JPH07301951A - Toner binder composition and toner composition - Google Patents

Abstract

PURPOSE:To obtain such a toner binder compsn. that when a toner is produced with using this binder, the toner shows good heat resistance and electric characteristics and excellent low temp. fixing property and shows high offset temp. by satisfying specified conditions for the binder resin and wax. CONSTITUTION:The compsn. consists of a binder resin and wax having <=70 deg.C melting point. The difference between absolute Sp values of the binder resin and the wax is <=1.5. The wax becomes compatible with the binder at 80-150 deg.C, and the wax is dispersed in a particle state having average <=5mum particle size in the binder resin at room temp. The binder resin is selected from polyester resin, polystyrene resin, styrene/(meth)acryl copolymer and epoxy resin, and is preferably polyester resin or styrene/(meth)acryl copolymer. If necessary, other resin (polyamide, polyurethane, or the like) may be used. As for the wax, paraffin wax, microcrystalline wax or the like is used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a toner binder composition for electrophotography and a toner composition.

[0002]

2. Description of the Related Art In an electrophotographic process, in order to fix toner transferred onto paper or the like, a contact heating type fixing device [method using a heat roll, a film or belt is interposed between a heating body and paper, etc.] Method (for example, Japanese Patent Laid-Open No. 4-7
No. 0688 and Japanese Patent Laid-Open No. 12558/1992)].
Is widely adopted. In this method, it is desirable that the minimum fixing temperature (hereinafter abbreviated as MFT) is low (low temperature fixing property), and the temperature at which hot offset occurs on the heat roll surface, film or belt (hereinafter abbreviated as HOT) is high. Is preferable (hot offset resistance).
Further, in the machine of the electrophotographic process, heat is generated from a fixing device and the like, so that heat-resistant storage stability must be satisfied so that the toner is not aggregated by the heat and the fluidity is not deteriorated.

In order to satisfy these three properties, a toner binder having a wide range of molecular weight distribution ranging from low molecular weight to high molecular weight and having a glass transition point of 50 to 80 ° C. is conventionally used as a binder resin ( For example, Japanese Patent Publication 6
0-20411, JP-A-61-215558).
Or a polyester resin using an oxyalkylene ether of a novolac type phenol resin (Japanese Patent Laid-Open No. 2747/1993).
No. 8) is proposed.

[0004]

However, the above method has been used in recent years due to the speeding up of copying machines and facsimiles, which requires a lower temperature fixing property, and due to the downsizing of printers, a trend toward a more heat-resistant storage property. It's hard to say that we are fully prepared. The present invention is intended to solve the above problems, and an object of the present invention is to obtain a toner binder which, when made into a toner, has good heat-resistant storage stability and electrical characteristics, high hot offset generation temperature, and excellent low-temperature fixability. And

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have an object to obtain a toner binder which, when made into a toner, has good heat resistance and electric characteristics, a high hot offset generation temperature, and excellent low-temperature fixability. As a result of intensive studies, the present invention has been achieved. That is, in the present invention, the binder resin (A) and the melting point of 7
It is composed of waxes (B) at 0 ° C. or less, and the absolute value of the difference between the Sp value of (A) and the Sp value of (B) is 1.5 or less.
For electrophotography, wherein (B) is compatible with (A) between 0 and 150 ° C., and (B) is dispersed in (A) at room temperature with an average particle size of 5 μm or less. Toner binder composition; a difference between the Sp value of (A) and the Sp value of (B) in an electrophotographic toner composition comprising a binder resin (A), waxes (B) having a melting point of 70 ° C. or less, and a colorant. Has an absolute value of 1.5 or less, (B) is compatible with (A) between 80 and 100 ° C., and (B) has an average particle size of 5 in (A) at room temperature.
a toner composition for electrophotography, characterized in that it is dispersed at a particle size of at most μm; a binder resin (A) and a compound (C) having a melting point of 120 ° C. or less and a melt viscosity at 120 ° C. of 10,000 cP or less, Satisfying (1), (C) is dispersed in (A) with an average particle size of 5 μm or less at room temperature, and (C) is compatible with (A) between 80 and 150 ° C. A toner binder composition for electrophotography, comprising: 4.0 ≦ ΔSp + 1.2 log MW ≦ 7.0 (1) [where ΔSp represents the absolute value of the difference between the solubility parameters (Sp values) of (A) and (C), and logMW represents the molecular weight of (C) ( However, when there is a molecular weight distribution, it represents the logarithmic value of (weight average molecular weight). ] And the melting point of the binder resin (A) is 120 ° C. or less and the melt viscosity at 120 ° C. is 10000.
It is composed of a compound (C) of cP or less and a colorant, satisfies the above formula (1), and (C) is dispersed in (A) at room temperature with an average particle size of 5 μm or less, and the temperature is 80 to 150 ° C. The toner composition for electrophotography is characterized in that (C) is compatible with (A).

The present invention will be described in detail below. The binder resin (A) used in the present invention can be selected from the group of polyester resin (A1), polystyrene resin (A2), styrene / (meth) acrylic copolymer (A3) and epoxy resin (A4). Among (A), (A1) and (A3) are preferable. If necessary, (A1) to (A4)
Other resins other than (polyamide, polyurethane, etc.) can be used together.

(A1) is not particularly limited, but may be obtained by using a divalent carboxylic acid, a divalent alcohol and, if necessary, a polycarboxylic acid component having a valence of 3 or more and / or an alcohol having a valence of 3 or more. it can.

