JPS5962868A - Production of toner - Google Patents

Abstract

PURPOSE:To obtain a toner for developing electrostatic charge having excellent fluidity and a uniform triboelectrification characteristic by dispersing a toner material in a dispersion medium, forming polymer particles and growing the polymer particles by a polymn. method using a specific polymn. initiator. CONSTITUTION:A toner material contg. a synthetic resin monomer, polymn. initiator and coloring material is dispersed in a dispersion medium which is hardly compatible with the monomer and is polymerized to form polymer particles. The resulting polymer particles are grown by a polymn. method using a polymn. initiator having an amino group at the terminal, whereby a toner is formed. The dispersion medium is used by incorporating a stabilizer, for example, PVA, gelatin, methyl cellulose or the like in an aq. phase and is used preferably in an about 0.1-10wt% range. The polymn. is accomplished by setting the polymn. temp. usually at 70-90 deg.C. An unsatd. alpha-beta monomer such as styrene, a vinyl monomer such as ethylene or the like is used as the synthetic resin monomer. A compd. having an amino group at the terminal, for example, 2,2'-azobis- isobutyl amidic salt or the like is used as the polymn. initiator used in the method for the growth.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a toner for developing electrostatic images and the like.

Traditionally, toners are typically melt-mixed into thermoplastic resins,
After uniformly dispersing, a toner having a desired particle size is produced using a pulverizer and a classifier. This manufacturing method is
Although it is possible to produce a toner with an excellent power of 1, there is a certain limitation (i), that is, the range of selection of materials for the toner is limited. For example, the resin M material dispersion is optically brittle and economically unsatisfactory.
14(1) at best if it can be crushed at a production speed of 4) J.

When actually finely pulverizing this hard water using Hr operation (U) where the resin M family dispersion is brittle to light, particles with a wide range of particle sizes are likely to be formed, and the particles may be relatively large. A problem arises in that this includes the proportion of imitators.Furthermore, when the materials used in this process are used for development in copying, they are often finely pulverized or powdered. Other requirements for the toner include that it be stable during storage, that it does not solidify, that it has suitable triboelectric properties during development, and that it forms a stable image. 1-
These requirements are combined with the additional requirements imposed on this toner formation process: the toner should not coat or stain the photoreceptor, and have a low melting point suitable for thermal fusing.

The electrostatic image developing toner obtained by suspension polymerization uses light to overcome the drawbacks of the pulverization method. In other words, there is no need for brittleness as there is no pulverization process involved, and the spherical shape has excellent fluidity.Furthermore, by appropriately controlling polymerization or using a crosslinking agent, we can create a heat-set eyebrow toner that is specially made to be excellent. can be obtained.

C. Polymerization methods have been proposed in Japanese Patent Application Laid-Open No. 17735/1983. These are monopolymerization initiator, coloring agent,
A toner is obtained directly by dispersing a magnetic material and other compositions in water.

However, a large amount of a dispersant such as a water-bathable polymeric substance or a poorly soluble i8: inorganic substance is required, and even if acid treatment or water washing is performed to remove this, a small amount of pIi remains on the toner surface. Moisture (humidity) in the air affects the toner's electrical conductivity, causing friction zones of the toner.
Makes the ton characteristics extremely unstable. Furthermore, in this suspension polymerization method and emulsion bundling, magnetic substances and colorants are present non-uniformly on the particle surface.

It's hard to get a clear picture pattern.

The object of the present invention is to provide a method for producing a toner for developing electrostatic images, etc., which overcomes the drawbacks of such polymerized toners.

Its features include: 1) A toner material containing a single piece of synthetic resin, a polymerization initiator, and a colorant.

The polymer particles are dispersed in a dispersion medium that is completely incompatible with the monomer, and the polymer particles are made with amino groups terminated using a polymerization initiator. There is a method for dispensing toner that is grown using a polymerization method.

From this, it is possible to provide a toner for h-charge development that has excellent fluidity and has uniform properties.

Allow the polymer particles to grow (this will become a substance that is stably dispersed in water). Sometimes, to obtain the best results, it is necessary to carefully control the monomer addition rate. If the addition rate becomes too small, the polymerization
If j becomes unnecessarily long and the speed of the applied force becomes too large, not only will fine L-shaped particles of Ogaki occur, but the seed particles will tend to coalesce, and aggregates will easily form. General number, monomer.

The monomer should be added at the same rate as it is absorbed by the particles. The surface of the polymer particle becomes swollen as it absorbs the mineral bodies. When this coating is carried out only on the surface, the surface is treated as a single polymer and polymerized by an initiator, so it is not contaminated with colored particles or magnetic substances.

Or, it is possible to have a smooth surface with less lI5 warpage.

At the same time, polymerization initiation C1] is added to charge tti
It has the function of C as a medicine. In addition, by adjusting the amount of monomer in the polymer particles ridge a, it becomes possible to control the particle size to a desired value.

The seed polymer particles include 1 synthetic resin side body, a polymerization initiator,
A monomeric toner material in which the magnetic substance and additives are uniformly dissolved or dispersed is added to a conventional continuous phase such as an aqueous phase containing a stabilizer. Disperse using a stirring vessel, homomixer, or homogenizer. Preferably, the monomeric material has the desired toner particle size,
In general, the stirring speed of particles with a size of 30μ or less is adjusted at 1i:Ijk, and the particles are stirred to prevent sedimentation of the particles, so that a hollow state is maintained by the action of a dispersion stabilizer. It is good to do this as much as possible. The mounting temperature is 50° C. or higher, which is generally 70° C. to 90° C. and the temperature is 70° C. to 90° C.

Suitable dispersion medium C'i used in the present invention.

For example, any unreasonable moderating agents such as polyvinyl alcohol, ceratin, methylcellulose.

Methylhydropropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic IJ and salts thereof.

Starch, gum alginate, zein, casein, tricalcium phosphate, talc, barium sulfate, petonite, aluminum hydrate, ferric hydroxide, titanium hydroxide,
Thorium hydroxide or the like can be included in the aqueous phase. This stabilizer is J! 1f+-, stabilized during the li continuation phase,
It is preferably within the range of about 0.1 to 10 weight fractions.

In addition, for fine dispersion of the Kuroiso dispersant, 0,001
It is also possible to use surfactants within the range of = O, l M. This is to promote the intended action of the above-mentioned dispersion stabilizer. As a specific example, No. 10 is dodecylbensene sulpon [λ sodium, tetradecyl m
t+M Sodium, Pencutisyl % fyW Sodium, Octyl Degraded Sodium, Allyl-Alkyl-Polyether Sulfo/Ba Sodium, Sodium Oleate.

Sodium laurate, sodium caprate.

Sodium caprylate, sodium caproate.

Old potassium stearin, calcium olein.

3.3'-Disulfone diphenyl urea-4,4'-diazo-bis-amino-8-naphthol-6-sulfoner
wave sodium, ortho-lupoxybenosenoazodimethylaniline, 2,2'.

5.5'-tetramethyl-triphenylmethane-4,4
'-Sea saw bis! - Sodium naphtholcisulponate, and others may be mentioned.

In addition, the monomers in water cause emulsion polymerization simultaneously in water, and the resulting suspended polymer is contaminated with small emulsion polymer particles. It is also good to prevent emulsion polymerization. Also, add chrycerin to the water to anneale the secondary and central 1st part and force the particles to coalesce.
It is also good to apply glycol water to gravity. Also, easy:'
(B to #'a 7th matsumar) 4 times (NaCt, KCl in the first place of a).

It is also possible to use salts such as N8gSO4.
It is Ko.

At the beginning of polymerization, the first column was azobisisobutyronitrile (AII3).
N), pembyl peroxide, methylenalol peroxycarbonate, isopropyl peroxycarbonate, quince/hydroperoxide.

2.4-Dichlorylbe/Zoyl N+-Oxide.

Monomer polymerization can be carried out using lauroyl peroxide. Generally about 0.5 to 5% initiator by weight of monomer is sufficient.

The polymerization temperature is usually 50°C to 120°C.

The lower the temperature, the more uniform the combination will be.

Synthesis 4 ■ As for the specifics and chestnuts of fat single employment bodies, the following can be applied to Hongen Akira. Examples of α-β unsaturated O[l monomers include styrene, 0-methylstyrene, m-methylstyrene, and p-methylstereno. p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, pLert-butylstyrene, p-n-hexylketone.

p-rho octylstyrene, p-n-7nylstyrene,
pn-tethylstyrene II pn-dodecylstyrene, p-methoxystyrene, p~phenylstyrene,
Styrene and its derivatives such as p-chlorostyrene and 3.4-dichlorostyrene are included, and among these, styrene monomer is most preferred. Examples of other vinyl spinning wheel extensions include ethylene-non-Showa monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl chloride, hynylidene chloride, and vinyl fluoride.

Vinyl halides such as vinyl fluoride 4; Vinegar 1 cubinyl, propion and vinyl, hinyl benzoate.

Vinyl esters with 100% alcohol; menal acrylate, ethyl acrylate, 11-) thousand acrylic acid, acrylic diisobutyl, acrylic propyl, acrylic IFI n-octyl, dodecyl acrylate, 2-acrylic acid Ethylhexyl, acrylic tn stearyl, acrylic 2-chloroethyl, acrylic phenyl, α-chloroacrylic methyl, methacrylate methyl, ethyl methacrylate, propyl methacrylate, methacrylic (i)
n-butyl, methacrylic acid, isobutyl, methacrylic acid n
-Octyl, methacrylic branched dodecyl.

α-methylene fat-extended monocarboxylic acids such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; acrylics such as acrylonitrile, methacrylic nitrile, and acrylamide Acid or methacrylic acid derivative; vinyl ether smoke such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinylpyrrole,
N-vinyl carbazole, N-vinylindole, N-
Examples include vinyl compounds such as vinyl pyrrolidone; vinyl naphthalene, etc.

The polymer according to the present invention may be polymerized (in the presence of a crosslinking agent) to form a crosslinking polymer. Preferably used crosslinking agents mainly include two or more polymerizable bicyclic bonds. Aromatic divinylated compounds such as ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene Diethylene carboxylic acids such as /gI nocol meccrylate, trimethylolpropanotriacrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimecacrylate f, etc. ester, N,N-divinylaniline, divinyl ether,
All divinyl compounds such as divinyl sulfide and divinyl sulfone and compounds having three or more vinyl groups Z are selected singly or as a mixture. Furthermore, ethylene glycol, triethylene glycol, 1.2-
Propylene glycol, 1,3-propylene glycol, 1°4-)'/nosiol, neopentyl glycol.

1.4-butynediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A1 water-added bisphenol A, polyoxyethylenated hisphenol A, polyoxypropylenated bisphenol A fl, etc. Alcohols; maleic acid, fumaric acid, mezaconic acid, citraconic acid, itaconic acid, glutaconic acid.

Phthalate, inphthalate, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, cepatine,
Dibasics such as malonic acids, their anhydrides or their esters with lower alcohols [numbers and their d conductors;
Glycerin.

Trivalent or higher valent alcohols such as trimethylolpropane and pentaerythritol, and trivalent or higher valent carboxylates such as trimellitic acid and pyromellit a can be used as crosslinking agents in the present invention.

How to swim to the moon body of MIJ on such an overhead plane [eyes 0.
005 to 20 car bt%, preferably 1112 range of 0.1 to 5 Tsumewarashiki is selected. If there is too much of this additive (D), the toner becomes insoluble and tends to lose its constant-4 properties as a toner.

If the amount is too low, the characteristics of the toner, such as durability, preservability, and sobriety, will be imparted and the properties will become too thick. The distribution of children will expand and its consequences will increase.

As the coloring agent, any one selected from pigments, dyes, etc. can be used. For example, carbon black, nigrosino dye, oil black, etc. can be used alone or in combination. A magnetic substance may also be used as a phosphorescent agent.

The magnetic material used for the toner paulownia material may be any material as long as it is strongly magnetized in that direction by a magnetic field. Preferably magnetite is used. Typical magnetic or.

Magnetic materials include strong metals such as cobalt, iron, and nickel; aluminum, cobalt, aluminum, copper, magnesium, 2/7-), soot, lead, anodyne, beryllium, hismuth, and iodomium. ,calcium,
Mancuff, Seren, Nakun.

Alloys of metals such as tanksten, vanadium, and their iJi' 9. Metal compounds containing metal oxides; nitrides such as vanadium nitride and silica nitride; carbides such as tungsten carbide and silica carbide; ferrites and soybeans; A mixture of these can be used.

The single mass used in the method of growing polymer particles is the seed described in 1M1J! 1 [Sayaji used when
Compounds similar to one can be used.

The polymerization initiator used in the growth method is a compound having an amine group at the end. An example is 2,2'-anhisine butyramidic salt.

