JPH01179951A - Binder for toner - Google Patents

Abstract

PURPOSE:To obtain a polyester type binder having good fixability in a wide temperature range by using a polyester type binder having at least one peak in each of 2 specified molecular weight ranges in a molecular weight distribution diagram. CONSTITUTION:The polyester type binder resin to be used for a toner has at least one peak in each of the lower molecular weight range of 5X10<4>-1X10<3>, and the higher molecular weight range of 2X10<6>-5X10<4> in the molecular weight distribution diagram measured by the gel permuation chromatography, thus permitting balanced good fixability covering fixing conditions in a wide temperature range to be ensured.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a binder for toner that can be used to develop electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. relates to a toner binder made of a polyester resin having multiple molecular weight peaks.

[Prior Art] Generally, toner binders include styrene resin,
Polyester resins are often used.

[Problems to be Solved by the Invention] Polyester resins generally have superior storage stability as toner binders compared to styrene/acrylic resins, exhibit good fixing behavior in a relatively narrow fixing temperature range, and have a strong Although these properties are being utilized, the reality is that they have poor pulverizability and high toner manufacturing costs, which limits their use. In particular, with the recent commercialization of high-speed copying machines and printers, maintaining good fixing properties over a wide temperature range required for toner fixing behavior is required in manufacturing aspects of polyester's inherent molecular weight distribution. It has the drawback that it is difficult to deal with it due to the restrictions. In other words, in order to support fixing in a wide temperature range from high to low temperatures, measures are generally taken to widen the molecular weight distribution, and in the case of polyester, polyhydric carboxylic acids are used as crosslinking agents. However, it is not possible to sufficiently meet the quality required from the toner characteristics. This is because the molecular weight distribution becomes essentially uniform due to the transesterification reaction during production. Furthermore, even within this range, if we try to widen the molecular weight distribution and increase the molecular weight as much as possible to widen the allowable fixing temperature range, the problem arises that the crushability during toner production is extremely reduced, making it difficult to achieve well-balanced binder properties. sea bream. The purpose of the present invention is to be able to appropriately respond to fixing conditions in a wide temperature range, to exhibit good fixing properties, and to reduce toner production costs due to good crushability, and to have the excellent properties originally possessed by polyester binders. The objective is to provide a biased polyester binder that maintains other properties such as shelf life.

[Means for Solving the Problems] The present invention provides a molecular weight distribution map measured by Nigel permeation chromatography (hereinafter abbreviated as GPC) of: a) 2 x 106 to 5 x 104; This is a toner binder characterized by comprising a polyester resin each having at least one peak in a molecular weight range.

The binder of the present invention can be used, for example, between polyesters (A) having a functional group (a) other than a hydroxyl group and a carboxyl group (a group capable of chain extension or a crosslinkable group capable of crosslinking) at the terminal, or (A) and (a). A polyfunctional compound that is reactive with (
It can be produced by reacting with B).

Specific examples of the functional group and i include an isocyanate group, an epoxy group, an alkoxyl group, an alkoxysilane group, and a (meth)acryloyl group [represents an acryloyl group and/or a methacryloyl group. Similar expressions will be used below. ], other α, β-unsaturated groups, furyl groups, amino groups, etc.

Among these, α,β-unsaturated groups are preferred, and (meth)acryloyl groups are particularly preferred.

The polyester (A) according to the present invention is a saturated or unsaturated polyester (E ) and a compound (F) having a functional group (a).

