JPS63169664A - Toner for electrostatic charge image development - Google Patents

Abstract

PURPOSE:To obtain the titled toner having the improved anti-sticking property to a soft PVC, and the improved image density, anti-fogging and anti-blocking properties by incorporating a polymer which is composed of a specific vinyl monomer contg. an imido group, as a constituting component to the titled toner as a binding agent. CONSTITUTION:The polymer contains the vinyl monomer contg. the imido group shown by formula I where R1 is H atom or methyl group, R2 is 1-6 C alkylene or a bivalent org. group having an alicyclic or an aromatic group, R3 is a group shown by formula II, III or IV (R4-R9 are each H, halogen atom or 1-3 C alkyl, -NO2, -SO3H or -N3 group, etc.), as the constituting component, and is incorporated as the binding agent resin to the titled toner. Thus, the titled toner has the improved anti-sticking property to the soft PVC by incorporating the monomer contg. the imido group shown by formula I to the binding agent resin. And, the titled toner has the good image density and anti-fogging and anti-blocking properties which are the properties necessary to the toner. Thus, the titled toner is widely applicable to various kinds of well-known developing methods.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for developing electrostatic images used in fields such as electrophotography and electrostatic recording.

[Conventional technology]

In electrophotography, electrostatic recording, etc., an electrostatic charge image is formed on a photoreceptor by various methods, and then the electrostatic charge image is developed with toner particles. A printed matter is obtained by transferring it to another transfer material and fixing it with a heating roll, pressure roll, hot pressure roll, or flash light from a xenon lamp.

Prints are often placed in paper containers made of soft PVC polymer sheets to prevent stains and damage and to allow long-term use or storage.

Toners for developing electrostatic images used in the fields of electrophotography and electrostatic recording include toners using polystyrene resin (Japanese Patent Publication No. 44-16118) and toners using styrene-butyl methacrylate copolymer resin ( Special Public Service 1986-11
Toner using a bisphenol-type epoxy resin obtained by reacting bisphenol with epichlorohydrin (Japanese Patent Application Laid-open No. 1982-96354), glycol having a bisphenol skeleton, etc. Toner using polyester resin obtained by reacting with polybasic acid (Japanese Patent Publication No. 52-25420)
However, compared to other resins, vinyl resins are extremely advantageous in terms of toner design, as their physical properties such as molecular weight, glass transition point, and melt viscosity can be controlled over a wide range. The majority of toners are toners using this vinyl resin.

[Problem that the invention seeks to solve]

By the way, in order to prevent stains and damage and to use or store the printed matter for a long time, the printed matter is often placed in a paper case made of a soft vinyl chloride polymer sheet. However, with conventional toners using vinyl resin, when printed matter made with the toner is sandwiched between soft PVC polymer sheets, the printed characters and figures adhere to the sheets, causing print defects and making them difficult to read. It had the serious drawback of becoming incapacitated.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a toner that has the image density fog resistance and blocking resistance necessary for a toner and does not adhere to a soft vinyl chloride polymer sheet.

[Means for solving problems]

The present invention uses a polymer having as a constituent component a vinyl monomer represented by the following general formula (I) as a binder [wherein R1 is hydrogen or a methyl group, and Rz has 1 to 1 carbon atoms]
6 alkylene group or alicyclic group, Ra, Ran
Ran R7t Ra and R9 are hydrogen, carbon number 1-3
may be an alkyl group or a halogen.

Specific examples of the divalent organic group having a t ring or an aromatic ring for R2 in the above formula include the following.

However, R' is an alkylene group having 1 to 6 carbon atoms, ←alkylene group having 1 to 6 carbon atoms→〇-1 or -(alkylene group having 1 to 6 carbon atoms→O←alkylene group having 1 to 6 carbon atoms) → is.

The binder resin of the toner for developing electrostatic images according to the present invention contains a vinyl monomer represented by the above general formula (I) (hereinafter referred to as "the specific monomer of the present invention") as an essential component. , for which the following are used as binders:

(A) A resin containing one kind of polymer, two or more kinds of copolymers, or a mixture thereof among the specific monomers of the present invention.

(B) A resin containing as a component a copolymer of one or more of the specific monomers of the present invention and one or more other addition-polymerizable monomers, or a mixture thereof.

(C) A mixture of the resin of (A) above and the resin of (B) above.

(D) A mixture of the resin of (A) above and/or the resin of (B) above and another resin.

At least one of the specific monomers of the present invention is contained in the binder as a component, preferably 5 to 90% by weight, more preferably 20 to 70% by weight, particularly preferably 25% by weight.
It is blended to contain up to 60% by weight. If the amount of the specific monomer of the present invention is too small, the adhesion resistance of the toner to the vinyl chloride polymer tends to be insufficient, and if it is too large, the performance as a toner tends to be insufficient.

The specific monomer of the present invention can be produced by, for example, imidizing an acid anhydride having a corresponding alicyclic structure with an alkylene group having 1 to 5 carbon atoms or an amino alcohol having an alicyclic ring or an aromatic ring, and then producing acrylic acid or an aromatic ring. It can be produced by adding methacrylic acid or a lower alkyl ester thereof and carrying out an esterification reaction or transesterification reaction, and typical monomers include the following monomers.

(Vinyl monomer A) (Vinyl monomer D) (Vinyl monomer B) Other addition-polymerizable monomers that can be copolymerized with the above specific monomers are used as necessary, but the total vinyl monomer that is the copolymerization component Specific examples of other addition-polymerizable monomers, which preferably have a distribution weight of 10 to 95% relative to the total weight, are shown below.

Styrene, methoxystyrene, butoxystyrene, α-
Methylstyrene, p-methylstyrene.

Styrene derivatives such as pt-butylstyrene and p-chlorostyrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, decyl methacrylate , undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate,
Methoxydiethylene glycol methacrylate.

Ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate,
Phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, Methacrylic nitrile, methacrylamide, N-methylolmethacrylamide, ethylmorpholine methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate.

Hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, diacetone methacrylamide, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Pentyl acrylate.

Hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxy acrylate Diethylene glycol, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate,
Methoxydipropylene glycol acrylate.

Phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinyl acrylate -2-pyrrolidone, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, glycidyl acrylate, acrylonitrile.

Acrylamide, N-methylolacrylamide.

Diacetone acrylamide, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, ethylmorpholine acrylate, vinylpyridine diethyl maleate, dibutyl maleate.

Vinyl monomers having one vinyl group in each molecule such as diethyl fumarate, dibutyl fumarate, and octyl fumarate, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid, such as ethylene glycol dimethacrylate, 1.3-butylene gelicol dimethacrylate, 1,4-butanediol dimethacrylate.

1.5-bentanediol dimethacrylate, 1゜6-
Hexanediol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate,
Trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, trismethacryloxyethyl phosphate,
Bis(methacryloyloxyethyl)hydroxyethyl isocyanurate.

Tris (methacryloyloxyethyl) isocyanurate, ethylene glycol diacrylate.

1.3-Butylene gelicol diacrylate, 1゜4-
Butanediol diacrylate, 1,5-bentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate.

Tripropylene diacrylate, hydroxypivalic acid pentyl glycol diacrylate.

Trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)isocyanurate, Two or more vinyls in one molecule, such as a halfester compound of glycidyl methacrylate and methacrylic acid or acrylic acid, a halfester compound of bisphenol-type epoxy resin and methacrylic acid or acrylic acid, and a halfester compound of glycidyl acrylate and methacrylic acid or acrylic acid. Mention may be made of vinyl monomers having groups.

Among these vinyl monomers, particularly preferred vinyl monomers having 41 vinyl groups in one molecule include styrene, styrene derivatives, methacrylic esters, acrylic esters, and especially those having 1 to 5 vinyl groups in the alkyl group. Among the vinyl monomers having two or more vinyl groups in one molecule, preferred are alkyl esters of methacrylic acid or acrylic acid having carbon atoms, such as divinylbenzene.

Dimethacrylates and diacrylates of methylene glycol having 2 to 6 carbon atoms are preferred.

These are used in an amount of 0 to 20% by weight based on the total vinyl monomers. These vinyl monomers having one vinyl group in one molecule and vinyl monomers having two vinyl groups in one molecule can be used alone or in combination of two or more.

The above vinyl monomer can be polymerized in solution or in bulk.

Polymerization can be carried out by any method such as emulsion polymerization or suspension polymerization.

In the polymerization of these monomers, the polymerization initiators used include 2,2'-azobisisobutyronitrile, 2.
2'-azobis-(2,4-dimethylvaleronitrile)
, azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), peroxy compounds such as t-butylperoxy(2-ethylhexanoate) 11-butylperoxyisobutyrate ester, 1.1-
Peroxyketals such as bis(t-butylperoxy)3,3.5-trimethylcyclohexane and 1,1-bis(t-butylperoxy)cyclohexane, dicumyl peroxide, 2,5-dimethyl-2,5 There are dialkyl peroxides such as -di(t-butylperoxy)hexane, diacyl peroxides such as benzoyl peroxide, and acetyl peroxide. Preferably, these are used in an amount of 0.1 to 15% by weight based on the total molecular monomers.

Furthermore, known chain transfer agents can be used during polymerization of these monomers. The chain transfer agent is preferably used in an amount of 0 to 5% by weight based on the total monomers.

The binder resin of the present invention has a glass transition temperature of 40 to 1
It is preferable to adjust the temperature to 00"C, especially 50 to 90"C.
If the temperature is less than 40°C, the blocking resistance of the toner tends to be poor, and if it exceeds 100°C, the crushability of the toner tends to decrease.

The toner of the present invention further contains a colorant and/or magnetic powder.

Colorants include carbon black, acetylene black, lamp black, graphite, iron black, aniline black,
Black colorants such as cyanine black.

Yellow coloring agents such as yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, naphthol yellow, Hansa yellow, pigment yellow, benzidine yellow, permanent yellow, quinoline yellow lake, anthrapyrimidine yellow, permanent orange, palkan fast orange, benzidine Orange, orange colorants such as indanthrene brilliant orange, iron oxide, amber, brown colorants such as permanent brown, red iron oxide, antimony vermilion, permanent red, fire red, brilliant carmine, light fast red toner, permanent carmine, pyrazolone red , Bordeaux, Heliobordeaux, Rhodamine Lake, Thioindigo Red,
Red colorants such as thioindigo reddon, purple colorants such as cobalt violet, fast violet, dioxazine violet, cobalt blue, cerulean blue, metal-free phthalocyanine blue, phthalocyanine blue.

Blue coloring agents such as indanthremble and indigo.

There are green coloring agents such as chrome green, cobalt green, green gold, phthalocyanine green, polychrome bromine copper phthalocyanine, etc., and when heat decomposition resistance is required, carbon black, iron black, cyanine black, yellow iron oxide, and titanium are used. Yellow, Hansa Yellow, Benzidine Yellow, Permanent Orange, Palkan Fast Orange.

Iron oxide, Red Garla, Fire Red, Light Fast Red Toner, Permanent Carmine, Pyrazolone Red, Bordeaux, Thioindigo Maroon, Cobalt Purple, Cobalt Blue, Cerulean Blue, Phthalocyanine Blue, Cobalt Green.

Particularly preferred are phthalocyanine green, polychrome bromine copper phthalocyanine, and the like. These colorants are preferably blended in an amount of 1 to 60% by weight in the total toner components. 1% by weight
If it is less than 60% by weight, the coloring is insufficient, and if it exceeds 60% by weight, the fixing strength of the toner tends to decrease.

Note that when the toner of the present invention is applied to a fixing method using a xenon flash irradiation method, the toner contains a Cannon light absorber that can absorb light of 800 to 11000 nm, which is the maximum intensity of Cannon light. Some of these compounds, such as carbon black, triazo compounds, phthalocyanine compounds, and naphthrocyanine compounds, have the ability to color themselves, so when using such Canon light absorbers, it is necessary to add another colorant. In some cases, it may not be necessary to add it. Other xenon light absorbers include polymethine compounds, azulenium salts + Cr F z g Cu CQ z +
FeCQs, Fe5Oa・7Hz○, MoCQ
s.

N1CQz, VCQa, VC+l14. VFa, VSO
a・7HxO, etc., and these contain 1% of the total toner components.
It is preferable that the amount of xenon is 20% by weight, especially 3-15% by weight.If it is less than 1% by weight, the absorption of xenon light will be insufficient and the fixing strength will tend to decrease, but if it exceeds 20% by weight, , higher effects cannot be expected, and the frequency of occurrence of adverse effects such as a decrease in chargeability tends to increase.

Magnetic powder is blended when the toner is used as a one-component toner. Magnetic powders include metal powders such as iron, manganese, nickel, and cobalt, aluminum, cobalt, steel, lead, magnesium, nickel, and tin.

Zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium.

Metal alloys and mixtures thereof such as tungsten, vanadium, metal compounds including metal oxides such as aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide, magnesium oxide, chromium oxide, or heat treatment. Alloys that exhibit ferromagnetism when applied, such as Boyceker alloys such as manganese-copper-aluminum and manganese-copper-tin, can be used. The particle size of the magnetic powder is preferably 10 μm or less, particularly preferably 1 μm or less. These magnetic powders are contained in the toner in an amount of 30 to 70% by weight. When using magnetic powder, the above colorant may be further added, and the amount thereof is preferably 10% by weight or less in the toner.

Further, the toner of the present invention may contain other resins and additives such as a charge control agent, a fluidity improver, a cleanability improver, and an anti-offset agent, if necessary.

Other resins include styrene resin, styrene agril resin, silicone resin, polyester carbonate resin, xylene resin, epoxy resin, phenol resin, diene resin, coumaron resin, amide resin, amino resin, urethane resin, etc. is preferably blended in the total toner components in an amount of 0 to 30% by weight.

As the charge control agent, nigerone dye, adipose-modified nigrosine dye, tetraalkylammonium halide, and trialkylammonium halide are used.

(In the formula, X' represents a halogen, R represents an alkylene group having 1 to 3 carbon atoms, and n represents 0 or 1), a polyamine compound having a structural unit.

Nitrilation (in the formula, R
C represents an alkoxy group or a phenoxy group, R8'
represents hydrogen, an alkoxy group or a phenoxy group), monoalkyltin oxide.

Dialkyltin oxide, monoaryltin oxide.

Formula: (In the formula, Rν, Rs', R,' and R7' represent hydrogen, an alkyl group having 1 to 9 carbon atoms, or a substituent having an aromatic ring or a cyclohexene ring, but two or more groups simultaneously It does not represent hydrogen, and Me is Cr.

CO or Fe, M represents hydrogen, potassium, sodium or fatty acid ammonium).

A compound of the formula: (wherein Rs' and Rg/ represent an alkylene group, an aromatic ring, or a cyclohexene ring having 1 to 9 carbon atoms, and Me and M represent the above), a compound of the formula: (wherein T, Y
and Z represent hydrogen, halogen, carboxyl group, hydroxyl group, nitro group, sulfone group or sulfonamide group; 1M and Me represent the above), tetrathiafulvalene, alumina fine powder, etc. can be used, and in the toner. It is usually added in an amount of 0 to 20% by weight.

However, among the specific monomers of the present invention, one molecule contains IO0gen, -〇-51-Rlz, -NOx or -5Oa.
The specific monomer having H1x imparts positive chargeability and negative chargeability to the polymer, respectively, so when a polymer containing these monomers is used as a component, it is necessary to produce a positively chargeable toner or a negatively chargeable toner.

It is not necessary to add charge control agents such as nigrosine dyes, azo compounds and metal salicylate complexes.

The fluidity improver imparts high fluidity to the toner, facilitates continuous toner supply, and forms visible images of good quality.As the fluidity improver, hydrophobicized silica powder is used as a fluidity improver. Optimal. Such hydrophobic silica powder is a fine powder of silicon dioxide in which one surface silicon atom is a silanol group, such as octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, 4-isopropylphenyltrichlorosilane, 4-tart- Butylphenyltrichlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane.

Didodecyl dichlorosilane, 4-tart-butylphenyl octyl dichlorosilane, dioctyl dichlorosilane, didecenyl dichlorosilane, dinonenyl dichlorosilane, di-2-ethylhexyl dichlorosilane, di-3
, 3-dimethylpentyldichlorosilane, trimethylchlorosilane, trihexylchlorosilane, trioctylchlorosilane.

By reacting with a compound such as tridecylchlorosilane, dioctylchlorosilane, octyldimethylchlorosilane, or 4-impropylphenyldiethylchlorosilane, a hydrophobic group is bonded to the surface silicon atoms of silicon dioxide particles via oxygen atoms. It is something that

These hydrophobic silica powders have an average particle size of 1vμm.
It is preferably within the range of ~1100u.

In particular, it is preferably between 2'p m and 50 μm, 1
If it is less than mμm, the powder tends to scatter and is difficult to handle, and if it exceeds 100μm, the photoreceptor is likely to be damaged.

Such hydrophobic silica powders include Aerosil R972,
Silica D-17, R812, RA200H.

It is commercially available under trade names such as RX-C (manufactured by Nippon Aerosil Co., Ltd.) and Tallanox 500 (manufactured by Tulco).

Although a toner may be manufactured by blending the hydrophobic silica powder as described above with other toner materials, it is preferable to manufacture the toner and then add the hydrophobic silica powder.

When adding hydrophobic silica powder, hydrophobic silica powder is
0.0 for toner powder without hydrophobic silica powder
It is preferably added in an amount of 1 to 15% by weight, especially 0.
The amount added is preferably 1 to 10% by weight. This addition amount is 0.
If the amount is less than 01% by weight, the effect of improving fluidity is difficult to appear, and even if it is added in excess of 15% by weight, the effect will not increase that much.

The cleaning performance improver prevents the so-called filming phenomenon, in which a portion of the toner components adheres to the photoreceptor or carrier surface, and plays the role of always forming clear visible images without capri, even after long-term continuous use. .

Cleanability improvers include metal salts of saturated or unsaturated fatty acids, such as maleic acid, stearic acid, oleic acid, valmitic acid, and caproic acid.

Linoleic acid, ricinoleic acid or ricylic acid with zinc, magnesium, calcium, cadmium.

Fine particles of salts with lead, iron, nickel, cobalt, steel or aluminum or other resins mentioned above may be mentioned, and zinc stearate, calcium stearate, magnesium stearate or resin particles of 1 to 10 μm are particularly preferred.

When a cleaning performance improver is used, it is particularly preferable to add the cleaning performance improvement agent in the same manner as the hydrophobic silica powder described above. % by weight, especially 0.1-1
It is preferable to add 0% by weight. If it is less than 0.01% by weight, the effect of improving cleaning performance is difficult to appear. However,
Addition of more than 25% by weight does not increase the effect.

Generally, toner images are fixed on image supports by heat fixing methods, and these heat fixing methods include non-contact heat fixing methods such as oven fixing, and contact heating methods such as heated roll fixing. However, the contact heat fixing method has high thermal efficiency;
Equipment can be made smaller.