A tight surface viscosity agent can be used to stabilize the 1M composite particles in the raw method.

For example, examples of anionic activators include potassium palmitin, potassium stearin, potassium caprate,
Oleic potassium, sodium dodecyl sulfonate,
Sodium laurate.

Rosin salts, alkyl sodium sulfosuccinates, long chain quaternary amine salts, etc.

Examples of non-ionic activators include rirunic acid, lauric acid, lysiruin decoction, ethylene oxide poly-16 compound of caproic acid, and oleyl alcohol.

Ethylene oxide condensation of cetyl alcohol, lauryl alcohol, etc.

The above surfactants can be used alone or in combination.

The tL agent r4 degree occupying the interface is generally determined by the critical micellar potency (O
MO2) or less is good, but it may be added to OMO or more for the purpose of increasing the emulsion particle size or stabilizing the particles. However, c. It is also possible to take a method of preventing emulsification in the aqueous phase and suppressing the formation of new particles by using a subpolymerizing agent such as NH, SON (ammonium thiocyanide) or the same item. can.

After the reaction is completed, the generated toner particles are washed.
It is collected and dried using unreasonable methods such as tectonation and centrifugation.

[Example 1. ] 400g of styrene and Fischer diameter 0.4μB T]
T ratio surface f 6. On? / g O') 240 g of magnetite 1 et PT-1 with particle size
0 o O and 24 g of petrolactam oxide metal salt (O
The mixture was uniformly mixed for about 20 minutes in a container equipped with a high-shear mixer such as that manufactured by Tokushu Kogyo (PL, Inc.). During this time, the temperature rose to about 50°C. During this time, the macnetite was separated into the styrene monomer.

30 g of lauroyl barochloride was stirred and mixed into the above magnetite-containing styrene monomer. 600 g of water (bathed with 9.0 g of polyvinyl alcohol) Y7
The temperature was lowered to 0° C., and the slurry was put into a homomixer while stirring, and stirred at 4000 rpm for 30 minutes. This reaction mixture yarn was stirred with a paddle blade stirring to complete the joining.

After that (100g of styrene for 2 hours?
Painting and then. 1 g of 2.2'-azobisisobunalamidic salt was added and polymerization was completed for 3 hours.

Wash with water, θ3 pass S'i. 1hiif number average diameter 10
．． 1μ. A 1-su was obtained with a number distribution of 6.35 μ or less of 15% and a volume distribution of 202 g or more of 1% (using a Coulter counter loop aperture). It was confirmed that it had a 1F-order surface using a scanning microscope.

Apply this toner to a commercially available dry method [Muko Photo Ishaiso Pc-1].
The image was rendered using 0. The result is clear, fog-free images! It was possible to set the il threshold to .rM. 1.20 was obtained by the reflection rate δ in the solid black area of the painting density button.

The toner properties are also impressive.

In particular, U1 was behind in terms of dynamics and continuous image output durability.

Example Metilef 80g. n-butyl methacrylate 2 (Ig.
) Limethylolbroban triacrylate 0.2g, p
10g of HaV Fuclocyanin Y Translation.

Moon in a ball mill - (komin 1■ (Kon'@- L 7ko. Shigaru I ρ.

3g of 2,2'-anhis-(2,4-dimethylpacinolonitrile)
3g tricalcium phosphate and 0. 0 5 g of dodecylbenzene 2 Hof's version sodium 3
00g of the aqueous phase while pressing the -4: button at a stirring speed of 000 rpm. After that, the face was heated at 60℃ for 7 hours.

The nail platform reaction was completed.

After that, warm it to 70℃ and add 50g of styrene to it.
Got 4. Thereafter, 1 gk of %2,2'-isobutylamidic acid was added, polymerized for 5 hours, and then introduced. 〆Currently II Colonel. 9.2μ aperture (using Coulter color/tar 400μ aperture).

Use this toner with commercially available dry-type Gunko Yohyotasha 4; WPC! -1
The image was drawn using 0. His tongue was clear, like that of Kafuri, and he served the family.

Personnel: Canon Corporation

Claims (1)

[Claims] A toner material containing a synthetic resin monomer, a heavy @-initiator, and an eyebrow tinting agent is dispersed in a dispersion medium that is almost incompatible with the monomer and polymerized to form polymer particles, and the small aggregate particles A method for producing a toner in which toner is grown by a bundling method using a polymerization initiator having an amino group at the end.