JP2003255589A - Additive for toner and toner binder composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for a toner which imparts an excellent anti-hot- offsetting properties and a toner binder composition. <P>SOLUTION: The additive for a toner comprises a modification (A1) obtained by modifying at least part of a wax (A) with a vinyl monomer (B) having 8-30 wt.% average concentration of ester groups and the toner binder composition comprises the additive for a toner, a polyester resin, and, optionally, a release agent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a toner additive and a toner binder composition used in electrophotography, electrostatic recording, electrostatic printing and the like.

[0002]

2. Description of the Related Art A heat fixing type toner is fixed on a support by a heat roll. At that time, energy saving,
From the viewpoint of downsizing of devices such as copying machines, the toner does not fuse to the hot roll even at a higher fixing temperature than before (hot offset resistance), and the toner can be fixed even at a low fixing temperature (low temperature fixing property). Is required. As a toner binder, a polyester resin has been studied because of its excellent low-temperature fixability, but when a release agent is added to improve hot offset resistance, the release agent is insufficiently dispersed in the polyester resin. However, there is a problem that the fluidity of the toner is lowered, white spots in a solid image are generated and image density is lowered when continuous copying is performed.
In order to solve these problems, it has been proposed to use oxidized polypropylene, maleic acid-modified polypropylene or the like as a release agent (see, for example, Patent Documents 1 and 2).

[0003]

[Patent Document 1] Japanese Patent Publication No. 43-9367

[0004]

[Patent Document 2] JP-A-48-46689

[0005]

However, when a modified polypropylene such as the above-mentioned oxidized polypropylene or maleic acid modified polypropylene is used as a mold release agent, the decrease in fluidity is improved, but the mold release agent is improved. It has a defect that the releasability, which is the original function, is deteriorated, the hot offset resistance is inferior to that of the unmodified product, and it is not sufficient.

[0006]

The present inventors have arrived at the present invention as a result of intensive studies to develop an additive for toners and a toner binder composition which give excellent hot offset resistance. That is, in the present invention, at least a part of the wax (A) has an average ester group concentration of 8 to 30% by weight.
Of the modified vinyl monomer (B) (A)
A toner binder composition comprising (1) and a toner binder composition comprising (A1) and a polyester resin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The wax (A) of the present invention includes a polyolefin wax,
Natural wax, aliphatic alcohol having 30 to 50 carbon atoms,
Examples include fatty acids having 30 to 50 carbon atoms and mixtures thereof.

As the polyolefin wax, an olefin (co) polymer (1-1), an olefin (co) polymer oxide (1-2), and a malein-modified product of the olefin (co) polymer (1 -3), a copolymer (1-4) of an olefin and an unsaturated carboxylic acid or its ester, and a sazol wax.

Examples of (1-1) include olefins having 2 to 30 or more carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and 2 of these. (Co) polymers such as mixtures of one or more species (eg polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / 1
A butene copolymer and a propylene / 1-hexene copolymer). The (co) polymerization can be carried out by a known method using a known catalyst. Examples of (1-1) include those obtained by (co) polymerization of olefins (1-1-1) and heat-reduced polyolefin (1-1-).
2) is included.

Examples of (1-1-2) include polyolefins obtained by thermally degrading a polyolefin resin (for example, polyethylene and polypropylene) having a weight average molecular weight (Mw) of 50,000 to 5,000,000. Thermal degradation is usually 270-
It is carried out at 450 ° C. Number average molecular weight (M
The double bond content per molecule corresponding to the number of molecules derived from n) is preferably 30 to 70%.

In the above and below, Mn and Mw of the polyolefin wax and its raw materials and the modified product (A1) are the same as those of gel permeation chromatography (G).
(PC) (solvent: orthodichlorobenzene, reference substance: polystyrene).

Examples of (1-2) include the oxides of (1-1) above. Oxidation can be performed by a known method using oxygen and / or ozone, for example, by the method described in US Pat. No. 3,692,877. The acid value of the oxide is preferably 1 to 60 (mgKOH / g, the same applies to the following acid values), and more preferably 2 to 50.

Examples of (1-3) include the maleic acid type monomer-modified products of the above (1-1). Maleic acid monomers include maleic acid and its derivatives [anhydrides, mono- or dialkyl (C1-4) esters,
Imide, amide, etc.], and specific examples thereof include maleic acid, maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, lauryl maleimide, maleamide and the like. The modification can be performed by a known method, for example, (1-1) and a maleic acid-based monomer [preferably 0.1 to 30 relative to (1-1).
%] Can be carried out by reacting with a known peroxide catalyst by either a solution method or a melting method. The acid value after modification is preferably 1 to 60, more preferably 2 to 50. In the above and below,% means% by weight unless otherwise specified.

As (1-4), the above olefin and an unsaturated carboxylic acid having 3 to 24 carbon atoms [(meth) acrylic acid (meaning acrylic acid and / or methacrylic acid. The same description method will be used hereinafter. ), Itaconic acid and maleic anhydride, etc.] and unsaturated carboxylic acid alkyl esters [alkyl (meth) acrylates (alkyl having 1 to 1 carbon atoms).
18) Ester, and alkyl maleates (alkyl C1-18 esters, etc.) and the like. The copolymerization molar ratio of olefin and unsaturated carboxylic acid (alkyl ester) is preferably 10/90 to 99 /.
1, more preferably 50/50 to 90/10.
The copolymerization may be random or block, and can be carried out by a known method using a known catalyst.

From the viewpoint of filming to a carrier and releasability, the Mn of the polyolefin wax is usually 40.
It is 0 to 40,000, preferably 1000 to 30000, and particularly 1500 to 2000.

Examples of natural waxes include carnauba wax, montan wax and rice wax.

Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontanecarboxylic acid.

Of these, preferred are polyolefin waxes, natural waxes and mixtures thereof, more preferably heat-reduced polyolefins, particularly preferably heat-reduced polyethylene and heat-reduced polypropylene.

The softening point of the wax (A) is preferably 8
It is 0 to 170 ° C. The lower limit is more preferably 90
℃, especially 100 ℃, the upper limit is more preferably 1
It is 60 ° C., especially 155 ° C. When the softening point is 80 ° C or higher, the fluidity of the toner is good, and when the softening point is 170 ° C or lower, a sufficient releasing effect is obtained. The softening point is JIS K 2
207-1996.

From the viewpoint of toner fixability, the melt viscosity of (A) is usually 2 to 10,000 mPa · s at 160 ° C.
s, preferably 3 to 7000 mPa · s, especially 5 to 45
It is 00 mPa · s.

From the viewpoint of toner developability, the penetration of (A) is usually 5.0 or less, preferably 3.5 or less, and particularly 1.
It is 0 or less. The penetration is JIS K 2207-
It is measured by the method specified in 1996.

(B) comprises an ester group-containing monomer as an essential component and another vinyl monomer as an optional component.

Examples of the ester group-containing monomer include the following monomers (1) to (4) and mixtures thereof. Unsaturated monocarboxylic acid ester: -1) Unsaturated monocarboxylic acid hydrocarbyl (C1-30) ester: As the unsaturated monocarboxylic acid, those having 3-24 carbon atoms are preferable, and (meth) acrylic acid is used. , (Iso) crotonic acid, cinnamic acid and the like. Examples of the hydrocarbyl group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an aralkyl. Specifically, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic Acid phenyl etc.

-2) Hydroxyalkyl (meth) acrylic acid (C2-6) ester and its monoalkyl (C1-12) ether: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, And α-ethoxyethyl (meth) acrylate.

Unsaturated dicarboxylic acid hydrocarbyl (having 1 to 30 carbon atoms) mono- or diester: As the dicarboxylic acid, those having 4 to 24 carbon atoms are preferable, such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid. Is mentioned. As a specific example, mono- or di (cyclo) alkyl fumarate (wherein the alkyl group has 2 to 2 carbon atoms)
8 straight-chain or branched-chain groups), and mono- or di- (cyclo) alkyl maleates (wherein the alkyl group is a straight-chain or branched-chain group having 2 to 8 carbon atoms).

Polyoxyalkylene (C2-4) mono- or poly (2-3) -ol unsaturated carboxylic acid ester having a degree of polymerization of 2-50 (C1-C24 excluding the monooxy polyoxyalkylene chain): Vinyl-based monomer having a polyalkylene (C2-4) glycol chain [polyethylene glycol (polymerization degree 7) mono (meth) acrylate, polypropylene glycol (polymerization degree 9) mono (meth) acrylate, glycerin EO5 mol adduct mono ( (Meth) acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate and the like. Above and below, EO represents ethylene oxide.

Unsaturated alcohol [vinyl, (meth) allyl, isopropenyl, etc.] or hydroxystyrene and mono or poly having 1 to 12 carbon atoms (2 to 6 or more)
Esters with carboxylic acids: vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, methyl-4-vinyl benzoate, vinyl methoxyacetate, vinyl benzoate and acetoxystyrene.

Nitrogen-containing vinyl monomer: Nitrogen-containing (meth)
Acrylate is preferable, for example, aminoalkyl (C2-8) methacrylate [aminoethyl (meth)]
Acrylate, etc.], mono- or dialkyl (having 1 to 1 carbon atoms
2) Aminoalkyl (C2-8) (meth) acrylate [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], heterocycle-containing (meth) acrylate [Morpholinoethyl (meth) acrylate and the like], and methyl α-acetaminoacrylate and the like.

Other vinyl monomers include the following monomers (1) to (4) and mixtures thereof. Aromatic vinyl monomer (having 8 to 20 carbon atoms): Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted product, for example, α-methylstyrene, m-methylstyrene, p-methylstyrene, 2 , 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene and crotylbenzene; and vinylnaphthalene.

Aliphatic vinyl monomer: 2 to 20 carbon atoms
Alkenes such as ethylene, propylene, butene,
Isobutylene, pentene, heptene, diisobutylene,
Octene, dodecene, octadecene and other α-
Olefins and the like; alkadienes having 4 to 20 carbon atoms, such as butadiene, isoprene, 1,4-pentadiene,
1,5-hexadiene and 1,7-octadiene.

Alicyclic vinyl monomers (having 5 to 3 carbon atoms)
0): mono- and dicycloalkenes and alkadienes,
For example cyclohexene, (di) cyclopentadiene, vinylcyclohexene and ethylidene bicycloheptene;
Terpenes such as pinene, limonene and indene.

Carboxyl group-containing vinyl monomer: unsaturated monocarboxylic acid having 3 to 30 carbon atoms, unsaturated dicarboxylic acid and its anhydride such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itacone acid,
Citraconic acid and cinnamic acid.

Hydroxyl group-containing vinyl monomer: alkenol having 2 to 12 carbon atoms, such as (meth) allyl alcohol, 1-buten-3-ol and 2-butene-1.
-Ol; alkenyl ether having 3 to 30 carbon atoms, such as 2-hydroxyethylpropenyl ether and sucrose allyl ether; p-hydroxystyrene and the like.

Amide group-containing vinyl monomer: (meth)
Acrylamide, N-methyl (meth) acrylamide,
N-butyl (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid amide, N, N-dimethyl (meth) acrylamide, N , N-dibenzyl (meth) acrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like.

Vinyl-based monomer containing nitrile group: (meth) acrylonitrile, cyanostyrene, etc. Epoxy group-containing vinyl monomer: diethylene glycol monoglycidyl ether, etc. Halogen-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, chlorostyrene, bromstyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, fluorinated olefins (having 2 to 2 carbon atoms). 10, F1
20) etc.

The weight ratio of the ester group-containing monomer and the other vinyl monomer in (B) is not particularly limited as long as the average ester group concentration is 8 to 30%, but preferably (20:80). ) To (100: 0), and more preferably (25:75) to (90:10).

Preferred as (B) are unsaturated carboxylic acid hydrocarbyl (C1-C30) esters and unsaturated carboxylic acid hydrocarbyl (C1-C3).
0) ester and aromatic vinyl monomer (having 8 to 2 carbon atoms)
0), more preferably alkyl (meth) acrylate (alkyl having 1 to 5 carbon atoms), and alkyl (meth) acrylate (alkyl having 1 to 5 carbon atoms) and styrene.

The average ester group concentration of (B) is defined by the following equation (1). Average ester group concentration = [Σ (44 × Ni × Wi / Mi) / ΣWi] × 100 (1) where Ni: number of ester groups in one molecule of monomer i Wi: amount of monomer i used Mi: molecular weight of monomer i Is.

The average ester group concentration of (B) is usually 8%.
~ 30%. The lower limit is preferably 9% and the upper limit is preferably 28%, especially 25%. If the average ester group concentration is lower than 8%, the compatibility with the binder resin will be poor, and if it exceeds 30%, the compatibility with the wax (A) or the release agent described below will be poor.

The modified product (A1) is obtained by modifying the wax (A) with the vinyl monomer (B). In addition to the wax grafted with (B), unreacted (A) and / or ( It may contain the (co) polymer of B). (A1)
From the viewpoint of the fluidity of the toner, the weight ratio of (A) and (B) in the production of is preferably 1 to 30:70 to 99, and particularly 2 to 27:83 to 98.

The glass transition point (Tg) of (A1) is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, and especially 55 to 75 ° C. When Tg is in the range of 40 ° C to 90 ° C, heat-resistant storage stability and low-temperature fixability are good. In the above and below, Tg is Seiko Electronics Co., Ltd.
ASTM D3 using DSC20, SSC / 580
It is measured by the method (DSC method) prescribed in 418-82.

The Mn of (A1) is preferably 2000-
It is 10,000, especially 2500 to 9000. Mn is 2
In the range of 000 to 10,000, the toner has good durability and pulverizability.

(A1) is obtained by, for example, dissolving or dispersing the wax (A) in a solvent (for example, toluene or xylene),
After heating to 100 ° C. to 200 ° C., (B) is added dropwise with a peroxide-based initiator (benzoyl peroxide, ditertiary butyl peroxide, tert-butyl peroxide benzoate, etc.) to polymerize, and then the solvent is distilled off. It is obtained by

The amount of the peroxide type initiator is usually 0.2 to 10%, preferably 0.5 to 5% based on the total weight of (A) and (B).

The toner binder composition of the present invention comprises the toner additive of the present invention and a polyester resin, and a release agent and other resins can be used in combination if necessary. The toner additive of the present invention has a function as a compatibilizing agent that improves the compatibility between the polyester resin and the release agent.

Examples of the polyester resin include polycondensates of polyol and polycarboxylic acid. As the polyol, a diol (a) and a polyol (b) having a valency of 3 to 8 or higher, and as the polycarboxylic acid, a dicarboxylic acid (c) and a polycarboxylic acid having a valency of 3 to 6 or higher (d) are used. ) Is mentioned.

The diol (a) has 2 to 36 carbon atoms.
Alkylene glycol (ethylene glycol, 1, 2
-Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); C4-C36 alkylene (carbon number of alkylene group: 2-4) ether glycol (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (Bisphenol A, bisphenol F,
Bisphenol S, etc.); AO [EO, propylene oxide (P
O), butylene oxide (BO), etc.] adduct (additional mole number 2 to 30) and the like. Above and below, AO represents an alkylene oxide having 2 to 4 carbon atoms.

Of these, preferred ones have 2 to 2 carbon atoms.
It is an alkylene glycol of 12 and / or an AO adduct of bisphenols. Further, the hydroxyl value of (a) is 1
80 to 1900 (mgKOH / g, the following hydroxyl values are the same) are preferable.

Examples of the trihydric to octahydric or higher polyol (b) include trihydric to octahydric or higher aliphatic polyhydric alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.). The above aliphatic polyhydric alcohol AO (EO, P
O, BO, etc.) adduct (additional mole number 2 to 30); trisphenols (Trisphenol PA, etc.); novolac resin (phenol novolac, cresol novolac, etc.):
Average degree of polymerization 3 to 60); AO of the above trisphenols
Additives (additional mole numbers 2 to 30); AO adducts of the above novolak resins (additional mole numbers 2 to 30) and the like.

Among these, preferred are aliphatic polyhydric alcohols having 3 to 8 valences or more, and AO adducts of novolak resins, and particularly preferred are AO adducts of novolak resins. The hydroxyl value of (b) is
It is preferably 150 to 1900.

The dicarboxylic acid (c) has an acid value of 18
A dicarboxylic acid of 0 to 1250, specifically, a carbon number of 4 to
36 alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, etc.);
Examples thereof include 36 alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.) and the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

The polycarboxylic acid (d) having a valence of 3 to 6 or higher is a polycarboxylic acid having an acid value of 150 to 1250, specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (tricarboxylic acid). Meritic acid, pyromellitic acid, etc.), vinyl polymer of unsaturated carboxylic acid [styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin /
Maleic acid copolymer, styrene / fumaric acid copolymer, etc.]
Etc. Of these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. still,
As (c) or (d), acid anhydrides or lower alkyl (C1-4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of the above may be used.

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

The toner binders are required to have different physical properties for monochrome and full color, respectively, and the design of the polyester resin is also different. That is, since a high-gloss image is required for full-color use, it is necessary to use a low-viscosity binder, but for monochrome use, gloss is not particularly necessary and hot offset properties are important, so it is necessary to use a high-elasticity binder. .

In order to obtain a low-gloss image useful for a monochrome copying machine, etc., (b) and / in addition to (a) and (c)
Alternatively, a non-linear polyester using (d) is preferable,
A polyester composed of four components (a), (b), (c) and (d) is particularly preferable. By using both (b) and (d), the hot offset resistance is further improved.

The ratio of (b) and (d) is usually 0.1 to 40 mol based on the sum of the mol numbers of (b) and (d) relative to the total of the mol numbers of (a) to (d). %, Preferably 0.5-
It is 25 mol%, especially 1 to 20 mol%. The molar ratio of (c) and (d) is usually 0/100 to 100/0, preferably 90/10 to 20/80, and particularly 85/15 to 3.
It is 0/70.

In the case of a monochrome polyester resin, from the viewpoint of hot offset resistance, the temperature (TG1) at which the polyester resin has a storage elastic modulus (G ') of 6000 Pa.
Is usually 130 to 230 ° C., preferably 140 to 230
C., especially 150 to 225.degree.

From the viewpoint of low-temperature fixability and heat-resistant storage stability, the complex viscosity (η *) of the polyester resin is 1000.
The temperature at which Pa · s is reached (TE1) is usually 80 to 140.
℃, preferably 90-135 ℃, especially 105-130 ℃
Is.

TG1 and TE1 are, for example, the blocks obtained by melt-kneading the resin using a Labo Plastomill at 130 ° C. and 70 rpm for 30 minutes, and using a dynamic viscoelasticity measuring device while changing the storage temperature of the resin. It is determined by measuring the modulus (G ′) and the complex viscosity (η *) under the following conditions. [Viscoelasticity measurement conditions] Dynamic viscoelasticity measurement device RDS-2 (R
(manufactured by hemometric Scientific) Measurement frequency: 20 Hz, start temperature: 90 ° C., end temperature:
200 ° C., heating rate: 10 ° C./min, Strain:
5%.

The monochrome polyester resin preferably contains tetrahydrofuran (THF) insoluble matter in an amount of 5 to 70%, more preferably 15 to 60%, especially 2%.
It is 0 to 50%. When the THF insoluble content is 5% or more, the hot offset resistance becomes good, and when it is 70% or less, good low temperature fixability is obtained.

The THF-insoluble matter and the THF-soluble matter can be obtained by the following method. About 0.5 g of the sample is precisely weighed in a 200 ml Meyer flask with a stopper, 50 ml of THF is added, the mixture is stirred and refluxed for 3 hours, cooled, and the insoluble matter is filtered off with a glass filter. The weight% of the THF insoluble content is calculated from the weight ratio of the resin content on the glass filter after being dried under reduced pressure at 80 ° C. for 3 hours and the weight ratio of the sample. This filtrate is used as a THF-soluble component in the measurement of the molecular weight described later.

In order to obtain a high-gloss image useful for a full-color copying machine or the like, a linear polyester using (a) and (c), or (a) and (c), and (b) and / or A non-linear polyester in which (d) is used in combination is preferable.

The ratio of (b) and / or (d) is (b)
The sum of the number of moles of (d) and (d) is usually 0 to 20% by mole, preferably 0 to 15% by mole, and particularly 0 to 10% by mole based on the total number of moles of (a) to (d).

In the case of a full-color polyester resin, the temperature (TE2) at which the complex viscosity becomes 100 Pa · s is usually 90 to 170 ° C., preferably 100 to 165 ° C., and particularly 105 to 150 ° C. Sufficient gloss is obtained at 170 ° C or lower, and heat resistant storage stability becomes good at 90 ° C or higher.
TE2 is obtained by the same method as TE1. Also,
The THF insoluble content is usually less than 10% from the viewpoint of glossiness,
It is preferably less than 5%.

Peak molecular weight of polyester resin (Mp)
Is preferably 1000 to 30000, more preferably 1500 to 2 in both cases of monochrome and full color.
It is 5,000, especially 1800 to 20,000. Mp is 1
When it is 000 or more, the heat-resistant storage stability and powder fluidity are good, and when it is 30,000 or less, the pulverizability of the toner is improved and the productivity is good.

In the above and below, the Mp of the polyester resin is measured for the THF-soluble content using GPC under the following conditions. Device: Tosoh HLC-8120 column: TSKgelGMHXL (two) TSKgelMultiporeHXL-M (one) Measurement temperature: 40 ° C. Sample solution: 0.25% THF solution injection amount: 100 μl Detector: Refractive index detector Reference substance : Polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram is called the peak molecular weight (Mp).

The Tg of the polyester resin is preferably 40 to 90 ° C. for both monochrome and full color.
More preferably, it is 50-80 degreeC, especially 55-75 degreeC. When Tg is in the range of 40 ° C to 90 ° C, heat-resistant storage stability and low-temperature fixability are good. The acid value of polyester resin is
It is preferably 0.1 to 80, more preferably 1 to 60. The hydroxyl value is preferably 0.1 to 100, more preferably 1 to 80.

The polyester resin is prepared by reacting a polyol and a polycarboxylic acid in the presence of a known esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide.
It is obtained by heating to 50 to 280 ° C. and dehydration condensation. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

In the toner binder composition of the present invention, polyester resins having different molecular weights, THF
It is also possible to use two or more kinds in combination, such as those having different soluble content, those having different Tg, and those having different acid value.

Examples of the releasing agent include those similar to the wax (A), and preferable ones are also the same. The release agent and the wax (A) can be used either in the same kind or in different kinds.

Examples of other resins include styrene resins, epoxy resins and urethane resins. The Mn of other resins is preferably 500 to 100,000. As the styrene-based resin, a copolymer of styrene and the above-mentioned ester group-containing monomer and other vinyl monomers can be used. A known polymerization reaction catalyst or the like can be used in the polymerization reaction.

As the epoxy resin, a polyaddition product of polyepoxide with the above (a) and / or (b), and a polyepoxide with an acid anhydride of the above (c) and / or (d), or a polyamine. A cured product can be used. Known catalysts and the like can be used in the polyaddition reaction and the curing reaction.

As the polyepoxide, aromatic polyepoxide, heterocycle-containing polyepoxide, alicyclic polyepoxide, aliphatic polyepoxide and the like are used.

As the aromatic polyepoxide, polyhydric phenol glycidyl ether (for example, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether,
Bisphenol AD diglycidyl ether and bisphenol S diglycidyl ether); aromatic polycarboxylic acid glycidyl ester (for example, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester and terephthalic acid diglycidyl ester); glycidyl aromatic polyamine (for example, N, N-diglycidylaniline,
And N, N, N ′, N′-tetraglycidyl xylylenediamine and N, N, N ′, N′-tetraglycidyl diphenylmethanediamine). Heterocyclic polyepoxides include trisglycidyl melamine. Examples of the alicyclic polyepoxide include vinylcyclohexenedioxide, limonenedioxide, dicyclopentadienedioxide and bis (2,2).
3-epoxycyclopentyl) ether is mentioned.

Examples of the aliphatic polyepoxide include polyglycidyl ethers of aliphatic polyhydric alcohols (for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and tetramethylene glycol diglycidyl ether); polyglycidyl aliphatic polycarboxylic acids. Esters (eg, diglycidyl oxalate and diglycidyl malate); glycidyl aliphatic amines (eg, N, N, N ′, N′-tetraglycidylhexamethylenediamine) and the like. The number of epoxy groups per molecule of these polyepoxides is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4. The epoxy equivalent is preferably 50.
~ 500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is further preferably 300, particularly preferably 200.

As the polyamine, an aliphatic polyamine having 2 to 18 carbon atoms (ethylenediamine, diethylenetriamine, etc.), an alicyclic polyamine having 4 to 15 carbon atoms (isophoronediamine, etc.), and an aromatic polyamine having 6 to 20 carbon atoms ( Metaphenylenediamine, etc.), heterocyclic polyamine having 4 to 15 carbon atoms (N-aminoethylpiperazine, etc.),
Polyamidoamine [A dimer acid mainly composed of a polymerized fatty acid having 36 carbon atoms and excess (2 mol or more per 1 mol of acid)
And the like obtained by reacting the polyamine of 1.

