JPS60247249A - 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 an electrostatic charge controller. 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, such as a bisphenol A type epoxy resin in an amt. of epoxy resin of 10-90wt% of the total resin to form a binder resin, and further, blending the charge controller, such as a triphenylmethane type dye shown by the formula, and a colorant, additives, 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 is made by using a vinyl resin such as styrene-acrylic copolymer as a binder and adding a coloring agent to the powder particles.
It is widely used because it is advantageous in terms of "and image forming properties."

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 desirable for toners to have excellent properties so that good results can be obtained in each process that the toner undergoes leading to the formation of a visible image.

[Purpose of the invention]

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

[Structure of the invention]

A feature of the present invention is that the monomer is composed of an alcohol monomer and a carboxylic acid monomer, and at least one of the alcohol monomer and the carboxylic acid monomer contains a trivalent or higher polyfunctional component. It contains a polyester resin obtained by polymerizing a polymer composition, an epoxy resin, and a charge control agent.

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 this contains a charge control agent, a coloring agent, and other necessary components. At least get some 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, ■, 3-propylene glycol, ■, 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, 1,2,3,6-hexanetetrol,
1.4-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, door sugar, 1
, 2.4-butanetriol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-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, 1.2.4-
Butanetricarboxylic acid, 1,2.5-hexanetricarboxylic acid, 1,3-dicarboxyl-2=methyl-2-methylenecarboxypropane, tetra(methylenecarboxyl)methane, 1,2,7.8-octanetetracarboxylic acid , embol trimer acid, and acid anhydrides thereof, and others.

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.

The polyester resin obtained as described above preferably has a softening point of 100 to 160° C., particularly 110 to 150° C., measured using a flow tester, for example.

The softening point was measured using Koka Type Flow Tester R CFT-500.
J (manufactured by Kinsei Seisakusho) under the conditions of a die pore diameter of 1 Tsuru, 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 outflow start point to the outflow end point when a sample of m3 is melted and outflowed.

The epoxy resin used as a binder together with the above polyester resin is not particularly limited, but has a melting point measured by the Durand mercury method of 60 to 160°C, preferably 85 to 120°C, and a glass transition point of 85 to 120°C. 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
3.1055.1004.1004F, 1o04AF
, 1005+1.1007.1009 (manufactured by Yuka Shell Epoxy Co., Ltd.), 7072.6084.7097.60 sold as rAraldite GYj
97 (manufactured by Ciba Geigy), 662.664.667.668 (manufactured by Dow Chemical International) sold as [D, E, and RJ, 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 I-toner of the present invention uses a mixture of the above-mentioned polyester resin and epoxy resin as a binder, and contains a charge control agent, a colorant, 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.

In the present invention, a charge control agent is an essential component, and a positive charge control agent or a negative charge control agent is contained. Specific examples of positive charge control agents include nigrosine dyes such as "Nigrosine Base EXJ", "Oil Black BSJ", and "Oil Black SO" (manufactured by Orient Chemical Co., Ltd.), triphenylmethane dyes such as formula % Examples include compounds represented by the formula % and quaternary ammonium compounds such as cetyltrimethylammonium bromide.

Examples of negative charge control agents include metal-containing azo dyes, such as Parifast 3804J (manufactured by Orient Chemical Co., Ltd.), Subilobra Tsuku TRHJ (manufactured by Odugaya Chemical Co., Ltd.), copper phthalocyanine dyes, and metal complexes of salicylic acid. , for example, Bontron E-81j (manufactured by Orient Chemical Co., Ltd.), and others.

The content of the above charge control agent is in the range of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the binder resin.

As a coloring agent, carbon black, nigrosine dye (
C, 1, No. 50415B), Aniline Blue (C,
T.

No. 50405), Calco Oil Blue (C, 1,
No, azoecBlue 3), Chrome Yellow (
C, 1, No, 14090), Ultramarine Blue (C, 1, No, 77103), DuPont Oil Red (C, 1, No, 26105), Quinoline Yellow (C, 1, No, 47005), Methylene Blue Chloride ( C, 1, No. 52015), Phthalocyanine Blue (C, I.

No. 74160), Malachite Green Off Sarate (C, 1, No. 42000'), Lamp Black (C91, No. 77266), Rose Hengal (C.
T, No. 45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image with sufficient concentration, and are usually 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, for example 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. And its content is toner 1
20 to 70 parts by weight per 00 parts by weight, preferably 40 to 7 parts by weight
It is 0 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 charge control agent. It has excellent properties as a developer, especially excellent developability and fixing properties, and can form good visible images.It also has high resistance to resin, so it can be used as a resin film for storage or other purposes. Alternatively, even when a cover such as a 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. As a result, the effect can be fully exhibited even when the charge control agent contained together is either positive or negative. Therefore, by selecting a carrier or using an appropriate charge control agent. For example, when developing an electrostatic image formed by negative charges, or by reversing developing a positive electrostatic image formed using a selenium photoreceptor with excellent photoconductive properties as a latent image support as in a laser printer. As a positively charged toner or a negatively charged toner used in various cases, a toner having excellent charging characteristics can be obtained.

In addition, since polyester resin generally has a low softening point1, a toner using this 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. Because the toner is obtained from a monomer composition of To achieve sufficient fixing at high speed with less energy consumption by fixing a toner image using a heat roller fixing method that is less likely to cause an offset phenomenon during fixing and has many advantages in itself. You will be able to do this.

Also, unlike conventional toners, the toner of the present invention has a sufficiently high resistance to resin, as will be clear from the experimental examples described later. Although a vinyl polymer or copolymer always contains a plasticizer, the polyester resin and epoxy resin, which are the binders of the toner of the present invention, are mixed together to form a polyester resin. The reason for this is presumed to be that, in addition to the fact that it has a crosslinked structure, it becomes almost unaffected by such plasticizers.

The toner of the present invention is mixed with a carrier to form a developer, or when it contains a magnetic substance, is used as a developer as it is for developing an electrostatic latent image or a magnetic latent image. In this case, a fluidity improver or the like may be added to the toner powder or developer.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

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 diptyltin 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
Polyester resin A was prepared at °C.

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°C, and the softening point was 13.
Polyester resin B was produced at 6°C.

Example 1 Polyester resin A 40 parts by weight Epoxy resin [Epicote 1004FJ (softening point 97
°C) 60 parts by weight Carbon blank "Mogalushi" (manufactured by Cabosoto) 5 parts by weight Charge control agent "Nigrosine Base EXJ 3 parts by weight The mixture according to the above formulation was premixed for 15 minutes in a Henschel mixer, and then melted in a two-wheeled extruder. After cooling to room temperature and solidifying, it was coarsely crushed with a hammer mill, and then finely crushed with a 1-set mill.The obtained fine powder was classified with an air classifier, and the average particle size was 12 to 13μ. I got the toner.

Examples 2 to 8 and Comparative Examples 1 to 4 Various toners were obtained in the same manner as in Example 1 according to the formulations shown in Table 1.

The charging characteristics of each of the toners obtained as described above were investigated. That is, 3 g of toner sample and iron powder rEFV-
After mixing 57 g of 3J (manufactured by Nippon Tetsuko Co., Ltd.) with a shaker for 20 minutes, the amount of charge per unit weight was reduced to 0 using the blow-off method.
/M (unit: microcoulomb/g) was measured.

On the other hand, 2.5 parts by weight of each toner was mixed with spherical iron powder r 1
A developer was prepared by mixing with 97.5 parts by weight of a carrier consisting of 00M-IJ (manufactured by Shinsha Blakey), and the surface layer was coated with Teflon (polytetrafluoroethylene, manufactured by DuPont).
and a pressure roller whose surface layer is made of silicone rubber rKE-1300RTVJ (manufactured by Shin-Etsu Chemical Co., Ltd.), with a release oil supply mechanism, and a fixing roller with a line speed of 35 On+m and 7 seconds. An electrophotographic copying machine equipped with an organic photoreceptor drum (when the toner is positively chargeable) or a selenium photoreceptor drum (when the toner is negatively chargeable)
x 2500J modified machine (manufactured by Konishiroku Photo Industry Co., Ltd.) was applied with each of the above-mentioned developers to develop an electrostatic image formed by ordinary electrophotography, and the formed toner image was transferred onto plain paper. , the fixing process is carried out by the fixing device, and then a blank sheet is sent to the fixing device under the same conditions to observe whether or not toner stains occur on it.The set temperature of the heat roller of the fixing device is varied variously. Repeat this in the same state to reach the temperature at which offset occurs.

In addition, a continuous copying test was performed with the temperature of the heat roller set at 180°C, and the visible images obtained were checked for fog or not. A wiper (manufactured by Jujo Kimberly Co., Ltd.) was used to rub the surface, and the degree of peeling was visually determined.

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 transition was observed, "△" indicates that transition was observed, and regarding offset occurrence temperature, "×" indicates that offset phenomenon occurred at all set temperatures. Show that.

The contents of the symbols in Table 1 are as follows.

X: Linear polyester resin "Atrac 3824" containing no polyfunctional components in the monomer composition
J (manufactured by Atlas Corporation, softening point 93°C) 1004F: Epicoat 1o04F 1007 F Epikoat 1007 1009F: Epicoat 1009F Es/Ep' Weight ratio of polyester resin/epoxy resin EX: Nigrosine base EX BS Nioil black BS TRH Nispiron black TRH 3804: Varifast 3804 E-81: Bontron E-81 Procedural amendment (method) % formula % 1. Indication of case 1982 Patent Application No. 101817 2. Name of invention Toner.

3. Relationship with the case of the person making the amendment 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 charge control agent. A toner characterized by containing: