JPH11153885A - Electrophotographic toner binder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a electrophotographic toner binder having both of low temperature stability and resistance to hot offset trouble and appropriate in charge amount and superior in stability to circumstances by preparing the binder specified on an acid value by reaction with a polyester resin having a nonlinear structure and a specified weight average molecular weight and a specified ratio of the weight average molecular weight to the number average molecular weight with a specified vinyl polymer. SOLUTION: The toner binder having an acid value of 5-50 is prepared by reaction of the polyester resin having a nonlinear structure and a weight average molecular weight of 5,000-200,000 and a ratio of a weight average molecular weight to number average molecular weight of 3-50 with the vinyl polymer represented by the formula in a weight ratio of 99:1 to 50:50. In the formula, each of R1 -R3 is an H atom or a methyl group, and R1 or R3 may be a -COOR'; each of R and R3 may combine with each other to form a carbonyl group; each of R and R' is an H atom or a 1-8C alkyl group; Z is a unit derived from one or more kinds of copolymerizable vinyl monomer; (m) is an integer of 1-100; and (n) is an integer of 2-100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner binder for electrophotography.

[0002]

2. Description of the Related Art Conventionally, as a dry toner used in electrophotography and the like, a toner obtained by melt-kneading a toner binder such as a styrene acrylic resin or a polyester resin together with a colorant and the like and finely pulverizing the same has been used. These dry toners are frictionally charged with a carrier such as ferrite powder or a charging member, and developed into an electrostatic latent image formed on a photoreceptor. Then, after transferring to paper or the like, fixing is performed by heating and melting using a hot roll. At this time, on the fixing surface, from the viewpoint of energy saving and miniaturization of a copying machine or the like, the toner does not fuse on the hot roll even at a higher hot roll temperature (hot offset resistance), and the hot roll temperature It is required that the toner can be fixed even at low values (low-temperature fixability). Further, in order to fix the image with a sufficient image density, it is necessary to have an appropriate charge amount. In addition, it is required that the difference in charge amount be small (environmental stability) at any temperature and humidity. In recent years, polyester-based toner binders have attracted attention because of their excellent low-temperature fixability as compared with styrene acrylic resins.

[0003]

SUMMARY OF THE INVENTION U.S. Pat.
No. 106 proposes a polyester using an alkylene oxide adduct of a polyhydric alcohol having a valence of 3 or more (such as trimethylolpropane). Further, U.S. Pat. No. 5,294,682 proposes a polyester resin using an oxyalkylene ether of a novolak type phenol resin. However, although the low-temperature fixability is satisfactory, sufficient hot offset resistance is still not obtained. Not been. In addition, a toner using a polyester-based toner binder has a problem in that the environmental stability of charging is insufficient, and when a magnetic toner is used, the charging amount is low and a sufficient image density cannot be obtained. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, and to provide a toner binder which has both low-temperature fixing property and hot offset resistance, has a proper charge amount, and is excellent in environmental stability.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have excellent low-temperature fixing property and hot offset resistance, and have an appropriate charge amount and excellent environmental stability. The present inventors have found an electrophotographic toner binder, and have reached the present invention.

That is, the present invention has a non-linear structure, a weight average molecular weight (Mw) of 5,000 to 200,000, and a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) of 3
And a vinyl resin (B) having a structure represented by the following general formula (1).
Are reacted at a weight ratio of 99: 1 to 50:50 to provide an electrophotographic toner binder comprising a resin (I) having an acid value of 5 to 50.

[0006]

Embedded image

Wherein R 1, R 2 and R 3 are a hydrogen atom or a methyl group, or R 1 or R 3 is —COO
It may be R ', or R and R3 may combine to form a carbonyl group. R and R 'each represent a hydrogen atom or 1 to 8 carbon atoms.
Represents an alkyl group. Z represents one or more units of a copolymerizable vinyl monomer. m is 1 to 100
N represents a number of 2 to 100. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The weight average molecular weight (Mw) of the polyester resin (A) is usually 5,000 to 200,000, preferably 10,000 to 150,000, more preferably 1 to 150,000.
000 to 100,000. When Mw exceeds 5000, the hot offset resistance becomes good, and
And low temperature fixability can be obtained. The ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is usually 3 to 50,
Preferably it is 4-30, More preferably, it is 5-20.
When Mw / Mn is more than 3, both low-temperature fixing property and hot offset resistance can be achieved, and when Mw / Mn is less than 50, the mixing property between the polyester resin (A) and the vinyl polymer (B) is improved and the homogeneity is improved. And a resin of stable quality can be obtained.

