JPS60247246A - Toner - Google Patents

Abstract

PURPOSE:To prevent adhesion between the toner of an obtained print and the cover made of a resin when the print is stored in the cover by incorporating a polyester resin comprising a tervalent or a higher-valent multifunctional structural component and an electrostatic positive charge controller 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; and mixing this polyester as a binder resin, the positive charge controller, such as a triphenylmethane type dye, as shown by the shown formula, or cetyltrimethylammonium bromide for giving positive chargeability characteristics, a colorant, and other necessary additives.

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 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 and a positive 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 polyester resin obtained by condensation polymerization of this monomer composition is used as a binder, and a positive charge control agent, a coloring agent, 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, 112-propylene glycol, 1,3-propylene glycol, and 1,4-butanediol. , neopentyl glycol, diols such as 1゜4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A1 hydrogenated bisphenol A1 polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, etc. Examples include etherified bisphenols, 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, cehatic 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,
114-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1
, 2.4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.
5-) hydroxymethylbenzene, and others.

In addition, as the trivalent or higher polyvalent carboxylic acid monomer, for example, 1
, 2.4-benzenetricarboxylic acid, 1,2.5=henzenetricarboxylic acid, L2.4-cyclohexanetricarboxylic acid, 2,5.7-naphthalenetricarboxylic acid, 1
, 2.4-naphthalenetricarboxylic acid, L2,4-bucuntricarboxylic 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 Kansei Seisakusho) under the conditions of a die pore diameter of 1 ml, a pressure of 20 kg/cm'', and a heating rate of 6°C/min.
This is the value when the softening point is defined as the height of 172 from the start point to the end point of the outflow when a sample of m3 is melted and outflowed.

The toner of the present invention uses the above-mentioned polyester resin as a binder, and includes a positive charge control agent that imparts positive charge characteristics to the binder.
It also contains a coloring agent and a property improving agent added as necessary. If the magnetic material is not a magnetic l-ner, a magnetic substance is contained together with or in place of the coloring agent.

The positive charge control agent that is an essential component in the present invention is
This is a substance that, when contained, shifts the position of toner particles in the triboelectrification order in the positive direction. Specific examples thereof include nigrosine dyes, such as [Nigrosine Base EX] [Oil Blank BSJ, "Oil Black SO" (manufactured by Orient Kagaku Co., Ltd.), triphenylmethane dyes, such as compounds represented by the formula, quaternary ammonium compounds, such as cetyltrimethylammonium bromide, and the like.

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

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

No. 504 (15), Calco Oil Blue (C, 1
, Nq, 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, T.

No. 74160), malachite green off-salate (C, No. 42000), lamp blank (C
, 1, No. 77266), Rose Hengar (C, f,
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. .

The magnetic material may be a metal or alloy exhibiting ferromagnetism, such as ferrite 1 or magnetite, such as iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Alloys that exhibit ferromagnetic properties, such as manganese-copper-
Aluminum, a type of alloy called Heusler alloy containing manganese and copper such as manganese-copper-tin, chromium dioxide, and others may be mentioned. 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, since the toner of the present invention uses a specific polyester resin as a binder and also contains a positive charge control agent, it is excellent as a developer, as will be understood from the description of the examples below. It has excellent properties, 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 or sheet for preservation or other purposes. Even when a cover is provided, this does not have any adverse effects, thus creating a visible image that can be stored semi-permanently.

To explain in detail, polyester resin generally has a strong negative chargeability, but by containing a positive charge control agent, the negative chargeability of the polyester resin itself is weakened, and the toner becomes negatively chargeable. As a result, for example, by selecting a carrier or by sweetening the inclusion of a suitable charge control agent, the toner formed by a negative charge can be developed by a positively charged toner. This method is extremely advantageous when developing an electrostatic charge image, or when reversing a positive electrostatic charge image formed using a selenium photoconductor with excellent photoconductivity as a latent image support as in a laser printer. .

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, so the toner has a low softening point and is less likely to cause offset phenomenon during fixing. Therefore, by fixing a toner image using a hot roller fixing method which itself has many advantages, it becomes possible to achieve sufficient fixing 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. However, the polyester resin that is the binder of the toner of the present invention has a crosslinked structure, so that it is hardly affected by such plasticizers. It is presumed that the reason is that it will not be accepted.

