JPH06266149A - Capsulated toner for heat press fixation and its production - Google Patents

Abstract

PURPOSE:To provide a capsulated toner ensuring satisfactory rise of triboelectric charge, having stable positive chargeability, excellent in anti-offsetting property in a heat press fixing system using a hot roll, fixable at a low temp. and capable of stably forming many clear images almost free from a surface stain. CONSTITUTION:This capsulated toner for heat press fixation consists of a heat meltable core material contg. at least a thermoplastic resin and a colorant and each shell formed so as to coat, the surface of the core material and the principal component of the shell is, an amorphous polyester having tert. amine groups. When this capsulated toner is produced, each shell is formed by coating the surface of the above-mentioned core material with the amorphous polyester having tert. amine groups by an in situ polymn. method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat and pressure fixing capsule toner used for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic printing method, an electrostatic recording method and the like, and a method for producing the same. More specifically, the present invention relates to a heat and pressure fixing capsule toner capable of low temperature fixing and having a positive charging property, and a method for producing the same.

[0002]

2. Description of the Related Art Conventional electrophotographic methods include US Pat. Nos. 2,297,691 and 235780.
As described in, for example, No. 9, the photoconductive insulating layer is uniformly charged, and then the layer is exposed to light to dissipate the charge on the exposed portion to form an electrical latent image. After being formed, and further visualized by adhering a fine powder having a colored charge called a toner to the latent image (developing step), after transferring the obtained visible image to a transfer material such as transfer paper (Transfer step), permanent fixing by heating, pressure or other suitable fixing method (fixing step). As described above, the toner must have the functions required not only in the developing step but also in the transfer step and the fixing step.

Generally, toner is subjected to a mechanical frictional force due to a shearing force and an impact force received during mechanical operation in a developing device,
It deteriorates during the copying of thousands to tens of thousands of sheets. To prevent such toner deterioration, a tough resin having a large molecular weight that can withstand mechanical friction may be used, but these resins generally have a high softening point and are a non-contact fixing method such as oven fixing and infrared fixing. In the radiant fixing method, the heat efficiency is poor and therefore the fixing is not sufficiently performed.Also, in the heat pressure fixing method which is widely used because the heat efficiency is good in the contact fixing method, it is necessary to fix the heat roller It is necessary to raise the temperature, which not only causes deterioration of the fixing device, curling of the paper, increase of energy consumption, etc., but also when such a resin is used, the pulverizability is poor,
When manufacturing a toner, the manufacturing efficiency is significantly reduced. Therefore, a binder resin having a too high degree of polymerization and a softening point cannot be used.

On the other hand, the heat pressure fixing method using a heat roller or the like has remarkably good thermal efficiency because the surface of the heat roller and the toner image surface of the sheet to be fixed are in pressure contact, and is widely used from low speed to high speed. When the surface and the toner image surface come into contact with each other, the toner tends to adhere to the surface of the heating roller and transferred to the subsequent transfer paper or the like, so-called offset phenomenon occurs. In order to prevent this phenomenon, the surface of the heating roller is processed with a material having an excellent releasing property such as a fluororesin, and a releasing agent such as silicone oil is applied to the surface of the heating roller to deal with the problem. However, the method of applying silicone oil or the like is not preferable because it easily causes a trouble because the fixing device becomes large and the cost becomes high, and it becomes complicated. Further, as described in JP-B-57-493, JP-A-50-44836, and JP-A-57-37353, there is a method of improving the offset phenomenon by asymmetrically or cross-linking the resin, but there is a fixing point. Has not been improved.

Generally, since the minimum fixing temperature is between the low temperature offset and the high temperature offset, the usable temperature range is between the minimum fixing temperature and the high temperature offset, and the minimum fixing temperature should be lowered as much as possible and the high temperature offset generation temperature should be as high as possible. By raising the temperature, the fixing temperature can be lowered and the usable temperature range can be widened, energy saving, high speed fixing and paper curl can be prevented. Therefore, there is always a demand for a toner having good fixability and offset resistance.

Conventionally, there has been proposed a technique for attaining low-temperature fixability by using a capsule toner composed of a core material and an outer shell provided so as to cover the surface of the core material as the toner. . Among them, when a low melting point wax that is easily plastically deformed is used as the core material (US Pat. No. 3,
269,626, Japanese Patent Publication No. 46-15876, Japanese Patent Publication No. 44-9880,
JP-A-48-75032 and JP-A-48-75033), fixing is possible only by pressure, but the fixing strength is poor and it can be used only in limited applications. Also, when a liquid core material is used, if the strength of the shell material is low, fixing can be done only by pressure, but it may crack inside the developing device and stain the inside of the machine. It takes a lot of pressure to break, resulting in images that are too glossy,
It was difficult to adjust the strength of the shell material.

Therefore, when used alone as a core material for heat and pressure fixing, blocking occurs at high temperatures, but a resin having a low glass transition point which improves the fixing strength is used, and blocking resistance and the like are provided as an outer shell. For this purpose, a heat roller fixing capsule toner in which a resin wall having a high melting point is formed by interfacial polymerization has been devised. However, in JP-A-61-56352, the wall material has a high melting point,
Furthermore, since it is tough and hard to crack, the performance of the core material has not been fully achieved. Further, a heat roller fixing capsule toner having an improved fixing strength of a core material has been proposed in the same way (Japanese Patent Laid-Open Nos. 58-205162 and 58-2051).
63 publication, 63-128357 publication, 63-128358 publication,
63-128359, 63-128360, and 63-1283.
No. 61, 63-128362), the manufacturing method is a spray-drying method, which imposes a burden on the manufacturing equipment, and the shell material has not been devised so that the performance of the core material has not been fully drawn out. . Further, in the capsule toner proposed in JP-A-63-281168, it is described that the shell material is thermotropic liquid crystal polyester, and in the capsule toner proposed in JP-A-4-185358, the crystalline property is Although polyester is used, in both cases, the resin melts sharply, but the amount of energy required for melting is large, and the Tg of the core material is high.

On the other hand, there is an attempt to control the chargeability of the capsule toner by allowing a charge control agent to exist in the outer shell of the capsule toner or on the surface of the capsule toner. For example, the toner is charged by friction with the carrier during the developing process. The control agent is detached and adheres to the carrier, the charge amount of the toner is reduced, and as a result, scumming and toner contamination in the machine occur.
There was a problem. Further, when the charge control agent is not present on the surface of the toner, the charging speed may be slow depending on the type of carrier, and when high speed printing is performed, scumming may occur.
Toner scattering and the like sometimes occurred.

The present invention has been made under the circumstances described above, and its object is to provide excellent offset resistance in a thermal pressure fixing system such as a heat roller, which can be fixed at a low temperature, and blocking resistance. It is an object of the present invention to provide a heat-pressure fixing capsule toner having excellent positive charging property and a method for producing the same.

[0010]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the presence of an amorphous polyester resin having a positive charging property on the surface of a capsule toner makes The rise of triboelectric charging is good,
Further, they have found that it is possible to provide a capsule toner for heat and pressure fixing, which has stable positive chargeability and can stably form a clear image with less background stains a number of times, and completed the present invention.

That is, the gist of the present invention is: (1) a heat-melting core material containing at least a thermoplastic resin and a colorant, and a heat shell formed so as to cover the surface of the core material. In a pressure fixing capsule toner, a main component of the outer shell is an amorphous polyester having a tertiary amine group, and (2) at least a thermoplastic resin and a colorant. In a process for producing a heat-and-pressure fixing capsule toner comprising a heat-fusible core material containing a core material and an outer shell provided so as to cover the surface of the core material, a tertiary amine group is added by an in situ polymerization method. The present invention relates to a method for producing a capsule toner for heat and pressure fixing, which comprises coating the surface of a core material with the amorphous polyester to form an outer shell.

The heat and pressure fixing capsule toner of the present invention comprises
The main component of the outer shell is an amorphous polyester having a tertiary amine group, and other materials constituting the outer shell include, for example, an amorphous polyester having no tertiary amine group, or styrene / anhydrous. A maleic acid copolymer or the like may be used for the purpose of controlling the level of charge amount. In addition, a small amount of polyamide, polyesteramide, polyurea or the like can be used together.

In the present invention, the amorphous polyester having a tertiary amine group is a monomer having a tertiary amine group, which is an essential component, as a monovalent alcohol having a tertiary amine group and having a valency of 2 or more. And / or divalent or higher carboxylic acid-based monomers are used, and they are obtained by polycondensation of a monomer mixture containing these. In the present invention, the amount of the monomer having a tertiary amine group is 5 to 30 mol% in all the monomers,
Polycondensation may be carried out using a divalent or higher alcohol monomer and / or a divalent or higher carboxylic acid monomer having no tertiary amine group in an amount of 95 to 70 mol% based on the total amount of all monomers. preferable. If the amount of the monomer having a tertiary amine group used is less than 5 mol% based on the total amount of the monomers, the effect of positively charging the polyester, which is normally negatively charged by frictional charging, is small.
This is because if it exceeds 0 mol%, the moisture resistance of the toner tends to deteriorate. On the other hand, a component having a primary or secondary amine group is less effective in making the charging characteristics positive because the amidation precedes during the condensation polymerization reaction, but in the present invention, a trace amount of the component is contained. It doesn't matter. In this specification, the carboxylic acid as a monomer, its anhydride, and its lower alkyl ester are collectively referred to as a carboxylic acid monomer. Here, the lower alkyl ester is an ester having an alkyl group having 1 to 4 carbon atoms.

As the monomer having a tertiary amine group used in the present invention, for example, a divalent or higher valent alcohol monomer having a chemical structure represented by the general formulas (I) to (III) in its molecule, and Carboxylic acid type monomer, and general formula (IV)
One or more selected from the group consisting of divalent or higher alcohol monomers represented by

[0015]

[Chemical 3]

(Wherein R ₁ , R ₂ , R ₅ , R ₇ , R ₈ ,
R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R _13, R ₁₄ and R ₁₆ are alkylene groups having 1 to 15 carbon atoms, R ₃ and R ₄ are alkyl groups having 1 to 10 carbon atoms, and R ₆ is an alkyl group or alkylene group having 1 to 10 carbon atoms, and R ₁₅ is 1 to 10 carbon atoms.
An alkyl group of 3 or

[0017]

[Chemical 4]

Represents R ₁₇ and R ₁₈ represent an alkyl group having 1 to 4 carbon atoms, and R ₁₇ and R ₁₈ may form a heterocyclic ring together with the nitrogen atom. X represents hydrogen or a hydroxyl group. )

In the general formulas (I) to (IV), R ₁ , R
₂ , R ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R
Examples of the alkylene group having 1 to 15 carbon atoms represented by _13, R ₁₄ and R ₁₆ are the same or different and each have a linear or branched chain, an aromatic ring or a saturated alicyclic ring. Examples of the alkyl group having 1 to 10 carbon atoms represented by R ₃ and R ₄ include the same or different ones having a linear or branched chain, and the alkyl group having 1 to 10 carbon atoms represented by R ₆ Examples of the alkyl group or alkylene group of 10 include those having the same or different and having a straight chain or a branched chain. Examples of the alkyl group having 1 to 3 carbon atoms represented by R ₁₅ include those having a straight chain or a branched chain. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁₇ and R ₁₈ include the same or different ones having a straight chain or a branched chain, and R ₁₇ and R ₁₈ are different from each other with a nitrogen atom. It may form a nodal ring, which means that R ₁₅ is

[0020]

[Chemical 5]

The same applies to the case represented by Further, X represents hydrogen or a hydroxyl group.

Specific examples include the following compounds (1) to (7). (1) Examples of the glycol having the chemical structure represented by the general formula (I) include N, N′-bis (hydroxymethyl) piperazine and N, N′-bis (hydroxymethyl).
Methylpiperazine, N, N'-bis (2-hydroxypropyl) piperazine, N, N'-bis (2-hydroxypropyl) -2,5-dimethylpiperazine, N, N'-
Bis (2-hydroxyethyl) -2,5-dimethylpiperazine, N, N'-bis (2-hydroxy-2-methylpropyl) piperazine, N, N'-bis (2-methyl-
2-hydroxynonyl) piperazine, N, N'-bis (2-hydroxy-3-methoxylpropyl) piperazine, N, N'-bis (3-phenyl-2-hydroxypropyl) piperazine and the like can be mentioned.

(2) Examples of the dicarboxylic acid having the chemical structure represented by the general formula (I) or its lower alkyl ester include N, N'-bis (carboxymethyl) piperazine and N, N'-bis (carboxyethyl). ) Piperazine, N, N'-bis (carboxymethyl) -2,6-dimethylpiperazine, N, N'-bis (3-carboxypropyl) piperazine, N- (2-carboxyethyl)-
Examples thereof include N ′-(carboxymethyl) piperazine and the like, or lower alkyl esters thereof.

(3) Examples of the alcohol having the chemical structure represented by the general formula (II) include N, N-bis (2-
Hydroxyethyl) methylamine, N, N-bis (2-
Hydroxyethyl) cyclohexylamine, N, N-bis (2-hydroxypropyl) methylamine, N, N-
Bis (2-hydroxypropyl) isopropylamine,
Examples include triethanolamine.

(4) Examples of the carboxylic acid having the chemical structure represented by the general formula (II) or its lower alkyl ester include N, N-bis (carboxymethyl) methylamine and N, N-bis (2-carboxy). Examples thereof include ethyl) methylamine, N, N-bis (2-carboxyethyl) -isopropylamine, N-carboxymethyl-N- (2-carboxyethyl) methylamine, nitrilotriacetic acid, and the like, or lower alkyl esters thereof.

(5) Examples of the glycol having the chemical structure represented by the general formula (III) include 2-methyl-2-
N, N-dimethylaminomethyl-1,3-propanediol, 2-methyl-2-N, N-diethylaminomethyl-1,3-propanediol, 2-ethyl-2-N, N
-Di-n-propylaminomethyl-1,3-propanediol, 2-methyl-2-N, N-di-n-butylaminomethyl-1,3-propanediol, 2-methyl-2
-N, N-dimethylaminoethyl-1,3-propanediol, 2-methyl-2-piperidinomethyl-1,3-
Propanediol, bis (2-N, N-dimethylaminomethyl) -1,3-propanediol, bis (2-N,
N-di-isopropylaminomethyl) -1,3-propadiol, 3-methyl-3-N, N-dimethylaminomethyl-1,5-pentanediol, 3-methyl-3-
N, N-diethylaminomethyl-1,5-pentanediol, 4-ethyl-4-N, N-di-isopropylaminomethyl-1,6-hexanediol and the like can be mentioned.

(6) Examples of the dicarboxylic acid having the chemical structure represented by the general formula (III) or its lower alkyl ester include 4-methyl-4-N, N-dimethylaminomethyl-azelaic acid and 5-methyl- 5-N, N-diethylaminoethyl-undecanedioic acid, 6-ethyl-6-N, N-di-n-propylaminomethyl-brassulinic acid, 9-methyl-9-N, N-dimethylaminomethyl-nonadecanedioic acid Etc. or a lower alkyl ester thereof.

(7) Examples of the alcohol represented by the general formula (IV) include N, N'-dimethyl-N, N'-bis (2-hydroxyethyl) ethylenediamine and N, N '.
-Dicyclohexyl-N, N'-bis (2-hydroxyethyl) hexamethylenediamine, N, N'-diethyl-N, N'-bis ((2-hydroxypropyl) ethylenediamine, N, N'-dibutyl-N, N'-bis (2
-Hydroxypropyl) pentamethylenediamine and the like.

In the present invention, a single or a plurality of monomers can be used from the divalent or higher alcoholic monomer or carboxylic acid monomer having these tertiary amine groups. Particularly preferably, N, N-bis (2-hydroxyethyl) methylamine, piperazine derivative, triethanolamine or nitrilotriacetic acid is used.

Next, the divalent or higher divalent alcohol monomer having no tertiary amine group and the divalent or higher divalent carboxylic acid monomer used in the present invention will be described. As the divalent or higher valent alcohol monomer, a divalent or trivalent or higher valent alcohol monomer is used. As the divalent or higher carboxylic acid-based monomer, a divalent or trivalent or higher carboxylic acid-based monomer is used. A quantity is used.

Examples of the dihydric alcohol monomer include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3).
-2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0)-
Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,
Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A , Bisphenol A
Propylene adduct, bisphenol A ethylene adduct, hydrogenated bisphenol A and the like.

Examples of the trihydric or higher alcohol monomer include sorbitol, 1,2,3,6-hexanetetrol, 1,
4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,
2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be mentioned. Trivalent alcohol is preferably used. In the present invention, these dihydric alcohol monomers and polyhydric alcohol monomers having a valence of 3 or more may be used alone or in combination.

On the other hand, examples of the divalent carboxylic acid type monomer include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid. , Azelaic acid, malonic acid, n-dodecenylsuccinic acid, n-dodecylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid and the like,
Examples thereof include anhydrides of these acids, lower alkyl esters and the like.

The trivalent or higher carboxylic acid type monomer includes
For example, 1,2,4-benzenetricarboxylic 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, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic Examples thereof include acids, enpol trimer acids, their acid anhydrides, and lower alkyl esters. Preferably, a trivalent carboxylic acid or its derivative is used. In the present invention, these divalent carboxylic acid-based monomers and trivalent or higher carboxylic acid-based monomers may be used alone or in combination.

The method for producing the amorphous polyester having a tertiary amine group in the present invention is not particularly limited, and a monomer mixture containing the above-mentioned monomer having a tertiary amine group is used. It can be produced by esterification and transesterification reaction according to a conventional method. At this time, all monomers may be mixed from the beginning to carry out the polymerization reaction, but for the purpose of adjusting the tertiary amine group content of the amorphous polyester, a monomer having a tertiary amine group is used. The polymerization reaction may be carried out by a method of introducing the body into the reaction system during the progress of the polymerization reaction. Here, amorphous is one which does not have a definite melting point, and when crystalline polyester is used in the present invention, the amount of energy required for melting is large and the toner fixability cannot be improved, which is not preferable.