[0009] The composition of the polyester resin (I) in the present invention is not particularly limited, but may be a divalent carboxylic acid (a) and a dihydric alcohol (b), a trivalent or higher polycarboxylic acid (c) and And / or trihydric or higher alcohols (d). Specific examples of the divalent carboxylic acids (a) include (1) C2 to C20.
Aliphatic dicarboxylic acids (maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, etc.);
(2) alicyclic dicarboxylic acids having 8 to 20 carbon atoms (such as cyclohexanedicarboxylic acid and methylmedic acid); (3)
Aromatic dicarboxylic acids having 8 to 20 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid, etc.); (4) having 4 to 3 carbon atoms in the side chain
Alkyl or alkenyl (anhydride) succinic acid having 5 hydrocarbon groups [dodecenyl (anhydride) succinic acid, pentadecenyl (anhydride) succinic acid, etc.];
Examples thereof include anhydrides of lower carboxylic acids and lower alkyl (methyl, butyl, etc.) esters. Among them, the above-mentioned (1), (3), (4) and anhydrides and lower alkyl esters of these dicarboxylic acids are preferable, and (anhydride) maleic acid, fumaric acid, isophthalic acid, terephthalic acid, dimethyl terephthalate, dodecenyl ( (Anhydride) succinic acid and the like are more preferred. (Anhydride) maleic acid and fumaric acid are preferred in terms of high reactivity, and isophthalic acid and terephthalic acid are preferred in terms of increasing the glass transition temperature of the polyester.

Specific examples of the trivalent or higher carboxylic acids (c) include (1) aliphatic polycarboxylic acids having 7 to 20 carbon atoms (1,2,4-butanetricarboxylic acid, 1,2,5-hexane). Tricarboxylic acid, 1,3-dicarboxyl-2-
Methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid and the like); (2) an alicyclic polycarboxylic acid having 9 to 20 carbon atoms (1,2,2 (3) an 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, and the like; and anhydrides and lower alkyls thereof ( Methyl, butyl, etc.) esters. Of these, (3) and its anhydrides and lower alkyl esters are preferred, and 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid and their anhydrides and lower alkyl esters are particularly preferred in price and price. It is preferable in terms of imparting offset resistance to the toner.

In the above carboxylic acids, the divalent carboxylic acid (a) may be used alone, or the trivalent or higher carboxylic acid (c) may be used alone. Alternatively, these may be used in combination. Particularly for black and white toner, the combination of (a) and (c) is preferable. Specific examples of the dihydric alcohols (b) include:
(1) alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2 propylene glycol, 1,3-
Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5
(2) alkylene ether glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol);
(3) alicyclic diols having 6 to 30 carbon atoms (such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A); and (4) bisphenols (such as bisphenol A, bisphenol F and bisphenol S); and ( 5) An alkylene oxide [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, or the like] of the above bisphenol may be added in an amount of 2 to 8 mol. Of these, (1) and (5) are preferred, and (5) is more preferred. In the above (1), ethylene glycol increases the reaction rate, and 1,2-propylene glycol and neopentyl glycol are preferred from the viewpoint of low-temperature fixability.
Further, among the above (5), in particular, E of bisphenol A
O and / or PO 2 to 4 mole adducts are preferred in that they impart good offset resistance to the toner.

Specific examples of the trihydric or higher alcohols (d) 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) C6-C20 aromatic polyhydric alcohol (1,
3,5-trihydroxylmethylbenzene, etc.); and their alkylene oxide adducts; (3) oxyalkylene ethers of novolak-type phenol resins;
(4) Oxyalkylene ethers of heterocyclic compounds having two or more active hydrogens in the molecule such as isocyanuric acid and the like. The oxyalkylene ether of the novolak phenol resin (3) is an alkylene oxide adduct of the novolak phenol resin (g1), and (g1) is a phenol (phenol or a compound having 1 to 1 carbon atoms).
Substituted phenols having 35 or more hydrocarbon groups and / or halogen groups as substituents, and mixtures thereof; phenols, cresols and t-butylphenols are preferred) and aldehydes (formalin, paraformaldehyde, trioxane, etc.) And those produced by the polycondensation of The average number of moles of alkylene oxide added to one phenolic hydroxyl group in (g1) is usually 0.1 to 10 mol, preferably 0.2 to 4 mol,
More preferably, it is 0.3 to 2 mol. As the alkylene oxide, EO and / or PO are preferable.
Of these, the compounds (1), (3) and (4) are preferred, and (1) and (3) are more preferred. Of the above alcohols, dihydric alcohols (b) may be used alone, or trihydric or higher alcohols (d) may be used alone. Alternatively, these may be used in combination. In particular, the combination of (b) and (d) is preferable for a full-color toner.

In the polyester resin (A) of the present invention, monocarboxylic acids, monoalcohols, etc. can be used as necessary together with polycarboxylic acids and polyols for the purpose of adjusting the molecular weight and controlling the reaction. Specific examples thereof include monocarboxylic acids such as benzoic acid, paraoxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, piperionic acid, and stearic acid; benzyl alcohol, toluene-4-methanol, nonylphenol EO
One mole adducts and monoalcohols such as cyclohexanemethanol are mentioned.