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, 211 g of polyoxypropylene 1(2,2)1,2-bis(4-hyroxyphenyl)propane, and 82 g of pentaerythritol,
Place it in a round-bottomed flask equipped with a thermometer, stainless steel stirrer, glass nitrogen gas inlet tube, and down-flow condenser, and set the flask on a heating mantle.
Nitrogen gas was introduced from the nitrogen gas introduction tube to raise the temperature while maintaining an inert atmosphere inside the flask. and 0.0
5 g of dibutyltin oxide was added and reacted at a temperature of 200° C. while monitoring the reaction at the softening point, thereby producing polyester resin A.

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
Polyester resin B was produced by reacting in the same manner as above at a temperature of 180°C.

Synthesis Example 3 270g of 1,4-butanediol and 15g of terephthalic acid
0 g and 231 g of Hensen-1,2,4-)licarboxylic acid anhydride, the same procedure as in Synthesis Example 1 was carried out at a temperature of 200 g.
Polyester resin C was produced by reacting at ℃.

Synthesis Example 4 300 g of triethylene glycol and 1 portion of isophthalic acid
82g and benzene-1,2,4-tricarboxylic acid 13
A polyester resin was produced by reacting at a temperature of 200° C. in the same manner as in Synthesis Example 1 using 8 g of polyester resin.

The softening point of the above polyester resin was measured using a flow tester. The results are shown in Table 1.

Table 1 Example 1 Polyester resin A 100 parts by weight Positive charge control agent [Nigrosin Hose EXJ 3 parts by weight Carbon blank "Mogal L" (:) - manufactured by Yabosoto Co., Ltd.] 5 parts by weight The mixture according to the above formulation was mixed with Henschel mini toner. 15
After pre-mixing for minutes, the mixture was melted and kneaded using a twin-screw extruder. After being cooled to room temperature and solidified, it was roughly pulverized using a hammer mill, and then finely pulverized using a 1-type mill. The obtained fine powder was classified using an air classifier, and the average particle size was 12 to 13.
1! I got the toner.

Examples 2 to 6 and Comparative Examples 1 and 2 Various toners were obtained according to the formulations shown in Table 2 by changing the type of polyester resin or charge control agent.

The charging characteristics of each of Samples 1 to 3 obtained as described above were investigated. That is, 3.0 g of toner sample and iron powder r
After mixing 57.0 g of EFV-3J (manufactured by Nippon Iron Powder Co., Ltd.) with a shaker for 20 minutes, the charge per unit weight was 1jitO/M (color: microcoulomb/g) by the blow-off method.
) 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 Shinra Blakey Co., Ltd.), and a heated roller whose surface layer was formed of Teflon (polytetrafluoroethylene manufactured by DuPont) and a silicone surface layer was prepared. Rubber rKE-13
00+1TVJ (manufactured by Shin-Etsu Chemical Co., Ltd.) An electrophotographic machine equipped with an organic photoreceptor drum, equipped with a fixing device that has a release oil supply mechanism, and a line speed of 350 mm and 7 seconds. Copy machine r U
Each of the above-mentioned developers was applied to a modified Bix 2500J machine (manufactured by Konishiroku Photo Industry Co., Ltd.) to develop the electrostatic charge image formed by ordinary electrophotography, and the formed toner image was
The operation of transferring the paper onto i11 paper, fixing it in the fixing device, and then sending the blank paper to the fixing device under the same conditions and observing whether 1-ner stains occur on it is performed using the heat roller of the fixing device. The temperature at which the offset occurred was determined by repeating the experiment while changing the set temperature in various ways.

Further, five consecutive copy tests were conducted with the temperature of the heat roller set at 180° C., and the presence or absence of fogging in the resulting visible images was examined.

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 2. Regarding durability against resin, "○" indicates that no transition was observed, "△" indicates that transition was observed, and regarding offset occurrence temperature, "×" indicates that an offset phenomenon occurred at all set temperatures. Show that.

6 18 Note that the binder r Atrac 382AJ of Comparative Example 1 is a polyester resin that does not contain any polyfunctional components in its mass composition.

Procedural amendment (method) September 1980, Japan Patent Office Commissioner Manabu Shiga1, Indication of the case, Patent Application No. 101814 of 19822, Name of the invention Toner3, 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, and a positive charge control agent. A toner characterized by: