JP2021071716A - Toner binder - Google Patents

Abstract

To provide a toner binder with low temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance.SOLUTION: A toner binder provided herein comprises polymer (A) containing a monomer (a) consisting of a (meth)acrylate having 18 to 24 carbon atoms in a chain hydrocarbon group and a monomer (x) that satisfies a relational expression (1) below as constituent monomers, where the polymer (A) has a cross-linked structure and satisfies a relational expression (2) below. The relational expressions are: {(dP)2+(dH)2}0.5≥8.3 ...expression (1), and Tm-Tg≥10 ...expression (2).SELECTED DRAWING: None

Description

The present invention relates to a toner binder.

A technique using a crystalline resin has been proposed as a method for satisfying low-temperature fixability and storage stability of toner (Patent Document 1). However, the crystalline resin has a problem that the molecular weight decreases due to hydrolysis under long-term storage stability and high temperature and high humidity, and the decrease in molecular weight is remarkable especially when an acid value is imparted. Furthermore, since crystalline resins are expensive, they are generally used in combination with amorphous resins (for example, polyester, polystyrene, etc.) or copolymerized with amorphous monomers to reduce costs. When used in combination with the above-mentioned amorphous resin having an acid value, there is a problem that the above-mentioned crystalline resin is hydrolyzed. On the other hand, a technique of imparting crystallinity to a vinyl polymer having excellent hydrolysis resistance and using it has also been proposed (Reference 2). However, even in this case, there is a problem that the alkyl group of the side chain is hydrolyzed under a specific high temperature and high humidity condition, and the characteristics of the resin are changed.

Japanese Unexamined Patent Publication No. 2010-077419 International Publication No. 2018/110593

An object of the present invention is to provide a toner binder having excellent low temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention comprises a monomer (a) which is a (meth) acrylate having 18 to 24 carbon atoms in a chain hydrocarbon group and a monomer (x) which satisfies the following relational expression (1). A toner binder containing a polymer (A) as a monomer, the polymer (A) having a crosslinked structure, and the polymer (A) satisfying the following relational expression (2). ..
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3
[In the relational expression (1), (dP) is the polar term of the Hansen solubility parameter (HSP) of the monomer (x), and (dH) is the Hansen solubility parameter (HSP) of the monomer (x). It is a hydrogen bond term of. ]
Relational expression (2): Tm-Tg ≧ 10
[In the relational expression (2), Tm is the peak top temperature (° C.) of the endothermic peak measured by DSC, and Tg is the glass transition temperature (° C.) measured by DSC. ]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner binder having excellent low temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance.

The toner binder of the present invention is a toner binder containing the polymer (A).
The polymer (A) is a polymer composed of the monomer (a) and the monomer (x) as constituent monomers, and the monomer (a) has the number of carbon atoms of the chain hydrocarbon group. Is 18 to 24 (meth) acrylates, and the monomer (x) satisfies the relational expression (1). Further, the polymer (A) has a crosslinked structure, and the polymer (A) satisfies the above relational expression (2).
In the present invention, "(meth) acrylate" means "acrylate" and / or "methacrylate".

The monomer (a) is a (meth) acrylate having 18 to 24 carbon atoms in a chain hydrocarbon group.
Examples of the (meth) acrylate having 18 to 24 carbon atoms in the chain hydrocarbon group include (meth) acrylates having a linear alkyl group having 18 to 24 carbon atoms [octadecyl (meth) acrylate, nonadecil (meth) acrylate, and the like. Eikosyl (meth) acrylate, heneicosanyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, etc.] and (meth) acrylate having a branched alkyl group having 18 to 24 carbon atoms [2-decyltetradecyl (meth) ) Acrylate, etc.].
Of these, from the viewpoint of storage stability of the toner, it is preferably a (meth) acrylate having a linear alkyl group having 18 to 24 carbon atoms, and more preferably having a linear alkyl group having 20 to 24 carbon atoms. It is a (meth) acrylate, more preferably a (meth) acrylate having 22 to 24 linear alkyl groups.
As the monomer (a), one type may be used alone, or two or more types may be used in combination.

The monomer (x) may be any monomer as long as it satisfies the above relational formula (1), but is crosslinked from the viewpoint of low temperature fixability, storage under high temperature and high humidity, and hydrolysis resistance. It is preferable to contain the sex monomer (b) and the non-crosslinkable monomer (d).
As the monomer (x), one type may be used alone, or two or more types may be used in combination.

Examples of the crosslinkable monomer (b) include a monomer (b1) having two or more vinyl groups, a vinyl polymerizable monomer (b2) having an isocyanate group or a blocked isocyanate group, and an epoxy group. Examples thereof include a vinyl polymerizable monomer (b3) having.

Examples of the monomer (b1) having two or more vinyl groups include di (meth) acrylic acid ester [ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate. , Polypropylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.], Poly (meth) acrylic acid ester of polyhydric alcohol [Trimethylol propantri (meth) acrylate, etc. ) Acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, etc.], and aromatic compounds having two or more vinyl groups [divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, etc.] And so on.
In the present invention, "(meth) acrylic acid" means "acrylic acid" and / or "methacrylic acid".

Examples of the vinyl polymerizable monomer (b2) having an isocyanate group or a blocked isocyanate group include dimethyl-m-isopropenylbenzyl isocyanate, 2-isocyanatoethyl (meth) acrylate, and 2- (0) methacrylate. -[1'-Methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and the like can be mentioned.

Examples of the vinyl polymerizable monomer (b3) having an epoxy group include glycidyl (meth) acrylate and (3-ethyloxetane-3-yl) methyl methacrylate.

Among the crosslinkable monomers (b), when acting as a crosslinker, the monomer (b1) having two or more vinyl groups is preferable from the viewpoint of low temperature fixability, and 1,6-hexanediol di (1,6-hexanediol di) ( Meta) acrylate is more preferred.

Examples of the non-crosslinkable monomer (d) include a styrene-based monomer (d1), a (meth) acrylic monomer (d2) excluding the monomer (a) among the (meth) acrylic-based monomers, and a vinyl ester monomer. (D3) and a single amount having an ethylenically unsaturated bond with at least one functional group selected from the group consisting of a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group. The body (d4) and the like can be mentioned.

Examples of the styrene-based monomer (d1) include styrene and alkylstyrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methylstyrene and p-methylstyrene).
Of these, styrene is preferable.

Examples of the (meth) acrylic monomer (d2) include acrylic acid, methacrylic acid, alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Hexadecyl (meth) acrylate, cyclohexyl methacrylate, ethoxydiethylene glycol methacrylate, methoxy-triethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [2-hydroxypropyl acrylate, 2-hydroxy Ethyl (meth) acrylate and ethyl-2- (hydroxymethyl) acrylate and the like], aminoalkyl group-containing (meth) acrylate [dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate and the like] and the like can be mentioned.
Of these, alkyl (meth) acrylates and mixtures of two or more thereof are preferred.

Examples of the vinyl ester monomer (d3) include aliphatic vinyl esters (eg, vinyl acetate, vinyl propionate, isopropenyl acetate, etc.) and aromatic vinyl esters (eg, methyl-4-vinylbenzoate, etc.).

As the monomer (d4) having an ethylenically unsaturated bond and at least one functional group selected from the group consisting of a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group. , A monomer having a nitrile group (d41), a monomer having a urethane group (d42), a monomer having a urea group (d43), a monomer having an amide group (d44), a single having an imide group. Examples thereof include a metric (d45), a monomer having an allophanate group (d46), and a monomer having a burette group (d47).

Examples of the monomer having a nitrile group (d41) include acrylonitrile and methacrylonitrile.

Examples of the monomer having a urethane group (d42) include alcohols having an ethylenically unsaturated bond having 2 to 22 carbon atoms (-2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms. A monomer obtained by reacting the above with a known method, and a monomer obtained by reacting an alcohol having 1 to 26 carbon atoms with an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms by a known method. Can be mentioned.
Examples of isocyanates having 1 to 30 carbon atoms include monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenylisocyanate, p-chlorophenylisocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate. , Dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenylisocyanate, 3,5-dimethylphenylisocyanate and 2,6-dipropylphenylisocyanate, etc.), aliphatic diisocyanate compounds (trimethylenediisocyanate, tetramethylenediisocyanate, hexamethylenediisocyanate, etc.) , Pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compound (1,3-cyclopentenediisocyanate, 1) , 3-Cyclohexanediisocyanate, 1,4-Cyclohexanediisocyanate, Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, etc.) and aromatic diisocyanate compounds ( Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'- Diphenyl ether diisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate, etc.) and the like.
Alcohols having 1 to 26 carbon atoms include methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol and dodecyl. Alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, ellaidyl alcohol, oleyl alcohol, linoleil alcohol, linolenyl alcohol, nonadecil alcohol, henei cosanol, behenyl alcohol and el Syl alcohol and the like can be mentioned.
Examples of the isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond include 2-isocyanatoethyl (meth) acrylate and 2- (0- [1'-methylpropyrine amino] carboxyamino) ethyl (meth) acrylate. , 2-[(3,5-Dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate and the like.
In the present specification, the carbon number in the compound having an isocyanate group and the structure does not include the carbon number contained in the isocyanate group (-NCO).

Examples of the urea group-containing monomer (d43) include amines having 3 to 22 carbon atoms [for example, primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.)) and secondary amines (dinormal ethylamine, etc.). Dinormal propylamine, dinormal butylamine, etc.), aniline, cyclohexylamine, etc.] and an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms are reacted by a known method.

As the monomer having an amide group (d44), an amine having 3 to 22 carbon atoms and a carboxylic acid having an ethylenically unsaturated bond having 3 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) are reacted by a known method. Examples thereof include the made monomer.

As the monomer having an imide group (d45), a carboxylic acid anhydride (maleic anhydride, dialic anhydride, etc.) having 4 to 10 carbon atoms having an ethylenically unsaturated bond with ammonia was reacted by a known method. Examples thereof include a monomer and a monomer obtained by reacting a primary amine having 3 to 22 carbon atoms with a maleic anhydride having 4 to 10 carbon atoms having an ethylenically unsaturated bond by a known method.

Examples of the monomer having an allophanate group (d46) include a monomer obtained by reacting a monomer having a urethane group (d42) with an isocyanate having 1 to 30 carbon atoms by a known method.

Examples of the monomer having a burette group (d47) include a monomer obtained by reacting a monomer having a urea group (d43) with an isocyanate having 1 to 30 carbon atoms by a known method.

Of these non-crosslinkable monomers (d), styrene-based monomers (d1) and (meth) are preferable from the viewpoints of low-temperature fixability, hydrolysis resistance, storage under high temperature and high humidity, and raw material price. A single having an ethylenically unsaturated bond with at least one functional group selected from the group consisting of an acrylic monomer (d2), a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group. The metric (d4) is preferable, and more preferably, at least selected from the group consisting of a (meth) acrylic monomer (d2) and a nitrile group, a urethane group, a urea group, an amide group, an imide group, an allophanate group and a burette group. It is a monomer (d4) having one kind of functional group and an ethylenically unsaturated bond, and more preferably a monomer (d41) having an alkyl (meth) acrylate and a nitrile group.

As described above, the monomer (x) in the present invention satisfies the relational expression (1). When {(dP) ² + (dH) ² } ^0.5 is in this range, the low temperature fixability is good. This is because the crystalline segment of the monomer (a) is easily phase-separated from the amorphous segment derived from the monomer (x), and the sharp melt property is improved.
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3

In the relational expression (1), (dP) is the polar term of the Hansen solubility parameter (HSP) of the monomer (x), and (dH) is the Hansen solubility parameter (HSP) of the monomer (x). It is a hydrogen bond term.

It preferably satisfies the relational expression (1-2), and particularly preferably satisfies the relational expression (1-3).
Relational expression (1-2): 18.8 ≧ {(dP) ² + (dH) ² } ^0.5 ≧ 8.3
Relational expression (1-3): 10.7 ≧ {(dP) ² + (dH) ² } ^0.5 ≧ 8.3

The definition and calculation of the Hansen solubility parameter are described by Charles M. et al. It is described in "Hansen Solubility Parameter; A User's Handbook (CRC Press, 2007)" by Hansen, and the unit of the Hansen solubility parameter in the present invention is (cal / cm ³ ) ^0.5 . Further, by using the computer software "HSPiP 4.1.0", the Hansen solubility parameter can be estimated from the chemical structure of a monomer whose parameter value is not described in the literature. In the present invention, the values are used for the monomers whose parameter values are described in the literature, and the numerical values in the list attached to "HSPiP 4.1.0" are used for the monomers whose parameter values are not described in the literature. For items not listed, use the parameter values estimated using the Y-BM estimation method. When there are a plurality of monomers (x) constituting the polymer (A), (dP) and (dH) are calculated based on the weight ratio.

Examples of the method for adjusting the Hansen solubility parameter include changing the functional group. By selecting a monomer containing a functional group having a high dipole moment such as a nitrile group or an ester group, or a monomer containing a functional group having hydrogen bonding properties such as an amide group, a hydroxyl group or a carboxyl group, ( The parameters of dP) and (dH) can be increased.

The weight ratio of the monomer (a) constituting the polymer (A) in the present invention is preferably 30 to 30 to 30 based on the total weight of the monomers constituting the polymer (A) from the viewpoint of low temperature fixability. It is 93% by weight, more preferably 45 to 85% by weight, and particularly preferably 55 to 70% by weight.
The weight ratio of the monomer (x) constituting the polymer (A) in the present invention is based on the total weight of the monomers constituting the polymer (A) under low temperature fixability and high temperature and high humidity. From the viewpoint of storage stability, it is preferably 7 to 70% by weight, more preferably 15 to 55% by weight, and particularly preferably 30 to 45% by weight.
Further, the weight ratio [(b) / (d)] of the crosslinkable monomer (b) to the non-crosslinkable monomer (d) is 0. It is preferably 1 / 99.9 to 20/80, and more preferably 1/99 to 10/90.

The polymer (A) in the present invention can be obtained by the following methods (1) to (3).
(1) The method for chain-polymerizing the above-mentioned monomer (x) containing a monomer (b1) having two or more vinyl groups and a monomer composition containing the monomer (a).
(2) A chain of a monomer (x) containing a vinyl polymerizable monomer (b2) having an isocyanate group or a blocked isocyanate group and a monomer composition containing the monomer (a). A method in which a compound having two or more active hydrogens that reacts with an isocyanate group such as a hydroxyl group or an amino group is added over the polymer after polymerization.
(3) The above-mentioned polymerization is carried out after chain-polymerizing the monomer (x) containing the vinyl polymerizable monomer (b3) having an epoxy group and the monomer composition containing the monomer (a). A method of polymerizing a substance and a compound having two or more functional groups that react with an epoxy group such as a carboxyl group.
Whether or not the polymer (A) has a crosslinked structure can be confirmed by whether or not the polymer (A) is dissolved in xylene and has a component insoluble in xylene (xylene insoluble component).
The method (1) is preferable from the viewpoint of the simplicity of the process among the above methods.

When the monomer composition containing the monomer (a) and the monomer (x) is chain-polymerized, a known method (for example, radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization) is used. And living cationic polymerization, etc.) can be produced by polymerization. In the case of radical polymerization, for example, it can be synthesized by a solution polymerization method (Japanese Patent Laid-Open No. 5-117330, etc.) in which the above-mentioned monomer is reacted with a radical reaction initiator (c) in a solvent (toluene or the like).

The radical reaction initiator (c) is not particularly limited, and examples thereof include an inorganic peroxide (c1), an organic peroxide (c2), and an azo compound (c3). Further, these radical reaction initiators may be used in combination.

The inorganic peroxide (c1) is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

The organic peroxide (c2) is not particularly limited, and is, for example, benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl). Peroxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butyl peroxyhexin-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5 Examples thereof include -trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylmonocarbonate and t-butylperoxyacetate.

The azo compound (c3) is not particularly limited, and is, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2. '-Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. Can be mentioned.

Among these, an organic peroxide (c2) is preferable because it has high initiator efficiency and does not produce by-products such as cyanide.

The polymer (A) in the present invention satisfies the relational expression (2). When Tm-Tg is in this range, the low temperature fixability of the toner becomes good. This is the temperature at which the polymer (A) shows the peak top temperature (Tm) of the heat absorption peak without being affected by the glass transition temperature (Tg) when the toner using the toner binder containing the polymer (A) is thermally fixed. This is because the toner binder is sharply melted to reduce the viscosity.
Relational expression (2): Tm-Tg ≧ 10
More preferably, 10 ≦ Tm-Tg ≦ 30.
Tm-Tg adjusts the carbon number of the monomer (a) constituting the polymer (A), adjusts the weight ratio of the monomer (a) constituting (A), and the weight of (A). Adjusting to the above-mentioned preferable range by adjusting the average molecular weight, adjusting the glass transition temperature calculated from the Fox-Flory equation of the monomer (x) constituting the polymer (A), or the like. Can be done. For example, the number of carbon atoms in (a) is increased, the weight ratio of (a) is increased, the weight average molecular weight of (A) is increased, the content of (A) is increased, and the monomer constituting the polymer (A) ( Tm-Tg can be increased by a method such as lowering the glass transition temperature calculated from the Fox-Poly equation of x).
Further, for example, the monomer (a) constituting the polymer (A) is a (meth) acrylate having a linear alkyl group having 18 to 24 carbon atoms, and the weight ratio of the monomer (a) is the polymer. Based on the total weight of the monomers constituting (A), the content is 30% by weight or more, and the monomer (x) constituting the polymer (A) is the non-crosslinkable monomer (d) (meth). ) By containing the acrylic monomer (d2), it becomes easy to satisfy the relational expression (2).

The peak top temperature (Tm) of the endothermic peak measured by the differential scanning calorimeter (DSC) of the polymer (A) is 40 to 100 ° C. from the viewpoint of low temperature fixability and storage under high temperature and high humidity. It is preferably, more preferably 50 to 70 ° C.

The peak top temperature (Tm) of the endothermic peak is a value measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC Q20, manufactured by TA Instruments Co., Ltd.). Specifically, the first temperature rise is performed from 20 ° C. to 10 ° C./min to 150 ° C., then cooled to 0 ° C. from 150 ° C. to 10 ° C./min, and then from 0 ° C. It is a temperature showing the top of the endothermic peak of the polymer (A) in the second temperature raising process when the temperature is raised to 150 ° C. for the second time under the condition of 10 ° C./min.

The glass transition temperature (Tg) of the polymer (A) measured by DSC is preferably 45 ° C. or lower, preferably 35 to 45 ° C., from the viewpoint of low temperature fixability and storage under high temperature and high humidity. Is more preferable, and 5 to 45 ° C. is even more preferable.

The glass transition temperature (Tg) is a value measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC Q20, manufactured by TA Instruments Co., Ltd.). Specifically, the first temperature rise is performed from 20 ° C. to 10 ° C./min to 150 ° C., then cooled to 0 ° C. from 150 ° C. to 10 ° C./min, and then from 0 ° C. A straight line equidistant in the vertical axis direction from a straight line extending each baseline of the DSC curve in the second heating process when the temperature is raised to 150 ° C. under the condition of 10 ° C./min. It is the temperature at the point where the curve of the stepwise change part of the glass transition intersects. When the glass transition temperature (Tg) of the polymer (A) and the peak top temperature (Tm) of the heat absorption peak overlap, the formula (T. The glass transition temperature calculated using G.FOX, Bull.Am.Phys.Soc., 1,123 (1950)) can be used as a substitute.

The weight average molecular weight of the polymer (A) in the present invention is preferably 30,000 to 3,000,000 from the viewpoint of storage stability and hydrolysis resistance under high temperature and high humidity.

The weight average molecular weight of the polymer (A) in the present invention is measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Equipment: HLC-8120 [manufactured by Tosoh Corporation]
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Mobile phase: tetrahydrofuran (without polymerization inhibitor)
Solution injection volume: 100 μL
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1, 090,280,000) [manufactured by Tosoh Corporation]
In the measurement of the weight average molecular weight, the sample was dissolved in THF so as to be 0.25% by weight, and the insoluble matter was filtered through a PTFE filter having a pore size of 1 μm to prepare a sample solution.

The acid value of the polymer (A) in the present invention is preferably 40 mgKOH / g or less from the viewpoint of hydrolysis resistance. When the acid value is 40 mgKOH / g or less, an acidic functional group such as a carboxyl group does not easily act as a catalyst, and the promotion of hydrolysis can be suppressed. The acid value of the polymer (A) is more preferably 0 to 15 mgKOH / g, still more preferably 0 to 3 mgKOH / g.
The acid value of the polymer (A) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of the polymer (A) is measured by a method such as JISK0070.

The polymer (A) preferably satisfies the relational expression (3) from the viewpoint of low temperature fixability and storage under high temperature and high humidity.
Relational expression (3): 8.0 × 10 ⁵ ≦ G'(40) ≦ 1.5 × 10 ⁸
In the relational expression (3), G'(40) is a storage elastic modulus (Pa) at 40 ° C. as measured by viscoelasticity.
G '(40) is conserved at high temperature and high humidity for hardness of the toner binder are sufficient When it is 8.0 × 10 ⁵ or more is good. On the other hand, low temperature fixing property becomes excellent when G '(40) is at 1.5 × 10 ⁸ or less. G'(40) can be adjusted by the ratio of Tg of the polymer (A) and the monomer (a) and the like.