The ratio of the carboxylic acid to the alcohol constituting the polyester resin (A) of the present invention is such that the hydroxyl group equivalent /
The ratio of the carboxyl group equivalent is usually 0.5 to 2.0, preferably 0.6 to 1.7, more preferably 0.6 to 1.
The ratio should be such that it becomes 6. When a carboxylic acid having a valency of 3 or more or an alcohol having a valency of 3 or more is used, from the viewpoint of low-temperature fixability, it is usually 3 times for black and white toner.
It is at most 5% by weight, preferably at most 25% by weight. When these are used in combination, the total is usually 35% by weight or less, preferably 25% by weight or less. Similarly, from the viewpoint of low-temperature fixability and glossiness, it is usually 20% by weight or less, preferably 15% by weight or less for a full-color toner. When these are used together, the total is usually 20
% By weight, preferably 15% by weight or less.

As an example of the method for producing the polyester resin (A) of the present invention, a polyester resin (A) is obtained by mixing a carboxylic acid and an alcohol at a predetermined ratio and performing a polyesterification reaction. The reaction is usually carried out in the presence of a catalyst at from 150 ° C to 300 ° C, preferably from 170 to 2 ° C.
It is performed under a temperature condition of about 80 ° C. The reaction can be performed under normal pressure, reduced pressure, or increased pressure. After reaching a predetermined reaction rate (for example, about 30 to 90%), the pressure of the reaction system is reduced to 200 mmHg or less, preferably 25 mmHg or less. It is desirable to carry out the reaction.

As the above-mentioned catalyst, those 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). The polyester resin (A) is stopped 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 stirring power of the reactor reaches a predetermined value. )
Can be obtained.

From the viewpoint of the reactivity between the polyester resin (A) and the vinyl polymer (B), the polyester resin (B)
The hydroxyl value is usually 5 to 100, preferably 7 to 80,
More preferably, it is 10 to 60. The acid value is usually 3 or less, preferably 2 or less from the viewpoint of controlling the reaction between the polyester resin (A) and the vinyl polymer (B) (suppressing side reactions).

In the general formula (1) representing the vinyl polymer (B) of the present invention, m is usually 1 to 100, preferably 1 to 70 for black and white toner from the viewpoint of hot offset resistance.
More preferably, it is 1 to 50, and similarly from the viewpoint of hot offset resistance and gloss, it is usually 1 to 100, preferably 1 to 30, and more preferably 1 to 20 for full color toner. From the viewpoint of the reaction rate between the polyester resin (A) and the vinyl polymer (B), n is usually 2 to 100, preferably 2 to 100, for black and white toner.
70, more preferably 2 to 50, and usually 2 to 100, preferably 2 to 30, and more preferably 2 to 20 for a full-color toner.

The vinyl polymer (B) of the present invention is a copolymer of the following general formula (2) and Z copolymerizable therewith.

[0020]

Embedded image

Wherein R 1, R 2 and R 3 are a hydrogen atom or a methyl group, or R 1 or R 3 is —COO
It may be R ', or R and R3 may combine to form a carbonyl group. R and R 'represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. As specific examples of the monomer represented by the general formula (2),
Acids (acid anhydrides) such as (meth) acrylic acid, (anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2
And (meth) acrylic esters such as -ethylhexyl. One or more of these are essential components, but two or more thereof may be used in combination.

Examples of Z include, but are not limited to, styrene, α-methylstyrene, p-methoxystyrene,
Examples thereof include styrene-based monomers such as p-hydroxystyrene and p-acetoxystyrene, vinyl ethers such as vinyl ethyl ether, and (meth) acrylonitrile. Of these, styrene monomers and (meth) acrylonitrile are preferred, and styrene and acrylonitrile are more preferred. One type of Z may be used, or two or more types may be used. In particular, a combination of styrenes and (meth) acrylonitrile is preferable, and by adjusting the composition ratio of styrenes and (meth) acrylonitrile, the compatibility between the vinyl polymer (B) and the polyester resin (A) is increased,
The reactivity can be improved. Styrenes and (meth)
The constituent ratio of acrylonitrile is preferably from 95: 5 to 50:50.

As the method for producing the vinyl polymer (B), methods such as solution polymerization, bulk polymerization, and suspension polymerization can be selected. Preferred is solution polymerization. The polymerization initiator is not particularly limited. For example, azo initiators such as azobisisobutyronitrile and azobisisovaleronitrile; benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl Peroxide initiator such as peroxide; 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Propane, 1,1-bis (t-butylperoxy) 3,
Polyfunctional polymerization initiators having two or more peroxide groups in one molecule such as 3,5-trimethylcyclohexane and di-t-butylperoxyhexahydroterephthalate; diallylperoxydicarbonate, t-butylperoxyallyl Examples include a polyfunctional polymerization initiator having one or more peroxide groups and one or more polymerizable unsaturated groups in one molecule such as carbonate. Of these, peroxide initiators are preferred.

The solvent used when the vinyl polymer (B) is obtained by solution polymerization is not particularly limited, but aromatic solvents such as toluene, xylene and ethylbenzene,
Examples thereof include ester solvents such as ethyl acetate and butyl acetate, dimethylformamide, dimethyl sulfoxide, and methyl ethyl ketone. Preferred are dimethylformamide, xylene and toluene.

The polymerization temperature of the vinyl polymer (B) is usually from 70 to 210 ° C., preferably from 100 to 200 ° C.
The atmosphere during the (co) polymerization is preferably carried out in the presence of an inert gas such as nitrogen or under a vapor atmosphere of a solvent, and is preferably carried out in a substantially oxygen-free state.

The acid value of the vinyl polymer (B) is usually 10 to 10 from the viewpoint of the reaction rate with the polyester resin (A).
700, preferably 20-600.

The number average molecular weight of the vinyl polymer (B) is usually from 300 to 100,000 from the viewpoint of hot offset resistance and low-temperature fixability. Preferably 30
It is 0-80000, more preferably 400-60,000. Glass transition point (Tg) of vinyl polymer (B)
Is usually 30 from the viewpoint of heat-resistant storage stability and low-temperature fixability.
To 120 ° C, preferably 35 to 110 ° C, more preferably 35 to 105 ° C.

The weight ratio of the polyester resin (A) of the present invention to the vinyl polymer (B) is usually from 99: 1 to 50:
50. It is preferably from 98: 2 to 60:40, and more preferably from 96: 4 to 65:35. Weight ratio 9
When the ratio exceeds 9: 1, good hot offset resistance is obtained,
When the ratio is less than 50:50, good resin uniformity and good low-temperature fixability can be obtained. Here, the uniformity of the resin means that the polyester resin (A) and the vinyl polymer (B) are completely homogeneously compatible and do not have a sea-island structure.

As an example of the method for producing the resin (I) of the present invention,
The resin (I) of the present invention can be obtained by mixing the polyester resin (A) and the vinyl polymer (B) at a predetermined ratio and performing an esterification reaction and / or a transesterification reaction. The reaction is usually carried out at 130 ° C. in the presence of a catalyst.
To 250 ° C., preferably about 150 to 230 ° C. The reaction can be performed under normal pressure, reduced pressure, or increased pressure. After reaching a predetermined reaction rate (for example, about 30 to 90%), the reaction system is reduced to 200 mmH.
g or less, preferably 25 mmHg or less. In order to assist the dissolution of the polyester resin (A) and the vinyl polymer (B), an aromatic solvent such as toluene, xylene and ethylbenzene, and a solvent such as dimethylformamide, dimethyl sulfoxide and methyl ethyl ketone may be used in combination. These solvents are eventually removed. The content of the solvent in the resin (I) is usually 1.0% by weight or less, preferably 0.5% by weight or less from the viewpoint of the heat-resistant storage stability of the toner.

The acid value of the resin (I) of the present invention is usually from 5 to 50, preferably from 7 to 40, more preferably from 10 to 35, from the viewpoints of charging startability and environmental stability. Similarly, from the viewpoints of charging startability and environmental stability, the resin (I) has a hydroxyl value of usually 100 or less, preferably 80 or less, more preferably 60 or less. From the viewpoints of heat resistance storage stability and low-temperature fixability of the toner, the Tg of the resin (I) is usually from 40 to 85 ° C, more preferably from 50 to 75 ° C. . The softening point of the resin (I) is usually from 90C to 200C, more preferably from 10C to 200C.
0 ° C to 170 ° C.

Specific examples of the resin (I) of the present invention include resins obtained by reacting the following (a) and (b). (A) Bisphenol A propylene oxide 2 mol adduct / propylene oxide adduct of phenol novolak resin / dimethyl terephthalate / dodecenyl succinic anhydride polycondensate (b) acrylic acid / methyl acrylate / styrene / methacrylonitrile copolymer ( a) cyclohexanedimethanol / bisphenol A propylene oxide 3 mol adduct / propylene novolak resin propylene oxide adduct / terephthalic acid / maleic anhydride polycondensate (b) maleic anhydride / styrene / acrylonitrile copolymer (a) bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct / propylene oxide adduct of phenol novolak resin / terephthalic acid / maleic anhydride polycondensate (b) acrylic acid Styrene / acrylonitrile copolymer (a) Bisphenol A propylene oxide 3 mol adduct / xylylene glycol / propylene oxide adduct of phenol novolak resin / isophthalic acid / trimellitic anhydride polycondensate (b) monomethyl maleate / styrene / Acrylonitrile copolymer

The toner binder of the present invention comprises the resin (I) of the present invention. If necessary, other toner binder resins may be contained within the range satisfying the above physical properties. Other resins for toner binder include polystyrene resin, styrene-acryl copolymer resin, styrene-butadiene copolymer resin, styrene-acrylonitrile copolymer resin, styrene-acryl-acrylonitrile copolymer resin, polyurethane resin, polyamide Resins, epoxy resins, polyester resins other than the present invention, and the like.

As an example of a method for producing a toner for developing an electrostatic image, which is used for 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, Sudan Black S
M, Fast Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Balanitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, orazol brown B, oil pink OP, etc.). Compounds such as cobalt, nickel, hematite, and ferrite) are usually used in an amount of 0 to 50% by weight. Furthermore, various additives [charge adjusting agent (Nigrosine dye, triphenylmethane derivative, quaternary ammonium salt compound, polymer containing polymerizable unit having quaternary ammonium base as a constituent unit, azo dye compound, salicylic acid metal complex , A copolymer containing a polymerizable monomer having an aromatic ring substituted with an electron-withdrawing group (such as a nitro group or a perfluoroalkyl group) and a polymerizable monomer having a sulfo group as constituent units, and the like. Mold agents (low-molecular-weight polyolefins or acid-modified products thereof; ester waxes such as carnauba wax and montan wax; long-chain fatty acid amide waxes and the like). The amount of these additives is usually 0 to 10% by weight based on the weight of the toner. The toner for developing an electrostatic image is dry-blended with the above components, melt-kneaded, then coarsely pulverized, and finally finely pulverized by using a jet pulverizer or the like to have a particle size of 5 to 20.
It is obtained as fine particles of μm.

The toner for developing an electrostatic image 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. A fluidity improver (hydrophobic colloidal silica fine powder or the like) can also be used to improve the fluidity of the powder. In addition, instead of the carrier particles, friction with a member such as a charging blade can be performed to form an electric latent image. The electrostatic image developing toner of the present invention is fixed on a support (paper, polyester film, or the like) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a support, a known hot roll fixing method, flash fixing method, or the like can be applied.

The method of the performance test of the toner in the present invention is described below. For a monochrome 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, and a magnetic toner using magnetic powder is used as it is. Tested as a component developer. (1) Monochrome toner (low gloss image) using carbon black Minimum fixing temperature (MFT) Monochrome copying machine (AR5030, Sharp Corporation)
The unfixed image developed by using a fixing unit of a commercially available monochrome copying machine (SF8400A, manufactured by Sharp Corporation) was modified at a process speed of 180 mm / sec using a fixing machine with a variable heat roller temperature. 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. Charge Amount 1 g of toner and 24 g of an electrophotographic ferrite carrier (FL961-150, manufactured by Powder Tech Co., Ltd.) are mixed for 20 minutes using a turbuler shaker mixer, and the charge amount is measured by a blow-off charge amount measuring device (manufactured by Toshiba Chemical). It measured using. The friction mixture and the charge amount were measured at room temperature and normal humidity (23 ° C., 50% RH) and the charge amount (N
/ N), and the value measured at high temperature and high humidity (28 ° C., 85% RH) is defined as the charge amount (H / H). (2) In the case of monochrome toner using magnetic powder (low gloss image) The minimum fixing temperature (MFT) and hot offset occurrence temperature are determined by using a commercially available laser printer (LBP-210;
The same test was conducted except that an unfixed image was obtained using Canon Inc.) and the fixing unit process speed was set to 72 mm / sec. The method for measuring the image density is shown below. Commercially available laser printer (LBP-
210; manufactured by Canon Inc.), and the image density was measured using a Macbeth densitometer. The image density (N / N) was obtained when development was performed at normal temperature and normal humidity (23 ° C., 50% RH), and the image density (H / H) was performed when development was performed at high temperature and high humidity (28 ° C., 85% RH). I do. (3) For full-color toner (high gloss image) Commercially available monochrome copier (AR5030, Sharp Corporation)
The unfixed image developed using the fixing device was fixed at a process speed of 80 mm / sec using a fixing unit of a commercially available full-color copying machine (CLC-1, manufactured by Canon Inc.). Commercially available gloss meter (MURAKAMI COLOR RE
GMX-20 manufactured by SEARCH LABORATORY
2-60 type) and the reflectance at 60 ° of the fixed image is 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. The measurement of the charge amount was performed in the same manner as described above.

[0036]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. Hereinafter, "part" indicates "part by weight". The methods for measuring the properties of the toner and toner binder obtained in Examples and Comparative Examples are described below. In addition, about the following 1 and 3, when the tetrahydrofuran insoluble matter 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. For the resin having a tetrahydrofuran insoluble content, the peak molecular weight was defined as the value of the 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 stirred and refluxed 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.

Preparation Example 1 of Polyester Resin (A) 1 In a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, 4742 parts of a propylene oxide 2 mol adduct of bisphenol A and 2 mol of an ethylene oxide adduct of bisphenol A 4458 parts, 5 mol ethylene oxide adduct of novolak type phenol resin (nucleus number: about 5)
97 parts, 3901 parts of terephthalic acid and 24 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream. The polyester reaction was proceeded under reduced pressure from the time when the reaction product became transparent, and reacted until the acid value became 1.5 to obtain a polyester resin (A1). This resin has a number average molecular weight of 30,50, a weight average molecular weight (Mw) of 21,500,
The hydroxyl value was 47.2.

Preparation Example 2 of Polyester Resin (A) 2 In a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen introducing tube, 5501 parts of a 3 mol adduct of propylene oxide of bisphenol A and a 2 mol adduct of ethylene oxide of bisphenol A 2983 parts, novolak type phenol resin (number of nuclei: about 5), ethylene oxide 5 mol adduct 6
05 parts, 3498 parts of terephthalic acid and 24 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream. The polyesterification reaction was proceeded under reduced pressure from the time when the reaction product became transparent, and reacted until the acid value became 2.4.
Next, 498 parts of dimethyl terephthalate and 500 parts of xylene were added thereto, reacted at 220 ° C. for 3 hours under normal pressure, and further reacted for 1.5 hours under reduced pressure of 10 to 15 mmHg to obtain a polyester resin (A2). . This resin has a number average molecular weight (Mn) of 3580, a weight average molecular weight (Mw) of 47900, an acid value of 1.0, and a hydroxyl value of 28.
It was one.

Production Example 1 of Vinyl-Based Polymer (B) 200 parts of xylene was placed in an autoclave equipped with a thermometer, a stirrer, and a dropping line, and the space was replaced with nitrogen. A mixture of 320 parts of styrene, 96 parts of monomethyl maleate and 62 parts of acrylonitrile and 6.7 wt% of ditertiary butyl peroxide
60 parts of a xylene solution were simultaneously added dropwise over 3 hours. Further, the solvent was distilled off at 180 ° C. under reduced pressure to obtain a vinyl polymer (B1). (B1) has a number average molecular weight of 5
390, weight average molecular weight was 21,100, and acid value was 158. Production Example 2 of Vinyl-Based Polymer (B) 2025 parts of xylene was put into an autoclave equipped with a thermometer, a stirrer and a dropping line, and the space was replaced with nitrogen. Styrene 3690
Parts, 475 parts of monomethyl maleate, 735 parts of acrylonitrile and 600 parts of a 6.7 wt% xylene solution of ditertiary butyl peroxide were simultaneously added dropwise over 3 hours. Further, the solvent was distilled off at 180 ° C. under reduced pressure to obtain a vinyl polymer (B2). (B2) had a number average molecular weight of 6690, a weight average molecular weight of 23,000 and an acid value of 38.

Production Example 3 of Vinyl Polymer (B) 684 parts of xylene was placed in an autoclave equipped with a thermometer, a stirrer, and a dropping line, and the space was replaced with nitrogen. 1934 parts of styrene,
2090 parts of monobutyl maleate, acrylonitrile 3
77 parts of the mixed solution and 320 parts of a 8 wt% toluene solution of ditertiary butyl peroxide were simultaneously added over 3 hours and 4 hours, respectively. Further, the solvent was distilled off at 180 ° C. under reduced pressure to obtain a vinyl polymer (B3). The number average molecular weight is 2250, the weight average molecular weight is 8120, and the acid value is 161.
Met. Production Example 4 of Vinyl-Based Polymer (B) Xylene (2260 parts) was placed in an autoclave equipped with a thermometer, a stirrer, and a dropping line, and the space was replaced with nitrogen. Styrene 2900
Parts, a mixture of 720 parts of monobutyl maleate, 1050 parts of butyl acrylate, and 336 parts of acrylonitrile, and 650 parts of a 4.3 wt% xylene solution of ditertiary butyl peroxide were simultaneously added over 3 hours and 4 hours, respectively. Further, the solvent was distilled off at 180 ° C. under reduced pressure to obtain a vinyl polymer (B4). (B4) has a number average molecular weight of 5
140, the weight average molecular weight was 16,400, and the acid value was 85. Comparative Vinyl Polymer Production Example 1010 parts of xylene was placed in an autoclave equipped with a thermometer, a stirrer, and a dropping line, and the space was replaced with nitrogen. 210 parts of styrene,
A mixture of 90 parts of acrylonitrile and 325 parts of a 5 wt% xylene solution of ditertiary butyl peroxide were simultaneously added over 1.5 hours. 180 ° C under reduced pressure
The solvent was distilled off to obtain a comparative vinyl polymer (V1). (V1) had a number average molecular weight of 1360, a weight average molecular weight of 3130, a Tg of 63.3 ° C., an acid value of 0.1 and a hydroxyl value of 0.

Example 1 8700 parts of (A2) and 1300 parts of (B1) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, and reacted at 190 ° C. under a nitrogen stream. From the point when the reaction product became transparent, proceed the polyesterification reaction under reduced pressure,
Melt flow rate (150 ° C, 5kg load) is 0.8
The reaction of the present invention (P
1) was obtained. This resin has a peak molecular weight of 3550, T
The HF insoluble content is 33%, the Tg is 55.9 ° C., and the acid value is 9.
9. The hydroxyl value was 15.2.

Example 2 7300 parts of (A2) and 2700 parts of (B2) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, and reacted at 190 ° C. under a nitrogen stream. From the point when the reaction product became transparent, proceed the polyesterification reaction under reduced pressure,
Melt flow rate (150 ° C, 5Kg load) is 6.1
g / 10 minutes until the resin of the present invention (P2)
I got This resin has a peak molecular weight of 4220, THF
30% of insoluble matter, Tg of 55.9 ° C., acid value of 10.1,
The hydroxyl value was 14.2.

Example 3 In a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen introducing tube, 2278 parts of adduct of 2 mol of propylene oxide of bisphenol A, 2631 parts of adduct of 3 mol of propylene oxide of bisphenol A, novolak type 263 parts of a 5 mol ethylene oxide adduct of a phenol resin (number of nuclei: about 5), 1997 parts of isophthalic acid and 14 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream. From the point when the reaction product became transparent, the polyesterification reaction was advanced under reduced pressure, and the reaction was continued until the acid value became 1.7 to obtain a polyester resin (A4). (A4) had a number average molecular weight of 4,270, a weight average molecular weight of 29,500, a peak molecular weight of 6,080, and a hydroxyl value of 34.0.
The temperature in the system was lowered to 190 ° C., 1728 parts of (B4) were added, and the reaction was carried out at 190 ° C. under a nitrogen stream. From the point when the reaction product became transparent, proceed the polyesterification reaction under reduced pressure,
Melt flow rate (150 ° C, 5Kg load) is 8.3
g / 10 minutes until the resin of the present invention (P3)
I got (P3) has a peak molecular weight of 6380, THF
39% insolubles, 58.2 ° C Tg, 15.1 acid value,
The hydroxyl value was 14.0.

Comparative Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a cooler, and a nitrogen inlet tube, 3773 parts of a 2 mol adduct of bisphenol A with propylene oxide, 3546 parts of a 3 mol adduct of bisphenol A with propylene oxide, a novolak type 968 parts of a 5-mol ethylene oxide adduct of a phenol resin (about 5 nuclei), 3406 parts of terephthalic acid, and 22 parts of dibutyltin oxide were added and reacted at 230 ° C. under a nitrogen stream. From the point when the reaction product became transparent, the polyesterification reaction was advanced under reduced pressure, and the melt flow rate (150 ° C.,
(5 kg load) until 2.3 g / 10 minutes to obtain a comparative resin (P4). (P4) had a peak molecular weight of 3940, a THF insoluble content of 36%, a Tg of 59.8 ° C.,
The acid value was 1.8 and the hydroxyl value was 47.1.

Comparative Example 2 8000 parts of (A1) and 2,000 parts of (V1) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, and heated at 190 ° C. under a reduced pressure of 10 to 15 mmHg. After reacting for an hour, the melt flow rate in the system (150 ° C,
(5 kg load) did not change. Removed resin (P
5) has a number average molecular weight of 2700 and a weight average molecular weight of 1
2000, peak molecular weight 4900, no THF insoluble matter, Tg 60.2 ° C, acid value 0.9, hydroxyl value 4
5.0.

Evaluation Example 1 Resin (P1) of Example 1 87 parts Carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) 8 parts Charge control agent (Spiron Black TRH manufactured by Hodogaya Chemical Co., Ltd.) 1 part Low molecular weight polypropylene ( 4 parts of Viscol 550P manufactured by Sanyo Chemical Industries, Ltd. The above materials were converted 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 about 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). The MFT of (T-1) is 140
° C and hot offset did not occur below 230 ° C. The charge amount (N / N) was −16.5 μC / g, and the charge amount (H / H) was −13.7 μC / g.

Evaluation Examples 2 and 3, Comparative Evaluation Examples 1 and 2, Evaluation Examples 1 and 2 were prepared using the resins (P2) and (P3) of Examples 2 and 3 and the resins (P4) and (P5) of Comparative Examples 1 and 2. In the same manner as in the above, toners (T-2) to (T-5) were obtained. Table 1 shows the evaluation results.

[0048]

[Table 1]

As shown in Table 1, it is understood that the resin of the present invention has a wide fixing temperature range and is excellent in environmental stability of charging.

Evaluation Example 4 Resin of Example 1 100 parts Magnetic powder (EPT1000 manufactured by Toda Kogyo Co., Ltd.) 100 parts Charge control agent (Spiron Black TRH manufactured by Hodogaya Chemical Co., Ltd.) 2 parts Low molecular weight polypropylene (Sanyo Chemical Industries, Ltd.) 1 part of low molecular weight polyethylene (Sunwax LEL400 manufactured by Sanyo Chemical Industry Co., Ltd.) 1 part Kneading, pulverizing and classifying in the same manner as in Evaluation Example 1 to obtain a particle diameter d50 of 8.1 μm. Magnetic toner particles were obtained. Next, 100 parts of the toner particles and 2 parts of colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) were mixed (externally added).
As a result, a toner (T-6) was obtained. MFT of (T-6) is 135
° C and hot offset did not occur below 230 ° C. The image density (N / N) was 1.41, and the image density (H / N
H) was 1.15.

Evaluation Examples 5 and 6, Comparative Evaluation Examples 3 and 4 Evaluation Examples 4 and 5 were conducted using the resins (P2) and (P3) of Examples 2 and 3 and the resins (P4) and (P5) of Comparative Examples 1 and 2. In the same manner as in the above, magnetic toners (T-7) to (T-10) were obtained.
Table 2 shows the evaluation results.

[0052]

[Table 2]

As shown in Table 2, it can be seen that the resin of the present invention has a wide fixing temperature range and is excellent in environmental stability of charging.

Example 4 9000 parts of (A1) and 1000 parts of (B1) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, and reacted at 190 ° C. under a nitrogen stream. From the point when the reaction product became transparent, proceed the polyesterification reaction under reduced pressure,
Melt flow rate (125 ° C, 1000g load) is 1
The reaction was carried out until 2.5 g / 10 minutes to obtain the resin (P6) of the present invention. (P6) has a number average molecular weight of 385.
0, weight average molecular weight (Mw) of 21,700, peak molecular weight of 7,380, no THF insoluble matter, Tg of 57.6
C, the acid value was 9.0, and the hydroxyl value was 35.2.

Example 5 9420 parts of (A1) and 580 parts of (B3) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler and a nitrogen inlet tube, and reacted at 190 ° C. under a nitrogen stream. When the reaction product became transparent, the polyesterification reaction was advanced under reduced pressure, and the melt flow rate (125 ° C., 1000 g load) was 1
The reaction was carried out until 5.5 g / 10 min to obtain the resin (P7) of the present invention. (P7) has a number average molecular weight of 342
0, weight average molecular weight of 14,800, peak molecular weight of 69
20, there was no THF insoluble matter, Tg was 59.2 ° C., acid value was 8.1, and hydroxyl value was 33.5.

Comparative Example 3 9865 parts of (A1) were placed in a reaction vessel equipped with a thermometer, a stirrer, a cooler, and a nitrogen inlet tube, and sufficiently dissolved at 200 ° C., and then 135 parts of trimellitic anhydride was obtained. Add. Under normal pressure, the acid value was 8.0 while tracking the acid value in the system.
Then, a take-out comparative resin (P8) was obtained.
(P8) had a number average molecular weight of 3,200, a weight average molecular weight (Mw) of 23,500, a Tg of 65.5 ° C., no THF insolubles, and a hydroxyl value of 42.8.

Evaluation Example 7 Resin (P6) in Example 4 100 parts Pigment (Cyanine Blue KRO manufactured by Sanyo Dyeing Co., Ltd.) 4 parts The temperature of PCM-30 was set to 80 ° C., and kneading and grinding were performed in the same manner as in Evaluation Example 1. And classified to obtain a cyan toner having a particle diameter d50 of 9.1 μm. Then, 100 parts of toner particles and colloidal silica (Aerosil R972 manufactured by Nippon Aerosil) 1
Of the toner (T-11).
MFT of (T-11) is 120 ° C., gloss development temperature is 13
At 5 ° C., hot offset did not occur below 200 ° C. The charge amount (N / N) was −14.2 μC / g, and the charge amount (H / H) was −12.0 μC / g.

Evaluation Example 8, Comparative Evaluation Examples 5 and 6 Using the resin (P7) of Example 5 and the resins (P8) and (P5) of Comparative Examples 3 and 2, the toner (T -12) to (T-14) were obtained. Table 3 shows the evaluation results.
Shown in

[0059]

[Table 3]

As shown in Table 3, it can be seen that the full-color toner using the resin of the present invention has a wide fixing temperature range, good gloss appearance, and excellent environmental stability of charging.

[0061]

The toner binder of the present invention has the following effects. 1. Excellent in both low-temperature fixability and hot offset resistance. 2. Appropriate charge amount and excellent environmental stability.

Claims (5)

[Claims] 1. A non-linear structure having a weight average molecular weight (M
w) is 5,000 to 200,000 and the weight average molecular weight (M
w) / polyester resin (A) having a number average molecular weight (Mn) ratio of 3 to 50 and vinyl polymer (B) having a structure represented by the following general formula (1) in a weight ratio of 9:
9: 1 to 50:50, an electrophotographic toner binder comprising a resin (I) having an acid value of 5 to 50. Embedded image [In the formula, R1, R2, and R3 may be a hydrogen atom or a methyl group, or R1 or R3 may be -COOR ', and R and R3 may combine to form a carbonyl group. R and R 'each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Z represents one or more units of a copolymerizable vinyl monomer. m is a number from 1 to 100; n
Represents a number of 2 to 100. ] 2. The vinyl polymer (B) has an acid value of 10
2. The electrophotographic toner binder according to claim 1, wherein the number average molecular weight is 400 to 100,000 and the number average molecular weight is 400 to 100,000. 3. The polyester resin (A) is a polyester resin obtained by polycondensation of at least a diol (a) and a dicarboxylic acid (b), and has an acid value of 3 or less and a hydroxyl value of 5 or less. 1 or 2.
The toner binder for electrophotography according to the above. 4. The toner binder for electrophotography according to claim 3, wherein said polyester resin (A) is obtained by polycondensing at least an alkylene oxide adduct of a novolak type phenol resin. 5. Z constituting the vinyl polymer (B)
Is one or two or more monomers selected from styrenes and (meth) acrylonitriles.
The toner binder for electrophotography according to any one of the above.