It has advantages such as low power consumption. However, in the contact heat fixing method, when the image support carrying the toner image passes through the heat roll, part of the toner image is transferred to the heat roll, and after the heat roll has made one revolution, the transferred toner image is transferred to the image support. The so-called offset, in which the particles are re-transferred and contaminated, is likely to occur.

The anti-offset agent does not cause offset even in the hot roll fixing method and plays a role in forming high-quality images.

Anti-offset agents include ethylene, propylene, butene, pentene, hexene, and heptene.

octene, nonene, decene, 3-methyl-1-butene,
Polymers of olefin monomers such as 3-methyl-2-pentene and 3-propyl-5-methyl-2-hexene, or copolymers of the above-mentioned olefin monomers with acrylic acid, methacrylic acid, vinyl acetate, etc., stearin Lower alcohol esters of fatty acids such as butyl stearate and propyl stearate, casta wax (manufactured by Ito Oil Co., Ltd.),
Polyhydric alcohol esters of fatty acids such as diamond wax (manufactured by Shin Nihon Rika Co., Ltd.), palm acetic acid (manufactured by Nippon Oil & Fats Co., Ltd.), Hoechst wax E, Hoechst wax-OP (manufactured by Hoechst Akchengesellschaft), carnauba wax Higher alcohol esters of fatty acids such as
Bisamide Plast Flow (manufactured by Nitto Chemical Industry Co., Ltd.)
, Amide 6L, 7S and 6H (manufactured by Yoken Fine Chemical Co., Ltd.), alkylene bis fatty acid amide compounds such as Hoechst Wax C (Hoechst Akchengesellschaft 11), zinc stearate, calcium stearate, magnesium stearate, stearic acid. Barium, copper stearate, aluminum stearate, zinc oleate, magnesium oleate, zinc caprylate,
Fatty acid metal salts such as magnesium caprylate, zinc linoleate, calcium linoleate, etc., Nirapol NBR, 20
57S.

Diene resins with a weight average molecular weight of 50,000 or more, such as 2007J and BR1220, hydroxyl group-containing vinyl resins,
Examples include carboxyl group-containing vinyl resins. The offset inhibitor is contained in the toner in an amount of 0.1 to 50% by weight, especially 1 to 3% by weight.
Preferably it is added in an amount of 0% by weight. If it is less than 0.1% by weight, the effect of preventing offset is difficult to appear, and if it is less than 50% by weight.
If it is added in excess of this amount, the fixing properties will deteriorate.

In the present invention, the other resins and various additives mentioned above may be added alone or in combination.

The above-mentioned materials can be mixed, for example, by the following method to produce a toner for developing electrostatic images.

The weighed materials are premixed using a W cone, (1) blender, Henschel mixer, etc., and then kneaded using a pressure kneader, Banbury mixer 1 hot roll, extruder, etc. at a temperature at which the resin melts. After cooling, the mixture is coarsely pulverized using a feather mill, pin mill, pulverizer, hammer mill, etc., and then sieved using an Accucut or Alpine classifier to adjust the particle size to preferably 5 to 30 μm.

When the toner of the present invention is used in a two-component manner, the toner and carrier are combined to prepare a developer.

Examples of carriers include flat, sponge-shaped, coin-shaped, pseudospherical, or spherical iron powder, the surface of the iron powder coated with thermoplastic or thermosetting resin such as Teflon, silicone, vinyl, or the like, or the present invention. It is preferable to use a one-component toner with a particle size, electrical resistance value,
Specific surface area etc. are adjusted.

The toner concentration of a two-component developer generally depends on the specific surface area of the carrier, and when the carrier used is amorphous or has a fine particle size, it is 1 to 3 to 10% by weight when the carrier is spherical or has a coarse particle size. Preferably it is 5% by weight.

The toner of the present invention can be applied to various known developing methods.

Further, the toner according to the present invention can be used in various fixing methods.

For example, it can be used in so-called oil-less and oil-coated heated roll methods, xenon flash irradiation methods, oven methods, pressure fixing methods, and the like.

Further, the toner of the present invention can be used in various cleaning methods such as the so-called fur brush method and blade method.

[Effect]

The electrostatic image developing toner of the present invention exhibits excellent adhesion resistance to soft vinyl chloride polymers due to the imide group-containing monomer represented by the general formula (R) contained in the binder resin. , fully satisfies the print density, fog resistance and blocking resistance required for toner.

〔Example〕

Next, examples of the present invention will be shown.

(I) Production of copolymers A-1 to A-6 and B-1 to B-2 Partially saponified polyvinyl alcohol (Denka Poval W
-24, manufactured by Denki Kagaku Kogyo Co., Ltd., in a reaction vessel containing 2000 parts by weight of an aqueous dispersion medium in which 3 parts by weight of the vinyl monomer having the composition shown in Table 1 and the polymerization initiator shown in Table 1 were added. Add in the amount shown in Table 1, under nitrogen stream, 80
The reaction was carried out at ~90°C for 10 hours. After cooling, the mixture was filtered and dried with hot air to obtain a copolymer.

(2) Production of toners of Examples 1 to 6 and Comparative Examples 1 to 2 After dry-mixing each component of the composition shown in Table 2,
The mixture was melt-kneaded at 160°C using a shaft kneader. After cooling, finely pulverize with jet air to obtain particles in the particle size range [5-25μm].
I got the toner.

(3) Evaluation toner of 3% by weight, iron oxide powder having an apparent density of 4 to 4.5 g/d, an electrical resistance value of 10δ to 108Ω, and a particle size content of 44 to 177 μm of 90% by weight or more. career 97
Using this developer, a selenium drum rotating at a circumferential speed of about 30 am/sec is uniformly positively charged with a corona voltage of +4 kV, and then information is generated using a He-Ne laser. was written and reversely developed using a magnetic brush method. Next, the toner image carried on the recording paper was fixed with a Teflon roll having a surface temperature of 170±5°C.

Subsequently, an evaluation test was conducted on the toner and the results are summarized in Table 2.

The test method is shown below.

(i) Print density and fog density Tokyo Juishiki Co., Ltd.! The measurement was performed using a reflection densitometer TC-6DS model No. 1.

(it) Adhesion resistance to soft vinyl chloride polymer After adhering the printed matter to a soft vinyl chloride polymer containing 30% by weight of dioctyl phthalate at a temperature of 40°C and a pressure of 5 gf/ad for 200 hours, the printed matter was After peeling off, the degree of print loss was judged based on the following criteria.

3: No printing defects at all 2: Printing defects are partially observed, but the printing is legible 1: There is a large amount of printing defects, and the printing is legible. After standing under %RH for 18 hours.
[Effects of the Invention] As is clear from the above results, the toner for developing electrostatic images of the present invention has excellent adhesion resistance to soft vinyl chloride polymers. It has good image density, fog resistance, and blocking resistance necessary for a practical toner.

11゛( Agent Patent Attorney Kunihiko Wakabayashi ・) (, department store 1 p) 1

Claims (1)

[Scope of Claims] 1. A toner for developing electrostatic images comprising, as a binder resin, a polymer having as a constituent component an imide group-containing vinyl monomer represented by the following general formula (I). General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ [However, in general formula (I), R_1 is hydrogen or a methyl group, and R_2 is an alkylene group having 1 to 6 carbon atoms or an alicyclic or aromatic ring. The divalent organic group and R_3 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R_4, R_5, R_6, R_7 , R_8 and R_9 are hydrogen, an alkyl group having 1 to 3 carbon atoms, halogen,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, -NO_2, -SO_3H or -N
_3, which may be the same or different, and R
_1_0, R_1_1 and R_1_2 are hydrogen or an alkyl group having 1 to 5 carbon atoms, and may be the same or different.