Polyhydric alcohols (C) include (1) ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol,
Aliphatic glycols such as 1,6-hexanediol and coadducts thereof such as alkylene oxa, ide [ethylene oxide (hereinafter abbreviated as EO), polycopylene oxide (hereinafter abbreviated as PO); (2) hydroquinone;
Alkylene oxide (EO
and/or PO); (3) glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, glucose, 3 to 8 alcohols such as fructose and sucrose (alcohols and their alkylene oxide adducts; (4) alkanolamines (triethanolamine, tripropaturamine, etc.), alkylene diamines (2 to 6 carbon atoms) [ethylene diamine , hexamethylene diamine, etc., polyalkylene (alkylene has 2 to 2 carbon atoms)
6) Polyamines [diethylenetriamine, triethylenetriamine, etc., aromatic amines (aniline, phenylenediamine, diaminotoluene, xylylenediamine,
(methylene dianiline, diethyltolylene diamine, diphenyl ether diamine, etc.), alicyclic amines (isophorone diamine, cyclohexylmethane diamine, cyclohexylene diamine, etc.), heterocyclic amines (piperazine, aminoedylpiperazine, and other stocks)
Examples include amino group-containing polyhydric alcohols obtained by adding alkylene oxide (EO and/or PO) to such as those described in Japanese Patent No. 044; and mixtures of two or more thereof.

Preferred among these are ethylene glycol, neopentyl glycol, bisphenols (especially bisphenol A) to which 2 to 3 moles of alkylene oxide are added, and mixtures thereof, and particularly preferred are bisphenols with alkylene oxide added to them. 2
~3 mole addition, neopentyl glycol, and mixtures of two or more of these. The use of neopentyl glycol improves the crushability of the resulting polyester resin.

Polybasic acids (D) include (1) succinic acid, maleic acid, fumaric acid, itaconic acid, azelaic acid, mesaconic acid, citraconic acid, cepacic acid, glutaconic acid, adipic acid, malonic acid, phthalic acid, isophthalic acid, Dibasic acids such as terephthalic acid, cyclohexanedicarboxylic acid, nadic acid, methylnadic acid, octylsuccinic acid, dodecenylsuccinic acid; (2) trimellitic acid, 1,2,4-cyclohexanedicarboxylic acid, 2,5.7- naphthalene tricarboxylic acid,
1゜2.4-butanetricarboxylic acid, 1,2,5-hexanetriorboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, pyromellitic acid, benz'phenonetetracarboxylic acid, cyclo Trivalent or higher polybasic acids such as pentadienetetracarboxylic acid, tetra(methylenecarboxyl)methane, and 1,2,7,8-octanetetracarboxylic acid; and anhydrides and lower alkyl esters of these acids. . Other polymerized fatty acids such as dimers and dimers of sulfuric acid can also be used.

(D) can be used alone or as a mixture of two or more.

Among these are succinic acid, maleic acid, fumaric acid,
Preferred are phthalic acid, isophthalic acid, terephthalic acid, and alkyl or alkenyl (4 to 18 carbon atoms) succinic acids such as octylsuccinic acid and dodecenylsuccinic acid.

The polyester (E) according to the present invention is preferably a linear type; C) and/or (
(usually 1 to 30 mol %, preferably 2 to 10 mol %)] in D) can also be used. In addition, in addition to polyhydric alcohol (C) and polybasic acid (D), amide bond-containing polyester produced using a small amount of polyamines such as hexamethylene diamine and methylene diamine can also be used as polyester (E) according to the present invention.
It can be used as

In the above-mentioned condensation reaction between polyhydric alcohol (C) and polybasic acid (D), the reaction ratio between hydroxyl group (or hydroxyl group + amino group) and carboxyl group is usually 1:1.3 to 1:0. 7, preferably 1:1.2 to 1:0.8.

The reaction can be carried out, if necessary, in the presence of an esterification catalyst (zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate, etc.) at any temperature, usually from 150 to 250°C. Further, the reaction can be carried out under normal pressure or reduced pressure, in the presence or absence of an inert gas or solvent (toluene, xylene, etc.).

The acid value and hydroxyl value of polyester (E) are each usually 100 or less, preferably 60 or less.

Examples of the compound (F) having a functional group (a) include polyisocyanate, epoxy resin, silane coupling agent, maricic anhydride, fumaric acid, glycidyl (meth)
Examples include acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl isocyanate, and polyamines.