Specific examples of divalent carboxylic acids include:
(1) Aliphatic dicarboxylic acid having 2 to 20 carbon atoms (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid,
Malonic acid, azelaic acid, mesaconic acid, citraconic acid,
(2) alicyclic dicarboxylic acid having 8 to 20 carbon atoms (cyclohexanedicarboxylic acid, methylmedic acid, etc.); (3) aromatic dicarboxylic acid having 8 to 20 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid) Acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.);
(4) Alkyl or alkenyl (anhydrous) succinic acid [dodecenyl (anhydrous) succinic acid, pentadodecenyl (anhydrous) succinic acid, etc.] having a hydrocarbon group having 4 to 35 carbon atoms in the side chain; and divalent carboxylic acids thereof. Examples thereof include anhydrides and lower alkyl (methyl, butyl etc.) esters. Among these, the above-mentioned (1), (3), (4) and anhydrides or lower alkyl esters of these dicarboxylic acids are preferable, and maleic acid, fumaric acid, isophthalic acid, terephthalic acid, dimethyl terephthalate, dodecenyl ((anhydrous)) are preferable. Anhydrous) succinic acid is more preferred. (Anhydrous) maleic acid and fumaric acid are preferable because they have high reactivity, and isophthalic acid and terephthalic acid are preferable because they increase the glass transition temperature of the polyester.

Examples of dihydric alcohols include (1)
C2-C12 alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentane Diol, 1,6-hexanediol, etc.);
(2) Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.); (3)
Alicyclic diol having 6 to 30 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.);
And (4) bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
(5) An alkylene oxide [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, and the like] 2 to 8 mol addition product of the above bisphenols can be mentioned. Of these, (1) and (5) are preferable, and (5) is more preferable. Among the above (1), ethylene glycol increases the reaction rate, and 1,2-propylene glycol and neopentyl glycol are preferable from the viewpoint of low temperature fixability. In addition, among the above (5), particularly EO of bisphenol A
And / or 2 to 4 mol of PO is preferable because it gives good offset resistance to the toner.

Specific examples of trivalent or higher carboxylic acids include (1) aliphatic polycarboxylic acids having 7 to 20 carbon atoms (1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-
Methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, etc.) (2) C9-C20 alicyclic polycarboxylic acid (1,2,2) 4-cyclohexanetricarboxylic acid, etc.); (3) aromatic polycarboxylic acid having 9 to 20 carbon atoms (1,2,4-benzenetricarboxylic acid,
1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, benzophenonetetracarboxylic acid, etc.); and their anhydrides and lower alkyl ( (Methyl, butyl, etc.) ester. Of these, (3) and its anhydrides and lower alkyl esters are preferable, and 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid and their anhydrides and lower alkyl esters are particularly preferred. It is preferable from the viewpoint of imparting offset resistance to the toner.

Specific examples of trihydric or higher alcohols include (1) aliphatic polyhydric alcohols having 3 to 20 carbon atoms (sorbitol, 1,2,3,6-hexanetetraol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,
4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2
-Methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc.); (2) Aromatic polyhydric alcohol having 6 to 20 carbon atoms (1,3,5-trihydroxylmethylbenzene, etc.); And alkylene oxide adducts thereof; (3) oxyalkylene ether of novolac type phenolic resin; (4) oxyalkylene ether of a heterocyclic compound having two or more active hydrogens in the molecule such as isocyanuric acid. Can be mentioned. Of these, the compounds (1), (3) and (4) are preferable, and (3) and (4) are more preferable.

In the present invention, for the purpose of adjusting the molecular weight and controlling the reaction, a monocarboxylic acid, a monoalcohol and the like can be used together with a carboxylic acid and an alcohol, if necessary. Specific examples thereof include monocarboxylic acids such as benzoic acid, paraoxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, propionic acid and stearic acid;
Mention may be made of monoalcohols such as benzyl alcohol, toluene-4-methanol and cyclohexanemethanol. The ratio of carboxylic acids and alcohols constituting the polyester resin of the present invention is such that alcoholic hydroxyl group equivalent / carboxyl group equivalent is usually 0.6 to 1.4, preferably 0.7 to 1.3, and more preferably 0. .8 to 1.2
The ratio may be such that In addition, when a carboxylic acid having a valence of 3 or more and / or an alcohol having a valence of 3 or more is used if necessary, the amount is usually 35% by weight or less, preferably 25% by weight or less. If the content of trivalent or higher carboxylic acids and / or trivalent or higher alcohols exceeds 35% by weight, the low temperature fixability of the toner is insufficient. Illustrating the production method of the polyester resin (A1) of the present invention, carboxylic acids and alcohols are mixed at a predetermined ratio and a polyesterification reaction is carried out to carry out the polyester resin (A1) of the present invention.
1) is obtained. The reaction is usually 150 to 3 in the presence of a catalyst.
It is carried out under a temperature condition of about 00 ° C, preferably about 170 to 280 ° C. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure, but at a predetermined reaction rate (for example, 30 to
After reaching about 90%), the reaction system is set to 200 mmHg or less,
It is desirable to carry out the reaction by preferably reducing the pressure to 25 mmHg or less.

As the above-mentioned catalyst, a catalyst usually used for polyesterification, for example, tin, titanium, antimony,
Metals such as manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and compounds containing these metals (dibutyltin oxide, orthodibutyl titanate, tetrabutyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, trioxide). Antimony and the like). The polyester of the present invention by stopping the reaction when the properties of the reactant (eg, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or power of the reactor reaches a predetermined value. A resin can be obtained.

(A1) is usually 0.2 to 30, preferably 0.3 to 20 mg KOH / g and an acid value of usually 5 to 100,
It preferably has a hydroxyl value of 10 to 70 mgKOH / g. When the acid value is less than 0.2, the charge amount of the toner becomes low, and when it exceeds 30, the humidity dependency of the charge amount becomes large.
If the hydroxyl value is less than 5, the low temperature fixing of the toner is adversely affected, and if it exceeds 100, the humidity dependency of the charge amount becomes large. The number average molecular weight of (A1) is usually 1500 to 150.
00, preferably 2000-10000, and more preferably 2500-8000.

The glass transition temperature (Tg) of (A1) is usually 40 to 85 ° C, preferably 45 to 80 ° C, more preferably 50 to 75 ° C. If the Tg is less than 40 ° C, the toner particles using the binder of the present invention tend to adhere to each other and aggregate (blocking), and if the Tg exceeds 85 ° C, the low temperature fixability of the toner deteriorates. The softening point of (A1) is usually 70 to 180 ° C, preferably 80 to 160 ° C. If the softening point is lower than 70 ° C., the offset resistance of the toner tends to deteriorate, and if it exceeds 180 ° C., the low temperature fixability becomes poor.

(A2) is not particularly limited, but is obtained by polymerizing styrenes. As styrenes, styrene, α-methylstyrene, p-methoxystyrene, p-
Examples include hydroxystyrene. The number average molecular weight of (A2) is usually 2,000 to 15,000, and if the number average molecular weight is less than 2,000, the heat-resistant storage stability is deteriorated.
If it is greater than 000, the low temperature fixability deteriorates. The weight average molecular weight of (A2) is usually 100,000 to 1,000,000, and when the weight average molecular weight is less than 100,000, HOT decreases, and
If it is larger than 10,000, the low temperature fixability deteriorates. In order to broaden the molecular weight distribution of (A2), the relatively low molecular weight portion and the relatively high molecular weight portion may be polymerized separately, or the remaining portion may be polymerized in the presence of either one. Examples of the polymerization method (A2) include a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.

(A3) is not particularly limited, but is obtained by polymerizing styrene and (meth) acrylic acid ester and / or (meth) acrylonitrile. As styrenes, styrene, α-methylstyrene, p-
Examples thereof include methoxystyrene and p-hydroxystyrene. Examples of (meth) acrylic acid esters include (meth) acrylic acid, methyl (meth) acrylate, and (meth).
Examples thereof include ethyl acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, maleic anhydride, and monobutyl maleate. The number average molecular weight of (A3) is usually from 2000 to
When the number average molecular weight is less than 2000, heat-resistant storage stability deteriorates, and when the number average molecular weight exceeds 15,000, low temperature fixability deteriorates. The weight average molecular weight of (A3) is usually 10
When the weight average molecular weight is less than 100,000, HOT is lowered, and when the weight average molecular weight is more than 1 million, low temperature fixability is deteriorated. The glass transition point of (A3) is usually 40 to 85.
C., preferably 45 to 80.degree. C. If it is lower than 40.degree. C., the heat-resistant storage stability of the toner is deteriorated, and if it is higher than 80.degree. C., the low temperature fixing property of the toner is deteriorated. In order to broaden the molecular weight distribution of (A3), the relatively low molecular weight portion and the relatively high molecular weight portion may be polymerized separately, or the remaining portion may be polymerized in the presence of either one. Examples of the polymerization method (A3) include a suspension polymerization method, a solution polymerization method and a bulk polymerization method. The Sp value of (A) is not particularly limited,
It is usually 6 to 13.

A specific example of (A4) is bisphenol A.
Type, bisphenol F type epoxy resin, novolac type epoxy resin, polyphenol type epoxy resin, polyglycidyl type epoxy resin and these epoxy resins and monocarboxylic acids (benzoic acid, paraoxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, propionic acid, Stearic acid and the like).

The melting point of the waxes (B) used in the present invention is preferably 70 ° C. or lower, more preferably 45 ° C. to 70 ° C. from the viewpoint of low temperature fixability, and the difference in Sp value from that of (A). There is no particular limitation as long as the absolute value of Sp is 1.5 or less, but specific examples include the following. Paraffin wax, microcrystalline wax, sazol wax, polyethylene wax, polypropylene wax, ester wax, amide wax, candelilla wax, carnauba wax,
Montan wax, rice wax, beeswax, wood wax, etc.
And these oxidized wax etc. Also, S of (B)
In order to adjust the p value so that the absolute value of the difference between the Sp value and (A) is 1.5 or less, the above wax is used as a vinyl monomer [(meth) acrylonitrile, (meth) acrylic acid, (meth)
Hydroxyalkyl acrylate, (meth) acrylic acid lower alkyl ester, and the like, and mixtures thereof], and various modifications such as maleic acid modification. When the absolute value of the difference in Sp value exceeds 1.5,
The low temperature fixability becomes insufficient. The molecular weight of (B) is not particularly limited as long as it has the above melting point, but is usually 10,000 or less,
It is preferably 5000 or less, more preferably 3000 or less.

The compound (C) used in the present invention may be any component that substantially satisfies the following formula (1), and specific examples thereof include (C1) and (C2) below. 4.0 ≦ ΔSp + 1.2 log MW ≦ 7.0 (1) [where ΔSp represents the absolute value of the difference between the solubility parameters (Sp values) of (A) and (C), and logMW represents the molecular weight of (C) ( However, when there is a molecular weight distribution, it represents the logarithmic value of (weight average molecular weight). ] (C1) Waxes (C1-1) Hydrocarbon waxes; paraffin wax, microcrystalline wax, sazol wax, polyethylene wax, polypropylene wax, chlorinated polyethylene wax, fluorocarbon wax and the like. (C1-2) Higher fatty acid type wax; stearic acid, coconut oil fatty acid, hydroxy fatty acid and the like. (C1-3) Higher fatty acid amide wax; higher fatty acid monoamide (stearic acid amide, N-stearyl erucic acid amide, etc.), higher fatty acid bisamide (N, N-ethylene bisoleic acid amide, etc.). (C1-4) higher fatty acid ester wax; glycerin fatty acid ester (stearic acid triglyceride, etc.), glycol fatty acid ester (ethylene glycol dioleate, etc.), sorbitan fatty acid ester, partial ester of fatty acid and polyhydric alcohol (pentaerythritol tetra) Stearates, trimethylolpropane tribehenate, etc.), partial esters of fatty acids with polyalkylene glycols, polyglycerol (Panasate R218 manufactured by NOF CORPORATION, etc.). (C1-5) Alcohol wax; higher aliphatic alcohol (stearyl alcohol, behenyl alcohol, etc.), polyhydric alcohol (mannitol, glycerin, sorbitol, pentaerythritol, etc.). (C1-6) Urethane wax; monovalent or polyvalent isocyanate compound [monoisocyanate compound (such as phenyl isocyanate), diisocyanate compound (such as isophorone diisocyanate, tolylene diisocyanate), or Polyisocyanate compounds (Sumijour N, Coronate AP made by Nippon Polyurethane, etc.)] and mono- or polyhydric alcohols [higher aliphatic alcohols, mannitol, glycerin, sorbitol, trimethylolpropane, pentaerythritol, polyalkylene glycol, Wax-like compound obtained by urethanization reaction with polyester glycol and the like]. (C1-7) Animal and plant waxes: candelilla wax, carnauba wax, rice wax, beeswax, wood wax and the like. (C1-8) mineral wax; montan wax, etc.
And these oxidized wax etc. In addition, the above wax may be grafted with a vinyl monomer [(meth) acrylonitrile, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, lower alkyl ester of (meth) acrylic acid, etc., or a mixture thereof], or maleic Various modifications such as acid modification can be used. (C2) Oligomers The following oligomers described in Oligomer Handbook (published by Kagaku Kogyo Nippo Co., Ltd.) can be used. (C2-1) Olefin-based oligomers; α-olefin oligomers and the like. (C2-2) diene-based oligomer; polybutadiene-based,
Cyclic oligomers, etc. (C2-3) Ring-opening polymerization type oligomer; polyethylene glycol type and the like. (C2-4) Vinyl polymerization type oligomer; polystyrene oligomer type, polystyrene / acrylic copolymer oligomer type and the like. (C2-5) Polycondensation, polyaddition type oligomer; polyester type oligomer (unsaturated polyester resin etc.), polyamide type oligomer (dimer acid / ethylenediamine condensate etc.), polyurethane type oligomer (toluene diisocyanate / 1, 1) 4-butanediol condensate etc.). (C2-6) addition condensation type oligomer; phenol resin type, amino resin type, xylene resin type, ketone resin type and the like. (C2-7) Petroleum resin; C5 petroleum resin, C9 petroleum resin, dicyclopentadiene petroleum resin and the like. (C2-8) Silicone type, fluorine type oligomer and the like. These can be used alone or as a mixture of plural kinds of waxes and oligomers. Among these, waxes (C1) are preferable from the viewpoint of melt viscosity, and more preferable are higher fatty acid amide wax (C1-3) and higher fatty acid ester wax (C1-).
4) and urethane wax (C1-6).

When (C) has a molecular weight distribution, the weight average molecular weight can be measured by gel permeation chromatography (GPC). When it does not have a molecular weight distribution, the calculated value from the structural formula can be used by a conventional method. The SP value can be calculated by examining the solubility in a solvent having a known Sp value alone or in a mixed solvent. The point of the present invention is
At room temperature, (C) is dispersed in (A) with an average particle size of 5 μm or less, and the dispersed state is maintained at a temperature of 50 ° C. or lower, but at least a part of (C) is kept at a temperature of 80 ° C. or higher. It is a binder composition having a property of dissolving in (A). By making (A) and (C) incompatible with each other at a temperature of 50 ° C. or lower to form a stable dispersion state, heat resistant storage stability is mainly satisfied, and (C) at a temperature of 80 ° C. or higher.
It is possible to satisfy the low-temperature fixability by making at least a part thereof dissolve in the phase (A).
Although waxes have been conventionally used as a release agent for the purpose of improving hot offset resistance, the wax used as a release agent is incompatible with the binder resin at 80 to 150 ° C. When melted, there is no release effect), so there is no effect in improving low temperature fixability.

The melting point of (C) is usually 45 to 120 ° C., preferably 50 to 110 ° C., and the melt viscosity at 120 ° C. is usually 10,000 cP or less, preferably 5000.
cP or less, more preferably 3000 cP or less.
If the temperature exceeds 120 ° C, the low temperature fixability will be insufficient and the temperature will be 45 ° C.
In the following, problems occur with the storage stability of the toner. Also, 12
If the melt viscosity at 0 ° C. is higher than this, no effect is observed on the low temperature fixability. The molecular weight of (C) is not particularly limited as long as it has the above melting point and melt viscosity, but is usually 10,000 or less, preferably 5000 or less, and more preferably 300.
It is 0 or less. The value of ΔSp + 1.2 log MW is 4.0
To 7.0, preferably 4.2 to 6.8, and more preferably 4.5 to 6.5.

The weight ratio of (A) to (B) or (C) is
Usually, it is 100 / 0.05 to 100/40, preferably 100 / 0.1 to 100/30. 100 /
If it is less than 0.05, the low-temperature fixability is insufficient, and 100
If it exceeds / 40, the HOT becomes low. The method of dispersing (B) or (C) in (A) to have an average particle size of 5 μm or less is not particularly limited, but a method of kneading in a heated and molten state, a method of devolatilizing after blending in the presence of a solvent, and the like can be used. Can be mentioned. Further, a compatibilizer can be used if necessary. When the dispersed particle size exceeds 5 μm, the colorant such as carbon black or the charge control agent is likely to be insufficiently dispersed in the toner. The average particle diameter of (B) or (C) is 400 at a fracture surface of the toner binder with an optical microscope (for example, OPTIPHOT-POL manufactured by Nikon) or a scanning electron microscope (for example, S-800 manufactured by Hitachi, Ltd.).
The average particle size of a photograph taken at about twice can be calculated by image analysis of the photograph using an image analyzer.
In addition, whether (B) or (C) is compatible with (A) at 80 to 150 ° C. is determined by an optical microscope equipped with a heating / cooling device for a microscope (for example, TH600RH manufactured by Japan High Tech) (for example, manufactured by Nikon Corporation). OPTIPHOT-PO
L) is used at a temperature rising rate of 5 to 30 ° C. per minute and a temperature of 80 to 150 ° C.
It can be confirmed by raising the temperature to.

As an example of a method for producing an electrophotographic toner which is an application of the binder of the present invention, the toner binder is usually 45 to 95% by weight based on the weight of the toner, and a known coloring agent (carbon black, iron black, benzidine yellow). , Quinacdrine, rhodamine B, phthalocyanine, etc.) is usually 5-10% by weight, and magnetic powder (compounds such as iron, cobalt, nickel, hematite, ferrite) is usually 0-5% by weight.
One used is 50% by weight. Further, various additives [charge control agents (metal complexes, nigrosine, etc.), release agents (polytetrafluoroethylene, low molecular weight polyolefins, fatty acids, or metal salts or amides thereof, etc.], etc. can be included. The amount of these additives is usually 0 to 10% by weight based on the weight of the toner. The electrophotographic toner is dry-blended with the above components, melt-kneaded, then coarsely pulverized, and finally finely pulverized using a jet pulverizer or the like to obtain fine particles having a particle size of 5 to 20 μm. The electrophotographic toner is mixed with carrier particles such as iron powder, glass beads, nickel powder, and ferrite, if necessary, and used as a developer for an electric latent image. In addition, hydrophobic colloidal silica fine powder may be used to improve the fluidity of the powder. The electrophotographic toner is used by being fixed on a support (paper, polyester film, etc.). The fixing method is as described above.

[0025]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Hereinafter, parts are parts by weight.

The methods for measuring the properties of the binder compositions obtained in Synthesis Examples, Examples and Comparative Examples are shown below. 1. Acid value The method specified in JIS K0070. However, if the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used as the solvent. 2. Glass transition temperature (Tg) Method prescribed in ASTM D3418-82 (DSC
Law). 3. Softening point flow tester (CFT-500, Shimadzu)
Using a 1.0mmφ × 1.0mm nozzle, load 10K
g, the temperature rising rate is 5 ° C./min, and the temperature at which 1/2 of the 1.5 g sample flows out is determined.

Example 1 EO of bisphenol F in a reaction vessel equipped with a thermometer, a stirrer equipped with a torque detector, a cooler and a nitrogen inlet tube.
320 parts of PO (1/1) adduct (hydroxyl value 320),
262 parts terephthalic acid, dodecenyl succinic anhydride 89
Part, 4 of novolac type phenol resin (about 5 nuclides)
150 parts of molar PO adduct and 2.5 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream.
When the reaction product became transparent, the reaction temperature was lowered to 190 ° C. and the polyesterification reaction was allowed to proceed under reduced pressure. When the viscosity of the reaction product gradually increased and the torque of the stirrer exhibited a predetermined value, the reaction was stopped to obtain the polyester resin (A) of the present invention having an Sp value of 9.8. (A) has an acid value of 1.7 and Tg5
The softening point was 7 ° C and the softening point was 131 ° C. Further, 15 parts of acrylonitrile-modified paraffin wax (B-1) having a melting point of 68 ° C. and an Sp value of 8.4 was added to 100 parts of (A), and the mixture was stirred and mixed for 1 hour, and the toner binder composition (TB
-1) was obtained. An optical microscope (Nikon OPTIPHOT-POL) equipped with a microscope heating and cooling device (Japan High-Tech TH600RH) for the fracture surface of (TB-1)
When observed in (B-1), the average particle size was 1.
It was dispersed at 5 μm. When the temperature was further raised at a temperature rising rate of 10 ° C./min, (B-1) was compatible with (A) at 146 ° C.

Example 2 88 parts of (A) obtained in Example 1, 7 parts of carbon black (MA100 manufactured by Mitsubishi Kasei Co., Ltd.), melting point 64 ° C.,
Acrylonitrile-modified wax with Sp value of 8.9 (B-
2) 25 parts and a charge control agent (Hodogaya Chemical Co., Ltd., Spiron Black TRH) 2 parts were uniformly mixed, and then kneaded with a Laboplast mill having an internal temperature of 120 ° C., and the cooled material was finely pulverized with a jet mill. The toner composition a of the present invention having an average particle diameter of 12 μm was obtained by classification with a dispersion separator. When the fracture surface of a was observed in the same manner as in Example 1, the average particle size was 0.8 μm, and (B) was compatible with (A) at 137 ° C.

Comparative Example 1 Melting point of 72 relative to 100 parts of (A) obtained in Example 1.
℃, put 15 parts of paraffin wax with Sp value 7.7, 1
Toner binder composition TB for comparison by stirring and mixing for hours
-10 was obtained. When the fracture surface of TB-10 was observed in the same manner as in Example 1, the average particle size was 3.6 μm, and 1
Even when the temperature was raised to 50 ° C, (B) was not compatible with (A).

USE EXAMPLE AND COMPARATIVE USE EXAMPLE 88 parts of each of the toner binder composition of the present invention of Example 1 and the toner binder composition of Comparative Example 1 were added with 7 parts of carbon black (MA100 manufactured by Mitsubishi Kasei Co.) and charge adjustment. After uniformly mixing 2 parts of the agent (Spirone Black TRH manufactured by Hodogaya Chemical Co., Ltd.), the mixture was kneaded with a twin-screw extruder having an internal temperature of 150 ° C, the cooled material was finely pulverized with a jet mill, and classified with a dispersion separator. Toner composition b and toner composition c having an average particle diameter of 12 μm were obtained.

Test Example 1 97 parts of a ferrite carrier (F-100 manufactured by Powder Tech Co., Ltd.) was uniformly mixed with 3 parts of each of toner composition a, toner composition b, and toner composition c, and a commercially available copying machine (( A toner image is transferred onto a paper sheet by using BD-7720 manufactured by Toshiba Corp., and the transferred toner is remodeled on a fixing portion of a commercially available copying machine (SF8400A manufactured by Sharp Corporation) to obtain 35 A4 sheets / The MFT was evaluated at the speed of minutes. The test results are shown in Table 1. The numbers in the table indicate that the black solid part with an image density of 1.2 was rubbed by the Gakshin-type fastness tester (rubbing part = paper) five times, and the image density of the solid part after rubbing was It is the heat roll temperature at the time of obtaining a copy in which 70% or more remained.

Test Example 2 To 3 parts of each of toner composition a, toner composition b and toner composition c, 97 parts of a ferrite carrier (F-100 manufactured by Powder Tech Co., Ltd.) was uniformly mixed, and a commercially available copying machine (( The toner image is transferred onto the paper using BD-7720 manufactured by Toshiba Corp., and the toner on the transferred paper is remodeled in the fixing section of a commercial copying machine (SF8400A manufactured by Sharp Corp.) to obtain 10 sheets of A4 paper / HOT was evaluated at the speed of minutes. The test results are shown in Table 1. The numbers in the table are the temperatures of the heat roll when the toner is hot offset.

Test Example 3 10 g of each of toner composition a, toner composition b and toner composition c were put into a 20 cc screw tube, and 50 ° C. × 4.
After being left at 0% RH for 24 hours, the heat-resistant storage stability was evaluated in four ranks according to the degree of toner aggregation. The test results are shown in Table 1. Rank A: No aggregation at all. Rank B: Aggregates slightly, but redisperses when a light impact is applied to the screw tube. Rank C: About 1/4 of the toner aggregates and does not redisperse even if a light impact is applied to the screw tube. Rank D: The degree of agglomeration is remarkable and does not redisperse even when a strong impact is applied to the screw tube.

Test Example 4 To 3 parts each of toner composition a, toner composition b and toner composition c, 97 parts of a ferrite carrier (F-100 manufactured by Powder Tech Co., Ltd.) was placed in a 50 CC glass bottle and 2
After left in a temperature / humidity control room at 5 ° C. and 50% RH for 12 hours, the mixture was stirred at 100 rpm for 30 minutes at 100 ° C. under a condition of 25 ° C. and 50% RH to be frictionally charged. Then, Table 1 shows the results of measurement with a blow-off charge amount measuring device manufactured by Toshiba Corporation.

[0035]

[Table 1]

Both the composition a and the composition b of the present invention are excellent in low-temperature fixability while maintaining heat resistant storage stability and hot offset resistance as compared with the comparative binder c. The toners of use examples a and b in Table 1 were continuously copied on 10,000 sheets. The image quality after copying 10,000 sheets was the same as the initial image quality. It can be seen that the toner using the toner binder of the present invention does not change even after long-term friction with the carrier and has excellent durability.

Examples 3 to 5 and Comparative Examples 2 to 3 PO adduct of bisphenol A (hydroxyl value 320) 320 in a reaction vessel equipped with a thermometer, a stirrer equipped with a torque detector, a cooler and a nitrogen inlet tube. Part, terephthalic acid 26
2 parts, dodecenyl succinic anhydride 89 parts, 4 mol PO adduct of novolac type phenolic resin (about 5 nuclides) 15
Add 0 parts and 2.5 parts dibutyltin oxide,
The reaction was carried out at 230 ° C under a nitrogen stream. When the reaction product became transparent, the reaction temperature was lowered to 190 ° C. and the polyesterification reaction was allowed to proceed under reduced pressure. When the viscosity of the reaction product gradually increased and the torque of the stirrer showed a predetermined value, the reaction was stopped to obtain a polyester resin (A1-1) having an SP value of 9.8. The acid value of (A1-1) was 1.5, Tg was 59 ° C, and the softening point was 131 ° C. Furthermore, to 100 parts of (A-1), 15 parts of the compound (C) shown in Table 2 (Examples C-1 to C-3, Comparative examples D-1 to D-2) were added, and mixed by stirring for 1 hour. To obtain a toner binder composition. Next, 87 parts of the toner binder composition, 7 parts of carbon black [MA100 manufactured by Mitsubishi Kasei Co., Ltd.], 4 parts of polypropylene wax [Viscor 550P manufactured by Sanyo Kasei], and a charge control agent [Spilon manufactured by Hodogaya Chemical Co., Ltd.] Black TR
H] 2 parts were uniformly mixed, then kneaded by a twin-screw extruder having an internal temperature of 150 ° C., the cooled product was finely pulverized by a jet mill, and classified by a dispersion separator to obtain a toner having an average particle diameter of 12 μm. The dispersibility of the compound (C) in the obtained toner at 50 ° C., the dispersed particle size, and the degree of the molten state at 80 ° C. or higher are determined by an optical microscope equipped with a heating / cooling device for a microscope (TH 600RH manufactured by Japan High Tech). It was confirmed using Nikon OPTIPHOT-POL). The results are shown in Table 3.

[0038]

[Table 2] ------------------ Compound SP value Mw Melting point Melt viscosity ° C (120 Deg. C.) -------------------------------------------- Example 3 (C-1) 7.5 1200 60 20 Example 4 (C-2) 8.4 600 100 35 Example 5 (C-3) 8.8 750 75 60 ----------------------- .. Comparative Example 2 (D-1) 6.1 600 50 10 Comparative Example 3 (D-2) 6.6 2000 110 1500 -------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−− (C-1): Pentaerythritol tetrastearate (C-2): NN-ethylene Bisoleic acid amide C-3): Urethane Wax (HAD8050 Nippon Seiro) (D-1): Paraffin wax (D-2): oxidized polyethylene wax

[0039]

[Table 3] ------------------------------------------------------------------------------------------------------------------------------------------------- 50% value of ΔSp + 1.2log MW at 100 ° C Dispersion particle size μm structural change at the time of temperature rise (Note 1) (Note 2) ---------------------------------------- --- Example 3 ○ 1.0 ◎ 6.0 Example 4 ○ 2.5 ○ 4.7 Example 5 ○ 1.5 ◎ 4.4 --- --- --- --- ----- −−−−−−−−−−−−−−−−−−−−− Comparative Example 2 ○ 10 <× 7.1 Comparative Example 3 × − × 7.2 −−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−− (Note 1): Take the dispersed state ... ○ Do not take the dispersed state ... × (Note 2): (C ) Completely dissolves in (A)… ◎ (C) partially dissolves in (A)… ○ (C) dissolves in (A) Don't get stuck ... ×

Test Example 5 Ferrite carrier (F-1 manufactured by Powder Tech Co., Ltd.) was added to 3 parts of each of the toners obtained in Examples 1 to 3 and Comparative Examples 1 and 2.
00) 97 parts were uniformly mixed to prepare a developer, and a toner image was transferred onto a paper using a commercially available copying machine (BD-7720 manufactured by Toshiba Corp.). The fixing unit of (SF8400A manufactured by Sharp Corporation) was modified to evaluate MFT at a speed of 35 sheets of A4 paper / minute. The test results are shown in Table 3. The numbers in the table indicate that the black solid part with an image density of 1.2 was rubbed by the Gakshin-type fastness tester (rubbing part = paper) five times, and the image density of the solid part after rubbing was It is the heat roll temperature at the time of obtaining a copy in which 70% or more remained.

Test Example 6 A ferrite carrier (F-1 manufactured by Powder Tech Co., Ltd.) was added to 3 parts of each of the toners obtained in Examples 3 to 5 and Comparative Examples 2 to 3.
00) 97 parts were uniformly mixed to prepare a developer, and a toner image was transferred onto a paper using a commercially available copying machine (BD-7720 manufactured by Toshiba Corp.). The fixing unit of (SF8400A manufactured by Sharp Corp.) was modified, and HOT was evaluated at a speed of 10 sheets of A4 paper / minute. The test results are shown in Table 3. In addition,
The numbers in the table are the temperatures of the heat roll when the toner is hot offset.

Test Example 7 10 g of each of the toners obtained in Examples 3-5 and Comparative Examples 2-3.
Put in a 20cc screw tube, 50 ℃ × 40% RH
After standing for 24 hours, the heat-resistant storage stability was evaluated in four ranks according to the degree of toner aggregation. Table 3 shows the test results
Shown in. ◎ ... No aggregation at all. ∘: Aggregates slightly, but redisperses when a light impact is applied to the screw tube. Δ: About 1/4 of the toner aggregates and does not redisperse even if a light impact is applied to the screw tube. X: The degree of agglomeration is remarkable and does not redisperse even when a strong impact is applied to the screw tube.

Test Example 8 Examples 3 to 5 and Comparative Examples 2 to 3 Ferrite carrier (F-10 manufactured by Powder Tech Co., Ltd.) was added to 3 parts of each of the obtained toners.
0) Put 97 parts in a 50 cc glass bottle at 25 ° C., 50
After leaving it in the temperature and humidity control room of% RH for 12 hours,
1 in a Turbula shaker mixer at 50% RH
The mixture was stirred at 00 rpm for 30 minutes and triboelectrically charged. Then, Table 4 shows the results of measurement with a blow-off charge amount measuring device manufactured by Toshiba Corporation.

[0044]

[Table 4]

Toners obtained according to the present invention (Examples 3 to
It can be seen that in 5), in comparison with Comparative Examples (Comparative Examples 2 to 3), the low temperature fixability is significantly excellent while maintaining the heat resistant storage resistance and the hot offset resistance. In addition, Example 3 in Table 3
About 10,000 toners were continuously copied on 10,000 sheets. The image quality after copying 10,000 sheets is the same as the initial image quality, and it can be seen that the occurrence of spent, filming and the like are not recognized and the durability is excellent.

Examples 6 to 308 parts of bisphenol A PO adduct (hydroxyl value 320), bisphenol A in a reaction vessel equipped with a thermometer, a stirrer equipped with a torque detector, a cooler and a nitrogen inlet tube
EO adduct (hydroxyl value 340) of 379 parts, terephthalic acid 312 parts and dibutyltin oxide 2.5 parts were added, and the reaction was stopped at the time when the acid value reached 10 in the same manner as in Production Example 1, and the Sp value was 9 A polyester (A1-2) of 0.9 was obtained. The Tg of (A1-2) was 59 ° C and the softening point was 110 ° C. Furthermore, for Example 3 to 100 parts of (A1-2)
10 parts of the compounds (C-1) to (C-3) used in Example 5 and (D-1) and (D-2) used in Comparative Examples 2 and 3 were added,
The mixture was stirred and mixed for 1 hour to obtain a toner binder composition. Next, 95 parts of the toner binder composition and chromatic pigment Fastgen Magenta [R manufactured by Dainippon Ink and Paper Co., Ltd.
-11] 5 parts were uniformly mixed, kneaded with a twin-screw extruder having an internal temperature of 150 ° C., the cooled product was finely pulverized with a jet mill, and classified with a dispersion separator to obtain toners having an average particle diameter of 9 μm. The dispersibility of the compound (C) in the obtained toner at 50 ° C., the dispersed particle size, and the degree of the molten state at 80 ° C. or higher are determined by an optical microscope equipped with a heating / cooling device for a microscope (TH 600RH manufactured by Japan High Tech). It was confirmed using Nikon OPTIPHOT-POL). The results are shown in Table 5.

[0047]

[Table 5] ----------------------------------------------------------------------------------------------------------------------------------------------------------------- 50% value of ΔSp + 1.2log MW at 100 ° C State Dispersion particle size μm structural change at the time of temperature rise (Note 1) (Note 2) ---------------------------------------- --- Example 6 ○ 0.5 ◎ 6.1 (C-1) Example 7 ○ 2.0 ○ 4.8 (C-2) Example 8 ○ 1.0 ◎ 4.5 (C-3 ) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 3 ○ 10 <× 7.2 (D-1 ) Comparative Example 4 x-x 7.3 (D-2) ----------------------------------------- (Note 1): Takes a dispersed state ... ○ Does not take a dispersed state ... × (Note 2): (C) completely dissolves in (A) ... (C) dissolves part in (A) ... ○ (C) does not dissolve in (A) ... ×

Heat resistance was measured in the same manner as in Test Examples 7 and 8 except that the fixing portions of Test Examples 5 and 6 were replaced with a heat roller made of silicone rubber and a fixing machine equipped with a silicon oil supply device. The storability and triboelectric charge were measured. The evaluation results are shown in Table 6.

[Table 6]

Toners obtained in accordance with the present invention (Examples 6 to 6)
It can be seen that in 8), in comparison with Comparative Examples (Comparative Examples 4 to 5), the low temperature fixability is significantly excellent while maintaining the heat resistant storage stability and the hot offset resistance. Example 9, Comparative Example 4 Styrene / n-butyl acrylate (80% by weight / 20% by weight) having a number average molecular weight of 280,000, a weight average molecular weight of 760,000 and a glass transition point of 62 ° C. obtained by suspension polymerization method 40 parts of polymer, 60 parts of polystyrene having a number average molecular weight of 2,500, a weight average molecular weight of 5,900, a glass transition point of 62 ° C. and 4 parts of (B-4) obtained by a solution polymerization method are equipped with a cooling pipe and a stirrer. After charging in Kolben and purging with nitrogen, 120 parts of xylene was added and further purged with nitrogen. The temperature was raised to the reflux temperature with stirring, and the stirring was continued for 3 hours under reflux. After that, the line was switched, and devolatilization was performed while raising the temperature to 180 ° C. under normal pressure. When the temperature reached 180 ° C., the pressure was switched to reduced pressure, and after reaching 20 mmHg, it was devolatilized for 1.5 hours to obtain a styrene / acrylic copolymer (A3) having an Sp value of 9.9.
10 parts of (C-1) was added to (A3), and the toner of the present invention having an average particle size of 10 μm was obtained in the same manner as in Examples 3 to 5. (C
-1) instead of polyethylene wax (D-3) (S
Example 9 except using a p-value of 6.1, molecular weight 2000)
In the same manner as described above, a toner having an average particle diameter of 10 μ for comparison was obtained.
The dispersibility of the compound (C) in the obtained toner at 50 ° C., the dispersed particle size, and the degree of the molten state at 80 ° C. or higher are determined by a heating / cooling device for a microscope (TH 60 manufactured by Japan High Tech).
Optical microscope equipped with 0RH (Nikon OPTIPH
OT-POL). The results are shown in Table 7.

[0050]

[Table 7] ----------------------------------------- 50 ° C. 100 ° C. ΔSp + 1.2 log MW value State Dispersion particle size μm structural change at temperature rise (Note 1) (Note 2) ------------------------------ --- Example 9 ○ 1.0 ○ 5.3 (C-1) -----------------------. −−−− Comparative Example 6 ○ 10 <× 7.1 (D-1) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− -----

MFT and HO were carried out in the same manner as in Examples 3-5.
T, heat-resistant storage stability and triboelectric charge were measured. The measurement results are shown in Table 8.

[Table 8] It can be seen that the toner (Example 9) obtained according to the present invention is significantly superior to the comparative example (Comparative Example 6) in low temperature fixability while maintaining heat resistant storage stability and hot offset resistance. Further, the toner of Example 9 was continuously copied on 10,000 sheets. The image quality after copying 10,000 sheets is the same as the initial image quality, and it can be seen that the occurrence of spent, filming and the like are not recognized and the durability is excellent.

[0052]

The toner binder composition and the toner composition of the present invention are heated to 80 to 150 ° C. at the time of fixing, so that the wax (B) or the melting point is 120 ° C. or less and the melt viscosity at 120 ° C. is 10,000 cP. Since the following compound (C) is compatible with the binder resin (A) and the melt viscosity is lowered, the low-temperature fixability is excellent, and at room temperature, (B) or (C) has an average particle size in (A). Since it is dispersed in a size of 5 μm or less, the heat-resistant storage stability and the hot offset resistance are also good. In addition, the chargeability and durability are also good. As described above, the toner composition using the toner binder composition of the present invention has not only the fixability (low temperature fixability and offset resistance) but also the performance required for practical use such as heat resistant storage stability, charging property and durability. Therefore, it is useful for copiers of various speeds (especially high speed copiers), printers, and full-color applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location 333 365

Claims (8)

[Claims] 1. A binder resin (A) and a wax (B) having a melting point of 70 ° C. or less, wherein the Sp value of (A) and the Sp value of (B).
The absolute value of the difference between the values is 1.5 or less, (B) is compatible with (A) between 80 and 150 ° C., and (B) has an average particle size of 5 μm in (A) at room temperature. A toner binder composition for electrophotography, which is dispersed below. 2. An electrophotographic toner composition comprising a binder resin (A), a wax (B) having a melting point of 70 ° C. or less, and a colorant, the difference between the Sp value of (A) and the Sp value of (B). Has an absolute value of 1.5 or less, (B) is compatible with (A) between 80 and 150 ° C., and (B) is dispersed in (A) with an average particle size of 5 μm or less at room temperature. A toner composition for electrophotography, comprising: 3. A binder resin (A) and a compound (C) having a melting point of 120 ° C. or less and a melt viscosity at 120 ° C. of 10,000 cP or less, satisfying the following mathematical formula (1), and (C) at room temperature. Is dispersed in (A) with an average particle diameter of 5 μm or less, and (C) is compatible with (A) at a temperature of 80 to 150 ° C., a toner binder composition for electrophotography. 4.0 ≦ ΔSp + 1.2 log MW ≦ 7.0 (1) [where ΔSp represents the absolute value of the difference between the solubility parameters (Sp values) of (A) and (C), and logMW represents the molecular weight of (C) ( However, when there is a molecular weight distribution, it represents the logarithmic value of (weight average molecular weight). ] 4. A binder resin (A), a compound (C) having a melting point of 120 ° C. or less and a melt viscosity at 120 ° C. of 10,000 cP or less, and a colorant, satisfying the following mathematical formula (1), and at room temperature: A toner composition for electrophotography, characterized in that (C) is dispersed in (A) with an average particle size of 5 μm or less, and (C) is compatible with (A) between 80 and 150 ° C. 4.0 ≦ ΔSp + 1.2 log MW ≦ 7.0 (1) [where ΔSp represents the absolute value of the difference between the solubility parameters (Sp values) of (A) and (C), and logMW represents the molecular weight of (C) ( However, when there is a molecular weight distribution, it represents the logarithmic value of (weight average molecular weight). ] 5. The (A) is at least one selected from the group consisting of a polyester resin (A1), a polystyrene resin (A2), a styrene / (meth) acrylic copolymer (A3) and an epoxy resin (A4). The composition according to any one of 1 to 4. 6. The composition according to claim 5, wherein (A) is a polyester resin. 7. The composition according to claim 5, wherein (A) is a styrene / (meth) acrylic copolymer. 8. The weight ratio of (A) to (B) or (C) is 100 / 0.1 to 100/30.
The composition according to any one of 1.