JPS63169663A - 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-R11 are each H atom or 1-3 C alkyl, -NO2 or -SO3H group, etc.), R3 is at least one of -NO2- and -SO3H groups, 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. 44-1.6118) and styrene-butyl methacrylate copolymer resin. Toner (Tokuko Showa 56-1
Toners using vinyl resins such as (Japanese Patent Application Laid-Open No. 1143), toners using bisphenol-type epoxy resins obtained by reacting bisphenol and epichlorohydrin (Japanese Patent Application Laid-open No. 1983-96354), glycols having a bisphenol skeleton and polybasic Toner using polyester resin obtained by reacting with acid (Japanese Patent Publication No. 52-25420)
However, compared to other resins, vinyl resins can be controlled in a wide range of resin properties such as molecular weight, glass transition point, and melt viscosity, which is extremely advantageous in terms of toner design. 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.

It is an object of the present invention to solve the above-mentioned problems and provide a toner that has the necessary image density, fog resistance, and blocking resistance as a toner and does not adhere to a soft vinyl chloride polymer sheet.

[Means for solving problems]

The present invention relates to an electrostatic image developing toner containing a polymer having as a constituent component a vinyl monomer represented by the following general formula (I) as a binder resin.

General formula (I) However, in general formula (I), R1 is hydrogen or a methyl group.

R2 is an alkylene group having 1 to 6 carbon atoms or a divalent organic group having an alicyclic ring or an aromatic ring, and Rδ is t', 7
KIIKIOKHKlo Kθni 8
and R41R5# Rap R7, Ra+ Re,
Rto and R11 are hydrogen and an alkyl group having 1 to 3 carbon atoms.

-No! , 5OaH or -N3, RaL! , h thousand angles, at least I J -Noz, -8OsH or Ns#, and the temperature is CHz r CH3 CH-.

Hs Specific examples of divalent organic groups having an alicyclic ring or an aromatic ring among 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+−0−, or −(alkylene group having 1 to 6 carbon atoms←0−+alkylene group having 1 to 6 carbon atoms←).

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

(A) A resin containing one type of polymer, two or more types of copolymers, or a mixture thereof among the specific polymers 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 above resin (A) and/or the above (B) resin and another resin.

The specific monomers of the present invention are blended so that at least one of them is contained in the binder as a component, preferably in an amount of 590 Bacillus, more preferably 20 to 70% by weight, particularly preferably 25 to 60% by weight. . If the specific monomer of the present invention is incorporated in an insufficient amount, the adhesion resistance of the toner to the vinyl chloride polymer will be insufficient, and if it is too large, the properties as a toner tend to be insufficient.

The specific monomer of the present invention can be produced by, for example, imidizing an acid anhydride having a corresponding cyclic structure with an amine alcohol having an achiline group having 1 to 6 carbon atoms or an alicyclic ring or an aromatic ring, and then producing acrylic or methacrylic acid. Alternatively, it can be produced by adding these lower alkyl esters and carrying out an esterification reaction or transesterification reaction, and representative monomers include the following monomers.

Other addition-polymerizable monomers that can be copolymerized with the above-mentioned specific monomers may be used as necessary, but they are preferably blended in an amount of 10 to 95% by weight based on the total vinyl monomers that are copolymerization components. . Specific examples of other addition polymerizable monomers are shown below.

Styrene or methoxystyrene, butoxystyrene, α
- Styrene derivatives such as methylstyrene, p-methylstyrene, p-t-butylstyrene, 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, methoxy methacrylate Ethyl, 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, Methacrylonitrile, 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 , methoxydiethylene glycol acrylate,
Ethoxydiethylene glycol acrylate, butoxyethylene glycol acrylate, phthoxytriethylene 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-2-pyrrolidone acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy acrylate -3-phenyloxypropyl, glycidyl acrylate, acrylonitrile, acrylamide, N-methylolacrylamide.

One per molecule of diacetone acrylamide, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, ethyl acrylate morpholine, vinylpyridine, diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, octyl fumarate, etc. Vinyl monomers having a vinyl group, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid 1, such as ethylene glycol dimethacrylate, 1,3-butylene gelicol dimethacrylate, 1.
4-butanediol methacrylate, 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 isocyanate Nurate, tris(methacryloyloxyethyl)in cyanurate, ethylene glycol diacrylate, 1.3-butylene glycol diacrylate, 1゜4-butanediol diacrylate, 1.5-bentanediol diacrylate, 1,6-hexanediol diacrylate,
Neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimecrylate, polyethylene glycol diacrylate.

Tripropylene diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, bis(methacryloyloxyethyl) Hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)in cyanurate,
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 preferable vinyl monomers having one vinyl group 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 of divinylbenzene.

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

These constitute 0 to 20 weight percent of 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 S-turbid polymerization.

In the polymerization of these seven polymers, the polymerization initiators used are 2,2'-azobisisobutyronitrile, 2.
Azo compounds such as 2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), t-butylperoxy(2-ethylhexano ate), peroxyethyl such as t-butylperoxyisobutyrate, 1,1-
Bis(t-butylperoxy)3. Peroxyketals such as 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. These are preferably used in an amount of 0.1 to 15% by weight based on the total 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 weight percent based on the total monomers.

The binder resin of the present invention has a glass transition temperature of 40 to 10
The temperature is preferably 0°C, particularly preferably 50 to 90°C. If it 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 be reduced.

The toner of the present invention contains a colorant and/or magnetic powder. Examples of the colorant include carbon black, acetylene black, and lamp black.

Black colorants such as graphite, iron black, aniline black, cyanine black, yellow lead, cadmium yellow, yellow iron oxide,
Yellow colorants such as titanium yellow, naphthol yellow, Hansa yellow, pigment yellow, benzidine yellow, permanent yellow, quinoline yellow lake, anthrapyrimidine yellow, and orange colors such as permanent orange, palcan fast orange, benzidine orange, and indanthrene brilliant orange. colorant, iron oxide,
Brown colorants such as amber and permanent brown, Red Garla, antimony vermilion, permanent red, fire red, and brilliant carmine.

Light Fast Red Toner, Permanent Carmine,
Red colorants such as Pyrazolone Red, Bordeaux, Heliobordeaux, Rhodamine Lake, Thioindigo Red, Thioindigo Maroon, purple colorants such as Cobalt Purple, Fast Violet, Dioxazine Violet, Gobalt Blue, Cerulean Blue, Metal-free Phthalocyanine Blue, Phthalocyanine 7 coloring agents such as blue, indanthremble, indigo, chrome green, cobalt green, green gold, phthalocyanine green,
Green colorants such as polychrome bromine copper phthalocyanine, and when heat decomposition resistance is required, carbon black, iron black, cyanine black, yellow iron oxide, titanium yellow, Hansa yellow, benzidine yellow, permanent orange, Palkane are used. Fast orange, iron oxide, red iron oxide,
- Fire Red, Light Fast Red Toner, Permanent Carmine, Pyrazolone Red, Bordeaux.

Thioindigo maroon, cobalt purple, cobalt blue,
Cerulean blue, phthalocyanine blue.

Particularly preferred are cobalt green, 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. If it is less than 1% by weight, the coloring is insufficient;
If the amount exceeds % 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, a Cannon light absorber that absorbs light of 800 to 11000 nm, which is the maximum intensity of Cannon light, is contained in the toner. 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 Cannon light absorbers include polymethine compounds, azulenium salts, CrFz, CrCQ2゜FeCQs,
Fe5Oa・7H20+ M o CQs.

N1Cl2z, VCQs, VCQa, VFa,
VSO4.7l-1zo and the like are preferably blended in an amount of 1 to 20% by weight, particularly preferably 3 to 15% by weight, in the total toner components. If it is less than 1% by weight, absorption of xenon light will be insufficient and the fixing strength will tend to decrease; if it exceeds 20% by weight, higher effects cannot be expected, and the frequency of occurrence of adverse effects such as a decrease in charging performance tends to increase. There is.

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, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese,
Alloys and mixtures of metals such as selenium, titanium, tungsten, vanadium, aluminum oxide, iron oxide,
Metal compounds containing metal oxides such as oxidized steel, nickel oxide, zinc oxide 1M titanium, magnesium oxide, chromium oxide, or alloys that exhibit ferromagnetism when heat treated, such as manganese-copper-aluminum, manganese-copper- A voice car alloy such as 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-mentioned colorant may be further added, and the amount thereof is preferably 10ffi% or less in the toner.

Further, the toner according to 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 acrylic 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 incorporated in the total toner components in an amount of 0 to 30% by weight.

Charge control agents include nigrosine dye, fatty acid-modified nigrosine dye, tetraalkylammonium halide, and trialkylammonium halide.

(In the formula, X' represents a halogen, R is an alkylene group having 1 to 3 carbon atoms, and n represents 0 or 1), a polyamine compound having a structural unit, R' -CH2-C(CN)□ ( A nitrile compound having a structural unit (R1' in the formula represents hydrogen or an alkyl group having 1 to 3 carbon atoms) (in the formula Rz
' represents an alkoxy group or phenoxy group, Ra' represents hydrogen, an alkoxy group or a phenoxy group),
Monoalkyltin oxide, dialkyltin oxide, monoaryltin oxide, formula: In the formula, Ra'*Re', Re' and R7' have hydrogen, an argyl group having 1 to 9 carbon atoms, or an aromatic ring or a cyclohexene ring. Represents a substituent, where two or more groups simultaneously represent hydrogen; Me represents Cr, Co or Fe; M
represents hydrogen, potassium, sodium or fatty acid ammonium).

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

However, among the specific monomers of the present invention, -NO
Specific monomers having 2 or -3O811 impart negative chargeability to the polymer, so when producing a negatively chargeable toner using these specific monomers, negative chargeability control agents such as azo compounds and salicylic acid metal complexes are used. It is not necessary to add agents.

The flow agent serves to impart high fluidity to the toner and facilitate continuous feeding of the toner to form a visible image of good quality. Hydrophobic silica powder is most suitable as the fluidity improver. Such hydrophobic silica powder is made by using fine powder of silicon dioxide whose surface silicon atoms are silanol groups, such as octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, 4-isopropylphenyltrichlorosilane, 4-tart- Butylphenyltrichlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, didodecyldichlorosilane, dioctyldichlorosilane, didodecyldichlorosilane, 4-tart-butylphenyloctyldichlorosilane, dioctyldichlorosilane, dibuceni dichlorosilane, dioctylchlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trimethylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tridecylchlorosilane, dioctyl By reacting with compounds such as chlorosilane, octyldimethylchlorosilane, 4-isoprobylfuninyldiethylchlorosilane, etc.
Hydrophobic groups are bonded to surface silicon atoms of silicon dioxide particles via oxygen atoms.

These hydrophobic silica powders have an average particle size of 3 to 1
It is preferably within the range of 00 μm, especially 2←Tsuru to 5
Preferably, it is at 0 μm. If it is less than 1θ (μ Q), the powder tends to scatter and is difficult to handle, and if it exceeds 100 μm, it is likely to damage the photoreceptor.

Such hydrophobic silica powders include Aerosil R972,
Silica D-17, R812, RA20011゜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
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 0.01% 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 accordingly.

The cleaning performance improver prevents the so-called filming phenomenon in which a part of the toner components adhere to the photoreceptor or carrier surface, and plays the role of forming clear visible images without fogging 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, palmitic 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, copper 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 that the cleaning performance improvement agent is added in the same manner as the hydrophobic silica powder described above. These are 0.01 to 25% by weight, especially 0.1 to 1% by weight, based on the toner powder not containing the additive.
Preferably, 0% by weight is added. If it is less than 0.01% by weight, the effect of improving cleaning performance is difficult to appear.
Addition of more than 5% 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;
There are advantages such as the device can be made smaller and consume less power. 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 Am Oil Co., Ltd.),
Polyhydric alcohol esters of fatty acids such as diamond wax (manufactured by Shin Nihon Rika Co., Ltd.), palm acetate (manufactured by Nippon Oil & Fats Co., Ltd.), Hoechstwax E, Hoechstwax-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 (manufactured by Hoechst Akchengesellschaft), zinc stearate, calcium stearate, magnesium stearate, stearic acid. barium,
Fatty acid metal salts such as copper stearate, aluminum stearate, zinc oleate, magnesium oleate, zinc caprylate, magnesium caprylate, zinc linoleate, calcium linoleate, Nirapol NBR, 205
7S.

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.
It is preferable to add it 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 50% by weight
If added in excess of 6, the fixing properties will deteriorate.6 In the present invention, the other resins and various additives mentioned above may be added alone or may be used 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 2 hot roll, extruder, etc. at a temperature at which the resin melts. After cooling, it is coarsely ground using a feather mill, pin mill, pulverizer, hammer mill, etc. Next, the particles are sieved using an Accucut or Alpine classifier to adjust the particle size to preferably 5 to 3 Qm.

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 component toner that is
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 is 3 to 10% by weight when the carrier used is amorphous or has a fine particle size, and 1 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 fixed using one of various fixing methods.

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

Furthermore, the toner according to the invention can be used in a variety of cleaning methods, such as the so-called fur brush method, blade method, and the like.

[Effect]

The toner for developing electrostatic images according to the present invention exhibits excellent adhesion resistance to soft vinyl chloride polymers due to the imide group-containing monomer represented by the general formula (I) contained in the binder resin. In addition, it satisfies the print density, fog resistance, and blocking resistance required for toners.

〔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 (Denkapoval W-
24, Denki Kagaku Kogyo Co., Ltd.! l) To a reaction vessel containing 2000 parts by weight of an aqueous dispersion medium in which 3 parts by weight was dissolved, 1000 parts by weight of vinyl monomer having the composition shown in Table 1 and the polymerization initiator shown in Table 1 were added in the amounts shown in Table 1, and nitrogen Under air flow, 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 melted and mixed at 160°C using a shaft kneader. After cooling, finely pulverize with jet air to a particle size range of 5 to 25 μm.
I got the toner.

Margin below (3) Evaluation toner 3% by weight, apparent density 4 to 4.5 g/d,
Iron oxide powder carrier 9 having an electrical resistance value of 10B to 109Ω and a content of particle size of 44 to 177 μm is 90% by weight or more
Using this developer, a selenium drum rotating at a circumferential speed of about 30 cm/sec was uniformly positively charged with a corona voltage of +4 kV, and then information was transferred using an Hθ-Ne laser. After writing and reversal development using a magnetic brush method, the toner image carried on the recording paper was heated to a surface temperature of 1.
It was fixed with a Teflon roll at 70±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 were measured using a reflection densitometer model TC-6DS manufactured by Tokyo Juishiki Co., Ltd.

(it) Adhesion resistance to soft vinyl chloride polymer The printed material was applied to a soft vinyl chloride polymer containing 30% by weight of dioctyl phthalate at a temperature of 40°C, a pressure of 5 gf/cd, and a time of 200.
After adhesion for a period of time, the printed matter was peeled off and the degree of print loss was judged according to the following criteria.

3: No printing defects at all 2: Printing defects are partially observed, but the printing is legible 1: Large printing defects make it difficult to read the printing (iii) Anti-blocking toner at 50°C, 60% After standing under RH for 18 hours,
Check for the presence of lumps.

Margin below [Effects of the Invention] As is clear from the above results, the toner for developing electrostatic images according to the present invention exhibits excellent adhesion resistance to soft vinyl chloride polymers, and is necessary as a practical toner. Good,
It has good image density, fog resistance and blocking resistance.

　　　　　　　　　,7--,.

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, an alicyclic ring, or an aromatic ring. R_3 is a divalent organic group having ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ 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, R_9, R
_1_0 and R_1_1 are hydrogen, an alkyl group having 1 to 3 carbon atoms, -NO_2, -SO_3H or -N_3, and R
_3 is at least one of -NO_2, -SO_3H or -N_
3, and R_1_2 is -CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc.▼, -CH_2-CH_2-, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ]