepared by suspension polymerisation using a particular dispersing agent and initiator.
Hitherto, there have been a large number of inventions relating to binder resins for dry toners.
Vinyl polymers used as a binder resin for toners are produced by suspension polymerization, bulk polymerizaton, solution polymerization, emulsion polymerization, etc. Suspension polymerization is preferred because the manufacturing costs are minimized.
However, it is not avoidable for the binder resin to contain the residual decomposition by-products of a dispersing agent and initiator used in the suspension polymerization. Toners using such a resin as a binder are undesirable because toners prepared from them have problems in terms of chargeability, and particularly stability (life) of the image quality.
SUMMARY OF THE INVENTION
The present inventors have studied these problems and found that if the toner is prepared using a vinyl polymer binder obtained by suspension polymerisation of a polymerised vinyl monomer with a non-ionic dispersing agent and an azo initiator, the resultant toner will have superior stability of image quality.
According to the present invention, there is provided a toner comprising a polymeric binder obtained by suspension polymerisation of a mixture of vinyl monomers including both styrene or a styrene derivative and a (meth) acrylic acid ester and an acid vinyl monomer in an amount of 0.5 to 10 wt. ~ based on the total weight of the vinyl monomers, the suspension polymerisation being carried out using a non-ionic dispersing agent and an azo initiator.
Preferably the polymerisable vinyl monomer includes an acid monomer in an amount of 1 to 10 wt. o.
The present invention further resides in the use of an acid vinyl monomer in a process for making a polymeric binder by suspension polymerisation of a mixture of vinyl monomers in the presence of a nonionic dispersing agent and an azo initiator, the vinyl monomer mixture including both styrene or a styrene derivative and a (meth)acrylic acid ester and including the acid monomer in an amount of 0.5 - 10 wt. ~ based on the total weight of the monomers, to provide enhanced stability of the image produced using the polymer in a toner.
PREFERRED EMBODIMENTS OF THE INVENTION
The polymerizable vinyl monomers, used in the present invention may be any of those that may be S polymerized by suspension polymerization. For example, there are mentioned styrene and styrene derivatives such as a-methylstyrene and substituted styrenes having methyl at the o- or m-position of the benzene ring, or methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl, methoxy, phenyl or vinyl at the p-position of the benzene ring, or methyl at 2- and 4-positions thereof;
acrylic acid esters and methacrylic acid esters - 2 (a) -1 represented by the formula: CH2 = CR-COOR', where R repre-Bents hydrogen or methyl, and R' represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, dodecyl, tridecyl, stearyl, docosyl, cyclohexyl, benzyl, phenyl, methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, etc. These polymerizable vinyl monomers are used alone or in admixture of two or more of them.
As an example of a combination of two or more polymerizable vinyl monomers, there are mentioned monomer mixtures comprising as main constituents styrene and/or its derivatives and alkyl (meth)acrylates.
When the acid monomer is,used as one component of the polymerizable vinyl monomer, the life of the toner obtained is further improved. The amount of the acid monomer is 0.5 to 10 wt.$ based on the total weight of the polymerizable vinyl monomers. When the vinyl polymer is obtained by copolymerizing 0.5 wt.$ or less of the acid monomer, toners containing this vinyl polymer as a binder exhibit no effect of copolymerization of the acid monomer.
On the other hand, when the vinyl polymer is obtained by copolymerizing 10 wt.~ or more of the acid monomer, toners containing this vinyl monomer as a binder exert adverse effects on their other characteristics.
The polymerizable vinyl monomers, used in the present invention may be any of those that may be S polymerized by suspension polymerization. For example, there are mentioned styrene and styrene derivatives such as a-methylstyrene and substituted styrenes having methyl at the o- or m-position of the benzene ring, or methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl, methoxy, phenyl or vinyl at the p-position of the benzene ring, or methyl at 2- and 4-positions thereof;
acrylic acid esters and methacrylic acid esters - 2 (a) -1 represented by the formula: CH2 = CR-COOR', where R repre-Bents hydrogen or methyl, and R' represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, decyl, dodecyl, tridecyl, stearyl, docosyl, cyclohexyl, benzyl, phenyl, methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, etc. These polymerizable vinyl monomers are used alone or in admixture of two or more of them.
As an example of a combination of two or more polymerizable vinyl monomers, there are mentioned monomer mixtures comprising as main constituents styrene and/or its derivatives and alkyl (meth)acrylates.
When the acid monomer is,used as one component of the polymerizable vinyl monomer, the life of the toner obtained is further improved. The amount of the acid monomer is 0.5 to 10 wt.$ based on the total weight of the polymerizable vinyl monomers. When the vinyl polymer is obtained by copolymerizing 0.5 wt.$ or less of the acid monomer, toners containing this vinyl polymer as a binder exhibit no effect of copolymerization of the acid monomer.
On the other hand, when the vinyl polymer is obtained by copolymerizing 10 wt.~ or more of the acid monomer, toners containing this vinyl monomer as a binder exert adverse effects on their other characteristics.
1 The polymerizableacid monomer used herein refers to monomers having in addition to one or more the acid substituents polymerizable vinyl group. For example, it includes acrylic acid, methacrylic acid, itaconic acid, citraconic acid, malefic acid, fumaricacid, crotonic acid, monobutyl itaconate, monomethyl maleate, monobutyl maleate, monooctyl maleate, monooctyl itaconate, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, 2-acrylamide-2-methylpropanesulfonic acid, vinylbenzenesulfonic acid, etc. These acid monomers are used alone or in admixture of two or more of them.
For obtaining the vinyl polymer used in the present invention, a suspension polymerization method is used.
The azo initiator used in this method is not critical, it being possible to use the well-known ones.
For example, there are mentioned azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyronitrile, 2,2'-azobis-(2-methylbutyro-nitrile), 1,1'-azobis-(cyclohexane-1-carbonitrile), 2,2'-azobis-(2-cyclopropylpropionitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), etc. Among these initiators, it is preferred to use azobisisobutyro-nitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyronitrile or 2,2'-azobis-(2-methylbutyronitrile) because these initiators have properties to keep a polymerization activity upon the monomer and complete the polymerization in a 1 relatively short time, and because they do not have a high tendency to leave their decomposition by-products in the resulting polymer.
These azo initiators are used alone or in admixture of two or more of them.
The toner of the present invention has a remarkably improved life as compared with toners contain-ing as a binder polymers obtained by the conventional methods, because it uses as a binder a vinyl polymer obtained by suspension polymerization with a nonionic dispersing agent.
Suitable examples of nonionic dispersing agents for use in the present invention include polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, gelatin, polyethylene oxide, etc. Of these nonionic dispersing agents, polyvinyl alcohol having a saponification degree of 70 to 90%
and a polymerization degree of 500 to 3000 is preferred because resins obtained with it have good characteristics as a binder for toners.
The nonionic dispersing agent is used in such an amount that the polymerization operation can be completed without causing aggregation of the produced resin particles in the course of the polymerization.
The amount of the agent is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight based on 100 parts by weight of water.
If necessary, a dispersion auxiliary may be used. It includes for example electrolytes such as 1 sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, etc.
The conditions of the suspension polymerization vary with the particular polymerizable vinyl monomers and azo initiators used, and the amounts thereof.
However, the polymerization temperature is generally 30° to 130°C, preferably 60° to 100°C, and the polymerization time is preferably from about 1 to about 10 hours.
After the completion of the suspension polymerization, the reaction solution is filtered, and the resulting polymer is thoroughly washed, dehydrated and dried. A coloring agent and other additives are added to this polymer to obtain the toner of the present invention. The toner thus obtained is one having an extremely superior life.
The present invention is illustrated below with reference to the following Examples. In the Examples, parts are by weight. However, these examples are not to-be construed to limit the present invention.
Example 1 3 Parts of azobisisobutyronitrile, an azo initiator, was dissolved in a polymerizable vinyl monomer comprising 83 parts of styrene, 17 parts of 2-ethylhexyl acrylate and 0.3 part of divinylbenzene.
The resulting mixture was mixed with a polymerization medium obtained by dissolving 0.2 part of partially 1 saponified polyvinyl alcohol (PVA-224E produced by KURARAY CO., LTD.) in 220 parts of deionized water.
The mixture was heated to 80°C, and suspension polymerization was carried out for 90 minutes at this temperature. The resulting polymer dispersion was cooled to room temperature and filtered. The solid matter obtained was thoroughly washed, dehydrated and dried to obtain a bead-form binder resin.
92 Parts of the above binder resin, 7 parts of carbon black (#40 produced by Mitsubishi Kasei Corp.) and 1 part of a charge control agent (BONTRON - S-34*
produced by ORIENT CHEMICAL INDUSTRIES, LTD.) were kneaded at 150°C for about 5 minutes on a twin-screw extruder. After cooling, the kneaded product was finely pulverized on a jet mill. The fine powders obtained were classified to collect fine powders having a particle size of 5 to 15 um. The volume mean diameter of the fine powders was 9.6 um.
A copying test was carried out on a commercial-ly available copying machine ("Ricopy"* FT 4510 produced by RICOH CO., LTD.) using the above fine powders as a toner. As a result, fog-free high-resolution clear images were obtained at the initial stage of copying and after 10,000 copying operations. After 20,000 copying operations, however, the images showed a faint touch of fog and a somewhat lowered resolution degree, which were however of such a degree as to be out of the question in practical use.
* Trademark -1 Example 2 A toner was obtained in the same manner as in Example 1 except that 82 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 1 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of the toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations.
Example 3 A toner was obtained in the same manner as in Example 1 except that 82.5 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 0.5 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of the toner were evaluated, and it was found that fog-free high-resolution clear images were obtained at the initial stage of copying and after 10,000 copying operations,' but after 20,000 copying operations, the images showed a faint touch of fog, which was however of such a degree as to be out of the question in practical use.
Example 4 A toner was obtained in the same manner as in Example 1 except that 73 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 10 parts of methacrylic acid and _ 8 _ ~Q~~~~~
1 0.3 part of divinyl.benzene were used as the polymerizable vinyl monomer. The performances of this toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations, but the fixability and grindability were somewhat lowered.
Comparative Example 1 A toner was obtained in the same manner as in Example 1 except that 3 parts of benzoyl peroxide, which is not an azo initiator, was used as the poly-merization initiator, and that the polymerization temperature was 85°C. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 2 A toner was obtained in the same manner as in Example 2 except that 3 parts of benzoyl peroxide was used as the initiator and the polymerization temperature was 85°C. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree ~t~lt~3'~~.
1 were obtained.
Comparative Example 3 A toner was obtained in the same manner as in Example 1 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.), which is not a nonionic dispersing agent, was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 4 A toner was obtained in the same manner as in Example 2 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this 'toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 5 A toner was obtained in 'the same manner as in 2S Example 1 except that 0.2 part of a cation-modified 1 polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example E
A toner was obtained in the same manner as ZO in Example 2 except that 0.2 part of a cation-modified polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high--resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
For obtaining the vinyl polymer used in the present invention, a suspension polymerization method is used.
The azo initiator used in this method is not critical, it being possible to use the well-known ones.
For example, there are mentioned azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyronitrile, 2,2'-azobis-(2-methylbutyro-nitrile), 1,1'-azobis-(cyclohexane-1-carbonitrile), 2,2'-azobis-(2-cyclopropylpropionitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), etc. Among these initiators, it is preferred to use azobisisobutyro-nitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyronitrile or 2,2'-azobis-(2-methylbutyronitrile) because these initiators have properties to keep a polymerization activity upon the monomer and complete the polymerization in a 1 relatively short time, and because they do not have a high tendency to leave their decomposition by-products in the resulting polymer.
These azo initiators are used alone or in admixture of two or more of them.
The toner of the present invention has a remarkably improved life as compared with toners contain-ing as a binder polymers obtained by the conventional methods, because it uses as a binder a vinyl polymer obtained by suspension polymerization with a nonionic dispersing agent.
Suitable examples of nonionic dispersing agents for use in the present invention include polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, gelatin, polyethylene oxide, etc. Of these nonionic dispersing agents, polyvinyl alcohol having a saponification degree of 70 to 90%
and a polymerization degree of 500 to 3000 is preferred because resins obtained with it have good characteristics as a binder for toners.
The nonionic dispersing agent is used in such an amount that the polymerization operation can be completed without causing aggregation of the produced resin particles in the course of the polymerization.
The amount of the agent is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight based on 100 parts by weight of water.
If necessary, a dispersion auxiliary may be used. It includes for example electrolytes such as 1 sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, etc.
The conditions of the suspension polymerization vary with the particular polymerizable vinyl monomers and azo initiators used, and the amounts thereof.
However, the polymerization temperature is generally 30° to 130°C, preferably 60° to 100°C, and the polymerization time is preferably from about 1 to about 10 hours.
After the completion of the suspension polymerization, the reaction solution is filtered, and the resulting polymer is thoroughly washed, dehydrated and dried. A coloring agent and other additives are added to this polymer to obtain the toner of the present invention. The toner thus obtained is one having an extremely superior life.
The present invention is illustrated below with reference to the following Examples. In the Examples, parts are by weight. However, these examples are not to-be construed to limit the present invention.
Example 1 3 Parts of azobisisobutyronitrile, an azo initiator, was dissolved in a polymerizable vinyl monomer comprising 83 parts of styrene, 17 parts of 2-ethylhexyl acrylate and 0.3 part of divinylbenzene.
The resulting mixture was mixed with a polymerization medium obtained by dissolving 0.2 part of partially 1 saponified polyvinyl alcohol (PVA-224E produced by KURARAY CO., LTD.) in 220 parts of deionized water.
The mixture was heated to 80°C, and suspension polymerization was carried out for 90 minutes at this temperature. The resulting polymer dispersion was cooled to room temperature and filtered. The solid matter obtained was thoroughly washed, dehydrated and dried to obtain a bead-form binder resin.
92 Parts of the above binder resin, 7 parts of carbon black (#40 produced by Mitsubishi Kasei Corp.) and 1 part of a charge control agent (BONTRON - S-34*
produced by ORIENT CHEMICAL INDUSTRIES, LTD.) were kneaded at 150°C for about 5 minutes on a twin-screw extruder. After cooling, the kneaded product was finely pulverized on a jet mill. The fine powders obtained were classified to collect fine powders having a particle size of 5 to 15 um. The volume mean diameter of the fine powders was 9.6 um.
A copying test was carried out on a commercial-ly available copying machine ("Ricopy"* FT 4510 produced by RICOH CO., LTD.) using the above fine powders as a toner. As a result, fog-free high-resolution clear images were obtained at the initial stage of copying and after 10,000 copying operations. After 20,000 copying operations, however, the images showed a faint touch of fog and a somewhat lowered resolution degree, which were however of such a degree as to be out of the question in practical use.
* Trademark -1 Example 2 A toner was obtained in the same manner as in Example 1 except that 82 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 1 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of the toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations.
Example 3 A toner was obtained in the same manner as in Example 1 except that 82.5 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 0.5 part of methacrylic acid and 0.3 part of divinylbenzene were used as the polymerizable vinyl monomer. The performances of the toner were evaluated, and it was found that fog-free high-resolution clear images were obtained at the initial stage of copying and after 10,000 copying operations,' but after 20,000 copying operations, the images showed a faint touch of fog, which was however of such a degree as to be out of the question in practical use.
Example 4 A toner was obtained in the same manner as in Example 1 except that 73 parts of styrene, 17 parts of 2-ethylhexyl acrylate, 10 parts of methacrylic acid and _ 8 _ ~Q~~~~~
1 0.3 part of divinyl.benzene were used as the polymerizable vinyl monomer. The performances of this toner were evaluated, and it was found that fog-free high-resolution clear images were obtained even after 20,000 copying operations, but the fixability and grindability were somewhat lowered.
Comparative Example 1 A toner was obtained in the same manner as in Example 1 except that 3 parts of benzoyl peroxide, which is not an azo initiator, was used as the poly-merization initiator, and that the polymerization temperature was 85°C. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 2 A toner was obtained in the same manner as in Example 2 except that 3 parts of benzoyl peroxide was used as the initiator and the polymerization temperature was 85°C. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree ~t~lt~3'~~.
1 were obtained.
Comparative Example 3 A toner was obtained in the same manner as in Example 1 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.), which is not a nonionic dispersing agent, was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 4 A toner was obtained in the same manner as in Example 2 except that 0.2 part of an anion-modified polyvinyl alcohol (KL-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this 'toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example 5 A toner was obtained in 'the same manner as in 2S Example 1 except that 0.2 part of a cation-modified 1 polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high-resolution clear ones, but that after 5,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Comparative Example E
A toner was obtained in the same manner as ZO in Example 2 except that 0.2 part of a cation-modified polyvinyl alcohol (C-318 produced by KURARAY CO., LTD.) was used as the dispersing agent. The performances of this toner were evaluated, and it was found that the images at the initial stage of copying were fog-free high--resolution clear ones, but that after 10,000 copying operations, only images having a touch of fog and a lowered resolution degree were obtained.
Claims (8)
1. A toner comprising a polymeric binder obtainable by suspension polymerisation of a mixture of vinyl monomers including both styrene or a styrene derivative and a (meth) acrylic ester, and an acid vinyl monomer in an amount of 0.5 to 10 wt. % based on the total weight of the vinyl monomers, the polymerisation being carried out using a non-ionic dispersing agent and an azo initiator.
2. A toner according to claim 1, including the acid vinyl monomer in an amount of 1 to 10 wt. %.
3. A toner according to claim 1 including the nonionic dispersing agent is polyvinyl alcohol.
4. A toner according to claim 3 wherein the polyvinyl alcohol has a saponification degree of 70 to 90%.
5. A toner according to claim 3 or claim 4 wherein the polyvinyl alcohol has a polymerisation degree of 500 to 3000.
6. A toner according to any one of claim 1 - 5 wherein the amount of nonionic dispersing agent is 0.05 to 2 parts by weight based on 100 parts by weight of water.
7. A toner according to any one of claims 1 - 6 wherein the azo initiator is at least one member selected from the group consisting of azobisisobutyronitrile, 2.2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2' -azobisisobutyronitrile).
8. Use of an acid vinyl monomer in a process for making a polymeric binder by suspension polymerisation of a mixture of vinyl monomers in the presence of a nonionic dispersing agent and an azo initiator, the vinyl monomer mixture including both styrene or a styrene derivative and a (meth)acrylic acid ester and including the acid monomer in an amount of 0.5 - 10 wt.
% based on the total weight of the monomers, to provide enhanced stability of the image produced using the polymer in a toner.
% based on the total weight of the monomers, to provide enhanced stability of the image produced using the polymer in a toner.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01-150537 | 1989-06-15 | ||
| JP15053789A JP2855447B2 (en) | 1989-06-15 | 1989-06-15 | toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2018371A1 CA2018371A1 (en) | 1990-12-15 |
| CA2018371C true CA2018371C (en) | 2001-05-01 |
Family
ID=15499039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2018371 Expired - Fee Related CA2018371C (en) | 1989-06-15 | 1990-06-06 | Toner |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0403178B1 (en) |
| JP (1) | JP2855447B2 (en) |
| CA (1) | CA2018371C (en) |
| DE (1) | DE69023553T2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004051830B4 (en) | 2004-10-25 | 2007-12-13 | Roche Diagnostics Gmbh | Multifunctional reference system for analyte determination by fluorescence |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849318A (en) * | 1986-10-31 | 1989-07-18 | Mita Industrial Co., Ltd. | Processes for producing electrophotographic toner |
| JP2760499B2 (en) * | 1986-11-05 | 1998-05-28 | 三菱レイヨン 株式会社 | Resin for toner and production method thereof |
| US4904560A (en) * | 1987-06-29 | 1990-02-27 | Bando Chemical Industries, Ltd. | Suspension polymerization process for producing electrophotographic toners |
-
1989
- 1989-06-15 JP JP15053789A patent/JP2855447B2/en not_active Expired - Fee Related
-
1990
- 1990-06-06 CA CA 2018371 patent/CA2018371C/en not_active Expired - Fee Related
- 1990-06-08 EP EP19900306269 patent/EP0403178B1/en not_active Expired - Lifetime
- 1990-06-08 DE DE1990623553 patent/DE69023553T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0403178B1 (en) | 1995-11-15 |
| CA2018371A1 (en) | 1990-12-15 |
| JP2855447B2 (en) | 1999-02-10 |
| EP0403178A3 (en) | 1991-04-10 |
| DE69023553D1 (en) | 1995-12-21 |
| JPH0317662A (en) | 1991-01-25 |
| EP0403178A2 (en) | 1990-12-19 |
| DE69023553T2 (en) | 1996-04-11 |
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