JPS60247247A - Toner - Google Patents

Abstract

PURPOSE:To prevent adhesion between the toner of an obtained print and the cover made of a resin during storage in the cover by adding a polyester resin comprising a tervalent or a higher-valent multifunctional structural component and an epoxy resin as a binder to 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, 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 a colorant and 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 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 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 and an epoxy resin.

The present invention will be specifically explained below.

In the present invention, in the φ-mer composition for producing polyester, which is composed of an alcohol monomer and a carboxylic acid monomer, at least 4) one of the alcohol monomer and the carboxylic acid monomer has a trivalent or higher valence. Contains a polyfunctional monomer component,
A mixture of a polyester resin obtained by condensation polymerization of this monomer composition and an epoxy resin is used as a binder, and a colorant and other necessary components are added to the binder to obtain a toner.

In the following, examples of alcohols for forming the monomer composition for polyester resins include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol.
Diols such as propylene glycol, 1,4-butanediol, neopentyl glycol, 1゜4-butynediol, ■, 4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A,
Etherified bisphenols such as polyoxyethylenated bisphenol A1 polyoxypropylenated bisphenol A, and dihydric alcohol monomers substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms,
Other dihydric alcohol monomers may be mentioned.

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, sucrose, L
2,4-butanetriol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-L2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.5-
Trihydroxymethylbenzene and others can be mentioned.

In addition, as the trivalent or higher polyvalent carboxylic acid monomer, for example, 1
2.4-benzenetricarboxylic acid, L2,5-benzenetricarboxylic acid, L2,4-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, Examples include 1,2,7.8-octane tetracarboxylic acid, embol trimer acid, 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.

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., measured using a flow tester, for example.

The softening point was measured using Koka Type Flow Tester I CFT-500.
J (manufactured by Kinsei Seisakusho) under the conditions of a die pore diameter of 1 cm, 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 cm3 sample 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, 1004AF
, 1005H.

1007.1009 (manufactured by Yuka Shell Epoxy Co., Ltd.)
, 7072.6084.7097.6097 sold as rAraldiLe GY j (manufactured by Chiha Geigy), 662.664.667.668 sold as rD, E, 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 is composed of a binder made of a mixture of a double polyester resin and an epoxy resin, and contains a colorant and a property improver added as necessary. , a magnetic material may be contained together with a coloring agent or in place of a coloring agent.

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

No. 50405), Calco Oil Blue (C, T,
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-salate (C, 1, No. 42000), lamp black (
C, 1, No. 77266), Rose Bengal (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 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, 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. The content thereof is 20 to 70 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of I.
It is 70 parts by weight.

〔Effect of the invention〕

As described above, since the toner of the present invention uses a mixture of a specific polyester resin and an epoxy resin as a binder, it has excellent properties as a developer, as will be understood from the description of the examples below. It has particularly excellent developability and fixability, and can form good visible images, and has high resistance to resin, so it can be used for storage or other purposes such as resin films or sheets. Even when a cover 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, for example, by choosing a career,
Alternatively, by containing an appropriate charge control agent,
When developing with a positively charged toner, for example when developing an electrostatic image formed with a negative charge, or when developing a positive image formed using a selenium photoreceptor with excellent photoconductive properties as a latent image support as in a laser printer. It is also very advantageously used in reversal development of electrostatic charge 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. Because it is obtained from a monomer composition, it has a molecularly branched and cross-linked structure.For this reason, even though the toner has a low softening point and contains epoxy resin, it has a low softening point during fixing. By fixing the toner image using a hot roller fixing method, which has many advantages in itself, the offset phenomenon is less likely to occur.
Sufficient fixing can be achieved at high speed and with less energy consumption.

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 epoxy resin, which are the binders of the toner of the present invention, are polymers or copolymers that always contain a clearing agent. However, when the polyester resin and epoxy resin are mixed, the polyester resin has a crosslinked structure. It is presumed that the reason for this is that, in addition to the fact that it has the following properties, it becomes almost unaffected by such softeners.

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-improving agent and others 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 introduction 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 2 299 g of isophthalic acid and polyoxypropylene 2 (2,2)-2,2-bis(4-hydroxyphenyl)
Polyester resin B having a softening point of 136°C was produced by reacting 211 g of propane and 74 g of glycerol at a temperature of 180°C in the same manner as in Synthesis Example 1.

Example 1 Polyester resin A 40 parts by weight Epoxy resin "Epicote 1004FJ (softening point 97
℃) 60 parts by weight Carbon blank "Mogulshi" (manufactured by Cabot) 5 parts sodium bicarbonate The mixture according to the above recipe was premixed for 15 minutes using a Henschel mixer, and then melted and kneaded using a two-wheeled extruder. After being cooled to room temperature and solidified, it was coarsely pulverized using a hammer mill, and then finely pulverized using a type 1 mill. The obtained fine powder was classified using an air classifier to obtain a toner having an average particle size of 12 to 13 μm.

Examples 2 to 4 and Comparative Examples 1 to 3 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 1004PJ 60 parts by weight Carbon blank "Mogull LJ" 5 parts by weight Example 3 Polyester resin A 40 parts by weight Epoxy resin [Epicoat 1007J (softening point 118°C) 60 parts by weight Carbon blank [ Mogul LJ 5 parts by weight Example 4 Polyester resin A 20 parts by weight Epoxy resin [Epicoat 1004Fj 80 parts by weight Carbon black [Mogul LJ 5 parts by weight Comparative example 1 Linear polyester resin A [Attrac 382^] (Atlas) (softening) point 93
°C) 40 parts by weight Epoxy resin [Epicoat 1004J 60 parts by weight Carbon blank "Mogul I4" 5 parts by weight Comparative example 2 Polyester resin A 100 parts by weight Carbon blank [Mogul LJ 5 parts by weight Comparative example 3 Epoxy resin [Epicor 11007J 100 parts by weight The charging characteristics of each of No. 1 to No. 1 obtained using 5 parts by weight or more of the carbon blank "Mogal I" were investigated. That is, after mixing 1.5 g of a toner sample and 58.5 g of a carrier coated with 1,1-cybide rubber-fluorooctyl methacrylate resin and having an average particle size of about 100 μm using a shaker for 20 minutes, the amount per unit weight was determined by a blow-off method. Charge amount 0/M (unit: 2 microcoulombs/
g) was measured. In addition, the softening point was measured using a flow tester.

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 the surface layer was made of Teflon (Bo5 Litetrafluoroethylene manufactured by DuPont). It consists of a roller and a pressure roller whose surface layer is made of silicone rubber rKE-1300+1TVJ (manufactured by Shin-Etsu Chemical Co., Ltd.), and is equipped with a fixing device with a release oil supply mechanism and a line speed set at 350 mm/sec. Each of the above-mentioned developers was applied to an electrophotographic copying machine r U-Bix 2500J modified m (manufactured by Konishi Roku Photo Industry Co., Ltd.) equipped with an organic photoreceptor drum, and an electrostatic charge image formed by a normal electrophotographic method was produced. The process involves developing, transferring the formed toner image onto plain paper, fixing it in a fixing device, sending the blank paper to the fixing device under the same conditions, and observing whether or not toner stains occur on it. The set temperature of the heat roller of the fixing device was varied and repeated to determine the offset occurrence temperature.

We also conducted a continuous copy test with the temperature of the heat roller set at 180 degrees Celsius, checked the visible images obtained for fogging, and checked the fixability of the formed visible images using an rJK wiper. (manufactured by Jujo Kimberly Co., Ltd.), and the degree of toner peeling was visually determined.

6 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 4a copy test, and a load of 100 g/cm2 was applied to the surface for 3 hours at a temperature of 70°C, and then the cover sheet was removed. 1. By peeling off the toner from the printed matter and visually judging the degree of toner transfer to the cover sheet at this time. The durability against resin was investigated.

The above results are shown in Table 1. Regarding durability to resin, "○" indicates that no transition was observed, "△" indicates that transition was observed, and "×" indicates that the offset generation temperature occurred at all set temperatures. Indicates that something has happened.

The binder [Atrac 382^] of Comparative Example 1 is a polyester resin that does not contain any polyfunctional components in its monomer composition.

Procedural amendment (method) % formula % 1. Indication of the case Patent Application No. 101815 of 1982 2. Name of the invention Toner 3. Person making the amendment Relationship with the case Patent applicant address 1 Nishi-Shinjuku, Shinjuku-ku, Tokyo Chome 26-2 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 at least one of these alcohol monomers and carboxylic acid monomers contains a polyester resin obtained by polymerizing a monomer composition containing a trivalent or higher polyfunctional component, and an epoxy resin. toner.