JPS60247251A - Toner - Google Patents

Abstract

PURPOSE:To prevent adhesion between the toner of an obtained copy and the cover made of a resin during its storage in the cover by incorporating a polyester resin comprising a tervalent or a higher valent multifunctional structural component and an epoxy resin as a binder, and a basic carbon black in the toner. CONSTITUTION:The intended toner can be obtained by mixing an alcohol monomer, such as ethylene glycol, and a carboxylic acid, such as maleic acid, so as to incorporate at least one kind of tervalent or higher-valent component selected from either group, such as sorbitol or 1,2,4-benzenetricarboxylic acid; polymerizing the obtained monomer mixture to prepare a polyester resin; mixing this polyester and an epoxy resin in an amt. of epoxy resin of 10-90wt% of the total resin to form a binder resin, and further, blending the basic carbon black, (when water is added to it and boiled, the supernatant is >=7pH after coling), a colorant, etc., with this binder.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for developing an electrostatic latent image, a magnetic latent image, or the like.

[Prior art]

Currently, as a method for forming a visible image from given image information, a method using electrostatic latent images is widely used, and a method using magnetic latent images is also being used. . In developing these latent images,
A powdered toner is used which adheres to the latent image and makes the latent image visible.

Conventionally, this type of toner has been produced by using a vinyl resin such as styrene-acrylic copolymer as a binder and adding a coloring agent to the powder particles, but due to manufacturing and image forming characteristics. It is widely used because of its advantages.

On the other hand, there are many cases where printed matter formed by toner development must be stored for a long period of time, or even semi-permanently. In such cases, the printed matter, which has a visible image formed on paper, is usually stored in a so-called document holder made of a resin sheet, or by covering one or both sides of the printed matter with a resin film laminated. Often.

However, when storage is carried out using such a resin cover, over time, the toner that forms the image sticks to the resin cover that is in close contact with the surface of the print, and when the print is separated from the cover, the toner peels off from the print. As a result, accidents often occur that actually damage the printed matter.

It is also desired that the l.ner has excellent properties so that good results can be obtained in each process that it undergoes up to the formation of a visible image.

[Purpose of the invention]

The present invention was completed as a result of intensive research based on the above circumstances, and its purpose is to suitably and stably develop and fix latent images without requiring any special conditions. To provide a toner which can be used in a variety of applications and which has sufficient durability and is not affected by the resin cover even when the obtained printed matter is placed in contact with the resin cover.

C Structure of the Invention] The present invention is characterized by being composed of an alcohol monomer and a carboxylic acid monomer, and at least one of the alcohol monomer and the carboxylic acid monomer is a trivalent or higher polyfunctional It contains a polyester resin obtained by polymerizing a monomer composition containing the following components, an epoxy resin, and a basic carbon blank.

The present invention will be specifically explained below.

In the present invention, in a monomer composition for producing polyester comprising an alcohol monomer and a carboxylic acid monomer, at least one of the alcohol monomer and the carboxylic acid monomer has a trivalent or higher polyfunctional monomer. A binder is a mixture of a polyester resin obtained by condensation polymerization of this monomer composition and an epoxy resin, and a coloring agent made of basic carbon blank and other necessary components are added to the binder. to obtain a toner.

In the above, examples of the alcohol for composing the monomer composition for the polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4- Diols such as butanediol, neopentyl glycol, 1°4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A Examples include etherified hisphenols such as, dihydric alcohol monomers substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, and other dihydric alcohol monomers. .

Examples of carboxylic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, cepatic acid, malonic acid, and divalent organic acid monomers substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, anhydrides of these acids, dimers of lower alkyl esters and liluic acid, and other divalent organic acid monomers. Examples include organic acid monomers of various types.

Furthermore, examples of trihydric or higher polyhydric alcohol monomers include sorbitol, L2,3,6-hexanetetrol, 1
, 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, L2
, 4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol,
Examples include 2-methyl-L2,4-butanetriol, trimethylolethane, trimethylolpropane, L3,5-trihydroxymethylbenzene, and others.

In addition, as the trivalent or higher polyvalent carboxylic acid monomer, for example, 1
, 2.4-benzenetricarboxylic acid, 1,2.5-benzenetricarboxylic acid, 1,2.4-cyclohexanetricarboxylic acid, 2,5.7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, L2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra(methylenecarboxyl) Methane, 1,2,7.8-octane tetracarboxylic acid, empol trimer acid, acid anhydrides thereof, and others can be mentioned.

It is desirable that the above trifunctional or higher polyfunctional monomer component be contained in a proportion of 5 to 80 mol % in each of the alcohol component or acid component as a structural unit in the polymer.

It is desirable that the polyester resin obtained as described above has a softening point of 100 to 160°C, particularly 110 to 150°C, as measured by a flow tester, for example.

The softening point was measured using a Koka type flow tester rcFT-500j (
(manufactured by Shimabara Seisakusho) under the conditions of a die pore diameter of 1 mm, a pressure of 20 kg/cm2, and a temperature increase rate of 6°C/min.
This is the value when the softening point is defined as 172, which is the height from the start point to the end point of the outflow when a sample of m' is melted and outflowed.

The epoxy resin used as a binder together with the polyester resins mentioned below is not particularly limited, but has a melting point of 60 to 160°C, preferably 85 to 120°C, according to the Durand mercury method, and has a glass transition temperature. Those having a temperature of 55° C. or higher are preferably used. In particular, bisphenol A type epoxy resin is preferred.

As a specific example of the epoxy resin suitably used in the present invention, 100
3.1055.1,004.1004F, 10048F, 1005+1.1007.1009 (manufactured by Yuka Shell Epoxy Co., Ltd.), 7072.6084.7097.6 sold as rAraldite GYJ
097 (manufactured by Ciba Geigy), 662.664.667.668 sold as rD, E, and RJ (manufactured by Dow Chemical International), and others.

The ratio of the above epoxy resin is 10 to 90% of the binder.
It may be % by weight, preferably 40 to 80% by weight,
More preferably, it is 50 to 70% by weight.

The toner of the present invention uses a mixture of the above-mentioned polyester resin and epoxy resin as a binder, and contains a coloring agent made of basic carbon black and a property improver added as necessary to form a magnetic toner. In some cases, a magnetic material is contained together with or instead of a colorant.

The basic carbon blank, which is an essential component in the present invention, refers to one with an r+H value of 7 or more as measured by the following test method.

Test method (according to JIS K51018) Sample 5.0
Add 100 ml of water to a container containing g and boil gently for 5 minutes. After replacing the amount of water lost through evaporation, seal the container and cool to room temperature. Then, take the supernatant liquid and check its pH. Measure with a pH meter equipped with a glass electrode.

Specific examples of such basic carbon blanks include those listed below and others.

Carbon black manufactured by Mitsubishi Kasei: r"44J (7,5), r"55J (8,4)
, "I'30" (9,0) Carbon black manufactured by Columbia Carbon: rRAVE
N 2100J (7,0), r RAVEN 12
00 j (8,0> Cabosoto carbon blank: rREG to -L 660RJ (7,5>, rNON
ARcI+ 880 J (8,0) Note that the numerical value in parentheses is the pH value determined by the above-mentioned method.

In the present invention, as the colorant, other carbon blanks and other pigments may be used in combination with the above-mentioned basic carbon blank. These colorants need to be contained in a sufficient proportion to form a visible image with sufficient concentration, and are usually contained in an amount of 1 to 20 parts by weight per 100 parts by weight of the binder.
Part by weight: Part by weight.

The magnetic material may be a metal or alloy that exhibits ferromagnetism such as ferrite, magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but can be made by subjecting it to appropriate heat treatment. Mention may be made of alloys which become ferromagnetic, such as alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others. These magnetic substances are uniformly dispersed in the binder in the form of fine powder with an average particle size of 0.1 to 1 micron. The content thereof is 20 to 70 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of toner.
It is 70 parts by weight.

〔Effect of the invention〕

As described above, the toner of the present invention uses a mixture of a specific polyester resin and an epoxy resin as a binder, and further contains a basic carbon blank. It has excellent properties as a developer, especially excellent developability and fixability, and can stably form good visible images, and has high durability against resin, so it can be used for storage or other purposes. Even when a cover such as a resin film or sheet is provided, there is no adverse effect due to this, and therefore a visible image that can be stored semi-permanently is formed.

To explain in detail, polyester resin generally has a strong negative chargeability, but by mixing epoxy resin, the negative chargeability of the polyester resin itself is weakened, and the toner becomes a toner with a small negative chargeability. In addition, the carbon blank contained is basic carbon black, which helps the toner to be positively charged. Therefore, when used as a positively charged toner, for example, when developing an electrostatic image formed by negative charges, Alternatively, when reversing a positive electrostatic charge image formed using a selenium photoconductor with excellent photoconductive properties as a latent image support as in a laser printer, an excellent charging state can be obtained and a good visible image can be obtained. can be formed.

Since the colorant contained in the toner is a basic carbon blank, as will be clear from the examples described below,
Compared to cases containing other carbon blanks, it has greater stability against changes in environmental conditions and can always form good visible images.

Furthermore, since polyester resin generally has a low softening point, a toner using it as a binder requires a low temperature for fixing. However, the polyester resin used as a binder in the present invention contains a polyfunctional component. Since it is obtained from a monomer composition, it has a molecularly branched and cross-linked structure, and therefore, even though the toner has a low softening point and contains an epoxy resin, it has a low softening point during fixing. By fixing the toner image using a hot roller fixing method, which itself has many advantages, it is possible to achieve sufficient fixation at high speed and with less energy consumption. Become.

Also, unlike conventional toners, the toner of the present invention has a sufficiently high durability against resin, as is clear from the experimental examples described later. The polyester resin and the epoxy resin, which are the binders of the toner of the present invention, are polymers or copolymers that always contain a plasticizer, but when these two are mixed, the polyester resin has a crosslinked structure. It is presumed that the reason is that, in addition to the fact that it has a 100% diameter, it is almost unaffected by such machinability.

The toner of the present invention is mixed with a carrier to form a developer, or when it contains a magnetic material, is used as a developer to develop an electrostatic latent image or a magnetic latent image. In this case, fluidity improvers and others may be added to the toner powder or developer.
In particular, the addition of charge control agents and mold release agents may be desirable.

〔Example〕

Examples of the present invention will be described below, but the zero invention is not limited to these.

Synthesis Example 1 299 g of terephthalic acid and polyoxypropylene (2,
2) 211 g of -2,2-bis(4-hydroxyphenyl)propane and 82 g of pentaerythritol were placed in a round bottom flask equipped with a thermometer, a stainless steel stirrer, a glass nitrogen gas inlet tube, and a down-flow condenser. The flask was placed in a mantle heater, and nitrogen gas was introduced from the nitrogen gas inlet tube to raise the temperature while maintaining an inert atmosphere inside the flask. and 0.05g
of dibutyltin oxide was added and allowed to react at a temperature of 200°C while monitoring the reaction at the softening point.
By flow tester. The same applies below. ) is 134
A polyester resin A was prepared at .

Synthesis Example 2 299g of isophthalic acid and polyoxypropylene (2,
2) Synthesis Example 1 using 211 g of -2,2-bis(4-hydroxyphenyl)propane and 74 g of glycerol
In the same manner as above, the reaction was carried out at a temperature of 180℃, and the softening point was 136.
A polyester resin B was prepared at .

Example 1 Polyester resin A 40 parts by weight Epoxy resin "Epicote 1004FJ (softening point 97
°C) 60 parts by weight Carbon black r''30J (manufactured by Mitsubishi Kasei Corporation, pH 9,0) 5 parts by weight The mixture according to the above formulation was prepared in a Henschel mixer for 15 minutes, and then melted and kneaded with a twin-screw extruder. After being cooled to room temperature and solidified, it was roughly pulverized with a hammer mill, and then finely pulverized with a 1-set mill.The obtained fine powder was classified with an air classifier to obtain a toner with an average particle size of 12 to 13μ. Ta.

Examples 2 to 4 and Comparative Examples 1 and 2 Various toners were obtained in the same manner as in Example 1 according to the following formulations.

Example 2 Polyester resin B 40 parts by weight Epoxy resin "Epicoat 1004FJ60 parts by weight Carbon black r" 30J 5 parts by weight Example 3 Polyester resin A 40 parts by weight Epoxy resin "Epicoat 1004FJ60 parts by weight Carbon black r, REGAL 660RJ (manufactured by CABOSOTO) , pH 7,5) 5 parts by weight Example 4 Polyester resin A 40 parts by weight Epoxy resin "Epicoat 1004F J60 parts by weight Carbon blank "R to VEN 1200" Ll Om Via Carbon Co., Ltd., pH 8,0) 5 parts by weight 5 Comparative example 1 Polyester resin A 40 parts by weight Epoxy resin [Epicor] 1004FJ60 parts by weight Carbon blank "Mogul L" (manufactured by Cabot, pH 3,0) 5 parts by weight Comparative example 2 Polyester resin 8 40 parts by weight Epoxy resin [Epicor 1004FJ60 parts by weight Carhon Bluff rRAVEN 2000J (:2
(manufactured by Nvia Carbon Co., Ltd., pH 4, 5) 5 parts by weight or more The softening point of each of the toners obtained in the above manner was measured using a flow tester, and the charging characteristics were also investigated.

That is, 1.5 g of toner sample and 1.1-cybide rubber.
After mixing 58.5 g of carrier coated with fluorooctyl methacrylate resin and having an average particle size of approximately 100 μm using a shaker for 20 minutes, the charge amount per unit weight (unit: microcoulombs/g) was determined by the pull-off method.
) in an atmosphere of 20°C and 55% relative humidity, and a temperature of 30°C.
, the measurement was carried out in an atmosphere (2) with a relative humidity of 80%.

On the other hand, a developer was prepared by mixing 2.5 parts by weight of each of the toners with 97.5 parts by weight of the resin-coated carrier, and a heated roller whose surface layer was made of Teflon (polytetrafluoroethylene manufactured by DuPont) was prepared. , an organic photosensitive material consisting of a pressure roller whose surface layer is made of silicone rubber rKE-1300RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.), equipped with a release oil supply mechanism, and a fixing device with a line speed of 350 mm/sec. Each of the above-mentioned developers was applied to an electrophotographic copying machine r U-Bix 2500j modified machine (manufactured by Konishi Roku Photo Industry Co., Ltd.) equipped with a body drum to develop an electrostatic image formed by a normal electrophotographic method. , transfer the formed toner image onto plain paper, fix it using a fixing device,
Next, the operation of sending a blank sheet of paper to the fuser under the same conditions and observing whether or not toner stains occur thereon is repeated while varying the set temperature of the heat roller of the fuser to determine the offset occurrence temperature. I met.

In addition, the set temperature of the heat roller was set to 180°C, and a continuous copy test was conducted in atmosphere I and atmosphere II.
The obtained visible images were examined for the presence or absence of fog.

Furthermore, a cover sheet made of commercially available polyvinyl chloride was brought into close contact with the surface of the printed matter formed by the continuous copy test, a load of 100 g/cm2 was applied, and the cover sheet was left in an atmosphere at a temperature of 70°C for 3 hours. The durability against the resin was examined by peeling off the cover sheet and visually determining the degree of toner transfer to the cover sheet.

The above results are shown in Table 1. Regarding durability to resin, "○" indicates that no transfer was observed, "△" indicates that transfer was observed, and regarding fog, "△J" indicates that fog was observed and the reflection density was 0. 01-0.03
Indicates that the range is within the range of

As can be understood from the results in Table 1, the toner of the present invention in which the carbon blank contained is a basic carbon blank exhibits stable charging characteristics even under fluctuations in environmental conditions, and is excellent in any atmosphere. However, toners that do not contain basic carbon black have charging characteristics that fluctuate greatly due to changes in environmental conditions, making it impossible to stably form good visible images. .

Agent Patent Attorney Masahiko Oi 1 Procedural amendment (method) % formula % 1. Indication of the case Patent Application No. 101819 filed in 1982 2. Name of the invention Toner 3. Person making the amendment Relationship with the case Patent applicant Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name:
(127) Roku Konishi Photo Industry Co., Ltd. 5 Date of amendment order (shipment date) August 28, 1980 6 Subject of amendment Full text of the specification 7 Contents of amendment Engraving of the specification originally attached to the application
As shown in the attached sheet (no change in content)

Claims (1)

[Claims] 1) Consists of alcohol monomer and carboxylic acid monomer,
and a polyester resin obtained by polymerizing a monomer composition in which at least one of these alcohol monomers and carboxylic acid monomers contains a trivalent or higher polyfunctional component, an epoxy resin, and a basic carbon blank. A toner characterized by containing.