The G'(40) of the polymer (A) in the present invention has a disk shape having a diameter of 8 mm and a thickness of 2.0 ± 0.3 mm using a viscoelasticity measuring device (ARES-24A, manufactured by Leometric Co., Ltd.). When the sample pressure-molded was mounted on a parallel plate, the temperature was raised from room temperature (25 ° C) to 100 ° C, the shape of the sample was adjusted, the sample was cooled to 40 ° C, and the temperature was measured from 40 to 180 ° C. The storage elastic modulus (Pa) at 40 ° C. The measurement is performed under the following conditions.
Jig: 8mm parallel plate Frequency: 1Hz
Distortion rate: 1%
Heating rate: 5 ° C / min

The xylene insoluble content of the polymer (A) is preferably 7 to 50% by weight from the viewpoint of storage stability under high temperature and high humidity and hydrolysis resistance. It is more preferably 7 to 30% by weight, still more preferably 7 to 15% by weight.
The method for measuring the xylene insoluble content of the polymer (A) is as follows.
To prepare a sample, 1.00 g of the polymer (A) was dissolved or dispersed in 100 g of xylene at a temperature equal to or higher than the peak top temperature of the heat absorption peak, cooled to 25 ° C., and centrifuged by a centrifuge to obtain a supernatant. After removing the liquid, the mixture is dried under reduced pressure (170 ° C., 2 hours) to obtain a xylene insoluble matter, the weight of the xylene insoluble matter is measured to the fourth digit after the decimal point, and the xylene insoluble matter of (A) is determined by the following formula. calculate.
Xylene insoluble content (% by weight) of polymer (A) = (weight of xylene insoluble content (g) /1.00) × 100
The conditions for centrifugation are as follows.
<Centrifugal conditions>
Centrifuge: H-19F (manufactured by Kokusan Co., Ltd.)
Rotation speed: 4000 rpm
Rotation time: 20 minutes

The concentration of the urethane group and the urea group of the polymer (A) is preferably 2.5 × ^10-5 mol / g or less from the viewpoint of storage stability and hydrolysis resistance under high temperature and high humidity. It is preferably 5.0 × ^10-6 mol / g or less. When the concentration of the urethane group and the urea group is 2.5 × 10 ^-5 mol / g or less, the influence of hydrolysis by the water molecules adsorbed on the urethane group and the urea group is small, and the polymer (A) has a small effect. Since the crosslinked structure is maintained without lowering the molecular weight, the storage stability under high temperature and high humidity is improved.
Since the urethane group and urea group concentrations are generated by the reaction of isocyanate with alcohol or isocyanate with active hydrogen amine, the concentration can be adjusted by adjusting the amount of these used.
The concentrations of the urethane group and the urea group of the polymer (A) can be determined by the following method.

The method for quantifying the concentrations of the urethane group and the urea group of the polymer (A) is not particularly limited, and examples thereof include a method of calculating from the urethane group and urea group concentrations of the raw materials used in the synthesis. In the case of an unknown sample, the following method can be mentioned.

The method of measuring the proton of the polymer (A) with a nuclear magnetic resonance apparatus (NMR) and quantifying it can be measured by, for example, the following method.
<Sample adjustment>
Weigh 100 mg of a sample into an NMR tube, 10 mg of sodium trimethylsilylpropanoic sulfonate as an internal standard, and 10 mg of Cr (AcAc) ₃ as a relaxation reagent, and add 0.45 mL of a deuterium solvent of dimethyl sulfoxide or dimethylformamide to dissolve the resin. Let me.
<Measurement conditions>
Equipment: Bruker Biospin "AVANCE III HD400"
Number of integrations: 32 times <Analysis and calculation>
For example, the NH protons of aromatic isocyanate derivatives have peaks in DMSO at 7.8 to 8.6 for urea groups and 8.7 to 9.6 for urethane groups. On the other hand, the NH protons of the aliphatic isocyanate derivative have peaks in DMSO at 5.7 to 6.2 for the urea group and 6.7 to 7.0 for the urethane group. The urea group and urethane group contents (mmol / g) are calculated from these integration ratios and the integration ratio of the proton peak (0 ppm) of the internal standard substance.

The toner binder of the present invention has a weight described in other polymers known as polymers for toner binders other than the polymer (A) (Patent No. 4493080, Japanese Patent No. 2105762, and Japanese Patent Application Laid-Open No. 06-194876). It may contain coalescence etc.).
In addition, the toner binder of the present invention may contain the compound used during the polymerization of the polymer (A) and its residue as long as the effects of the present invention are not impaired.

The weight ratio of the polymer (A) in the toner binder shall be 5 to 100% by weight based on the weight of the toner binder from the viewpoint of low temperature fixability, storage under high temperature and high humidity, and hydrolysis resistance. Is preferable, more preferably 50 to 100% by weight, and particularly preferably 70 to 100% by weight.

A method for manufacturing a toner binder will be described.
The toner binder is not particularly limited as long as it contains the polymer (A). For example, the mixing method for mixing the polymer (A), other polymers and additives may be a known method, and the mixing method may be used. Examples include powder mixing, melt mixing, solvent mixing and the like. Further, (A), other polymers and additives may be mixed at the same time when the toner is produced. In this method, melt mixing that mixes uniformly and does not require solvent removal is preferable.

Examples of the mixing device for powder mixing include a Henschel mixer, a Nauter mixer, a Banbury mixer and the like. A Henschel mixer is preferred.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include a static mixer, an extruder, a continuous sneaker, and a three-roll device.

As a method of solvent mixing, a method of dissolving the polymer (A) and other resins in a solvent (ethyl acetate, tetrahydrofuran, acetone, etc.), homogenizing the mixture, and then removing the solvent and pulverizing the solvent, or the polymer (A). , Other resins are dissolved in a solvent (ethyl acetate, tetrahydrofuran, acetone, etc.), dispersed in water, and then granulated and desolved.

The toner containing the toner binder of the present invention may contain a colorant, a mold release agent, a charge control agent, a fluidizing agent, and the like, if necessary.

As the colorant, all of the dyes and pigments used as the colorant for toner can be used. For example, Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Paranitroaniline Red, Truisin Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamin. FB, Rhodamin B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP and the like. The colorant may be one of these alone or a mixture of two or more. Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt or nickel or a compound such as magnetite, hematite or ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder of the present invention. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight, based on 100 parts by weight of the toner binder of the present invention.

The release agent preferably has a flow softening point [T _1/2 ] of 50 to 170 ° C. by an enhanced flow tester, and is an aliphatic hydrocarbon such as polyolefin wax, microcrystallin wax, paraffin wax, and Fishertropch wax. Examples thereof include based waxes and their oxides, carnauba wax, Montan wax and their deoxidizing waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and mixtures thereof.

The method of measuring the flow softening point [T _{1/2] is described.}
Using a high-grade flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, a load of 1.96 MPa is applied by a plunger while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min. , Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop (flow value)" and "temperature", and set the temperature corresponding to 1/2 of the maximum value of the plunger drop. Let the flow softening point [T _1/2 ].

The polyolefin wax is a (co) copolymer obtained by [(co) polymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof). And those obtained by further heat-decomposing it], (eg low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxidation of (co) copolymers of olefins with oxygen and / or ozone. Maleic anhydride modified products of (co) polymers of olefins [eg maleic anhydride and derivatives thereof (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.)], olefins and unsaturated carboxylic acids [ (Meta) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl ester [(meth) alkyl acrylate (1-18 carbon atoms of alkyl) ester and alkyl maleate (alkyl carbon number 1) ~ 18) Esters, etc.] and the like.

Examples of microcrystalline wax include Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, and Hi-Mic- manufactured by Nippon Seiro Co., Ltd. 1045, Hi-Mic-2045 and the like can be mentioned.

Examples of the paraffin wax include Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, and HNP-manufactured by Nippon Seiwa Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

Examples of Fischer-Tropsch wax include Sasolwax C80 manufactured by Sazole.

Examples of carnauba wax include refined carnauba wax specially manufactured No. 1 manufactured by Hiroyuki Kato Co., Ltd.

Examples of the ester wax include fatty acid ester waxes (for example, Nissan Electol WEP-2, WEP-3, WEP-4, WEP-5, WEP-8, etc. manufactured by Nichiyu Co., Ltd.).

Examples of higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, and examples thereof include triacontanol. Examples of fatty acids include fatty acids having 30 to 50 carbon atoms, and examples thereof include triacontane carboxylic acid.

The charge control agent may contain either a positive charge control agent or a negative charge control agent, and is a triphenylmethane dye containing a niglosin dye or a tertiary amine as a side chain, and a quaternary ammonium salt. , Polyamine resin, imidazole derivative, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, salicylate metal salt, boron complex of benzylic acid, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic ring-containing polymer, etc. Can be mentioned.

Examples of the fluidizing agent include silica, titania, alumina, calcium carbonate, fatty acid metal salt, silicone resin particles, fluororesin particles, and the like, and two or more of them may be used in combination. Silica is preferable from the viewpoint of toner chargeability. Further, the silica is preferably hydrophobic silica from the viewpoint of toner transferability. Further, the silica is preferably hydrophobic silica from the viewpoint of toner transferability.

The content of the toner binder in the toner is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, still more preferably 45 to 92% by weight, based on the weight of the toner. The content of the colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.5 to 50% by weight, based on the toner weight. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight, based on the toner weight. The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7.5% by weight, based on the toner weight. The content of the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, still more preferably 0.1 to 4% by weight, based on the weight of the toner. The total content of the colorant, mold release agent, charge control agent and fluidizing agent is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, still more preferably 5 to 50% by weight, based on the toner weight. %. By setting the composition ratio of the toner in the above range, it is possible to easily obtain a toner having good storage stability under high temperature and high humidity.

When the toner binder of the present invention is used as a toner, the method for producing the toner is not particularly limited, and known methods such as a kneading and pulverizing method, an emulsification phase inversion method, an emulsification polymerization method, a suspension polymerization method, a dissolution suspension method and an emulsion aggregation method It may be obtained by any of the above methods.
Of these production methods, the kneading and pulverizing method and the dissolution and suspension method are preferable from the viewpoints of productivity, low temperature fixability and storage stability.

For example, when the toner is obtained by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended with a Henschel mixer, a Nauter mixer, a Banbury mixer, etc. It is melt-kneaded with a continuous mixer such as three rolls, then coarsely pulverized with a mill or the like, and finally finely divided using an air flow type fine pulverizer (for example, a supersonic jet pulverizer or the like), and further. By adjusting the particle size distribution with a classifier such as an air flow classifier, toner particles [preferably particles having a volume average particle size (D50) of 5 to 20 μm] can be produced by mixing with a fluidizing agent. it can. The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].

When toner is obtained by the emulsification phase inversion method, the components constituting the toner excluding the fluidizing agent can be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. it can. The volume average particle size of the toner is preferably 3 to 15 μm.

As the emulsification polymerization method and the suspension polymerization method, known methods [methods described in Japanese Patent Publication No. 36-10231, Japanese Patent Publication No. 47-518305, Japanese Patent Publication No. 51-14895, etc.] can be used.

As the dissolution suspension method and the emulsification / aggregation method, known methods [methods described in Japanese Patent No. 3596104, Japanese Patent No. 3492748, etc.] can be used.

The toner used in the toner binder of the present invention is a carrier particle such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite and a resin (acrylic polymer, silicone polymer, etc.), if necessary. Is mixed with and used as a developer for electrically latent images. The weight ratio of the toner to the carrier particles is 1/99 to 100/0. Further, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

The toner containing the toner binder of the present invention is fixed to a support (paper, polyester film, etc.) as an electrophotographic toner by a copying machine, a printer, or the like to be used as a recording material. As a method of fixing to the support, a known heat roll fixing method, flash fixing method, or the like can be applied.

The toner produced by using the toner binder of the present invention is used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified, parts indicate parts by weight.

<Production Example 1> [Production of polymer (A-1)]
After charging 46 parts of toluene into an autoclave and replacing it with nitrogen, the temperature was raised to 105 ° C. in a sealed state with stirring. Behenyl acrylate [manufactured by Nichiyu Co., Ltd., same below] 60 parts, acrylonitrile [manufactured by Nacalai Tesque Co., Ltd., same below] 10 parts, styrene [manufactured by Idemitsu Kosan Co., Ltd., same below] 8 parts, methyl acrylate [Nakarai] Tex Co., Ltd., same below] 21.5 parts, 1,6-hexanediol diacrylate [Kyoeisha Chemical Co., Ltd., same below] 0.5 parts, t-butylperoxy-2-ethylhexa A mixed solution of 0.359 parts of Noate [Perbutyl O, Nichiyu Co., Ltd., the same applies hereinafter] and 23 parts of toluene was added dropwise over 2 hours while controlling the temperature inside the autoclave to 105 ° C. for polymerization. .. Further, the polymerization was completed by keeping at the same temperature for 4 hours. Then, the solvent was removed at 100 ° C. to obtain a polymer (A-1).

<Production Examples 2 to 15, Comparative Production Examples 1 to 5> [Production of Polymers (A-2) to (A-15), (A'-1) to (A'-5)]
Polymers (A-2) to (A-15), (A') are the same as in Production Example 1 except that each monomer is designated by weight based on the composition of the monomers shown in Table 1. -1) to (A'-5) were obtained.
In addition, octadecyl acrylate, behenyl methacrylate, lignoceryl acrylate, methacrylonitrile, 2-hydroxypropyl acrylate, methoxy-triethylene glycol acrylate, methoxy-polyethylene glycol acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid, hexadecyl acrylate and 2 -The following reaction products of isocyanatoethyl methacrylate and methanol were used.
Octadecyl acrylate: Behenyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd .: Lignoceryl acrylate manufactured by NOF CORPORATION: Described in Production Example 16.
Methacronitrile: 2-hydroxypropyl acrylate manufactured by Tokyo Kasei Kogyo Co., Ltd .: Methoxy-triethylene glycol acrylate (light acrylate MTG-A) manufactured by Tokyo Kasei Kogyo Co., Ltd .: Methoxy-polyethylene glycol acrylate (light acrylate) manufactured by Kyoeisha Chemical Co., Ltd. 130A): Kyoeisha Chemical Co., Ltd. Methyl methacrylate: Tokyo Kasei Kogyo Co., Ltd. Butyl methacrylate: Tokyo Kasei Kogyo Co., Ltd. Methacrylate: Tokyo Kasei Kogyo Co., Ltd. Hexadecyl acrylate: Tokyo Kasei Kogyo Co., Ltd. 2-Isocyanatoethyl A reaction product of methacrylate [Karens MOI, manufactured by Showa Denko Co., Ltd., the same applies hereinafter] and methanol: described in Production Example 17.

<Manufacturing Example 16> [Manufacturing of lignoceryl acrylate]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, air introduction tube, decompression device, and water reducing device, 870 parts of lignoceryl alcohol [manufactured by BASF], 1000 parts of toluene, acrylic acid [manufactured by Mitsubishi Chemical Co., Ltd.] ] 280 parts and 2 parts of hydroquinone were added and stirred to make them uniform. Then, 4 parts of paratoluenesulfonic acid was added, and after stirring for 30 minutes, the reaction was carried out for 5 hours while removing water generated at 100 ° C. while blowing air at a flow rate of 30 mL / min. Then, the pressure in the reaction vessel was adjusted to 300 mmHg, and the reaction was carried out for another 3 hours while removing the generated water. The reaction solution was cooled to room temperature, 20 parts of a 10 wt% sodium hydroxide aqueous solution was added, the mixture was stirred for 1 hour, and then allowed to stand to separate the organic phase and the aqueous phase. The organic phase was sampled by liquid separation and centrifugation, 1 part of hydroquinone was added, and the solvent was removed under reduced pressure while blowing air to obtain lignoceryl acrylate.

<Production Example 17> [Production of reaction product of 2-isocyanatoethyl methacrylate and methanol]
After charging 50 parts of dehydrated methyl ethyl ketone into an autoclave and aerating with dry air, 50 parts of 2-isocyanatoethyl methacrylate, 30 parts of dehydrated methanol, Neostan U-600 [Nitto Kasei Kogyo Co., Ltd., the same applies hereinafter] 0.039 parts Was added, and the reaction was carried out at 80 ° C. for 10 hours. Then, the solvent was removed at 80 ° C. while substituting with air to obtain a 2-isocyanatoethyl methacrylate and methanol reaction product in which the reaction was quantitatively completed.

<Production Example 18> [Production of Polymer (A-16)]
46 parts of dehydrated toluene was charged into a sufficiently dried autoclave, replaced with nitrogen, and then the temperature was raised to 105 ° C. in a sealed state with stirring. Dehydrated behenyl acrylate [manufactured by Nichiyu Co., Ltd., same below] 60 parts, acrylonitrile [manufactured by Nacalai Tesque Co., Ltd., same below] 10 parts, styrene [manufactured by Idemitsu Kosan Co., Ltd., same below] 8 parts, methyl Acrylate [manufactured by Nacalai Tesque, Inc., the same applies hereinafter] 21.5 parts, 2-isocyanatoethyl methacrylate 0.1 parts, t-butylperoxy-2-ethylhexanoate [Perbutyl O, Nichiyu Co., Ltd., The same applies hereinafter] A mixed solution of 0.359 parts and 23 parts of toluene was added dropwise over 2 hours while controlling the temperature inside the autoclave to 105 ° C. for polymerization. Further, the polymerization was completed by keeping at the same temperature for 4 hours. Then, after cooling to 50 ° C., 0.1 part of 1,6-hexanediol [manufactured by Tokyo Chemical Industry Co., Ltd.] and 0.044 part of Neostan U-600 [Nitto Kasei Kogyo Co., Ltd., the same applies hereinafter] were added to 80 parts. The reaction was carried out at ° C. for 10 hours. Then, the solvent was removed at 140 ° C. to obtain a polymer (A-16).

The compositions and physical property values of the polymers (A-1) to (A-16) and (A'-1) to (A'-5) are shown in Tables 1 and 2.

<Manufacturing Example 19> [Manufacturing of other resin (B-1)]
In the reaction vessel, 697 parts of propylene oxide 2 mol adduct of bisphenol A, 297 parts of terephthalic acid, and 0.5 part of tetrabutoxytitanate as a condensation catalyst were placed, and the reaction was carried out at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa. The mixture was allowed to react for 10 hours while distilling off the produced water. When the acid value became 1 mgKOH / g or less, the mixture was cooled to 180 ° C., 25 parts of trimellitic anhydride was added, the reaction was carried out for 1 hour, and then the resin was taken out from the reaction vessel and was taken out from the reaction vessel. B-1) was obtained.
The glass transition temperature of the other resin (B-1), which is an amorphous polyester resin, is 67 ° C., the flow softening point is 114 ° C., the number average molecular weight is 2,800, the weight average molecular weight is 6,500, and the acid value is 12 mgKOH /. It was g.

<Examples 1 to 17 and Comparative Examples 1 to 5>
Comparative Production Examples 1 to 19 93 parts and other resins of the polymers (A-1) to (A-16) and (A'-1) to (A'-5) obtained in Production Examples 1 to 5 respectively. (B-1) 7 parts were mixed with tetrahydrofuran to prepare a uniform solution having a solid content of 50% after evaporation. Subsequently, the solvent was removed at 80 ° C. to obtain a resin mixture having a solid content of 99.90% or more after evaporation, which was used as toner binders (D-1) to (D-16) as toner binders (D-1) to (D-16) by the method described below. (Ts-1) to (Ts-16), (Tf-1) and (Ts'-1) to (Ts'-5) were obtained.

<Manufacturing of toner (Ts-1) by dissolution / suspension method>
[Manufacturing of fine particle dispersion liquid 1]
In a reaction vessel with a stirring rod and a thermometer set, 683 parts of water, 11 parts of sodium salt of ethylene methacrylate adduct sulfate [eleminol RS-30, manufactured by Sanyo Kasei Kogyo Co., Ltd.], 139 parts of vinylbenzene, 138 parts of methacrylic acid. A white emulsion was obtained when 184 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes. After heating, the temperature inside the system was raised to 75 ° C. and the reaction was carried out for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution is added and aged at 75 ° C. for 5 hours to obtain a vinyl polymer (copolymer of a sodium salt of vinylbenzene-methacrylic acid-butyl acrylate-ethylene methacrylate adduct sulfate ester). An aqueous dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by a laser diffraction / scattering particle size distribution measuring device [LA-920, manufactured by HORIBA, Ltd.] was 0.15 μm.
[Manufacturing of wax dispersion liquid 1]
15 parts of carnauba wax and 85 parts of ethyl acetate were put into a reaction vessel equipped with a cooling tube, a thermometer and a stirrer, heated to 80 ° C. to dissolve, cooled to 30 ° C. over 1 hour, and carnauba. The wax was crystallized into fine particles and further wet-ground with an "Ultra Viscomill" (manufactured by IMEX) to prepare a [wax dispersion 1].
[Manufacturing of pigment masterbatch]
1200 parts of water, 40 parts of carbon black (manufactured by Cabot, Legal 400R), and 20 parts of the polymer (A-4) manufactured in Production Example 4 are mixed with a Henshell mixer (manufactured by Mitsui Mining Co., Ltd.), and three rolls of the mixture are rolled. After kneading at 90 ° C. for 30 minutes, the mixture was rolled and cooled and pulverized with a palpelizer to obtain a pigment masterbatch [MB1].
[Manufacturing of aqueous phase s1]
In a container in which a stirring rod is set, 955 parts of water, 15 parts of [fine particle dispersion liquid 1], and 30 parts of an aqueous solution of sodium dodecyldiphenyl ether disulfonate (eleminol MON7, manufactured by Sanyo Kasei Kogyo) are put into a milky white liquid [aqueous phase s1]. Got

[Manufacturing of toner (Ts-1)]
・ 191 parts of toner binder (D-1), 25 parts of pigment masterbatch [MB1], 67 parts of [wax dispersion 1], and 124 parts of ethyl acetate were put into a particle beaker to dissolve and homogenize the mixture, and then [oil]. