JPS63234263A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To improve the fixing property of the titled toner, and to prevent the titled toner from the trouble caused by contacting with a soft polyvinyl chloride polymer by using a polymer contg. a specified polymerizable monomer and a specified carboxylic acid ester as an essential component for the titled toner. CONSTITUTION:The polymer contg. the additional polymerizable monomer (a) contg. hydroxylic group and the unsatd. aliphatic polycarboxylic acid ester (b) as the essential component is used for the binding resin of the titled toner. And, the polymer is preferably formed by polymerizing 13-45wt.% of 2- hydroxypropyl methacrylate as the component (a), and 5-30wt.% of dibutyl fumarate as the component (b), 25-82wt.% of styrene and 0-20wt.% of an another additional polymerizable monomer such as (meth)acrylate. And, the compounding ratio of said polymer in the binding resin is preferably >=50wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic recording, etc.

(Prior art) In electrophotography, electrostatic recording, etc., amorphous selenium,
A photoconductive material such as OPC is used as a photoreceptor, and after forming an electrostatic latent layer on the photoreceptor by various means, the latent area or non-latent image area is injected with positively or negatively charged toner. The toner that has formed a visible image is then transferred to another transfer material such as paper or Mylar film, and is fixed by a method such as a heat pressure method, a xenon flash irradiation method, or a pressure method, and is visualized. .

Devices that apply electrophotography, electrostatic recording, etc. include printers, facsimile machines, and copying machines.

In particular, its use in fields such as computer information output and information transmission is remarkable.

Polystyrene is used for toner that visualizes information.

Toner using vinyl resin such as styrene-acrylic copolymer (Japanese Patent Publication No. 44-16118, Japanese Patent Publication No. 56-1
1143), a toner using a bisphenol type epoxy resin (Japanese Patent Application Laid-open No. 57-96354), a toner using a polyester resin (Japanese Patent Publication No. 52-25420), etc. Vinyl resins have a wide range of control over resin properties such as molecular weight, melt viscosity, and glass transition point, making it easy to design a variety of toners; therefore, most toners are made using vinyl resins. There is.

(Problem that the invention attempts to solve) Printers, fax machines, copiers, etc. are becoming faster.

There is a trend towards miniaturization and energy saving, and in order to respond to these trends, it is not enough to improve only the machine side; it is also essential to improve the toner side.

That is, toners are required to be fixed with lower energy than conventional ones.

Also, printers, fax machines, etc.? As the usefulness of J-photographers, etc. is recognized, their fields of use are expanding.
Recently, it has come to the point where it processes important information such as insurance cards and resident records. In order to protect these important documents from damage and contamination.

Because it is housed in a case made of soft vinyl chloride polymer.

Toners are required to not cause any damage upon contact with soft vinyl chloride polymers.

Generally, in order to improve the fixability of a toner, a method is used to lower the melt viscosity of a polymer that makes up the majority of toner components.

In other words, the viscosity during melting is lowered by increasing the blending ratio of long-chain alkyl esters of acrylic acid or methacrylic acid such as butyl acrylate and butyl methacrylate, making the polymer softer, or by designing the molecular weight of one polymer to be smaller. .

JP-A No. 60-164754 and JP-A No. 60-60 as toners that do not cause damage even when they come into contact with soft vinyl chloride polymers.
-225168 publication etc. are known. However, when trying to impart a high level of fixing ability to the toner by the above-described method, there was a problem in that the resistance to the soft vinyl chloride polymer decreased, although the fixing ability did not improve much.

In addition, as a toner with good fixing properties, JP-A-60-150
No. 056 has been published. but.

The toner disclosed in this publication had poor resistance to soft vinyl chloride polymers, and moreover, did not exhibit a high level of fixing performance.

As described above, there are no conventional toners that have excellent fixing properties and do not cause odor problems when they come into contact with soft vinyl chloride polymers, and there is a strong need for an early solution to this problem.

An object of the present invention is to solve the above-mentioned problems and provide a toner that has excellent fixing properties and does not cause trouble when in contact with a soft vinyl chloride polymer, and also provides a toner that has good print density and capri density. With the goal.

(Another Means to Solve the Problems) The present invention provides a static resin comprising a polymer containing a hydroxyl group-containing addition-polymerizable monomer and an unsaturated aliphatic polycarboxylic acid ester as a binder resin. The present invention relates to a toner for developing a charge image.

The present invention will be explained in detail below.

In the present invention, hydroxyl group-containing addition polymerizable monomers include 2-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate.

3-hydroxybutyl methacrylate, methacrylic acid
2-hydroxy-3-phenyloxypropyl, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, etc. compounds containing a hydroxyl group bonded to a class carbon atom and 2-hydroxyethyl methacrylate,
Hydroxyl bonded to a primary carbon atom such as 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc. There are compounds containing groups. Among these, compounds containing a hydroxyl group bonded to a secondary carbon atom are preferred from the viewpoint of blocking resistance and moisture absorption resistance under high temperature and high humidity conditions of 40°C and 60% RH or higher, and in particular, compounds containing hydroxyl groups bonded to secondary carbon atoms are preferred. -Hydroxypropyl is preferred.

The unsaturated aliphatic polycarboxylic acid ester according to the present invention has 1
A compound represented by the following general formula (1) is preferred.

FL3 R4 [In the formula, R+, Rze Rs and R4 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or a hydroxyl group.

CORs or -Ra CORs (where R6
is an alkyl group having 2 to 18 carbon atoms.

(R6 is an alkyl group having 1 to 6 carbon atoms) has at least two ester bonds in each 9 molecule] Compounds other than these tend to have poor fixing properties.

A specific example is shown below.

CzHs CzHs , C4t(s C4Hs
.

CllHI3 C6HI3 + CI! H25
C12825+C15Hyy Cl8H37.

4H9 6HI3 ■ 8H13 〇=C Hs Among these, dibutyl fumarate is preferred because it exhibits particularly good fixing properties. Further, other addition polymerizable monomers include the following.

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, dicyclohentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone methacrylate , methacrylic nitrile, methacrylamide, N-methylol methacrylamide, methacrylic nitrile 4-)v,
2-Hydroquinoethyl methacrylate. Hydroxypropyl methacrylate.

Hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, diacetone acrylamide, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, acrylic acid Heptyl, octyl acrylate, nonyl acrylate, ethyl acrylate, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, Ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate.

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

Acrylamide, N-methylolacrylamide.

Vinyl monomers having one vinyl group in one molecule such as diacetone acrylamide, diethylaminoethyl methacrylate, 2-phthalimidoethyl methacrylate, morpholinoethyl acrylate, vinylpyridine, divinylbenzea, /jIr cole, etc. Reaction products with methacrylic acid or acrylic acid 1 For example, ethylene glycol diacrylate tacrylate 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 ,
Tris (methacryloyloxyethyl) phosphate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, tris (methacryloyloxyethyl) isocyanurate.

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 diacrylate, polyethylene glycol diacrylate, tripropylene diacrylate, hydroxypipalic acid neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpronotriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Acrylic V-), iJ acryloxyethyl phosphate.

Bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)isocyanurate, halfesterified product of glycidyl methacrylate and methacrylic acid or acrylic acid, nophesterified product of bisphenol type epoxy resin and methacrylic acid or acrylic acid, Examples include vinyl monomers having two or more vinyl groups in one molecule, such as glycidyl acrylate and methacrylic acid, or esterified products of acrylic acid.

Among these, preferred vinyl monomers having one vinyl group in one molecule include styrene, styrene derivatives, methacrylic esters, acrylic esters, and the like.

especially styrene, 1 to 5 carbon atoms in the alkyl group,
An alkyl ester of methacrylic acid or acrylic acid having the following is preferable. Preferred vinyl monomers having two or more vinyl groups in one molecule include divinylbenzene, dimethacrylate and diacrylate of methylene glycol having 2 to 6 carbon atoms, and the like.

In the present invention, one polymer includes 10 to 70 weight units, particularly 13 to 45 weight units of hydroxyl group-containing addition polymerizable monomers,
Unsaturated aliphatic polycarboxylic acid ester 3 to 35 double stitches,
Especially 5 to 30 double bond width and other addition polymerizable monomers θ~
87 weight range, especially one obtained by blending and polymerizing 25 to 82 weight range so that the total weight is about 100 is preferable.

If the weight of the hydroxyl group-containing addition-polymerizable monomer is less than 10% by weight, the toner tends to adhere to the soft vinyl chloride polymer, and if it exceeds 50% by weight, moisture absorption resistance and chargeability tend to decrease. .

In addition, unsaturated aliphatic polyhydric carbo/acid ester is 3 weight 1
If it is less than this, the fixing properties will be poor, the melt viscosity of the dipolymer will be low, and the resistance to the dying soft vinyl chloride polymer will tend to be insufficient. On the other hand, if it exceeds 3,589 degrees, the toner tends to have insufficient blocking resistance.

Incidentally, among the other addition polymerizable monomers, vinyl monomers having two or more vinyl groups in one molecule are preferably blended in a weight ratio of θ to 1. If it exceeds 1% by weight, fixing properties tend to be poor.

The polymer obtained by combining these monomers satisfies various toner performances such as print density and fog density, so 1.
Melt viscosity at 40°C is 5 x 102 to 5 x 10'
It is preferable to adjust it to poise.

2-Hydroxypropyl methacrylate 13 to 45 weight range, dibutyl fumarate 5 to 30 weight range, and styrene 25 to 30 weight range because they meet various toner performance requirements and have excellent fixing properties and resistance to soft vinyl chloride polymers. It is preferable to mix and polymerize components consisting of 82% by weight and other addition polymerizable monomers θ to 20% by weight so that the total amount exceeds 100% by weight.

In the polymerization of these monomers, the polymerization initiator used is 2,2'-azobisisobutyronitrile.

Azo compounds such as 2.2'-77"bis-(2,4-dimethylvaleronitrile), 2.2'-azobis(4-methoxy-λ4-dimethylvaleronitrile), t-7'thylperoxy(2-ethyl hexanoate).

Peroxy esters such as t-butylperoxyisobutyrate, 1,1-bis(t-7” tylperoxy)a
&5-trimethylcyclohexane, 1.1-bis(1-
butyl peroxy) cyclohexane and other peroxyketals, dicumyl peroxide.

2.5-dimethyl-45-di(t-butylperoxy)
There are dialkyl peroxides such as 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 vinyl monomers.

As the polymerization method, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used.

In the present invention, it is preferable that 1'l@ or two or more of the above polymers are contained in the binder resin in an amount of 50 Ji or more. If the proportion of the polymer is too low.

It becomes difficult to obtain sufficient fixing properties and sufficient resistance against soft vinyl chloride polymers. Binder resin components other than the polymer include styrene resin, styrene-acrylic resin,
Silicone resin, polyester carbonate resin, Kinshin resin. Epoxy resin.

Phenolic resin, diene resin, coumaron resin.

Known resins such as amide resins, amino resins, and urethane resins can be used.

The toner according to the present invention contains a colorant and/or magnetic powder. The colorant is carbon black.

Black colorants such as acetylene black, lamp black, graphite, iron black, aniline black, cyanine black, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, naphthol yellow, Hansa yellow, pigment yellow, benzidine yellow.

Permanent yellow, quinoline yellow lake.

Yellow coloring agents such as Acisrapyrimidine Yellow, Permanent Orange, Palcan Fast Orange.

Orange coloring agents such as benzidine orange, indanthrene priliant orange, iron oxide, amber.

Brown coloring agent such as Permanent Brown, red iron.

Red coloring agents such as antimony, hermanent red, fire red, brilliant carmine, light fast red toner, nokumanent carmine, pyrazolone red, Bordeaux, heliobordeaux, rhodamine lake, thioindigo red, thioindigo red, Violet colorants such as cobalt purple, fast violet, dioxazine violet, blue colorants such as gobalt blue, cerulean blue, metal-free phthalocyanine blue, phthalocyanine blue, indanthremble, indigo, chrome green, cobalt green, green gold,
There are green colorants such as phthalocyanine clean and polychrome bromine copper phthalocyanine, and when heat decomposition resistance is required, carbon black, iron black, cyanine black,
Yellow iron oxide.

f Tough 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,
Particularly preferred are cobalt purple, cobalt flu, cerulean blue, phthalocyanine blue, cobalt green, phthalocyanine green, polychrome bromine copper phthalocyanine, and the like. These colorants are blended in 1 to 60 parts by weight in the total toner components.

If it is less than 1 weight width, the coloring is insufficient, and if it exceeds 60 weight width, the fixing properties of the toner tend to deteriorate.

Note that when the toner according to the present invention is applied to a fixing method using a xenon flash irradiation method, the toner contains a xenon light absorber that can absorb light with a wavelength of 800 to 1000 nm, which is the maximum intensity of xenon light. Some of these, such as carbon black, triazo compounds, phthalocyanine compounds, and nattocyanine compounds, have the ability to color themselves, so when using such xenon light absorbers, it is necessary to add other In some cases, it may not be necessary to add colorants. “Other xenon light absorbers include polymethine compounds, azulenium tji, CrFz, CuC1!
z+Fe C1! l* Fe 804 ・7 HzO*
MoCI! s s N i CZ2 r VC! ! 3
@VC1a, VFs, VSO4・7 H2O, etc.;h le. Choleraba.

1-20i in all toner ingredients! It is preferable to mix 1%, and preferably 3 to 15% by weight in 411F. 1 layer ts
If the weight is less than 20%, the absorption of xenon light will be insufficient and the fixing strength will tend to decrease, even if the weight exceeds 20%.

Higher effects cannot be expected, and the frequency of occurrence of adverse effects such as a decrease in charging property 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, as well as aluminum and cobalt.

Steel, lead, magnesium, nickel, Q; zinc.

antimony, beryllium, bismuth, cadmium.

Alloys and mixtures of metals such as calcium, manganese, chlorine, titanium, tungsten, vanadium, metals such as aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide, magnesium oxide, chromium oxide Metal compounds containing oxides or alloys that exhibit ferromagnetism when heat treated.

For example, whisker alloys such as hamanganese-copper-aluminum, manganese-copper-tin, etc. can be used. ,
The particle size of the magnetic powder is preferably 10 μm or less.

In particular, the thickness is preferably 1 μm or less. These magnetic powders are contained in the toner in an amount of 30 to 70 liters by weight. When using magnetic powder, the above-mentioned coloring agent may be further added, and the amount thereof is preferably 10% by weight or less in the toner.

A charge control agent can be appropriately added to the toner according to the present invention. Charge control agents include nigrosine dye, fatty acid-modified nigrosine dye, resin-modified nigrosine dye, tetraalkylammonium halide, and trialkylammonium halide.

(In the formula, V represents 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.

(4) A nitrile compound having a structural unit of 〇H〇-〇(CN)- (in the formula, 〇 represents hydrogen or an alkyl group having 1 to 3 carbon atoms).

Formula (wherein, nail represents an alkoxy group or a phenoxy group a
RS represents hydrogen, an alkoxy group or a phenoxy group), monoalkyltin oxide, dialkyltin oxide, monoaryltin oxide.

Formula: (In the formula, R'4 s R'+ + R'6 and a/ represent hydrogen, an alkyl group having 1 to 9 carbon atoms, or a substituent having an aromatic ring or a cyclohexene ring, but 2 or more groups do not represent hydrogen at the same time + Me is Cr, co or F
9M represents hydrogen, potassium, sodium or ammonium fatty acid) Compound 1 formula: (wherein R'6 and R'9 represent an alkylene group having 1 to 9 carbon atoms, an aromatic ring or a cyclohexene ring) and Me and M represent the above-mentioned compound formula 1: (wherein T, Y and Z represent hydrogen, halogen, carboxyl group, hydroxyl group, nitro group, sulfone group or sulfonamide group) 9M and Me (represents the above), tetrathiafulvalene, alumina fine powder, etc. can be used, and are usually added in an amount of 0 to 20 parts by weight to the toner.

The toner according to the present invention may contain known additives such as a fluidity improver, a cleaning performance improver, and an anti-offset agent, if necessary.

Fluidity improvers provide toner with high fluidity.

It facilitates the continuous supply of toner and forms visible images of good quality. Hydrophobic silica powder is most suitable as the fluidity improver. Such hydrophobic silica powder is made by mixing fine powder of silicon dioxide, in which one surface silicon atom is a silanol group, with one part, for example, octyltrichlorosilane,
Decyltrichlorosilane, nonyltrichlorosilane, 4
-isopropylphenyltrichlorosilane, 4-t
ert-phthylphenyltrichlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dinonyldichlorosilane, didecyldichlorosilane.

Didodecyldichlorosilane, 4-tert-7
'Tylphenyloctyldichlorosilane, dioctyldichlorosilane, didecenyldichlorosilane, dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trimethylchlor Silane, trihexylchlorosilane, trioctylchlorosilane.

Tridecylchlorsilane. Dioctylchlorosilane, octyldimethylchlorosilane, 4-isopropylphenyldiethylchlorosilane, etc. (1) Hydrophobic groups were bonded to surface silicon atoms of silicon dioxide particles via oxygen atoms by reacting with the compound f'flJ. It is something.

These hydrophobic silica powders have an average particle size of 1 mμm.
It is preferably within the range of ~100 μm, particularly 2 mμ
It is preferably in the range of m to 50 μm.

If it is less than 1 mμm, the powder tends to scatter and is difficult to handle, and if it exceeds 100 μm, the photoreceptor is likely to be damaged.

Such hydrophobic silica powder is Aerosil R97L
Silica D-17, R812, R, A200H, RX-
C (manufactured by Nippon Aerosil ■) and Taranox 5
It is commercially available under trade names such as 00 (manufactured by Tulco).

The toner may be manufactured by blending the hydrophobic silica powder as described above with other toner materials.

In particular, it is preferred to manufacture the toner in part with toner materials excluding the hydrophobic silica powder, and then add the hydrophobic silica powder.

When adding hydrophobic silica powder, hydrophobic silica powder is
It is preferable to add it in an amount of 0 to 15% by weight relative to the toner not containing the hydrophobic silica powder.

In particular, the amount added is preferably 0.1 to 10 parts by weight.

Even if it is added in excess of 15% by weight, the effect will not increase accordingly.

A part of the toner component of the cleaning property improving agent adheres to the surface of the photoreceptor or carrier. It prevents the so-called filming phenomenon and always forms a clear visible image 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, palmitic acid, cabrozoic acid.

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

Lead e iron, salts with cobalt, copper or aluminum, or fine particles of other resins mentioned above,
Particularly preferred are zinc stearate, calcium stearate, magnesium stearate, or resin particles of 1 to 10 μm.

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.

It is preferable to add 0 to 25 parts by weight, especially 1 to 10 parts by weight, to the toner not containing the additive.

Adding more than 25% by weight does not increase the effect.

Generally, toner images are fixed on an image support by a heat fixing method, and these heat fixing methods include non-contact heat fixing methods such as open fixing, and contact heating methods such as hot roll fixing. However, the contact heat fixing method has high thermal efficiency9
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, phthene, pentene, hexene, and heptene.

octene, nonene, decene, 3-methyl-1-butene,
3-Methyl-2-pente7.3-7'rovir-5-7'
Polymers of olefin monomers such as tyl-2-hexene, copolymers of the above-mentioned olefin monomers with acrylic acid, methacrylic acid, vinyl acetate, etc., lower alcohol esters of fatty acids such as butyl stearate, propyl stearate, etc.

Polyhydric alcohol esters of fatty acids such as Casta Wax (manufactured by Ito Oil Co., Ltd.), Diamond Wax (manufactured by Shin Nippon Rika Co., Ltd.), Palm Acetate (manufactured by Nippon Oil & Fats Co., Ltd.), Hoechst Wax E, Hoechst Wax-OP (Hoechst Wax E, Hoechst Wax-OP (Hoechst Akchengesellschaft Co., Ltd.) manufactured by).

Higher alcohol esters of fatty acids such as carnauba wax, Bisur, Mitoplast Flow (Nitto Kagaku Kogyo Co., Ltd.), Amide 6L, 78 and 6H (Yoken Fine Chemicals (Kiki)), Hoechst Wax C (Hoechst Akchen Gesellschaft) Alkylene bis fatty acid amide compounds such as H[), zinc stearate, calcium stearate, magnesium stearate, barium stearate,
Copper stearate, aluminum stearate, zinc oleate, magnesium oleate, zinc caprylate, magnesium caprylate, zinc linoleate.

Fatty acid metal salts such as calcium linoleate, Nilaball N
Diene resins with a weight average molecular weight of 50,000 or more, such as BR, 20578, 2007J, and FSR1220.

There are hydroxyl group-containing vinyl resins, carboxyl group-containing vinyl resins, and the like. The off-cent prevention agent is 0 to 50 times heavy in the toner, 4! 1 to 30 weight j! It is preferable to add it in an amount of [. If it is added in excess of 50% by weight, the fixing properties tend to deteriorate.

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

A toner for developing an electrostatic image can be produced by mixing the above-mentioned materials, for example, by the following method.

The weighed materials are premixed using a W cone, a blender, a Henschel mixer, etc., and then kneaded using a pressurized Negoo, Banbury mixer-9 heat Lorel, extruder, etc. at a temperature at which the resin melts. After cooling, it is coarsely ground using a feather mill, bottle mill, pulverizer, hammer mill, etc. Next, it is sieved using an Accucut, Alpine classifier, etc. to adjust the grain size to a fine particle size of 5 to 30 μm.

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

Such carriers are flat and spongy.

Preferably, iron powder is coin-shaped, hard spherical, etc., the surface of the iron powder is coated with a thermoplastic or thermosetting resin such as Teflon, silicone, or vinyl, or the one-component toner of the present invention. Furthermore, the particle size, electrical resistance value, specific surface area, etc. of the carrier are adjusted depending on the purpose of use.

The toner concentration of the two-component developer generally depends on the specific surface area of the carrier, but is generally preferably 1 to 10% by weight.

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

Furthermore, the toner according to the present invention can be prepared using various fixing methods.

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

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

(Function) The toner according to the present invention has chemical properties caused by the hydroxyl group-containing addition polymerizable monomer, which is an essential component of the polymer contained as the binder resin, and an unsaturated aliphatic polycarboxylic acid ester. The synergistic effect of the physical properties caused by these properties increases the adhesion to transfer materials such as paper, resulting in excellent fixing properties.

Furthermore, in addition to the action of the hydroxyl group, the toner according to the present invention contains the above-mentioned bipolar monomer as a component, so even if the melt viscosity of the 1st polymer is reduced, the solubility parameter of the 9th polymer can be maintained at a high value. It also has excellent resistance to soft vinyl chloride polymers.

(Example) Next, examples of the present invention will be shown.

(1) Polymers A-1 to A-6 and B-1 to B-3 partially saponified polyvinyl alcohol (Tenkahopal W-24.
This dispersion medium 20 in which 3 parts by weight (manufactured by Denki Kagaku Kogyo ■) was dissolved
1000 parts by weight of the monomer having the composition shown in Table 1 and the polymerization initiator shown in Table 1 were added to a reaction vessel containing 00 parts by weight using the lid shown in Table 1.

The reaction was carried out at 80 to 90°C for 10 hours under a nitrogen stream.

After cooling, it was filtered and dried with hot air to obtain polymers A-1 to A-6 and B-1 to B-3.

Table 1 shows the melt viscosity of the polymer.

(2) Production of toner (Examples 1 to 5 and Comparative Examples 1 to 3)
The toner components shown in Table 2 were dry-mixed all at once, and then melt-kneaded at 160° C. using a twin-screw kneader. After aging, the toner was pulverized with jet air to obtain a toner having a particle size range of 5 to 25 μm.

(3) Evaluation toner of 3% by weight, 9 sheets of iron oxide powder gear with an apparent density of 4 to 4.567 cm3, an electrical resistance value of 108 to 109 ΩC, and a particle size content of 44 to 177 μm of 90% by weight or more. A developer was prepared by mixing 9 widths and 10 cm.

After uniformly positively charging a selenium drum rotating at a speed of about 30 cm/sec with a corona voltage of +6.5 KV using the developer, information was written using an e-Ne laser, and the drum was reversed using a magnetic brush method. Developed. Next, the toner image carried on the recording paper was fixed using a heated roll whose surface was coated with Teflon and whose surface temperature was 140±5°C.

The obtained printed matter was evaluated and summarized in Table 2.

The test method is shown below.

(:) Print density and Kabu IJ Il1 degree were measured using a reflection densitometer model TC-6DS manufactured by Tokyo Denshoku ■.

(11) Fixability After applying cellophane tape (manufactured by Tanemizu Kagaku Kogyo ■) to the printed matter, the cellophane tape was peeled off and the fixing strength was calculated using the 9th equation.

(Iii) The printed matter with the defective print was placed on a soft vinyl chloride polymer containing 30% by weight of dioctyl phthalate at a temperature of 40°C.

The shell was bonded at a pressure of 5 gf/cm for 200 hours.

The printed matter was peeled off and 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, making it difficult to read the printing Less than a margin (effect of the invention) The above results clearly show that As can be seen, the toner for developing electrostatic images according to the present invention exhibits a high level of fixing performance.

Moreover, it does not cause printing defects when it comes into contact with soft vinyl chloride polymer.

Further, the toner properties such as print density and capri density are also good.

Claims (1)

[Scope of Claims] 1. A toner for developing electrostatic images comprising a polymer having as essential components a hydroxyl group-containing addition-polymerizable monomer and an unsaturated aliphatic polycarboxylic acid ester as a binder resin. 2. The polymer contains 10 to 70% by weight of a hydroxyl group-containing addition-polymerizable monomer, 3-30% by weight of an unsaturated aliphatic polycarboxylic acid ester, and 0 to 0% of other addition-polymerizable monomers.
The toner for developing an electrostatic image according to claim 1, which is obtained by blending and polymerizing 87% by weight to give a total of 100% by weight. 3. The toner for developing electrostatic images according to claim 1 or 2, wherein the hydroxyl group-containing addition polymerizable monomer contains a hydroxyl group bonded to a secondary carbon atom. 4. Unsaturated aliphatic polycarboxylic acid ester has the general formula (
I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2, R_3 and R_4 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, ▲Mathematical formula, chemical formula , tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R_5 is an alkyl group having 2 to 18 carbon atoms, and R_6 is an alkylene group having 1 to 6 carbon atoms), The toner for developing an electrostatic image according to claim 1, 2 or 3, which is a compound represented by the following formula: having at least two ester bonds in the molecule. 5. Claim 3, wherein the hydroxyl group-containing addition polymerizable monomer is 2-hydroxypropyl methacrylate.
The toner for developing electrostatic images described in Section 1. 6. The toner for developing electrostatic images according to claim 4, wherein the unsaturated aliphatic polycarboxylic acid ester is dibutyl fumarate. 7. The polymer contains 13 to 45% by weight of 2-hydroxypropyl methacrylate and 5 to 30% by weight of dibutyl fumarate.
, 25-82% by weight of styrene and 0-20% by weight of addition-polymerizable monomers other than these in a total amount of 100% by weight, which is obtained by polymerizing the mixture. Toner for developing electrostatic images. 8. Claims 1, 2, and 3, wherein the proportion of the polymer in the binder resin is 50% by weight or more;
The toner for developing an electrostatic image according to item 4, 5, 6, or 7.