JP2000075549A - Resin composition for toner, toner binder composition and toner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. for a toner excellent in anti-hot-offsetting property, less liable to lower its flowability and free from trouble such as the occurrence of voids in a solid image and the lowering of image density in continuous copying. SOLUTION: The resin compsn. consists of (1) a polyolefin resin having 80-170 deg.C softening point, (2) a vinyl resin having an SP value of 10.6-12.6 and (3) a graft polymer having a structure obtd. by grafting a vinyl monomer forming the vinyl resin (2) on the polyolefin resin (1). The vinyl resin (2) is a polymer comprising a monomer (A) whose homopolymer has an SP value of >=11.0 and the monomer (A) is a (meth)acrylonitrile monomer (A1) and/or α,β-unsated. carboxylic acids (A2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for electrophotography, electrostatic recording, electrostatic printing, and the like, a resin composition for the toner used for the toner, and a toner binder composition.

[0002]

2. Description of the Related Art A heat fixing type toner is fixed on a support by a heat roll. At that time, energy saving,
From the viewpoint of miniaturization of a copying machine or the like, the toner does not fuse to the hot roll even at a higher fixing temperature than before (hot offset resistance), and the toner can be fixed even at a low fixing temperature (low temperature fixing property). Is required. Conventionally,
Means for improving hot offset resistance by using a crosslinked resin as a binder resin, and means for achieving both low-temperature fixability and hot offset resistance by expanding the molecular weight distribution of the binder resin have been taken. In order to improve hot offset resistance, a release agent has been conventionally used. In particular, in a toner using a styrene resin as a toner binder, a low molecular weight polyethylene, a polyolefin release agent such as a low molecular weight polypropylene, or a resin composition obtained by grafting a styrene resin to these polyolefin resins is effective. (For example, Japanese Patent Publication No. 52-3304, Japanese Patent Publication No. 7-82255).

On the other hand, polyester resins have been studied as toner binders because of their excellent low-temperature fixability. However, low-molecular-weight polyethylene and low-molecular-weight polypropylene, which are highly effective release agents for toners using styrene-based resins, have insufficient dispersibility in polyester-based resins. In addition, there is a problem that the fluidity of the toner is reduced, and when continuous copying is performed, troubles such as occurrence of white spots on a solid image and reduction in image density occur. The resin composition obtained by grafting the styrene-based resin has no effect on the problem of poor dispersibility of the polyolefin-based release agent in the polyester-based resin, and has not been put to practical use.

To solve these problems, oxidized polypropylene (for example, JP-B-43-9367) and maleic acid-modified polypropylene (for example, JP-A-48-4)
No. 6689) is used as a release agent.

[0005]

However, the modified low-molecular-weight polypropylene resin as described above has improved dispersibility as compared with the unmodified one, and adverse effects such as a decrease in fluidity of the toner are improved. However, since the melt viscosity is higher than that of the unmodified product, the releasability, which is the original function of the release agent, is reduced, and the hot offset resistance is inferior to that of the unmodified product. And it is still not satisfactory.

[0006]

Means for Solving the Problems The present inventors have developed a toner which is excellent in hot offset resistance, has little decrease in fluidity, and has no trouble such as solid image white spots or image density decrease during continuous copying. As a result of intensive studies for development, the present invention has been reached. That is, the present invention provides the following (1):
A resin composition for a toner comprising (2) and (3). (1); a polyolefin resin having a softening point of 80 to 170 ° C. (2); a vinyl resin having an SP value of 10.6 to 12.6 (3); a vinyl monomer constituting (2) is grafted on (1). Graft polymer having an improved structure

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Examples of the olefin constituting the polyolefin resin of the present invention include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, and 1-octadecene. As the polyolefin resin (1),
Olefin polymer (1-1), Olefin polymer oxide (1-2), Modified olefin polymer (1-3) Other monomers copolymerizable with olefins (1-4) and the like. Examples of (1-1) include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-hexene copolymer and the like. Further, in the present invention, it is sufficient that the polymer structure has a polyolefin structure, and the monomer does not necessarily have to have an olefin structure. For example, polymethylene (such as Sasol wax) can be used.
Examples of (1-2) include the oxides of (1-1) and the like. As (1-3), maleic acid derivatives of the above (1-1) (maleic anhydride, monomethyl maleate,
Adducts of monobutyl maleate, dimethyl maleate, etc.). Examples of (1-4) include unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.], unsaturated carboxylic acid alkyl esters [(meth)
Such as alkyl acrylate (C1-C18) ester, alkyl maleate (C1-C18) ester and the like, and olefins. Among these polyolefin resins (1), preferred are (1)
-1), (1-2) and (1-3), more preferably polyethylene, polymethylene, polypropylene,
Ethylene / propylene polymers, oxidized polyethylene, oxidized polypropylene, maleated polypropylene are preferred, with polyethylene and polypropylene being particularly preferred.

[0008] The softening point of the polyolefin resin (1) is usually from 80 to 170 ° C, preferably from 90 to 160 ° C, more preferably from 100 to 155 ° C. When the softening point exceeds 80 ° C., the fluidity of the toner becomes good, and
When the temperature is lower than 70 ° C., a sufficient releasing effect is exhibited.

The melt viscosity of (1) at 160 ° C. is usually from 2 to 10,000 (mPa · s), preferably from 3 to
7000 (mPa · s), more preferably 5-450
0 (mPa · s).

