JPH01297662A - Binder resin for toner, developing toner for electrostatic charge image, and developing agent for electrostatic charge image - Google Patents

Abstract

PURPOSE:To prevent fluctuation of density of inking and to inhibit occurrence of defects in inking such as generation of white spots, etc., by incorporating a specified monomer as a component of a binder resin for toner, into the binder resin. CONSTITUTION:A monomer expressed by the formula I is incorporated as a constituting component for a binder resin for toner. In the formula I, each R1 and R2 is an H atom, or a methyl group. The binder resin consists of (A) a copolymer of at least one kind of said monomer with another monomer, (B) a mixture consisting of said copolymer with another resin, or (C) a mixture of at least one kind of monomer expressed by the formula I and/or a copolymer of >=2 kinds of the specified monomers of this invention with a copolymer (A) and/or (B). Thus, fluctuation of density of inking, occurrence of defects in inking such as generation of white spots, deterioration of resolution, etc. are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a binder resin for a toner, a toner for developing an electrostatic image, and an electrostatic image developer used in fields such as electrophotography and electrostatic recording.

(Prior art) The electrophotographic method is described in US Pat. No. 2,297,691, British Patent No. 1.165.406 and British Patent No. 1.16.
As described in No. 5,405.

A charging process that uses a photoconductive substance to apply various electrostatic charges onto the photoreceptor, an exposure process that irradiates light to form a static latent image, a development process that attaches toner to the latent image area, and a toner image support. Transfer process to transfer.

From the fixing step of fixing the toner image to the image support using heat, pressure, flash light, etc., the cleaning step of removing toner remaining on the photoreceptor, and the static charge removal step of removing static charge on the photoreceptor and returning it to its initial state. These steps are repeated to obtain a number of printed materials.

Toners for developing electrostatic images used in the field of electrophotography include toners using polystyrene resin (Japanese Patent Publication No. 44-
16118), toners using styrene/acrylic resins such as toners using styrene-butyl methacrylate copolymer resin (% Publication No. 11143/1983), and bisphenol-type epoxy resins obtained by reacting bisphenol and epichlorohydrin. Toners using a polyester resin obtained by reacting a glycol having a bisphenol skeleton with a polybasic acid (Japanese Patent Publication No. 52-25420) are known. Although it is.

Compared to other resins, styrene/acrylic resin can be controlled over a wide range of resin properties such as molecular weight, glass transition point, and melt viscosity, which is extremely advantageous in toner design, so the majority of toners are made using styrene/acrylic resin. It is occupied by the used toner.

In addition, in order to impart preferable positive chargeability to these toners, a substance that imparts positive chargeability to the binder resin (hereinafter referred to as a positive chargeability imparting substance) 1, for example, nigrosine dye (Japanese Patent Publication No.
9-11901).

Triphenylmethane dye (JP-A-58-192048
Publication No.), quaternary ammonium salt (% 1989-915
4), or positively charging monomers such as vinylpyridine (Japanese Patent Publication No. 51-27598), 9 morpholinoethyl methacrylate (%
41729).

Dialkylaminoalkyl (meth)acrylate (Japanese Patent Publication No. 41-9472), etc. are copolymerized.

There is a method of making the binder resin itself positively chargeable.

(Problem to be solved by the invention) However, Japanese Patent Publication No. 59-11901.

JP-A-58-192048 and JP-A-58-91
In the toner disclosed in Publication No. 54, in which the positive chargeability imparting substance is added, the positive chargeability imparting substance is not uniformly dispersed in the binder resin, and the charge of each toner particle is distributed over a wide range. , Capri tends to occur, or positively charged substances adhere to the photoconductor surface, magnet roll surface, and carrier surface, causing a filming phenomenon, resulting in printing problems such as changes in print density, white spots, and decreased resolution. There were problems such as ease of use.

On the other hand, Japanese Patent Publication No. 51-27598, Japanese Patent Publication No. 54-4
In Japanese Patent Publication No. 1729 and Japanese Patent Publication No. 41-9472, since the binder resin itself is positively chargeable, there is no problem caused by non-uniform dispersion of the positively chargeable substance. However, perhaps because the binder resin is easily hygroscopic, toners using this resin are sensitive to changes in environmental conditions and are prone to print problems such as changes in print density and white spots, making them impractical.

An object of the present invention is to provide a binder resin for toner, a toner, and a developer that solve these problems.

(Means for Solving the Problems) The present invention provides a binder resin for toner having as a constituent component a monomer represented by -murder (I); (wherein R1 and R8 represent hydrogen or methyl group); The present invention relates to a toner and a developer containing the following.

The binder resin for toner according to the present invention is a monomer represented by the above-mentioned (1) (hereinafter referred to as "specific monomer of the present invention").
) as an essential component.

That is, the following binder resins are used.

A copolymer of at least one of the specific monomers of the present invention and another monomer (B1) A mixture of the copolymer of (3) above and another resin (C1 A copolymer of at least one of the specific monomers of the present invention and another monomer) Combine and/
or a mixture of two or more copolymers of the specific monomers of the present invention and the above copolymer (3) and/or another resin.The specific monomers of the present invention, at least one of which constitutes the binder resin. Preferably 1 to 90 in the total amount of monomers
The content is preferably 3 to 60% by weight, particularly preferably 5 to 40% by weight. If the amount of the specific monomer of the present invention is too small, the positive chargeability will be insufficient.

Eventually, the assistance of a charge control agent is required, resulting in the occurrence of the above-mentioned printing failure. On the other hand, if the amount is too large, problems may arise such as the toner not having the essential properties (fixing properties, storage stability, etc.).

Specific monomers of the present invention include the following.

The above-mentioned specific monomers include - a method of esterifying the above-mentioned acidic acid or methacrylic acid, a method of reacting the above-mentioned alcohol with acrylic acid chloride or methacrylic acid chloride in the presence of an acid binder, a method of reacting the above-mentioned alcohol with a lower alkyl ester or It can be obtained by a known production method such as a method of transesterifying a lower alkyl methacrylic acid ester in the presence of a neutral or basic transesterification catalyst.

Further, as the other monomers mentioned above, 9th order monomers can be used.

Styrene derivatives such as styrene, α-, methylstyrene, p-methylstyrene, pt-butylstyrene, p-chlorostyrene, and hydroxystyrene.

Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, Φyl methacrylate, hebutyl methacrylate, o-cutyl methacrylate, nonyl methacrylate, decyl methacrylate, methacrylic acid Undecyl,
Dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate.

Butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene methacrylate Glycol, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-vinyl-2 methacrylate
-pyrrolidone, methacrylonitrile, methacrylamide, N-methylolmethacrylamide, methacrylic acid 2-
hydroxyethyl, hydroxypropyl methacrylate,
Hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, phthalimidoethyl methacrylate, phthalimidopropyl methacrylate, morpholinoethyl methacrylate.

Morpholinopropyl methacrylate, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate,
Diacetone methacrylamide, acrylic acid, methyl acrylate, ethyl acrylate.

Propyl acrylate, butyl acrylate, hentyl acrylate, hexyl acrylate, butyl 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, methoxyethylene glycol acrylate, butoxyethyl acrylate oxytriethylene glycol, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, hensyl acrylate,
Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, N-vinyl-2-vinyl acrylate, 7-hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic Hydroxybutyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, glycidyl acrylate, acrylonitrile, acrylamide, N-methylolacrylamide, diacetone acrylamide, vinylpyridine, phthalimidoethyl acrylate.

Phthalimidopropyl acrylate, morpholinoethyl acrylate, morpholinopropyl acrylate.

Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, divinylbenzene, reaction products of glycol and methacrylic acid or acrylic acid (e.g. ethylene glycol dimethacrylate), 1,3-butylene glycol diacrylate hydro-5-pentanediol diol methacrylate), 1,6-hexanethiol dimethacrylate, 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 glycol diacrylate, 1.
4-butanediol diacrylate, 1,5-bentanediol diacrylate, 1,6-hexanediol diacrylate, neobentyl glycol diacrylate I)V
-), diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene diacrylate, neopentyl hydroxypivalate glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, trisacryloxyethyl phosphate,
Bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, tris(methacryloyloxyethyl)isocyanurate, half ester of glycidyl methacrylate and methacrylic acid or acrylic acid, half ester of bisphenol type epoxy resin and methacrylic acid or acrylic acid, acrylic Half ester of glycidyl acid and methacrylic acid or acrylic acid.

Among these other monomers, preferred are:
Those having one vinyl group in one molecule include styrene, styrene derivatives, methacrylic esters, acrylic esters, and 9% of them include methacrylic acid or acrylic acid having 1 to 5 carbon atoms in the alkyl group. Alkyl esters are preferred.

In monomers having two or more vinyl groups in one molecule,
Preferred are divinylbenzene, dimethacrylates and diacrylates of alkylene glycols having 2 to 6 carbon atoms, and these are used in an amount of 0 to 20% by weight based on the total monomers.

The specific monomer of the present invention or a mixture of it and other monomers can be polymerized into a single polymer by any method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. In this polymerization, the polymerization initiators used include acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, and 244-peroxide.
Dichlorobenzoyl, diisopropyl perdicarbonate, di-2-ethylhexyl perdicarbonate, acetylcyclohexane sulfonyl peroxide, tert-butyl peracetate, tert-butyl perisobutyrate, azobisisobutyronitrile, λ2'-azobis-2.4- Dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2,4-
Dimethylvaleronitrile, per2-ethylhexanoate
Known polymerization initiators such as rt-butyl and tert-butyl perbenzoate are used. These are preferably used in an amount of 0.1 to 15 weight i1% based on the monomer af&. Moreover, it is preferable to use it by dissolving it in a monomer.

The binder resin for toner of the present invention has a glass transition temperature of 50 to 9.
Particular preference is given to adjusting the temperature to 0°C.

If the glass transition temperature is less than 50° C., the toner is likely to cause caking (a phenomenon in which toner particles aggregate to form lumps) during storage or in a developing machine. Further, when the glass transition temperature exceeds 90° C., when the toner is manufactured by a process of melting, mixing, and pulverizing into nine classifications.

The grinding process takes time and tends to reduce productivity.

Furthermore, if the method of fixing toner on the transfer material is a heat roll method or an open method, the fixing temperature must be increased, which goes against energy conservation.

In the toner of the present invention, the above toner binder resin is an essential component, but other resins may be used in combination.

Examples of the other resins include polymers of only the other monomers mentioned above, KR-216, KR-220, KR-152, KR-216, KR-220, KR-152, K
R-271, KR-255 (manufactured by Shin-Etsu Chemical),
Silicone resins such as 5R-2400, SR, -2406°5H-840 (Silicone split), norbornene polymer of 1-Solex (manufactured by CdF chemical), and C-20OA.

C-25OA (manufactured by Mitsubishi Chemical Corporation), Kneepilon P
Polyester carbonate such as -1000 (manufactured by Mitsubishi Gas Chemical ■), Rig Tool R-70, 几-120, R-14
Xylene resin such as 0, P-2 (made of lignite),
Eviny) 1004°100? , 1009, 1010
．． YL-903°906, Epicoat 604 (all manufactured by Shell).

Epoxy resins such as EboMitsuku R304, R307, 309 (manufactured by Mitsui Petrochemical Industries), Nilaball BR-
1220, 1032, 1441, Nirapol I R22
00, Nila Ball NBR.

Diene resins such as 20578.2007J (manufactured by Nippon Zeon ■), PC-RESIN 2H, 3H.

8H, IIA (manufactured by Hitachi Chemical), ATR200
5, 2009, 2010f or more (manufactured by Kao Soap ■), polyester resin, phenolic resin.

Coumaron resin, amide resin, amide imide resin.

These resins, such as butyral resin, amine resin, urethane resin, etc., are preferably added to the toner in an amount of 0 to 30% by weight.

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

Coloring agents include carbon blank, acetylene black, Hansa Yellow G, cadmium yellow, MoIJ F7” orange, permanent orange, pen color, rhodamine lake B, first violet B, methyl violet lake, navy blue, phthalocyanine blue,
Chrome green, pigment green B, zinc oxide, titanium oxide, nigrosine dye, methylene blue, rose bengal.

Quinoline Yellow, Ultramarine Blue, Chrome Yellow, Aniline Blue, Calco Oil Blue, Rhodamine 6G Lake, Watching Red Barium, Watching Red Strontium.

Malachite green octylate. There are conventionally known pigments or dyes such as DuPont Oil Red and mixtures thereof, and these are preferably used in the toner in an appropriately selected range of 1 to 60% by weight.

When the toner of the present invention is used as a one-component toner, magnetic powder is added.

Magnetic powders include metal powders such as iron, manganese, nickel, and cobalt, as well as aluminum and cobalt.

Steel, lead, magnesium, nickel, tin, zinc.

antimony, beryllium, bismuth, cadmium.

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

Examples Whisker alloys such as evaporated manganese-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% 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 and 11% or less in the toner.

Additives such as a charge control agent, a fluidity improver, a cleaning performance improver, an offset inhibitor, and the like can be appropriately added to the toner of the present invention.

Known charge control agents such as nigrosine dyes, fatty acid-modified nigrosine dyes, dibutyltin oxide, metal complexes of salicylic acid, azo dyes, and metal complexes of azo dyes are added to the toner in an amount of 0 to 20% by weight.

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 9 silicon atoms on the surface are silanol groups, with 1, for example, octyltrichlorosilane,
Decyltrichlorosilane, nonyltrichlorosilane, 4
-isopropylphenyltrichlorosilane, 4-t
ert -butylphenyltrichlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane.

Dinonyldichlorosilane, didenyldichlorosilane, didodecyldichlorosilane, 4-tert-butylphenyloctyldichlorosilane, dioctyldichlorosilane, didecenyldichlorosilane, dinonenylcyclosilane, di-2-ethyl Xyldichlorosilane, G3.
React with compounds such as 3-dimethylpentyldichlorosilane, trimethylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tritesylchlorosilane, dioctylchlorosilane, octyldimethylchlorosilane, 4-isopropylphenyldiethylchlorosilane, etc. As a result, a hydrophobic group is bonded to the surface silicon atoms of silicon dioxide particles via oxygen atoms.

These hydrophobic silica powders have an average particle size of 1 mμm.
It is preferably within the range of ~100 μm.

In particular, it is preferably in the range of 2 mβm to 50 μm. 1mμm
If it is less than 100 μm, 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 powders include Aerosil R972,
Silica D-17, R812, RA200H.

It is commercially available under trade names such as RX-C (manufactured by Nippon Aerosil) and Tallanox 500 (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
0.0 for toner powder without hydrophobic silica powder
It is preferably added in an amount of 1 to 15% by weight. In particular, 0.
The amount added is preferably 1 to 10% by weight. This addition amount is 0.
It is less than 0.01% by weight.

The effect of improving fluidity does not appear, and 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.

As a cleaning property improver, pj! Metal salts of unsaturated or unsaturated fatty acids 1 For example, maleic acid, stearic acid, oleic acid, palmitic acid, caproic acid.

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

salts with lead, iron, nickel, cobalt, copper or aluminum, and in particular zinc stearate.

Calcium stearate or magnesium stearate is preferred.

When a cleaning performance improver is used, the cleaning performance improvement agent is preferably added at 2% in the same manner as the hydrophobic silica powder. The fatty acid metal salt is 0.0% relative to the toner powder not containing the fatty acid metal salt and the hydrophobic silica powder.
It is preferable to add 0.1 to 10 wt-Jt% to 0.01 to 25 wt% and 9%. 0.01 heavy f! If it is less than -%, the effect of improving cleaning performance will not appear. However, even if it is added in excess of 25% by weight.

It does not increase the effect.

It is generally advantageous to fix a toner image on an image support by a heat fixing method, and this heat fixing method includes a non-contact heat fixing method such as oven fixing, and a contact heating method such as hot roll fixing. However, the contact heat fixing method has high thermal efficiency2
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. There is a serious problem of re-metastasis and contamination. 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,
Polymers of olefin monomers such as 3-methyl-2-pentene and 3-propyl-5-methyl-2-hexene, or copolymers of olefin monomers as described above with acrylic acid, methacrylic acid, vinyl acetate, etc., stearin Lower alcohol esters of fatty acids such as butyl acid and propyl stearate, 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.),
Hoechstwax E, Hoechstwax-〇P (Hoechstwax-0P) company.

Higher alcohol ester of fatty acids such as carnauba wax, Bisamide Blast Flow (manufactured by Nitto Chemical Industry ■)
, Amide 6L, 78 and 6H (manufactured by Yoken Fine Chemicals ■), alkylene bis fatty acid amide compounds such as Hoechst Wax C (manufactured by Hoechst Akchengesellschaft), 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
Examples include diene resins having a weight average molecular weight of 50,000 or more, such as BR, 20578, 2007J and BR1220, hydroxyl group-containing vinyl resins, and carboxyl group-containing vinyl resins.

The anti-offset agent is contained in the toner in an amount of 0.1 to 50% by weight,
It is particularly preferable to add it in an amount of 1 to 30 weights. 0.1
If the amount is less than 50% by weight, the offset prevention effect will be less than 50% by weight.
Even if added in excess of % by weight, the effect will not increase.

In the present invention, the fluidity improver as described above is used.

The cleaning performance improver and the offset inhibitor may be added alone or in combination.

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

The weighed materials are premixed using a W cone, a blender, a Henschel mixer, etc., and then kneaded using a pressurized eta++, a Banbury mixer 9 hot roll, an extruder, etc. at a temperature at which the resin melts. After cooling, feather
Coarsely grind with a mill, pin mill, pulperizer, hammer mill, etc. Next, the particles are sieved using an Accucut, Alpine classifier, etc., and adjusted to a particle size of preferably 5 to 30 μm.

The toner of the present invention can be applied to two types of known development methods.

Furthermore, the toner according to the present invention uses the fixing method of S.

For example, so-called oil-less and oil-coated heat roll methods,
It can be used in a flash method, an oven method, a pressure fixing method, etc., and is particularly suitable for heat roll fixing.

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

The above-mentioned toner and carrier can be combined to form an electrostatic image developer of the present invention. The carriers are oblate, cavernous, coin-shaped and bispherical.

Iron oxide powder and manganese in two different shapes, including spherical.

Cobalt, nickel, zinc, tin, magnesium.

Ferrites such as lead, strontium, barium, and lithium, as well as Teflon resin, acrylic resin, polyester resin, silicone resin, and melamine resin.

Examples include iron oxide powder and ferrite whose surfaces are coated with butadiene resin, butyral resin, etc., and particles made of a mixture of various resins and magnetic powder.

The toner concentration of the 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.2 to 1 to 10% when the carrier is spherical or has a coarse particle size.
Preferably it is 5% by weight.

(Example) Next, the present invention will be explained in detail based on examples.

The present invention is not limited to this.

(1) Production of specific monomers The above-mentioned specific monomer was manufactured by the following method.

The alcohols and unsaturated acids shown in Table 1 were added to toluene in an amount twice their total weight, and hydroquinone was added to the reaction solution at a concentration of 300 μg/9.
The esterification reaction proceeded at 20°C for 10 hours. After that, the monomer is precipitated by dropping it into a large amount of methanol, and the monomer is filtered.
Drying was performed to obtain each monomer.

Table 1 Raw materials (2) Production of copolymer 2000 parts by weight of water, 3 parts by weight of polyvinyl alcohol (Denka Poval W-24 manufactured by Denki Kagaku Kogyo ■), 0.1 part by weight of sodium nitrite, and monomers with the formulation shown in Table 2. and a polymerization initiator were placed in a reaction vessel and kept at 80 to 90°C for 10 hours, and then P was removed and dried to obtain a copolymer.

(3) Production of toner The ingredients shown in Table 3 were premixed at once in a Henschel mixer, and then melted and kneaded in a kneader.

Next, the cooled mixture was finely pulverized using a pin mill and a jet mill and classified into 9 parts to obtain a toner having an average particle size of 10 to 15 μm.

(4) Manufacture and testing of developer With 3 parts by weight of toner and an apparent density of 3.5 to 4.5 g/ci.

A developer was obtained by mixing with 97 parts by weight of iron oxide powder carry'p containing 90% by weight or more of particles with a particle diameter of 44 to 177 μm.

First, under environmental conditions of 20 to 30° C. and 60 to 80% RH, the Selendar drum rotating at a circumferential speed of 30 cm/sec was uniformly positively charged with a corona voltage of +6 kV, information was written with a He-Ne laser, and the development was performed as described above. Reversal development was carried out using a magnetic brush method using a reversal agent. Next.

It was fixed with a Teflon heat roll at 160±5°C.

Print density and fog density were measured initially and after printing 200,000 sheets using a microphotometer MPM type (manufactured by Union Optical Co., Ltd.).

Then, the environmental conditions were changed to 10-15°C, 30-40% RH.
After adjusting to , perform reversal development in the same way.

The initial print density was measured and the presence or absence of any influence due to environmental conditions was investigated.

Comparative Example 2 Using 800 parts by weight of styrene, 160 parts by weight of butyl acrylate and 40 parts by weight of vinylpyridine.

A toner consisting of 88% by weight of the copolymer produced in the same manner as in (2) above as a binder resin, 10% by weight of carbon black Φ4410% and 2% by weight of Viscoel 550P was mixed with the above (2).
3), a developer was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. As shown in Table 2, the developer was inferior in continuous printability and environmental resistance.

The binder resin for toner, toner for electrostatic image development, and electrostatic image developer of the present invention maintain excellent print quality (print density, fog density) even during long-term printing, and are also resistant to changes in environmental conditions. It also shows characteristics that are difficult to be affected by.

Claims (1)

[Claims] 1. General formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R_1 and R_2 represent hydrogen or methyl groups) as a constituent component Binder resin for toner. 2. A toner for developing an electrostatic image, comprising the toner binder resin according to claim 1. 3. An electrostatic image developer comprising the electrostatic image developing toner according to claim 2 and a carrier.