Examples of the polyisocyanate include aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding carbon in the NCO group), alicyclic polyisocyanates having 4 to 15 carbon atoms, and 8 to 12 carbon atoms.
Aroaliphatic polyisocyanates, aromatic polyisocyanates having 6 to 20 carbon atoms, and modified products of these polyisocyanates (containing carposiimide groups, uretdione groups, uretdione groups, urea groups, biuret groups, and/or isocyanurate groups) modified products, etc.) can be used. Such polyisocyanates include ethylene diamine diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (IIDI), dodecamethylene diisocyanate, 1,6.11-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,
6-Diucyanate methyl caproate, bis(2-
isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diitsocyanate hexanoate; isophorone diisocyanate 1- (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexyl Silene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated MDI), bis(2-isocyanateethyl)4-cyclohexene-1,2-dicarboxylate; xylylene diisocyanate, diethylbenzene diisocyanate); IIDI marine products, IP
Trimerized products of DI, etc.; tolylene diisocyanate (TD
I), crude TDI, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (crude ID1), modified M[)l (such as carposiimide-modified MDI), naphthylene diisocyanate; and mixtures of two or more thereof. It will be done. Among these, preferred are H[)I, IPDl, TI')I
, ID1 and modified MI')I.

Epoxy resins include (1) phenol ether epoxy resins [condensates of bisphenols and epichlorohydrin, condensates of novolak phenol resin and epichlorohydrin, etc.]
(2) Ether-based epoxy resins [condensates of polyols, polyether polyols, etc., and epichlorohydrin, etc.]; (3) Ester-based epoxy resins [glycidyl (meth)acrylate and ethylenically unsaturated monomers (acrylonitrile, etc.) (4) Glycidylamine-based epoxy resins [Condensates of amines and epichlorohydrin, etc.; (5) Non-glycidyl-type epoxy resins [
Examples include cyclic epoxy resins, epoxidized polybutadiene, epoxidized soybean oil, and mixtures of two or more thereof.

Among these, preferred are (1) and (4).

Examples of the silane coupling agent include alkoxylated silanes having groups such as amino groups, epoxy groups, and isocyanate groups, such as γ-aminopropyltriethogysilane, N-(β-aminoethyl)- γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-, isocyanate Examples include propyltriethoxysilane.

Examples of the polyamines include the various polyamines described in the section of the amino group-containing polyhydric alcohol (C) above.

Preferred among (F) are maleic anhydride, silane coupling agents, glycidyl methacrylate and polyisocyanates, and among these, glycidyl methacrylate and 'maleic anhydride are particularly preferred.

The reaction ratio of (E) and (F) is usually 1:1.3 on a molar basis
1:0.7 to 1:0.7, preferably l:1.2 to 1:0.8.

In (A) containing (a), the content of (a) is (A)
The amount is usually 5 to 100 mol%, preferably 10 to 50 mol%.

(A) may have an 0H1COOH group in addition to (a).

Among the polyesters (A), those derived from neopentyl glycol polyesters and bisphenol alkylene oxide adduct polyesters are preferred.

The former is particularly preferred.

As the compound (B) having reactivity with the functional group (a),
Examples include ethylenic polyfunctional monomers.

Also, polyfunctional compounds having a functional group selected from the group consisting of a silicon hydride group, an amino group, an epoxy group, a hydroxyl group, an isocyanate group, and an acid anhydride group, such as polyamines, polysilicon compounds, polyisocyanates, and epoxy Examples include resin.

The ethylenic polyfunctional monomer includes a compound (I) having at least two polymerizable double bonds and at least one functional group having at least one polymerizable double bond and reactive with the monomer. Compound (II) is mentioned. Examples of compound (I) include the following compounds.

(1) Bis(meth)acrylamide: N,N'-alkylene (C1-6) bis(meth)acrylamide, such as N,N'-methylene acrylamide.

(2) Di- or polyester of polyols and unsaturated mono- or polycarboxylic acids: Polyols [ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol,
Di- or tri-(meth)acrylic esters of polyoxypropylene chloride, etc.: Unsaturated polyesters [obtained by reaction of the above polyols with unsaturated acids such as maleic acid] and di- or tri-(meth)acrylic acid Esters [such as those obtained by the reaction of polyepoxide and (meth)acrylic acid.

(3) Carbamyl ester: polyisocyanate [tolylene diisocyanate, hexamethylene diisocyanate, 4,4ξ diphenylmethane diisocyanate and NCO group-containing prepolymer (
carbamyl ester obtained by the reaction of the above-mentioned polyisocyanate and a compound containing an active hydrogen atom) and hydroxyethyl (meth)acrylate.

(4) Di- or polyvinyl compounds; divinylbenzene, divinyltoluene, divinylxylene, divinyl ether, divinyl ketone, trivinylbenzene, etc.

(5) Di- or poly(meth)acrylic ether of polyols: Polyols [alkylene chloride, glycerin, polyalkylene glycol, polyalkylene polyol,
Di- or poly(meth)allyl ethers such as carbohydrates such as polyethylene glycol diallyl ether and allylated starches, allylated celluloses.

(6) Sea or polyallyl esters of polycarboxylic acids: diallyl phthalate, diallyl adipate, etc.

(7) Esters of unsaturated mono- or poly-carboxylic acids and mono(meth)allyl ethers of polyols: (meth)acrylic acid esters of polyethylene glycol monoallyl ethers, etc.

(8) Allyloxyalkanes: such as tetraallyloxyethane.

Examples of compound (II) include carboxyl groups, groups reactive with carboxylic acid anhydride groups (hydroxyl groups,
Examples include ethylenically unsaturated compounds containing epoxy groups, cationic groups, etc. Specifically, unsaturated compounds containing nonionic groups, such as unsaturated compounds containing hydroxyl groups [
N-methylol (meth)acrylamide, etc.] and epoxy group-containing unsaturated compounds [gutosidyl (meth)acrylate, etc.] and cationic group-containing unsaturated compounds,
For example, unsaturated compounds containing quaternary ammonium bases [N,
N,N-trimethyl-N-(meth)acryloyloxyethyltrimethylammonium chloride, N,N.

N-triethyl-N-(meth)acryloyloxyethyl ammonium chloride, etc., and unsaturated compounds containing tertiary amino groups [dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.] Can be mentioned.

As the polyhydride silicon compound, one having 2 to 20 silicon atoms can be used, but an orcappolysiloxane compound is preferable. The organopolysiloxane compound is any linear, branched, cyclic, or network compound, and the organo group is a monovalent hydrocarbon having 1 to 12 carbon atoms selected from alkyl groups, aryl groups, etc. Groups are preferred. Specifically, 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,5°7.7,7-octamethyltetrasiloxane and, for example, JP-A-554376
Examples include those described in Publication No. 7.

The same polyamines, polyisocyanates, and epoxy resins as mentioned in (F) can be used.

Among (B), preferred is compound (1). Among compounds (I), preferred are the above (2) and (4).
), among which divinylbenzene is particularly preferred.

(A) and (B) (7) in the production of polyester resin
) The preparation weight ratio is usually 1.0:0.7~0.7:
There is 1.0 te. The reaction temperature is usually 20 to 200°C and the reaction time is usually 0.1 to 20 hours.

The peak molecular weight of the low molecular weight peak of the obtained polyester resin is usually 5 x 104 to 1 x 103. Preferably 8x
103 to 2x103, and the peak molecular weight of the high molecular weight peak is usually 2x106 to 5x104, preferably 5x1
05~8x104.

The following ratio of the peak molecular weight of the high molecular weight peak to the peak molecular weight of the low molecular weight peak is the peak molecular weight of the high molecular weight peak, the peak molecular weight of the low molecular weight peak, and is usually 10 or more, preferably 10 to 500. When this ratio is less than 10, and when there is no peak in each of a) and 0), the balance between low temperature fixing properties as a binder and double-sided copying properties becomes poor.

The number average molecular weight of polyester resin is usually 2×10
4~2X103, weight average molecular weight is usually 3x10
5 to 1×104.

Its glass transition point is usually 40-90°C, and its softening point is usually 80-180°C. If the glass transition point and softening point are below this range, the toner will have insufficient fluidity, and if it exceeds this range, the low-temperature fixability will be poor.

Note that the molecular weight of the binder according to the present invention was measured by GPC. Tetrahydrofuran was used as a solvent, and the molecular weight was expressed in terms of polystyrene.

Examples of the reaction format between (A) and the reaction format between (A) and (B) of the present invention include those shown in Tables 1 and 2.

Reaction between Table 1 (A) Reaction between Table 2 (A) and (B) Specific examples of the polyester resin in the present invention include the following.

(A): Products manufactured by reacting (A) with each other (
1) A reaction between (meth)acryloyl groups - A reaction product of polyester (E) and glycidyl methacrylate (A), such as a condensate of bisphenol A with 2 moles of EO and terephthalic acid. (
A product produced by reacting polyesters (A) obtained by adding glycidyl methacrylate to E).

(2) Reaction between isocyanate groups - Reaction between polyester (E) and diphenylmethane diisocyanate reactant (A) (isocyanurate formation).

(3) Reaction between alkoxysilane groups - Polyester (E) and γ-isocyana! - A product obtained by reacting the reaction product (A) with propyltriethoxysilane.

(4) Reaction between epoxy groups - Reaction between polyester (E) and bisphenol A diglycidyl ether (A).

(5) Reaction product of α, β-unsaturated group and (meth)acryloyl group ・Reaction product of polyester (E) and maleic anhydride (A
) is reacted with a reaction product (A') of polyester (E) and glycidyl methacrylate.

(6) Other examples include the following.

i) Reaction between epoxy group-containing polyester and amino group-containing polyester ii) Reaction between epoxy group-containing polyester and isocyanate group-containing polyester 1ii) Reaction between amino group-containing polyester and isocyanate group-containing polyester Among the above, preferred are ( 1).

(B): Products produced by reacting (A) and (B) (1) Products produced by the reaction of α-β unsaturated groups and ethylenic polyfunctional monomers / Products produced by the reaction of polyester (E) and maleic anhydride Reactant (A
) is reacted with divinylbenzene, for example, produced by reacting a reaction product (A) of polyester (E) from isophthalic acid, trimellitic anhydride and neopentyl glycol with maleic anhydride (A) with divinylbenzene. thing.

(2) A product obtained by reacting a (meth)acryloyl group with an ethylenic polyfunctional product - A product obtained by reacting a reaction product (A) of polyester (E) and glycidyl methacrylate with divinylbenzene.

- A product obtained by reacting a reaction product (A) of polyester (E) and glycidyl methacrylate with hexamethylene glycol diacrylate.

(3) Reaction of isocyanate and diamine - Reaction product (A) of polyester (E) and diphenylmethane diisocyanate with hydrogenated diphenylmethane diamine.

(4) By reaction between an allyl group and a polyhydride silicon compound - Polyester (E) and allyl isocyanate-1 - Which reactant (A) is reacted with 1.1,3.3-tetradimethyldisiloxane Something.

(5) Other examples include:

i) A product obtained by reacting an epoxy group-containing polyester with a polyamine.

11) A product obtained by reacting an epoxy group-containing polyester with a polyisocyanate.

1ii) A product obtained by reacting an amino group-containing polyester with a polyepoxy compound.

A product made by reacting an ugly amino group-containing polyester with a polyisocyanate compound.

(2) A product obtained by reacting an isocyanate group-containing polyester with a polyepoxy compound.

Among the above, preferred are (1) and (2).

When the polyester resin according to the present invention is made into a toner, a known toner binder such as styrene or styrene/acrylic resin may be added to the polyester resin according to the present invention, if necessary.

The polyester resin according to the present invention is mixed with a colorant to form a toner, and when preparing the toner, it is necessary to add a charge control agent, a magnetic substance, a wax as an anti-offset agent, and a hydrophobic agent as a fluidity improver. Additives such as silica can be added.

Coloring agents include carbon black, red iron, acetylene black, phthalocyanine blue, benzidine yellow, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine B.
Base, Solvent Red 49, Solvent Red 14
6. Pigments and dyes such as Solvent Blue 35 can be mentioned, and about 1 to 20 parts by weight are used per 100 parts by weight of the binder of the present invention.

When producing a magnetic toner using the binder of the present invention, examples of the magnetic substance include ferromagnetic powders such as iron, cobalt, and nickel, or metals or compounds containing ferromagnetic elements such as ferrite, hematite, and magnetite. can. The magnetic material is usually in the form of a fine powder with an average particle size of 0.1 to 1 micron, and can be used by dispersing it in an amount of about 40 to 70 parts by weight per 100 parts by weight of the binder of the present invention.

Further, in the present invention, when forming a toner, a known toner binder such as styrene or styrene/acrylic resin may be used in addition to the polyester resin in the present invention, if necessary.

The toner according to the present invention is manufactured by approximately the following method. That is, after mixing the polyester resin of the present invention, a coloring agent, and other additives if necessary in a desired ratio, this is kneaded using an extrusion kneader or the like, and the kneaded product is cooled and coarsely ground using a pulverizer. The coarsely ground material is then pulverized using an air jet mill or the like. If necessary, this fine powder is treated with hot air at 150 to 250 DEG C. to form fine spheres, and then classified to 15 to 20 microns, which is used as a toner.

[Examples] Hereinafter, the present invention will be specifically explained using production examples, examples, comparative examples, and usage examples, but the present invention is not limited thereto. The compositions of the raw materials used in the production examples, examples, comparative examples, and usage examples are as follows. Naobu increase%
represent parts by weight and % by weight, respectively.

(1) Glyco-non-A: EO2 of bisphenol A,
2 molar adduct (2) Glyco-Non-B: PO2,2 molar adduct of bisphenol A (3) NPG: Neopentyl glycol (
4) IPA: Isophthalic acid (5) TPA
: Terephthalic acid (6) PA : Phthalic acid (7) DMT : Dimethyl terephthalic acid 1.
(8) DSA Nidodecenyl succinic anhydride (9)
TMAA: I-limellitic anhydride (10) MAA
: Maleic anhydride (11) DVB Nidivinylbenzene (approx. 54% purity) (12) MD I : 4,4'-diphenylmethane diisocyanate I (13) Hydrogenated DAM : Hydrogenated diaminodiphenylmethane (14) BPO : Benzoyl Veroxa. Ido (15)
IPTES: γ-isocyanatopropyltriethoxysilane (16) DBTDL: dibutyl tin dilaure 1.
Moreover, the conditions for molecular weight measurement by GPC are as follows.

Equipment: Toyo Soda M IILc-802A Column: TSK get GMl16 2 pieces (
(manufactured by Toyo Soda) Measurement temperature: 25°C Sample reservoir 11ν: 0.5wt% tetrahydrofuran solution Injection volume: 200/11 Detection device: Refractive index detector The molecular weight calibration curve was created using standard polystyrene.

Production Example 1 Glycol A 7100 parts, Glycol B 192 parts, T
4 parts of 232 parts of PA and 0.8 parts of dibutyltin oxide
Place in a Tulo flask, attach a thermometer, stainless steel stirring bar, condenser and nitrogen inlet tube, and heat to 200°C under a nitrogen stream.
and reacted. The acid value of the obtained polyester was 2.7.011 mg/g, the hydroxyl value was 47.011 mg/g,
The glass transition temperature measured by DSC (differential calorimeter) was 58°C.

The GPC measurement results are a number average molecular weight of m2,200, a weight average molecular weight of 6,200, and a peak molecular weight of 5.600.
Met.

Production Example 2 287 parts of glycol A, 505 parts of glycol B, TPA
130 parts of dibutyltin oxide and 0.6 parts of dibutyltin ogicide were placed in a 4-tube flask, and reacted in the same manner as in Production Example 1 until the acid value became 3 or less. The glass transition temperature of the obtained polyester was 55°C, and the results of GPC measurements were a number average molecular weight of 5.500, a weight average molecular weight of 1'7.000, and a peak molecular weight of 13,000.

Production Example 3 194 parts of DMT, 187 parts of IPA, 300 parts of NPC, and 1 part of cobalt acetate were placed in the same reactor as in Production Example 1, and the reaction was gradually proceeded from about 140°C until the maximum temperature was 200°C.
The reaction was carried out until the acid value reached 3 or less. Then, 72 parts of TMAA was added to continue the reaction. The acid value was monitored and the reaction was terminated when it reached 1. The glass transition temperature of the obtained polyester was 57°C. The GPC measurement results are a number average molecular weight of 5,200 and a weight average molecular weight of 130,000.
, Atta with a peak molecular weight of 16,000.

Production Example 4 7136 parts of DM, 30 parts of PA, 124 parts of NPC, and 0.2 parts of dibutyltin oxide were placed in the same reactor as in Production Example 1, and the reaction was gradually proceeded from about 140°C until the maximum temperature was 200'CT: acid value The reaction was carried out to 3 or less. The GPC measurement results were a number average molecular fi of 3,800, a weight average molecular weight of 9.200, and a peak molecular weight of 5,200.

Example 1 300 parts of the polyester of Production Example 1 and 5 parts of MAA were placed in a 4-pro flask and reacted at 170° C. for 3 hours under a nitrogen atmosphere. After diluting with 300 parts of toluene, DVD
12 parts and 2 parts of T3P0 were added and heated at 85°C for 5 hours.
The reaction was further continued at 100°C for 2 hours. Then add 1 low volatile matter
The binder of the present invention, which is a polyester resin having an acid value of 6.2 and a glass transition temperature of 60'C, was obtained by distillation at 10 to 170°C. In addition, this polyester resin has 180,0
It had clear molecular weight peaks at 00, 5, and 500.

Ta.

Example 2 300 parts of the polyester of Production Example 2 was dissolved in 450 parts of toluene in a 4-tube flask. Next, MDllll, 7
of the mixture and reacted at about 80° C. for 3 hours under a nitrogen stream.

After cooling to about 30°C, a mixed solution of 9.8 parts of hydrogenated DAM and 50 parts of toluene was dropped over 30 minutes, and after the dropping was completed, the temperature was gradually raised and the reaction was carried out at 80°C for 3 hours. 110-170
Distill low volatiles at ℃, glass transition temperature 58℃ 1580
A binder of the present invention, which is a polyester resin having distinct molecular weight peaks at ,000 and 14,000, was obtained.

Example 3 300 parts of the polyester of Production Example 1 was dissolved in 450 parts of toluene in a 4-tube flask. Next, IPTES 2
0 part was added, and the reaction was carried out at about 90° C. for 8 hours under a nitrogen stream. Next, add 2 parts of DBTDL and 10 parts of water, and add 5 parts at the same temperature.
After reacting for an hour, the volatiles were distilled off at 110-170°C, and the glass transition temperature was 59°C; 350,000 and 5.80.
A binder of the present invention, which is a polyester resin having a clear molecular weight peak at 0, was obtained.

Example 4 300 parts of the polyester of Production Example 4 and 5 parts of MAA were placed in a 4-tube flask, and heated at 170'C under a nitrogen atmosphere for 30 minutes.
Allowed time to react. After the reaction solution was cooled, it was diluted with 300 parts of toluene, and then 312 parts of DVI and 2 parts of 13P0 were added thereto and reacted at 85° C. for 5 hours and then at loO'c for 2 hours.

The low volatile matter was distilled off at 110 to 170°C, and the acid value was 5.8+n.
gKOIl/g, glass transition temperature 58°C; 210,0
The binder of the present invention, which is a polyester resin having distinct molecular weight peaks of 00, 5, and 800, was obtained.

Comparative Example 1 300 parts of each of the polyesters of Production Example 1 and Production Example 3 were placed in a 4-ton flask and mixed at about 200° C. under a nitrogen atmosphere. The glass transition temperature of the obtained polyester was 57°C, and its molecular weight distribution diagram had only one peak at molecule ff19,200.

Comparative Example 2 Styrene/acrylic copolymer (weight average molecular weight 70.0
00).

Comparative Example 3 166 parts of TPA, 320 parts of Glyco/1zA, TMAA
Production Example 1: 9 parts of I and 0.1 part of dibutyltin oxide
and reacted at 200 to 2200C, acid value 0°8mgKOH/g, glass transition point 58°C1 number average molecular ff15,100, weight average molecular weight 230,00.
A polyester having a peak molecular weight of 0.0 and a peak molecular weight of 7,000 was obtained.

Usage Example 1 (Minimum fixing temperature of toner and double-sided copyability) 7 parts of carbon black was mixed with 893 parts of the binder of Examples 1 to 4 and Comparative Examples 1 and 2, then melted and kneaded with a pressure kneader, and after cooling. , crushed and classified, with an average particle size of 13
Adjusted micron toner.

95 parts of resin-coated iron powder was added to 30 parts of the obtained toner.
0 parts was added and mixed to prepare a developer, and image production was evaluated using a commercially available electrophotographic copying machine (photoreceptor is amorphous selenium, heat roller temperature of fixing device is variable). The results are shown in Table-3.

The minimum fixing temperature here is j l 5-LO840-
1-71 D Using a specified friction tester, rub the toner fixing surface and a white rubbing cloth against each other, measure the optical reflection density of the image surface before and after rubbing with a Macbeth reflection densitometer, and calculate the following formula: The temperature of the heat roller when the fixing rate exceeds 70%.

The double-sided copying properties were graded from 1 to 10 depending on the degree of staining on the lining of the copy paper. Practical double-sided copyability requires grade 6 or higher, preferably grade 7 or higher.

Table 3 Evaluation Results (1) Usage Example 2 (Toner Crushability) The binders obtained in Example 4 and Comparative Example 3 were made into toner according to the evaluation example. The particle size of the toner obtained by pulverizing with a jet mill type pulverizer under the same conditions is shown in Table 4 below.

Table 4 Evaluation Results (2) It was found that Example 4 according to the present invention had excellent crushability.

[Effects of the Invention] The binder of the present invention exhibits a well-balanced and good fixing behavior that can withstand fixing conditions in a wide temperature range that could not be achieved with polyester binders conventionally available on the market. The unavoidable difficult grindability has also been improved, reducing toner manufacturing costs.

Claims (1)

[Claims] 1. In the molecular weight distribution map measured by gel permeation chromatography, a) 2 x 10^6 to 5 x 10^4, b) 5 x 10^4 to 1 x 10^3 1. A toner binder comprising a polyester resin each having at least one peak in the molecular weight range. 2. The polyester resin has a functional group (a) other than a hydroxyl group and a carboxyl group at the end of the polyester (A), or (A) and a polyfunctional compound (B) that is reactive with (a). Claim 1 manufactured by reacting
Binder described in section. 3. The binder according to claim 2, wherein (a) is an α,β-unsaturated group. The binder according to claim 3, wherein the 4, α, β-unsaturated group is a (meth)acryloyl group. 5. The binder according to claim 2, wherein (a) is a functional group selected from the group consisting of an isocyanate group, an amino group, an epoxy group, and an alkoxy silicon group. 6. The binder according to any one of claims 2 to 5, wherein (B) is an ethylenic polyfunctional monomer. 7. The binder according to claim 6, wherein the ethylenic polyfunctional monomer is divinylbenzene. 8. Claims 2 to 8, wherein (B) is a polyfunctional compound having a functional group selected from the group consisting of a silicon hydride group, an amino group, an epoxy group, a hydroxyl group, an isocyanate group, and an acid anhydride group. The binder according to any one of Item 5. 9. The binder according to any one of claims 2 to 8, wherein (A) is derived from neopentyl glycol polyester. 10. The binder according to any one of claims 1 to 9, wherein the polyester resin has a softening point of 80 to 180°C and a glass transition point of 45 to 90°C. 11. The binder according to any one of claims 1 to 10, wherein the following ratio of the polyester resin is that the peak molecular weight of the high molecular peak/the peak molecular weight of the low molecular peak is 10 or more.