The number average molecular weight of (1) is usually from 500 to 20 from the viewpoint of filming into a carrier or the like and releasability.
000, the weight average molecular weight is 800 to 100,000, preferably the number average molecular weight is 1,000 to 15,000,
The weight average molecular weight is 1500 to 60000, more preferably the number average molecular weight is 1500 to 10000, and the weight average molecular weight is 2000 to 30000.

The degree of penetration of the needle in (1) is usually 5.0 or less, preferably 3.5 or less, and more preferably,
1.0 or less.

The SP value (solubility parameter) of the vinyl resin (2) is usually from 10.6 to 12.6.
(Cal / cm ³ ) ^1/2, preferably 10.6 to 12.0
(Cal / cm ³ ) ^1/2 , more preferably 10.7 to 1
1.8 (cal / cm ³ ) ^1/2 , particularly preferably 1
0.8~11.5 (cal / cm ³⁾ is ^1/2. If the SP value exceeds 12.6 or less than 10.6, the SP value difference from the binder resin becomes too large, and the dispersion of the release agent becomes poor. Note that the SP value can be calculated by a known Fedors method.

As the vinyl resin (2), the (a) homopolymer has an SP value of 10.6 to 12.6 (cal / c).
m ³ ) It may be a homopolymer of a monomer which is ^1/2 ,
(B) a vinyl monomer (A) having an SP value of 11.0 to 18.0, particularly preferably 11.0 to 16.0 (cal / cm ³ ) ^1/2 , and a homopolymer; SP value of 8.0 to 11.0, particularly preferably 9.0 to 10.8
A copolymer with the monomer (B) having (cal / cm ³ ) ^1/2 is more preferable.

Examples of (A) include unsaturated nitrile monomers (A1) and α, β-unsaturated carboxylic acids (A2).

Examples of (A1) include (meth) acrylonitrile, cyanostyrene and the like. Of these, (meth) acrylonitrile is preferred. (A
Examples of 2) include unsaturated carboxylic acids and their anhydrides [(meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and its anhydrides], unsaturated dicarboxylic acid monoesters [monomethyl maleate, monobutyl maleate] And monomethyl itaconate].
Of these, preferred are (meth) acrylic acid and unsaturated dicarboxylic acid monoesters, and particularly preferred are (meth) acrylic acid and maleic acid monoester [monomethyl maleate, monobutyl maleate].

(B) includes styrene monomers [styrene, α-methylstyrene, p-methylstyrene, m
-Methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene, etc.], alkyls of unsaturated carboxylic acids (C1 to C1)
18) Ester [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, etc.], vinyl ester monomers [vinyl acetate, etc.], vinyl ether monomers [vinyl methyl ether, etc.], vinyl monomers containing halogen elements [vinyl chloride, etc.], diene monomers (butadiene, isobutylene, etc.) ) And combinations thereof. Among these, preferred are styrene-based monomers, unsaturated carboxylic acid alkyl esters and their combination, and particularly preferred are styrene and the combination of styrene and alkyl (meth) acrylate.

The vinyl resin (2) has a number average molecular weight of 1500 to 100,000 and a weight average molecular weight of 5
2,000 to 20,000, preferably 2500 to 50,000 in number average molecular weight and 6000 in weight average molecular weight.
~ 100,000, particularly preferred is a number average molecular weight of 28
00-20,000, 7000-500 in weight average molecular weight
00.

The Tg (glass transition point) of (2) is usually 40
To 90 ° C, preferably 45 to 80 ° C, particularly preferably 50 to 70 ° C. When the Tg is 40 ° C. or higher, the storage stability is good, and when the Tg is 90 ° C. or lower, the low-temperature fixability is good.

(1) and (2) constituting a graft polymer (3) having a structure in which the vinyl monomer constituting (2) is grafted on (1) are the same as (1) and (2) above. And preferred ones are also the same.
The amount of each component constituting (3) is usually 1 to 90% by weight, preferably 5%, based on the weight of (3) produced.
The content of (2) is usually 10 to 99% by weight, preferably 20 to 95%.

The above (1) constituting the resin composition of the present invention
(1) is usually 0.5 to 70% by weight, and (2) is usually 2%, based on the weight of the resin composition produced.
9 to 98.5% by weight, and (3) is usually 1 to 70% by weight.

Specific examples of the resin composition of the present invention include the following (1), (2), and (1) a graft polymer (3) having a structure in which a vinyl monomer constituting (2) is grafted. ). (1): Oxidized polypropylene (2): Styrene / acrylonitrile copolymer (1): Polyethylene / polypropylene mixture (2): Styrene / acrylonitrile copolymer (1): Ethylene / propylene copolymer (2): Styrene / Acrylic acid / butyl acrylate copolymer (1): polypropylene (2): styrene / acrylonitrile / butyl acrylate / monobutyl maleate copolymer (1): maleic acid-modified polypropylene (2): styrene / acrylonitrile / acryl Acid / butyl acrylate copolymer (1): Maleic acid-modified polypropylene (2): Styrene / acrylonitrile / acrylic acid / 2-ethylhexyl acrylate copolymer (1): Polyethylene / maleic acid-modified polypropylene mixture (2): Acrylonitrile / Butyl acrylic acid / styrene / monobutyl maleate copolymer

As an example of the method for producing the resin composition of the present invention,
For example, first, the polyolefin resin (1) is dissolved or dispersed in a solvent such as toluene, xylene, and the like.
After heating to 0 ° C., drop polymerization of (A) or a mixture of (A) and (B) together with a peroxide initiator (benzoyl peroxide, ditertiary butyl peroxide, tertiary butyl peroxide benzoate, etc.) The resin composition of the present invention is obtained by removing the solvent.

The amount of the peroxide initiator used for synthesizing the solution of the above polymer mixture is usually 0.2 to 10% by weight, preferably 0.5 to 5% by weight based on the weight of the polymer mixture formed. %.

The toner binder composition of the present invention comprises the above resin composition and a polyester toner binder.

Examples of the polyester-based toner binder include a polycondensate of a polyol and a polycarboxylic acid. The polyol includes a diol (a) and a trivalent or higher valent polyol (c), and the polycarboxylic acid includes a dicarboxylic acid (b) and a trivalent or higher polycarboxylic acid (d).

The diol (a) may have a hydroxyl value of 180
~ 1900 mg KOH / g diols, specifically
Alkylene glycol (ethylene glycol, 1,2-
Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether) Glycols, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); C2-C4 alkylene oxides of the above alicyclic diols ( Adducts of ethylene oxide, propylene oxide, butylene oxide, etc .; C2-C4 alkylene oxides of the above bisphenols (ethylene oxide, Pyrene oxide, and the like butylene oxide, etc.) adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols, and those having 2 to 12 carbon atoms.
In combination with an alkylene glycol. As the trivalent or higher polyol (c), a hydroxyl value of 150 to 1900 m
gKOH / g polyols, specifically, tri- to octa- or higher-valent aliphatic polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); C2-C4 alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct; trisphenols (trisphenol PA, etc.); novolak resins (phenol novolak, cresol novolak, etc.); C2-C4 alkylene of the above trisphenols Oxide adducts: C2 to C4 alkylene oxide adducts of the above novolak resins. Preferred of these are:
An alkylene oxide adduct of a tri- or higher-valent or higher aliphatic polyhydric alcohol and a novolak resin,
Particularly preferred are alkylene oxide adducts of novolak resins.

The dicarboxylic acid (b) has an acid value of 180
~ 1250 mgKOH / g dicarboxylic acid, specifically, alkylenedicarboxylic acid (succinic acid, adipic acid,
Sebacic acid, dodecenyl succinic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid,
Naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. The trivalent to hexavalent or higher polycarboxylic acid (d) includes an acid value of 150 to 1250 mgKOH /
g of a polycarboxylic acid, specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and a vinyl polymer of an unsaturated carboxylic acid (styrene /
Maleic acid copolymer, styrene / acrylic acid copolymer,
α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.). Of these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the dicarboxylic acid (b) or the trivalent or higher polycarboxylic acid (d), the above-mentioned acid anhydride or lower alkyl ester (eg, methyl ester, ethyl ester, isopropyl ester) may be used.

The ratio of the polyol to the polycarboxylic acid is usually 2/1 to 1/2 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH].
It is preferably from 1.8 / 1 to 1 / 1.8, more preferably from 1.5 / 1 to 1 / 1.5.

The toner binder is required to have different physical properties for monochrome and full color, respectively, and the design of the polyester toner binder is also different. That is, since a high gloss image is required for a full color image, it is necessary to use a low-viscosity binder. However, for a monochrome image, a high elasticity binder needs to be used because gloss is not particularly required and hot offset property is emphasized. .

In order to obtain a low gloss image useful for a monochrome copying machine or the like, a tri- or higher valent polyol (c) and / or a tri- or higher valent polycarboxylic acid (d) may be used together with the diol (a) and the dicarboxylic acid (b). Non-linear polyesters using (a), (a), (b), (c), and (d)
Polyesters consisting of components are particularly preferred. By using both (c) and (d), the hot-off set resistance is further improved. The ratio of the trivalent or higher polyol (c) and the trivalent or higher polycarboxylic acid (d) is such that the sum of the number of moles of (c) and (d) is based on the total number of moles of (a) to (d). hand,
Usually, it is 0.1 to 40 mol%, preferably 0.5 to 25 mol%, and more preferably 1 to 20 mol%. (B)
The molar ratio between (d) and (d) is usually 0/100 to 100/0,
It is preferably 90/10 to 20/80, and more preferably 85/15 to 30/70.

In this case, the storage elastic modulus (G ′) of the polyester-based toner binder is such that the temperature (TG1) at which it becomes 60000 dyne / cm ² is usually 130 to 230 ° C., preferably 14 to 30,000 from the viewpoint of hot offset resistance.
The temperature is from 0 to 230C, more preferably from 150 to 230C. As the complex viscosity (η *) of the polyester, the temperature (TE1) at which the viscosity becomes 10,000 poise is usually 80 to 140 ° C., preferably 90 to 135 ° C., and more preferably 105 from the viewpoint of low-temperature fixability and heat-resistant storage stability. ~ 130 ° C
It is. Good low-temperature fixability was obtained at less than 140 ° C.
If it exceeds 0 ° C., the heat-resistant storage stability will be good. TG1 and TE1 are obtained, for example, by converting the resin to 1
The block after melt-kneading at 30 ° C. and 70 rpm for 30 minutes was subjected to storage elastic modulus (G ′) and complex viscosity (η) while changing the resin temperature using a commercially available dynamic viscoelasticity measuring device.
*) Is measured.

The molecular weight of the polyester toner binder for monochrome is determined by GPC in the range of 1000 to 100.
00 preferably has a maximum value, more preferably a maximum value of 2000 to 8500, and particularly preferably a maximum value of 2500 to 8000. When it is 1,000 or more, heat-resistant storage stability and powder fluidity are good, and when it is less than 10,000, pulverizability of the toner is improved, and productivity is good. Further, it preferably contains 5 to 70% by weight of a tetrahydrofuran (THF) insoluble matter, and more preferably,
It is 15 to 60%, particularly preferably 20 to 50%. T
If the HF insoluble content exceeds 5%, the hot offset resistance becomes good, and if it is less than 70%, good low-temperature fixability is obtained.

When a high gloss image useful for a full-color copying machine or the like is obtained, the diol (a), the dicarboxylic acid (b)
Is a linear polyester using a diol (a), a dicarboxylic acid (b), and a trivalent or higher polyol (c).
And / or non-linear polyesters using a trivalent or higher polycarboxylic acid (d) in combination. In the case of a non-linear polyester, the ratio of the trivalent or higher polyol (c) and / or the trivalent or higher polycarboxylic acid (d) is such that the sum of the moles of (c) and (d) is (a) to (d). It is usually at most 20 mol%, preferably at most 15 mol%, more preferably at most 10 mol%, based on the total number of moles of d).

As for the complex viscosity of the polyester toner binder for full color, the temperature (TE2) at which the viscosity becomes 1000 poise is 90 to 170 ° C., preferably 100 to 16 ° C.
The temperature is 5 ° C, more preferably 105 to 150 ° C. If the temperature is lower than 170 ° C., sufficient gloss is obtained, and if the temperature exceeds 90 ° C., the heat-resistant storage stability is improved. TE2 is determined by measuring in the same manner as for monochrome.

The molecular weight of the polyester toner binder for full color is such that the number average molecular weight by GPC is usually from 1,000 to 10,000, preferably from 1500 to 850.
0, more preferably 1800 to 6500. When the number average molecular weight is 1,000 or more, heat resistance storage stability and powder fluidity are good, and when it is less than 10,000, toner pulverizability is improved, and productivity is improved. Further, the content of tetrahydrofuran (THF) insoluble matter is usually less than 10% by weight, preferably less than 5% by weight from the viewpoint of glossiness.

The method for producing the polyester toner binder of the present invention will be exemplified. Polyester, polyol and polycarboxylic acid, tetrabutoxy titanate, in the presence of a known esterification catalyst such as dibutyltin oxide,
It is obtained by heating to 150 to 280 ° C. and performing dehydration condensation. It is also effective to reduce the pressure in order to increase the reaction rate at the end of the reaction.

In the toner binder composition of the present invention, other resins can be contained together with the polyester-based toner binder. Other resins include styrene resins (copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers, etc.), epoxy resins (addition condensates of bisphenol A and epichlorohydrin, etc.), urethanes Resins (polyaddition products of diol and diisocyanate) and the like.

Specific examples of the polyester-based toner binder include the following. : Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct / phenol novolak ethylene oxide adduct /
Terephthalic acid / trimellitic anhydride polycondensate: bisphenol A propylene oxide 3 mol adduct / phenol novolak ethylene oxide adduct / maleic anhydride / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate: bisphenol A ethylene Oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / phenol novolak propylene oxide adduct / terephthalic acid / dimethyl terephthalate / trimellitic anhydride polycondensate: bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene Oxide 3 mol adduct / Propylene oxide adduct of phenol novolak / terephthalic acid polycondensate: bisphenol A propylene oxide 2 mol adduct / bispheno A propylene oxide 3 mol adduct / phenol novolak propylene oxide adduct / isophthalic acid / dimethyl isophthalate / trimellitic anhydride polycondensate

The toner binder composition of the present invention comprises the toner resin composition (I) of the present invention and a polyester-based toner binder (II). The amount of the toner resin composition (I) of the present invention in the present toner binder composition is usually 0.1 to 3 based on the amount of the toner binder.
0% by weight, preferably 0.3 to 20% by weight, and the amount of the polyester-based toner binder (II) is usually 65 to 99.9% by weight based on the amount of the toner binder.
Preferably it is 75 to 99.7% by weight.

The toner binder composition may contain a wax as a release agent component other than the polyolefin resin derived from the resin composition for toner of the present invention. As the waxes, the aforementioned polyolefin resin,
Examples include ester waxes (carnauba wax, montan wax, rice wax, etc.), long-chain (C30 or more) aliphatic alcohols, long-chain (C30 or more) fatty acids, and mixtures thereof. The amount of these waxes is usually 0 to 50% by weight, preferably 0 to 30% by weight, based on the amount of the toner binder composition.

In order to obtain the toner binder composition, powders of (I) and (II) and, if necessary, other members may be mixed, or a twin-screw extruder or a mixing vessel capable of heating and stirring. May be melt-mixed in the presence of (I).
I) may be polymerized.

The toner composition of the present invention comprises the above toner binder composition and a colorant. Known dyes, pigments, and magnetic powders can be used as the colorant. Specifically, carbon black, Sudan Black SM, Fast Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Baranitoaniline Red, Toluidine Red, Carmine, Pig FBment Orange R, Lake Red 2G , Rhodamine FB, Rhodamine B lake, Methyl Violet B lake, Phthalocyanine blue, Pigment blue, Priliant green, Phthalocyanine green, Oil yellow GG, Kayaset YG, Orazol brown B, Oil pink OP, Magnetite, Iron black, etc. . The content of the colorant in the toner is usually 2 to 15% by weight when using a dye or a pigment, and usually 20 to 70% by weight when using a magnetic powder.
It is.

If necessary, various additives such as a release agent, a charge control agent and a fluidizing agent are mixed. Examples of the release agent include the above-mentioned polyolefin resins and ester waxes. The amount of the release agent is usually 0 to 10% by weight in the toner. Known charge control agents include nigrosine dyes, quaternary ammonium salt compounds, quaternary ammonium base-containing polymers, metal-containing azo dyes, salicylic acid metal salts, sulfonic acid group-containing polymers, fluorinated polymers, and halogen-substituted aromatics. Ring-containing polymers and the like. The content of the charge control agent in the toner is usually 0 to 5% by weight.
It is. In addition, fluidizing agents can be used. Known fluidizers such as colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder can be used.

As a method for producing the toner, a known kneading and pulverizing method can be used. After the above-mentioned toner components are dry-blended, they are melt-kneaded, then finely pulverized using a jet mill or the like, and further subjected to air classification to have a particle size of usually 2 to 20.
Obtained as μm particles.

The toner using the toner binder of the present invention may contain carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. And used as a developer for an electric latent image. Further, instead of the carrier particles, an electric latent image can be formed by friction with a member such as a charging blade. Next, the recording material is fixed on a support (paper, polyester film, etc.) by a known heat roll fixing method or the like.

The method of the performance test of the toner according to the present invention is described below. (1) Minimum fixing temperature, hot offset generation temperature, gloss generation temperature For a monochrome toner and a full-color toner using carbon black, 30 parts of the toner and 800 parts of a ferrite carrier (F-150, manufactured by Powder Tech) are uniformly mixed. And tested as a two-component developer. (I) In the case of monochrome toner using carbon black (low gloss image) Minimum fixing temperature (MFT) Commercially available monochrome copying machine (AR5030, Sharp Corporation)
The unfixed image developed by using the fixing unit of a commercially available monochrome copying machine (SF8400A, manufactured by Sharp Corporation) was fixed at a process speed of 145 mm / sec by modifying the fixing unit and changing the temperature of the heat roller. The heat roller temperature at which the residual ratio of the image density after rubbing the fixed image with a cloth pad was 70% or more was defined as the minimum fixing temperature. Hot offset occurrence temperature Fixing was performed in the same manner as in the above-mentioned MFT, and the presence or absence of hot offset to the fixed image was visually determined. The temperature at which hot offset began to occur was taken as the hot offset occurrence temperature. (Ii) Monochrome toner using magnetic powder (low gloss image) An unfixed image is obtained using a commercially available monochrome printer (LBP-210, manufactured by Canon Inc.), and the process speed of the fixing unit is set to 72 mm / sec. The test is the same as above, except that (Iii) In the case of full-color toner (high gloss image) Commercially available monochrome copying machine (AR5030, Sharp Corporation)
The unfixed image developed by using a fixing unit of a commercially available full-color copying machine (CLC-1, manufactured by Canon Inc.) is processed at a process speed of 8%.
The image was fixed at 0 mm / sec. Commercially available gloss meter (MURAKA
MI COLOR RESEARCH LABORAT
GMX-202-60 manufactured by Ory Co., Ltd.), and the heat roller temperature at which the reflectance at 60 ° of the fixed image exceeds 10% was defined as the gloss development temperature. The temperature at which hot offset began to occur in the visual judgment was defined as the hot offset occurrence temperature.

(2) Fluidity of toner The quietness density of the non-externally added toner pulverized and classified to about 9 μm was measured with a powder tester manufactured by Hosokawa Micron, and determined according to the following criteria. Δ or more is the practical range. Quietness density 36 g / 100 ml or more; powder fluidity ○ 33 to 36; ○ △ 30 to 33; Δ27 to 30; Δx less than 27; × In the case of magnetic toner, measured value was multiplied by 0.65. The numerical values were determined based on the above criteria.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. Hereinafter, "part" indicates "part by weight".

[0049]

EXAMPLES The methods for measuring the properties of the toner and toner binder obtained in the examples and comparative examples are described below. In addition, about the following 1,3,5, when tetrahydrofuran insoluble content exists in a sample, the thing after melt-kneading by the following method was used as a sample. Kneading device: Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.
MODEL 30R150 Kneading conditions: 100 ° C., 70 rpm, 30 minutes, sample amount 65 g Acid value and hydroxyl value Method specified in JIS K0070. 2. Glass transition point (Tg) The method (DSC) specified in ASTM D3418-82
Law). Apparatus: DSC20, SSC manufactured by Seiko Electronic Industry Co., Ltd.
/ 580 3. Molecular weight The soluble matter in THF was measured by gel permeation chromatography (GPC). The conditions for molecular weight measurement by GPC are as follows. Apparatus: HLC-802A manufactured by Toyo Soda Column: 2 TSK GEL GMH6 (manufactured by Toyo Soda) Measurement temperature: 25 ° C. Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 200 μl Detector: Refractive index detector The molecular weight showing the maximum peak height on the chromatogram is referred to as the peak molecular weight. The molecular weight calibration curve was created using standard polystyrene. 4. Tetrahydrofuran (THF) insoluble matter 50 ml of THF is added to 0.5 g of a sample, and the mixture is refluxed with stirring for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter and dried under reduced pressure at 80 ° C. for 3 hours. The insoluble content is calculated from the weight ratio of the resin on the glass filter to the weight of the sample. 5. Measurement of storage elastic modulus (G ') and complex viscosity (η *) Apparatus: RDS-7700II Dynamic Spectrometer Test Fixture: 25 mmφ cone plate manufactured by Rheometrics Measurement frequency: 20 Hz (125.6 rad / sec) Strain rate : 5% fixed

Polyester resin production example 1 In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 4533 parts of a 2-mol adduct of bisphenol A propylene oxide, 4460 parts of a 2-mol adduct of bisphenol A ethylene oxide, and a phenol novolak resin 5 moles of ethylene oxide adduct of (about 5 nuclei) 6
18 parts, terephthalic acid 2789 parts, maleic anhydride 41
4 parts and 24 parts of dibutyltin oxide were added and subjected to a dehydration reaction at 230 ° C. under a nitrogen stream until the acid value became 1.5. Then, 1720 parts of dimethyl terephthalate and 400 parts of xylene were added thereto, and the mixture was added at 220 ° C. under normal pressure.
The reaction was continued for 2 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 439 parts of trimellitic anhydride was added and reacted at a reduced pressure of 10 to 15 mmHg. When the melt index (150 ° C., 5000 g) reached 2.1 g / 10 minutes, the polyester was taken out of the reaction tank.
-1) was obtained. The THF-insoluble content of (F-1) is 32.4.
%, The peak molecular weight is 3600, and the acid value is 8.1 mgK.
OH / g and hydroxyl value were 15.6 mgKOH / g.
Further, the glass transition point is 59.7 ° C, TG1 is 165 ° C,
TE1 was 120 ° C. Polyester resin production example 2 In a reaction vessel equipped with a cooling pipe, a stirrer and an element introduction pipe, a 2-mol adduct of bisphenol A propylene oxide 37 was added.
73 parts, 3546 parts of bisphenol A ethylene oxide 2 mol adduct, 968 parts of phenol novolak resin (about 5 nuclei) ethylene oxide 5 mol adduct, 3406 parts of terephthalic acid, 22 parts of dibutyltin oxide Dehydration reaction at 230 ° C, then 10-1
The reaction was continued under a reduced pressure of 5 mmHg, and when the melt index (150 ° C., 5000 g) reached 2.3 g / 10 minutes, the reaction mixture was taken out of the reaction tank and the polyester (F-2) was obtained.
I got The THF-insoluble content of (F-2) was 36%, the peak molecular weight was 3940, the acid value was 1.8 mgKOH / g, and the hydroxyl value was 47.1 mgKOH / g. The glass transition point is 59.8 ° C., TG1 is 161 ° C., and TE2 is 11
7 ° C. Polyester resin production example 3 In a reaction vessel equipped with a cooling pipe, a stirrer and an element introduction pipe, a bisphenol A propylene oxide 2 mol adduct 23 was added.
10 parts, 2172 parts of bisphenol A ethylene oxide 2 mol adduct, 1892 parts of terephthalic acid and 18 parts of dibutyltin oxide were added.
The reaction was carried out for a further time, and the reaction was further performed under reduced pressure of 10 to 15 mmHg until the acid value became 1.3 mgKOH / g to obtain a polyester (F-3). (F-3) has no THF-insoluble matter, has a number average molecular weight of 3020, and a weight average molecular weight of 8
040, and the hydroxyl value was 35 mgKOH / g. Also,
Glass transition point was 63.7 ° C and TE2 was 132 ° C. Polyester resin production example 4 A 2-mol bisphenol A ethylene oxide adduct 745 was placed in a reaction vessel equipped with a cooling pipe, a stirrer, and an element introduction pipe.
6 parts, 529 parts of a 5 mol ethylene oxide adduct of a phenol novolak resin (about 5 nuclei), 3320 parts of terephthalic acid, and 20 parts of dibutyltin oxide were added, and the reaction was carried out at 225 ° C. for 10 hours under normal pressure. ~ 15m
The reaction was performed under a reduced pressure of mHg until the acid value became 1.3 mgKOH / g. To this, 151 parts of trimellitic anhydride were added and reacted until the acid value became 7.0 mgKOH / g to obtain a polyester (F-4). (F-4) had no THF insolubles, had a number average molecular weight of 3,340, a weight average molecular weight of 19,800, and a hydroxyl value of 42 mgKOH / g.
Further, the glass transition point was 59.7 ° C, and the TE2 was 131 ° C.

Example 1 In an autoclave reactor equipped with a thermometer and a stirrer, 600 parts of xylene and low molecular weight polypropylene (Viscol 440P manufactured by Sanyo Chemical Industries, Ltd .: softening point 153)
C) 480 parts, low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128)
120 ° C.) and sufficiently dissolved therein, and after purging with nitrogen, a mixed solution of 1992 parts of styrene, 168 parts of acrylonitrile, 240 parts of monobutyl maleate, 78 parts of di-t-butylperoxyhexahydroterephthalate and 455 parts of xylene was heated at 175 ° C. For 3 hours, and the mixture was kept at this temperature for 30 minutes. Subsequently, the solvent was removed to obtain the resin composition for toner (E-1) of the present invention. The SP value of the graft chain of (E-1) is 11.13 (cal / cm ³ )
^1/2 , number average molecular weight 2950, weight average molecular weight 1
0900, the glass transition point was 83.9 ° C., and the acid value was 20.9 mgKOH / g.

Example 2 In an autoclave reactor equipped with a thermometer and a stirrer, 1020 parts of xylene and low molecular weight polypropylene (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd .: softening point 1)
45 ° C.) Add 750 parts and sufficiently dissolve. After purging with nitrogen, 2385 parts of styrene, 264 parts of acrylonitrile, 330 parts of butyl acrylate, 21 parts of acrylic acid, 32.5 parts of di-t-butylperoxyhexahydroterephthalate and 32.5 parts of xylene 570 parts of the mixed solution was added dropwise at 175 ° C. over 3 hours, and the mixture was kept at this temperature for 30 minutes. Subsequently, the solvent was removed to obtain the resin composition for toner (E-2) of the present invention. The SP value of the graft chain of (E-2) is 11.14 (c
al / cm ³ ) ^1/2 , the number average molecular weight was 3,000, the weight average molecular weight was 8200, the glass transition point was 57.5 ° C., and the acid value was 3.4 mg KOH / g.

Example 3 In an autoclave reactor equipped with a thermometer and a stirrer, 340 parts of xylene and low molecular weight polypropylene (Viscol 440P manufactured by Sanyo Chemical Industries, Ltd .: softening point 153)
C) 200 parts, low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 12)
8 [deg.] C.) 50 parts were sufficiently dissolved and replaced with nitrogen. After replacement with nitrogen, 839 parts of styrene, 44 parts of acrylonitrile, 110 parts of butyl acrylate, 7 parts of acrylic acid, 32.5 parts of di-t-butylperoxyhexahydroterephthalate and xylene 148 parts of the mixed solution was added dropwise at 175 ° C. over 3 hours, and the mixture was kept at this temperature for 30 minutes. Subsequently, the solvent was removed to obtain the resin composition for toner (E-3) of the present invention.
The SP value of the graft chain of (E-3) was 10.84 (cal)
/ Cm ³ ) ^1/2 , number average molecular weight was 2990, weight average molecular weight was 7,970, glass transition point was 57.4 ° C., and acid value was 4.6 mg KOH / g.

Comparative Example 1 In an autoclave reaction vessel equipped with a thermometer and a stirrer, 400 parts of xylene and low molecular weight polypropylene (Viscol 440P, manufactured by Sanyo Chemical Industries, Ltd., softening point: 153)
50 ° C.) Add 50 parts and sufficiently dissolve. After purging with nitrogen, styrene 7
A mixed solution of 82 parts, 218 parts of butyl acrylate, and 8.5 parts of di-t-butylperoxyhexahydroterephthalate was added dropwise at 160 ° C. over 2 hours, and the mixture was maintained for 1 hour. Next, the solvent was removed to obtain a resin composition (E-4). The SP value of the graft chain of (E-4) was 10.41 (c
al / cm ³ ) ^1/2 , the number average molecular weight was 8310, the weight average molecular weight was 22,900, and the glass transition point was 60.5 ° C.

Comparative Example 2 1200 parts of xylene was placed in an autoclave reactor equipped with a thermometer and a stirrer, and after purging with nitrogen, styrene 1
A mixed solution of 992 parts, 168 parts of acrylonitrile, 240 parts of monobutyl maleate, 78 parts of di-t-butylperoxyhexahydroterephthalate and 455 parts of xylene was added dropwise at 175 ° C. over 3 hours, polymerized at this temperature, and further at this temperature for 30 minutes. Held. Next, the solvent was removed to obtain a resin composition (E-5). The SP value of (E-5) is 11.13.
(Cal / cm ³ ) ^1/2 , number average molecular weight was 2900, weight average molecular weight was 9800, glass transition point was 80.6 ° C., and acid value was 25.8 mgKOH / g.

Example 4 100 parts of the resin composition for toner (E-1) and 2900 parts of a polyester-based toner binder (F-1) were preliminarily mixed using a Henschel mixer (FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.). Later, a twin-screw kneader (PCM- manufactured by Ikegai Co., Ltd.
30), and the toner binder of the present invention (G-
1) was obtained.

Example 5 After adding 439 parts of trimellitic anhydride in Preparation Example 1 of polyester, the reaction temperature was lowered to 170 ° C., and 420 parts of the resin composition for toner (E-2) was further added to a low molecular weight polypropylene (Sanyo). 560 parts of Biscol 550P (manufactured by Kasei Kogyo Co., Ltd.) were added, and a melt index (150 ° C., 5000
g) was 3.0 g / 10 minutes to obtain a toner binder (G-2) of the present invention.

Example 6 When the acid value became 1.3 in Polyester Production Example 3, the temperature was lowered to 160 ° C., and 60 parts of the resin composition for toner (E-3) was added to low molecular weight polyethylene (Sanyo Chemical Industries, Ltd.). 60 parts of Sunwax 171P manufactured and mixed with stirring for 1 hour to obtain a binder for toner (G-4).

Evaluation Example 1 100 parts of polyester resin (F-1) of Production Example 1 3 parts of resin composition for toner (E-1) of Example 1 8 parts of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control 1 part of low-molecular-weight polypropylene (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.) 3 parts Low-molecular-weight polyethylene (Sunwax LEL400 manufactured by Sanyo Chemical Industries, Ltd.) 1 part To Henschel Mixer (Mitsui Miike Kakoki Co., Ltd.)
FM10B), and then melt-kneaded with a twin-screw kneader (PCM-30 manufactured by Ikegai Co., Ltd.) set to a temperature of 130 ° C. After cooling the kneaded material, it is roughly pulverized, and the supersonic jet pulverizer LabJet (Nippon Pneumatic Industries, Ltd.)
Pulverized using an air flow classifier (MDS-I, manufactured by Nippon Pneumatic Industries, Ltd.) to obtain a particle size d50.
Was 9.0 μm. Next, 100 parts of the toner particles and 0.3 part of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added) to obtain a toner (T-1). When T-1 was observed with an electron microscope, the average dispersion particle size of the release agent was about 0.7 μm, and the release agent was in a uniform and favorable dispersion state. The minimum fixing temperature of T-1 was 145 ° C, and no hot offset was observed at 230 ° C or lower.

Evaluation Examples 2 to 5, Comparative Evaluation Examples 1 to 3 Premixed, melt-kneaded, coarsely pulverized, finely pulverized, and externally added toner with the composition shown in Table 1 as in Evaluation Example 1. ~ Toner (T-8). Table 2 shows the toner particle size, release agent dispersion particle size, release agent dispersion state, fluidity, and fixing test results of these carbon toners.

[0061]

[Table 1]

[0062]

[Table 2]

In Table 2, the dispersion state of the release agent was observed with an electron microscope, and was judged according to the following criteria. Release agent dispersed state: Release agent is uniformly dispersed throughout and the particle size is uniform △: Release agent with small particle size is present but coarse particles are present ×: Large number of release agent coarse particles

As shown in Table 2, the toner for monochrome using the resin composition for toner of the present invention has a better releasing agent dispersibility and excellent fluidity than the conventional toner, and has a wide fixing temperature range. You can see that there is.

[0065]

[Table 3]

In Table 3, EPT1000 is a product of Toda Kogyo Co., Ltd.
Made of magnetic powder.

[0067]

[Table 4]

In Table 4, the state of dispersion of the release agent was determined in the same manner as in Table 2. As shown in Table 4, the magnetic toner for monochrome using the resin composition for toner of the present invention has a good releasing agent dispersibility and excellent fluidity as compared with the conventional toner, and has a wide fixing temperature range. I understand. In the case of full-color toner, the temperature of PCM-30 was set to 80 ° C.

[0069]

[Table 5]

In Table 5, sun wax 171 as a release agent was used.
P is a low molecular weight polyethylene manufactured by Sanyo Chemical Industry Co., Ltd., and Cyanine Blue KRO which is a pigment is manufactured by Sanyo Dyeing Co., Ltd.

[0071]

[Table 6]

In Table 6, the state of dispersion of the release agent was determined in the same manner as in Table 2. As shown in Table 6, the full-color toner using the resin composition for toner of the present invention has a good release agent dispersibility and excellent fluidity as compared with the conventional toner, and has a wide fixing temperature range. Understand. From the above results, it can be seen that the toner using the resin composition of the present invention is excellent in the dispersion of the release agent, has a wide fixing temperature range, and is excellent in the fluidity as compared with the conventional toner.

[0073]

By using the resin composition for a toner of the present invention in a toner, the fixing temperature range is wide and the fluidity is good. Therefore, even when continuous copying is performed, troubles such as white spots and a decrease in image density are prevented. A toner that does not generate can be used. When a toner is prepared using the composition of the present invention, the release agent is uniformly dispersed, so that a toner having good image quality can be easily obtained.

Claims (8)

[Claims] 1. A toner resin composition comprising: (1) (2) and (3) below. (1); a polyolefin resin having a softening point of 80 to 170 ° C. (2); a vinyl resin having an SP value of 10.6 to 12.6 (3); a vinyl monomer constituting (2) is grafted on (1). Graft polymer having an improved structure 2. The method according to claim 2, wherein the homopolymer has an SP value of 1
The resin composition for a toner according to claim 1, which is a polymer comprising the monomer (A) having a ratio of 1.0 or more. 3. The resin composition for a toner according to claim 2, wherein (A) is a (meth) acrylonitrile monomer (A1) and / or an α, β-unsaturated carboxylic acid (A2). 4. The resin composition for a toner according to claim 2, wherein (2) is a copolymer of (A) and a styrene-based monomer (B). 5. A toner binder composition comprising the resin composition according to claim 1 and a polyester toner binder. 6. A toner composition comprising the resin composition according to claim 1, a polyester-based toner binder, and a colorant. 7. The polyester-based toner binder is a polycondensate of a diol (a), a dicarboxylic acid (b), a trivalent or higher polyol (c) and / or a trivalent or higher polycarboxylic acid (d). The temperature (TG1) at which the storage elastic modulus of the polyester-based toner binder becomes 60000 dyne / cm ² is 130 ° C. or more, and the temperature (TE1) at which the complex viscosity becomes 10,000 poise is 80 to 14
The composition according to claim 5 or 6, wherein the composition is at 0 ° C. 8. A polyester-based toner binder obtained by polycondensing a polyol containing at least a diol (a) and a polycarboxylic acid containing at least a dicarboxylic acid (b). Temperature at which the complex viscosity becomes 1000 poise (TE
The composition according to claim 5 or 6, wherein 2) is 90 to 170 ° C.