The amorphous polyester having a tertiary amine group thus obtained further has a glass transition point of 5
It is preferably 0 to 80 ° C. If it is less than 50 ° C, the storage stability of the toner will be poor, and if it exceeds 80 ° C, the fixing property of the toner will be poor. In the present invention, the glass transition point is a difference between a base line extension and a peak below the glass transition point when measured with a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd.) at a heating rate of 10 ° C./min. It is the temperature at the intersection with the tangent line that indicates the maximum slope from the rising portion to the apex of the peak.

The acid value of the amorphous polyester is preferably 1 to 50 (KOHmg / g), more preferably 5 to 30 (KOHmg / g). When it is less than 1 (KOHmg / g), the above-mentioned amorphous polyester as a shell material is less likely to come out at the interface during in situ polymerization, resulting in poor storage stability of the toner and 50 (KOHmg).
If it exceeds OHmg / g), the polyester is apt to migrate to the aqueous phase and the production stability is deteriorated. Here, the method for measuring the acid value is according to JIS K0070.

On the other hand, examples of the resin used as the main component of the heat-fusible core material of the capsule toner of the present invention include thermoplastic resins such as polyester resin, polyester / polyamide resin, polyamide resin, vinyl resin, and the like. , And vinyl resins. The glass transition point derived from the thermoplastic resin which is the main component of the heat-fusible core material is preferably 10 to 50 ° C., more preferably 10 to 40 ° C., but the glass transition point is 10 If it is lower than 50 ° C, the storage stability of the capsule toner deteriorates, and if it exceeds 50 ° C, the fixing strength of the capsule toner deteriorates, which is not preferable.

Among the above-mentioned thermoplastic resins, examples of the monomer constituting the vinyl resin include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene and p-ethylstyrene. , 2,4-
Styrene or styrene derivatives such as dimethylstyrene, p-chlorostyrene, vinylnaphthalene, etc., ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene, etc., such as vinyl chloride,
Vinyl esters such as vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl formate, vinyl caproate, etc., such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, N-Butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, acrylic acid Stearyl, methoxyethyl acrylate, acrylic acid 2-
Hydroxyethyl, glycidyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, methacrylic acid. Decyl, lauryl methacrylate, methacrylic acid 2
-Ethylhexyl, stearyl methacrylate, methoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, phenyl methacrylate,
Ethylenic monocarboxylic acids such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like, and esters thereof such as ethylenic monocarboxylic acid substitution products such as acrylonitrile, methacrylonitrile, acrylamide, etc., such as ethylenic acid such as dimethyl maleate. Dicarboxylic acids and their substitution products, vinyl ketones such as vinyl methyl ketone, vinyl ethers such as vinyl methyl ether, vinylidene halides such as vinylidene chloride, eg N-
Examples thereof include N-vinyl compounds such as vinylpyrrole and N-vinylpyrrolidone.

Of the components constituting the resin for the core material according to the present invention, 50 to 90% by weight of styrene or a styrene derivative is used to form the main skeleton of the resin, and ethylenic is used to adjust the thermal characteristics such as the softening temperature of the resin. It is preferable to use 10 to 50% by weight of monocarboxylic acid or its ester because the glass transition point of the resin for core material can be easily controlled.

When a crosslinking agent is added to the monomer composition constituting the resin for the core material according to the present invention, for example, divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diethylene Acrylate, 1,3-
Butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-methacryloxydiethoxyphenyl) propane, 2 General crosslinking such as 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dibromoneopentyl glycol dimethacrylate, diallyl phthalate Appropriate agent (2 if necessary
A combination of two or more species can be used.

The amount of these crosslinking agents used is 0.001 to 15% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer. The amount of these crosslinkers used is 15
If it is more than 5% by weight, the toner is less likely to be melted by heat, resulting in poor heat fixing property or heat pressure fixing property. Also the amount used
If the amount is less than 0.001% by weight, it is difficult to prevent the offset phenomenon in which a part of the toner adheres to the roller surface without being completely fixed to the paper and is transferred to the next paper in the heat and pressure fixing. Further, the above monomer may be polymerized in the presence of unsaturated polyester to give a graft or crosslinked polymer, which may be used as a resin for the core material.

Further, as the polymerization initiator used in producing the thermoplastic resin for the core material, 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4
-Dimethylvaleronitrile, other azo or diazo polymerization initiators: benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, dicumyl peroxide Examples thereof include peroxide-based polymerization initiators such as oxides.

Two or more polymerization initiators may be mixed and used for the purpose of controlling the molecular weight and the molecular weight distribution of the polymer or the reaction time. The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerized monomer.

In the present invention, a charge control agent may be further added to the core material, and the negatively chargeable charge control agent to be added is not particularly limited and may be, for example, a metal-containing azo dye "Vari. First Black 3804 "," Bontron S-31 "," Bontron S-32 "," Bontron S-34 "(above, manufactured by Orient Chemical Co., Ltd.)," Eisenspiron Black TVH "(manufactured by Hodogaya Chemical Co., Ltd.)
Etc., copper phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, such as “Bontron E-81”, “Bontron E-82”, “Bontron E-85” (above, manufactured by Orient Chemical Co.), quaternary ammonium salt, for example. "CO
PY CHARGE NX VP434 ”(manufactured by Hoechst), nitroimidazole derivatives and the like can be mentioned.

The positively chargeable charge control agent is not particularly limited and, for example, as a nigrosine dye, "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron N-01", "Bontron". N-07 "," Bontron N-11 "(above, manufactured by Orient Chemical Co., Ltd.), triphenylmethane dye containing a tertiary amine as a side chain, quaternary ammonium salt compound, for example," Bontron P-51 "( Orient Chemical Co., Ltd.),
Cetyl trimethyl ammonium bromide, "COPY CHARG
Examples thereof include EPX VP435 "(manufactured by Hoechst) and the like, and polyamine resins such as" AFP-B "(manufactured by Orient Chemical Co.) and imidazole derivatives. The above charge control agent is contained in the core material in an amount of 0.1 to 8.0% by weight, preferably 0.2 to 5.0% by weight. In the core material, if necessary, for the purpose of improving offset resistance in heat and pressure fixing, for example, polyolefin, fatty acid metal salt, fatty acid ester, partially saponified fatty acid ester, higher fatty acid, higher alcohol, paraffin wax, amide series Any one or more kinds of offset preventing agents such as wax, polyhydric alcohol ester, silicon varnish, aliphatic fluorocarbon, and silicone oil may be contained.

The polyolefin is, for example, a resin such as polypropylene, polyethylene or polybutene and has a softening point of 80 to 160 ° C. Examples of the fatty acid metal salt include maleic acid and zinc, magnesium,
Metal salts with calcium, etc .; Metal salts with stearic acid and zinc, cadmium, barium, lead, iron, nickel, cobalt, copper, aluminum, magnesium, etc .; Dibasic lead stearate; Oleic acid and zinc, magnesium, iron , Metal salts with cobalt, copper, lead, calcium, etc .; metal salts with palmitic acid, aluminum, calcium, etc .; caprylate; lead caproate; metal salts with linoleic acid, zinc, cobalt, etc .; calcium ricinoleate; Examples thereof include metal salts of ricinoleic acid and zinc, cadmium, and the like, and mixtures thereof. Examples of the fatty acid ester include maleic acid ethyl ester, maleic acid butyl ester, stearic acid methyl ester, stearic acid butyl ester, palmitic acid cetyl ester, montanic acid ethylene glycol ester and the like. Examples of the partially saponified fatty acid ester include partially saponified calcium of montanic acid ester. Examples of the higher fatty acid include dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, arachidic acid, behenic acid, lignoceric acid, ceracoleic acid, and mixtures thereof. You can Examples of the higher alcohols include dodecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, aralkyl alcohol, and behenyl alcohol. Examples of the paraffin wax include natural paraffin, microwax, synthetic paraffin, and chlorinated hydrocarbon. Examples of the amide wax include stearic acid amide, oleic acid amide, palmitic acid amide, lauric acid amide, behenic acid amide, methylenebisstearamide, ethylenebisstearamide, N, N'-m-xylylenebis. Examples thereof include stearic acid amide, N, N'-m-xylylenebis-12-hydroxystearic acid amide, N, N'-isophthalic acid bisstearylamide, and N, N'-isophthalic acid bis-12-hydroxystearylamide. Examples of the polyhydric alcohol ester include glycerin stearate,
Glycerin ricinoleate, glycerin monobehenate,
Examples thereof include sorbitan monostearate, propylene glycol monostearate and sorbitan trioleate. Examples of the silicon varnish include methyl silicon varnish and phenyl silicon varnish. Examples of the aliphatic fluorocarbon include low-polymerization compounds of tetrafluoroethylene and propylene hexafluoride, and fluorine-containing surfactants described in JP-A-53-124428. The ratio of these offset preventing agents to the resin in the core material is preferably 1 to 20% by weight.

In the present invention, the colorant is contained in the core material of the encapsulated toner, but all the dyes, pigments and the like used in the conventional colorant for toner can be used. The colorant used in the present invention, various carbon black produced by thermal black method, acetylene black method, channel black method, lamp black method and the like,
Grafted carbon black coated with resin on the surface of carbon black, Nigrosine dye, Phthalocyanine blue, Permanent brown FG, Brilliant fast scarlet, Pigment green B, Rhodamine-B base, Solvent red 49, Solvent red 14
6, Solvent Blue 35, etc., and mixtures thereof, etc., usually 1 per 100 parts by weight of resin in the core material.
About 15 parts by weight is used.

In order to produce the magnetic capsule toner, magnetic particles may be added to the core material. As magnetic particles,
For example, ferrous metals such as ferrite and magnetite, cobalt, nickel, or other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or ferromagnetism by being subjected to an appropriate heat treatment without containing ferromagnetic elements. An alloy such as manganese-copper-aluminum, a type of alloy called Heusler alloy containing manganese and copper such as manganese-copper-tin, or chromium dioxide.
Others can be mentioned. These magnetic materials are uniformly dispersed in the core material in the form of fine powder having an average particle size of 0.1 to 1 μm. The content is 20 to 70 parts by weight, preferably 30 to 70 parts by weight, per 100 parts by weight of the encapsulated toner. When magnetic fine powder is added to form a magnetic toner, the same treatment as in the case of the colorant may be performed.
Since the core material has a low affinity for organic substances such as monomers as it is, the magnetic fine powder is treated with a so-called coupling agent such as a titanium coupling agent, a silane coupling agent, and lecithin, or with a coupling agent. When used above, the magnetic fine powder can be uniformly dispersed.

The method of manufacturing the heat and pressure fixing capsule toner according to the present invention simplifies the manufacturing equipment and manufacturing process.
Although the n situ polymerization method is preferable, for example, mother particles as a core material and child particles of an outer shell forming material having a number average particle diameter of 1/8 or less of the number average particle diameter of the mother particles are stirred at high speed in an air stream. May be performed by a dry method such as forming an outer shell.

The production method of the present invention by the in situ polymerization method will be described below. In this manufacturing method, the outer shell is formed by dispersing a mixed liquid of a core constituent material and an outer shell constituent material containing a tertiary amine group-containing amorphous polyester as a main component in a dispersion medium. Can be carried out by utilizing the property of uneven distribution on the surface of the droplet. That is, the core material-constituting material and the outer shell-constituting material are separated from each other in the droplets of the mixed solution due to the difference in solubility index, and in this state, the polymerization proceeds to form a capsule structure. According to this method, since the outer shell is formed as a layer made of an amorphous polyester having a tertiary amine group and having a substantially uniform thickness, the toner has the characteristic that the charging characteristics are uniform.

In the case of this method, it is necessary to contain a dispersion stabilizer in the dispersion medium in order to prevent aggregation and coalescence of dispersoids. Examples of the dispersion stabilizer include gelatin, gelatin derivatives, polyvinyl alcohol, polystyrene sulfonic acid, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, sodium polyacrylate, sodium dodecylbenzene sulfonate, sodium tetradecyl sulfate, and pentadecyl sulfate. Sodium, sodium octyl sulfate, sodium allyl-alkyl-polyethersulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, 3,3-disulfonediphenyl Urea-4,4-diazo-bis-amino-β-
Naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-
Tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-sodium disulfonate, colloidal silica, alumina, tricalcium phosphate, ferric hydroxide, titanium hydroxide, aluminum hydroxide and others are used. can do. Two or more kinds of these dispersion stabilizers may be used in combination.

Examples of the dispersion medium of the dispersion stabilizer include water, methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, acetonitrile, acetone, isopropyl ether, tetrahydrofuran and dioxane. It is also possible to use these individually or in mixture.

In the production method of the present invention, the amount of the amorphous polyester having a tertiary amine group added is usually 3 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the core material. Is. If it is less than 3 parts by weight, the thickness of the outer shell becomes too thin and the storage stability of the toner deteriorates.
If the amount exceeds 0 parts by weight, the viscosity becomes high and atomization becomes difficult, resulting in poor production stability.

Further, for the purpose of charge control, an appropriate amount of the charge control agent as exemplified above may be added to the outer shell material of the capsule toner of the present invention, or this charge control agent may be mixed with the toner. However, even if they are added, the addition amount can be small because the chargeability is controlled by the outer shell itself.

The particle size of the capsule toner of the present invention is not particularly limited, but the average particle size is usually 3 to 30.
It is assumed to be μm. The thickness of the outer shell of the capsule toner is 0.01-1
If it is less than 0.01 μm, the blocking resistance is deteriorated, and if it exceeds 1 μm, the heat melting property is deteriorated, which is not preferable.

If desired, the capsule toner of the present invention may contain a fluidity improver, a cleaning improver and the like. As the fluidity improver, for example, silica,
Alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, Magnesium oxide, zirconium oxide,
Examples thereof include barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride. Fine silica powder is particularly preferable. The fine silica powder is Si
It is a fine powder having a —O—Si bond and may be produced by a dry method or a wet method. In addition to anhydrous silicon dioxide, it may be any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate, etc., but 85% by weight of SiO ₂
Those including the above are preferable. Further, a fine powder of silica surface-treated with a silane coupling agent, a titanium coupling agent, a silicone oil, a silicone oil having an amine in a side chain, or the like can be used.

Examples of the cleaning property improver include metal salts of higher fatty acids typified by zinc stearate and fine particles of fluorine-based high molecular weight particles. Further additives for adjusting the developability, for example, methacrylic acid methyl ester,
Fine particles of a polymer such as methacrylic acid butyl ester may be used. Further, a small amount of carbon black may be used for toning and resistance adjustment. As the carbon black, conventionally known ones, for example, various ones such as furnace black, channel black and acetylene black can be used.

The capsule toner of the present invention is used alone as a developer when it contains magnetic fine powder, and it is a non-magnetic one-component developer when it contains no magnetic fine powder. Alternatively, a two-component developer can be prepared and used by mixing with a carrier. The carrier is not particularly limited, but iron powder, ferrite, glass beads and the like, or those coated with a resin thereof,
Further, a resin carrier prepared by kneading magnetite fine powder and ferrite fine powder into a resin is used, and the mixing ratio of the toner to the carrier is 0.5 to 20% by weight. The carrier has a particle size of 15 to 500 μm.

The capsule toner of the present invention gives good fixing strength by fixing to a recording material such as paper by using heat and pressure together. As a heat and pressure fixing method, if heat and pressure are used together. , A known heat roller fixing method, or, for example, as described in JP-A-2-190870, an unfixed toner image on a recording material is passed through the heat-resistant sheet by a heating means composed of a heating section and a heat-resistant sheet. To heat and melt,
A fixing method of fixing, or a heating body fixedly supported as described in, for example, Japanese Patent Laid-Open No. 162356/1990, and a pressurizing member that is in pressure contact with the heating body and is in close contact with the heating body through a film. A method such as a method of heating and fixing the visible image of the toner on the recording material depending on the member is suitable for fixing the capsule toner of the present invention.

[0061]

EXAMPLES The present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples.

Resin Production Example 1 Propylene oxide adduct 630 of bisphenol A
g (hereinafter abbreviated as BPA / PO), 585 g of an ethylene oxide adduct of bisphenol A (hereinafter abbreviated as BPA / EO), 780 g of dimethyl terephthalate, and 35 g of isophthalic acid were placed in a glass 3-liter four-necked flask,
A thermometer, a stainless steel stirring rod, a downflow condenser, and a nitrogen introduction tube were attached, and the reaction was carried out at 220 ° C. in a mantle heater under a nitrogen stream. The degree of polymerization is AS
Tracking from the softening point according to TM E28-67,
When the softening point reached 115 ° C., 60 g of triethanolamine was added and the reaction was continued at 200 ° C. When the softening point reached 110 ° C., the reaction was terminated. The third obtained
Amorphous polyester having a primary amine group is referred to as resin A.

Resin Production Example 2 630 g of BPA · PO, 585 g of BPA · EO, and 600 g of terephthalic acid (hereinafter abbreviated as TPA) were made of glass 3
It was put in a 4-liter four-necked flask, equipped with a thermometer, a stainless stir bar, a downflow condenser, and a nitrogen introduction tube, and in a mantle heater under a nitrogen stream at 220 ° C.
I made it react. The degree of polymerization is ASTM E28-67.
Follow the softening point in accordance with the above, and when the softening point reaches 115 ° C, add 60 g of triethanolamine and add 2
The reaction was continued at 00 ° C and terminated when the softening point reached 110 ° C. The obtained amorphous polyester having a tertiary amine group is referred to as Resin B.

Resin Production Example 3 367.5 g of BPA / PO and 146.BPA / EO.
4g, 126.0g of TPA, 40.2g of dodecenyl succinic anhydride, and 77.7g of trimellitic anhydride were placed in a glass 2 liter 4-necked flask, and a thermometer, a stainless steel stirring rod, a falling condenser, and nitrogen were used. Attach an introduction tube, and in a mantle heater, under nitrogen stream 220
The reaction was allowed to proceed at ℃. The degree of polymerization is ASTM E28-6.
Followed from the softening point according to 7, the softening point is 110 ℃
The reaction was terminated when was reached. The obtained amorphous polyester having no tertiary amine group is referred to as Resin C.

The glass transition point of the obtained resin was measured by a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo KK), and the softening point and acid value of each resin are shown in Table 1 together. The acid value is JIS
It was measured by a method according to K0070.

[0066]

[Table 1]

Example 1 69.0 parts by weight of styrene, 2-ethylhexyl acrylate
31.0 parts by weight, 0.9 parts by weight of divinylbenzene, 7.0 parts by weight of carbon black "# 44" (manufactured by Mitsubishi Kasei) and resin A
20 parts by weight and 3.5 parts by weight of 2,2′-azobisisobutyronitrile were added, and the mixture was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) and dispersed at 15 ° C. for 5 hours to give a polymerizable composition. Obtained.
Next, 240 g of the above polymerizable composition was added to 560 g of an aqueous colloid solution containing 4% by weight of tricalcium phosphate, which had been prepared in advance in a 2 liter glass separable flask, and TK
Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was emulsified and dispersed at 15 ° C. and a rotation speed of 12000 rpm for 5 minutes. Then, a 4-port glass lid was attached, a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stainless steel stirring rod were attached, and the glass was placed in an electric heating mantle heater. While continuing stirring under nitrogen, the temperature was raised to 85 ° C. and the reaction was performed for 10 hours. After cooling, 10
% Dissolve the dispersion medium with hydrochloric acid aqueous solution, filter, wash with water,
It was dried under reduced pressure at 20 mmHg for 12 hours at 45 ° C. and classified by an air classifier to obtain a capsule toner having an outer diameter of 8 μm and an amorphous polyester having a tertiary amine group as an outer shell. To 100 parts by weight of this capsule toner, 0.4 parts by weight of hydrophobic silica fine powder "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner of the present invention. This is designated as Toner 1. The glass transition point derived from the resin in the core material was 32.7 ° C, and the flow tester softening point of Toner 1 was 119.2 ° C.

The flow tester softening point here means a high-lower flow tester (Shimadzu Corporation) and a load of 20 kg / cm ² by a plunger while heating a 1 cm ³ sample at a heating rate of 6 ° C./min. And a nozzle having a diameter of 1 mm and a length of 1 mm is extruded, whereby a plunger drop amount (flow value) -temperature curve of the flow tester is drawn, and when the height of the S-shaped curve is h, it is h / 2. Refers to the temperature corresponding to.

Example 2 69.0 parts by weight of styrene, 2-ethylhexyl acrylate
31.0 parts by weight, divinylbenzene 0.7 parts by weight, 2,2'-azobisisobutyronitrile 4.0 parts by weight, resin B 20.0 parts by weight, carbon black "GPT-505P" (manufactured by Ryoyu Kogyo Co., Ltd.) 20 parts by weight Was added and dispersed for 1 hour using a magnetic stirrer to obtain a polymerizable composition. Next, an aqueous colloidal solution 5 containing 4% by weight of tricalcium phosphate prepared in advance in a 2-liter glass separable flask.
240 g of the above polymerizable composition was added to 60 g, and a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) was used to rotate at 15 ° C.
It was emulsified and dispersed at 10,000 rpm for 2 minutes. Next, a 4-port glass lid was attached, a reflux cooling tube, a thermometer, a nitrogen introduction tube, and a stainless steel stirring rod were attached, and the glass was installed in an electric heating mantle heater. While continuing stirring under nitrogen, the temperature was raised to 85 ° C. and the reaction was performed for 10 hours. After cooling, dissolve the dispersion medium with 10% aqueous hydrochloric acid, filter, wash with water, and then at 45 ° C for 12 hours.
It was dried under reduced pressure at 20 mmHg and classified by an air classifier to obtain a capsule toner in which the outer shell having an average particle diameter of 8 μm is an amorphous polyester having a tertiary amine group. This capsule toner
Hydrophobic silica fine powder "Aerosil R-97" is added to 100 parts by weight.
2 "(manufactured by Nippon Aerosil Co., Ltd.) was added and mixed to obtain a capsule toner of the present invention. This is designated as toner 2. The glass transition point derived from the resin in the core material is 29.5 ° C,
Further, the softening point of the flow tester of Toner 2 was 123.3 ° C.

Example 3 The procedure of Example 2 was repeated except that the resin B (20 parts by weight) was replaced with the resin A (15 parts by weight) and the resin C (5 parts by weight). Is the third
An encapsulated toner composed of an amorphous polyester having a primary amine group was obtained. This is designated as toner 3. The glass transition point derived from the resin in the core material was 26.8 ° C, and the flow tester softening point of the toner was 119.8 ° C.

Comparative Example Amorphous polyester whose outer shell does not have a tertiary amine group was subjected to the same surface treatment as in Example 1 except that the resin A was replaced with the resin C. To obtain a capsule toner. This is used as a comparative toner. The glass transition point derived from the resin in the core material was 27.4 ° C, and the flow tester softening point of the toner was 121.2 ° C.

Test Example For each toner obtained in the above Examples and Comparative Examples,
The storage stability and the charge amount were evaluated. The storage stability was evaluated for each toner alone, and the charge amount was 4 for each toner.
Parts by weight and 96 parts by weight of spherical ferrite powder coated with a phenyl silicone resin having a particle size of 250 to 400 mesh were placed in a poly container, and the mixture was rotatably mixed on a roller together with the container for 20 minutes at a rotation speed of 150 rpm. The developer was measured.

(1) Regarding storage stability, each toner 5
g is weighed in a 90 mmφ aluminum cup and the temperature is 50 ° C.
The degree of agglomeration generated when left for 24 hours under the condition of relative humidity of 40% was evaluated. The results are shown in Table 2.

[0074]

[Table 2]

(2) The charge amount was measured by the blow-off type charge amount measuring device described below. That is,
Using a specific charge measuring device equipped with a Faraday gauge, condenser, and electrometer, first, 500 mesh
W (g) (0.15 to 0.20 g) of the prepared developer was put in a brass measuring cell equipped with a stainless mesh (which can be appropriately changed to a size in which carrier particles do not pass). Next, after suctioning for 5 seconds from the suction port, the air pressure regulator is 0.6 kgf.
Blow was performed for 5 seconds at a pressure indicating / cm ² to remove only the toner from the cell.

At this time, the voltage of the electrometer 2 seconds after the start of blowing was set to V (volt). Here, if the electric capacity of the condenser is C (μF), the specific charge Q / m of this toner is obtained by the following equation. Q / m (μC / g) = C × V / m Here, m is the weight of the toner contained in the developer in W (g), and the weight of the toner in the developer is T (g). When the weight of the developer is D (g), the toner concentration of the sample is expressed as T / D × 100 (%), and m is calculated by the following formula. m (g) = W x (T / D) Table 3 shows the result of measurement of the charge amount of the developer prepared under the normal environment. In addition, the prepared developer is a commercially available electrophotographic copying machine (the photoconductor is an organic photoconductor, and the rotation speed of the fixing roller is
Image output using 255 mm / sec, toner density 4%), charge amount measurement after copying 50,000 sheets, image density during continuous printing durability test, image quality (generation of background stain), and The flight scattering was also evaluated. The results are shown together in Table 3.

[0077]

[Table 3]

(3) The fixability was evaluated by the method described below. That is, the prepared developer described above is used as a commercially available electrophotographic copying machine (photoreceptor is an organic photoconductor, the rotation speed of the fixing roller is 255 mm / sec, the thermal pressure temperature in the fixing device is variable, and the oil coating device is removed. Image) was used. The fixing temperature was controlled from 70 to 220 ° C., and the fixing property and offset property of the image were evaluated. The results are shown in Table 4. The minimum fixing temperature here is 15 mm on the bottom.
Apply a load of 500 g to a 7.5 mm sand eraser, rub the image fixed five times through the fixing device, and measure the optical reflection density with a reflection densitometer of Macbeth before rubbing. The temperature of the fixing roller when the fixing rate exceeds 70%. Fixing rate = (image density after rubbing / image density before rubbing)

[0079]

[Table 4]

As is clear from Tables 2 to 4, the toners 1 to 3 of the present invention had a good rise in the charge amount, a small change in the charge amount after copying 50,000 sheets, and excellent charge stability. Further, there was little change in image density and image quality, scattering in the machine was not recognized, and storage stability was good. Further, in Toner 3, the positive chargeability could be controlled by using the amorphous polyester having a tertiary amine group and the polyester not having the same together. Further, all of the toners 1 to 3 have a low minimum fixing temperature and a wide non-offset region,
The fixability was good. On the other hand, since the comparative toner does not contain a tertiary amine group in the constituent components of the amorphous polyester, the positive charging property is extremely low and it is difficult to form an image.

[0081]

According to the capsule toner for heat and pressure fixing of the present invention, the rise of triboelectrification is particularly good and the toner has a stable positive charging property, and the offset resistance is excellent in the heat and pressure fixing method such as a heat roller. It is excellent and can be fixed at low temperature, and a clear image with little background stain can be stably formed many times.

Claims (8)

[Claims] 1. A capsule toner for heat and pressure fixing comprising a heat-fusible core material containing at least a thermoplastic resin and a colorant, and an outer shell provided so as to cover the surface of the core material. A capsule toner for heat and pressure fixing, characterized in that the main component of the shell is an amorphous polyester having a tertiary amine group. 2. An amorphous polyester having a tertiary amine group is obtained by polycondensation of a monomer mixture containing a monomer having a tertiary amine group. A divalent or higher-valent alcohol monomer or carboxylic acid monomer in which the group-containing monomer has the chemical structure represented by the general formulas (I) to (III) in the molecule, and the general formula (IV)
2. The heat and pressure fixing capsule toner according to claim 1, wherein the heat and pressure fixing capsule toner is one or more selected from the group consisting of divalent or higher valent alcohol monomers. [Chemical 1] (Wherein R ₁ , R ₂ , R ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R _13, R ₁₄ and R ₁₆ are alkylene groups having 1 to 15 carbon atoms, R ₃ and R ₄ are alkyl groups having 1 to 10 carbon atoms, and R ₆ is 1 carbon atom. An alkyl group having 10 to 10 or an alkylene group, R ₁₅ is an alkyl group having 1 to 3 carbon atoms, or Represents R ₁₇ and R ₁₈ represent an alkyl group having 1 to 4 carbon atoms, and R ₁₇ and R ₁₈ may form a heterocyclic ring together with the nitrogen atom. X represents hydrogen or a hydroxyl group. ) 3. The capsule toner for heat and pressure fixing according to claim 2, wherein the amount of the monomer having a tertiary amine group used is 5 to 30 mol% based on all the monomers. 4. The heat and pressure fixing capsule toner according to claim 1, wherein the amorphous polyester having a tertiary amine group has a glass transition point of 50 to 80 ° C. 5. The heat and pressure fixing capsule toner according to claim 1, wherein the amorphous polyester having a tertiary amine group has an acid value of 1 to 50 (KOHmg / g). 6. The glass transition point derived from a thermoplastic resin as a main component of a heat-meltable core material in an encapsulated toner is 10 to 10.
3. The heat and pressure fixing capsule toner according to claim 1, wherein the temperature is 50.degree. 7. A method for producing a capsule toner for heat and pressure fixing, comprising a heat-fusible core material containing at least a thermoplastic resin and a colorant, and an outer shell provided so as to cover the surface of the core material. A method of producing a capsule toner for heat and pressure fixing, comprising forming an outer shell by coating the surface of a core material with an amorphous polyester having a tertiary amine group by an in situ polymerization method. 8. The amount of the amorphous polyester having a tertiary amine group added during the in-situ polymerization method is the core material 1.
The manufacturing method according to claim 7, wherein the amount is 3 to 50 parts by weight with respect to 00 parts by weight.