Examples of the polyurethane resin include polyisocyanate and an active hydrogen-containing compound [eg, diol (a), polyol having a valency of 3 to 8 or more (b), dicarboxylic acid (c) and valence of 3 to 4 or more). Polycarboxylic acid (d) and the like] and polyaddition products thereof can be used. A known polyaddition reaction catalyst or the like can be used in the polyaddition reaction.

As the poly (2 to 8 or more) isocyanate, an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), 2 carbon atoms
To C18 aliphatic polyisocyanate, C4 to C15 alicyclic polyisocyanate, C8 to C15 araliphatic polyisocyanate and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea) Group, burette group, uretdione group,
(Uretimine group, isocyanurate group, oxazolidone group-containing modified product, etc.) and a mixture of two or more kinds of these are used.

Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4 , 4'-Diphenylmethane diisocyanate (MDI) and crude M
DI may be mentioned.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HD
I) and dodecamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated M
DI), cyclohexylene diisocyanate and methylcyclohexylene diisocyanate (hydrogenated TDI).

As the araliphatic polyisocyanate,
For example, m- or p-xylylene diisocyanate (XD
I) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

The content of the toner additive (A1) of the present invention, the polyester resin, the release agent and the other resin in the toner binder composition is preferably, respectively.
0.5-30%, 25-99%, 0-15%, and 0
30%, more preferably 1 to 20% (particularly lower limit is 2%, upper limit is 10%), 50 to 98%, 1 to 10%,
And 0 to 20%. The weight ratio of the toner additive and the release agent is preferably (0.1: 1) to (10: 1), more preferably (0.2: 1) to (5: 1). The ratio of the polyester resin to the other resin is preferably (1: 0) to (1: 1), more preferably (1: 0).
~ (1: 0.4). The total content of the toner additive and the release agent in the composition is preferably 1 to 45%,
It is more preferably 2 to 30%, and the total content of the polyester resin and other resins in the composition is preferably 55 to 99%, more preferably 70 to 98%.

To obtain the toner binder composition,
The toner additive, the polyester resin, and if necessary, the release agent and other resins may be powder-mixed, or may be melt-mixed in a twin-screw extruder or a compounding pot capable of heating and stirring. And / or the additive for toner may be produced in the presence of other resin and optionally a releasing agent.

The toner using the toner binder composition of the present invention comprises the toner binder composition of the present invention, a colorant and the like, and if necessary, various additives such as a releasing agent, a charge control agent and a fluidizing agent are added. Mix the agents.

As the colorant, known dyes, pigments and magnetic powders can be used. Specifically, Carbon Black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Balanitoaniline Red, Toluidine Red, Carmine, Pig FBment Orange R, Lake Red 2G , Rhodamine FB, Rhodamine B lake, Methyl violet B lake, Phthalocyanine blue, Pigment blue, Priliant green, Phthalocyanine green, Oil yellow GG, Kayaset YG, Orazol brown B, Oil pink O
P, magnetite, iron black and the like can be mentioned. The content of the colorant in the toner is usually 2 to 15% when the dye or pigment is used, and is usually 15% when the magnetic powder is used.
˜70%, preferably 30-60%.

Examples of the releasing agent include the same releasing agents as described above. The amount of the release agent in the toner is usually 0 to 1
It is 0%.

As the charge control agent, known agents, that is, nigrosine dye, quaternary ammonium salt compound, quaternary ammonium salt group-containing polymer, metal-containing azo dye, salicylic acid metal salt, sulfonic acid group-containing polymer, fluorine-containing polymer, Examples thereof include halogen-substituted aromatic ring-containing polymers. The content of the charge control agent in the toner is usually 0 to 5%.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and other known agents. The content of the fluidizing agent in the toner is usually 0 to 5%.

As a method for producing the toner, a known kneading and pulverizing method and the like can be mentioned. For example, the above toner constituents are dry-blended, melt-kneaded, and then finely pulverized using a jet mill or the like, and further classified by wind to obtain toner particles. The particle size D50 is preferably 2 to 20 μm.
The particle size D50 is measured using a Coulter counter [eg, trade name: Multitizer III (manufactured by Coulter)].

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

[0092]

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

The test method is as follows. (1) Release agent dispersed particle size The major axis and the minor axis of the release agent in the sample are measured using an electron microscope, and the average value thereof is used as the release agent dispersed particle size.

(2) A sample of the release agent in a dispersed state is observed with an electron microscope and judged according to the following criteria. ◯: The release agent is uniformly dispersed throughout, and the particle size is uniform, and coarse particles (5 μm or more) do not exist. Δ: A release agent having a small particle size is mainly present, but coarse particles are slightly present. X: The number of coarse particles of the release agent is 10% or more.

(3) Toner fluidity The quietness density of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the toner fluidity was judged according to the following criteria. △
The above is the practical range. Quietness density 36 g / 100 ml or more: Toner fluidity ○ 33 to 36: ○ △ 30 to 33: △ 27 to 30: △ × less than 27: ×

(4) Gloss generation temperature and hot offset generation temperature 30 parts of toner and 800 parts of ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.) are uniformly mixed and tested as a two-component developer. An unfixed image developed using a commercial copying machine [AR5030, manufactured by Sharp Corporation] is processed at a process speed of 80 mm / se using a fixing unit of a commercial full-color copying machine [LBP-2160, manufactured by Canon Inc.].
Fix with c. Commercial gloss meter (MURAKAMI COL
OR RESEARCH LABORATORY G
MX-202-60 type), and the heat roller temperature at which the reflectance of the fixed image at 60 ° exceeds 10% is defined as the gloss generation temperature. Further, the temperature at which hot offset begins to occur by visual determination is the hot offset occurrence temperature.

Production Example 1 In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe,
6053 parts of PO2 mol adduct of bisphenol A, 1896 parts of EO2 mol adduct of bisphenol A, 668 parts of terephthalic acid, 356 parts of trimellitic anhydride and 15 parts of dibutyltin oxide were added, and dehydration esterification was carried out at 225 ° C under a nitrogen stream. It was When no distilled water came out, the pressure was reduced and the esterification was continued until the acid value became 1.0. Then, the temperature is set to 180 ° C. and maleic anhydride 15
58 parts, 20 parts of hydroquinone, and 15 parts of dibutyltin oxide were added, and dehydration esterification was performed under a nitrogen stream. When no distilled water came out, the pressure was reduced and the melt viscosity was measured by a flow tester to trace the reaction. When the melt viscosity by a flow tester reached 1000 Pa · s at 111 ° C., it was taken out from the reaction tank to obtain polyester (F). (F) had an Mp of 8,800, an acid value of 15, a hydroxyl value of 20, a Tg of 61 ° C., a THF insoluble content of 0%, and a TE2 of 140 ° C.

Example 1 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
2261 parts of xylene, heat-reduced molded polyethylene [Sun Wax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 1
28 ° C.] 750 parts was sufficiently dissolved and, after nitrogen substitution, 2763 parts of styrene, 1488 parts of methyl methacrylate, di-
t-Butylperoxyhexahydroterephthalate 17
A mixed solution of 2 parts and 595 parts of xylene was added dropwise at 155 ° C. for 3 hours for polymerization, and the mixture was kept at this temperature for 30 minutes. Then, the solvent was removed to obtain a toner additive (E-1). The average ester group concentration of the used monomer is 15.4.
%, Mn of (E-1) was 3300, and Tg was 65.2 ° C.

Example 2 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
2261 parts xylene, carnauba wax (softening point 75
750 parts by weight and sufficiently dissolved, and after nitrogen substitution, 2975 parts of styrene, 1275 parts of methyl methacrylate, di-t-
A mixed solution of 172 parts of butylperoxyhexahydroterephthalate and 595 parts of xylene was added dropwise at 155 ° C. for 3 hours for polymerization, and the mixture was kept at this temperature for 30 minutes. Then, the solvent was removed to obtain a toner additive (E-2).
The average ester group concentration of the used monomers was 13.2%,
Mn of (E-2) was 3400 and Tg was 64.8 ° C.

Example 3 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
2261 parts of xylene, heat-reduced molded polyethylene [Sun Wax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 1
28 ° C.] 1000 parts was sufficiently dissolved and after nitrogen substitution, 3000 parts of styrene, 1000 parts of butyl acrylate, di-
t-butyl peroxyhexahydroterephthalate 81
A mixed solution of 1 part and 595 parts of xylene was added dropwise at 155 ° C. over 3 hours for polymerization, and the mixture was kept at this temperature for 30 minutes.
Then, the solvent was removed to obtain a toner additive (E-3). The average ester group concentration of the monomer used was 8.6%,
The Mn and Tg of (E-3) were 5300 and 52.0 ° C, respectively.

Example 4 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
2261 parts of xylene, heat-decreased polypropylene [Viscole 440P manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 153
[Deg.] C., 500 parts, heat-decreased polyethylene [SANYO WAX LEL-400 manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 12
8 ° C.] 250 parts was sufficiently dissolved and after nitrogen substitution, 1488 parts of styrene, 2763 parts of methyl methacrylate, di-t
-Butyl peroxyhexahydroterephthalate 172
A mixed solution of 1 part and 595 parts of xylene was added dropwise at 150 ° C. over 2 hours for polymerization, and the mixture was kept for 1 hour. Then, the solvent was removed to obtain a toner additive (E-4). The average ester group concentration of the used monomer was 28.6%, Mn of (E-4) was 3300, and Tg was 58.8 ° C.

Comparative Example 1 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
400 parts of xylene, heat-reduced polypropylene [Viscole 440P manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 153 ° C.]
Pour 50 parts into it and dissolve it thoroughly. After replacing with nitrogen, styrene 782
Part, 218 parts of butyl acrylate, 8.5 parts of di-t-butylperoxyhexahydroterephthalate and 120 parts of xylene were added dropwise at 160 ° C. over 2 hours for polymerization, and the mixture was kept for 1 hour. Then, the solvent was removed to obtain a toner additive (E-5). The average ester group concentration of the used monomer was 7.5%, Mn of (E-5) was 8310,
Tg was 60.5 ° C.

Comparative Example 2 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
2261 parts of xylene, heat-decreased polypropylene [Viscole 440P manufactured by Sanyo Chemical Industry Co., Ltd .: softening point 153
[° C] 1000 parts by weight and sufficiently dissolved, and after substituting with nitrogen, 1000 parts of styrene, 3000 parts of methyl methacrylate, di-t
-Butyl peroxyhexahydroterephthalate 172
A mixed solution of 1 part and 595 parts of xylene was added dropwise at 160 ° C. over 2 hours for polymerization, and the mixture was kept for 1 hour. Next, the solvent was removed to obtain a toner additive (E-6). The average ester group concentration of the used monomer was 33.0%, Mn of (E-6) was 3200, and Tg was 55.3 ° C.

Comparative Example 3 In an autoclave reaction vessel equipped with a thermometer and a stirrer,
After adding 2261 parts of xylene and replacing with nitrogen, styrene 350
A mixed solution of 0 part, 1500 parts of methyl methacrylate, 172 parts of di-t-butylperoxyhexahydroterephthalate and 595 parts of xylene was added dropwise at 155 ° C. over 2 hours for polymerization, and the mixture was kept at this temperature for 1 hour. Next, the solvent was removed to obtain a toner additive (E-7). The average ester group concentration of the used monomer is 13.2%, (E-7)
Had a Mn of 3,500 and a Tg of 68.8 ° C.

Toner Binder Composition Example Based on the formulation shown in Table 1, a polyester resin, a toner additive and, if necessary, a releasing agent were preliminarily used by using a Henschel mixer [FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.]. After mixing, the temperature of the twin-screw kneader was set to 150 ° C [K.
Ikegai PCM-30] is melt-kneaded to obtain toner binder compositions (G-1) to (G-4) of Examples and toner binder compositions (G-5) to (G-7) of Comparative Examples. Got The sun wax 171P in Table 1 is a heat-reduced polyethylene manufactured by Sanyo Kasei Co., Ltd.

[0106]

[Table 1]

Evaluation Examples 1 to 7 and Comparative Evaluation Examples 1 to 3 Based on the formulation shown in Table 2, a toner binder composition, a pigment and, if necessary, a release agent were added to a Henschel mixer [FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.]. ], And the mixture was melt-kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.] whose temperature was set to 80 ° C. After cooling the kneaded material,
Coarsely crushed and finely crushed using a supersonic jet crusher Labo Jet [Nippon Pneumatic Mfg. Co., Ltd.], then air classifier [MDS-I Nippon Pneumatic Mfg. Co., Ltd.]
The toner particles having a particle diameter D50 of about 9 μm are obtained by classification.
Then, 108 parts of the toner particles and 0.7 part of a fluidizing agent [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] are mixed (externally added), and toners (T-1) to (T- of the examples).
7) and toners (T-8) to (T-10) of comparative examples. Cyanine blue KRO in Table 2 is a pigment manufactured by Sanyo Dye Co., Ltd.

[0108]

[Table 2]

Using the toners shown in Table 2, the toner particle diameter D50, the release agent dispersed particle diameter, the release agent dispersed state, the toner fluidity, the gloss generation temperature and the hot offset generation temperature were measured. The toner fluidity was measured on the toner particles before the fluidizing agent was mixed (externally added). The results are shown in Table 3.

[0110]

[Table 3]

From Table 3, the full-color toner using the toner additive of the present invention has a better releasing agent dispersibility, better fluidity, and a wider fixing temperature range than the conventional toner. Recognize.

[0112]

By using the toner additive of the present invention, the release agent is uniformly dispersed, so that a toner having excellent hot offset resistance, a wide fixing temperature range and good fluidity can be obtained. Even if continuous copying is performed, troubles such as occurrence of white spots and reduction in image density do not occur, and therefore, it can be suitably used for electrophotography, electrostatic recording, electrostatic printing and the like.

Claims (11)

[Claims] 1. A toner additive comprising a modified product (A1) obtained by modifying at least a part of a wax (A) with a vinyl monomer (B) having an average ester group concentration of 8 to 30% by weight. 2. (A1) comprises a wax grafted with (B) and a (co) polymer of (B).
The additive for toners described. 3. The weight ratio of (A) to (B) is 1 to 30:
The toner additive according to claim 1, which is 70 to 99. 4. The method according to claim 1, wherein (B) is an alkyl (meth) acrylate (alkyl having 1 to 5 carbon atoms) (B1), or (B1) and an aromatic vinyl monomer (B2). Or the additive for toner as described above. 5. The toner additive according to claim 1, which has a glass transition point of 40 to 90 ° C. 6. The toner additive according to claim 1, which has a number average molecular weight of 2,000 to 10,000. 7. The toner additive according to claim 1, wherein (A) is a polyolefin wax and / or a natural wax. 8. The toner additive according to claim 7, wherein the polyolefin wax is a heat-reduced polyolefin. 9. The toner additive according to claim 8, wherein the heat-reduced polyolefin is heat-reduced polyethylene or polypropylene. 10. A toner binder composition comprising the toner additive according to any one of claims 1 to 9 and a polyester resin. 11. A toner binder composition comprising the toner additive according to claim 1, a polyester resin, and a release agent.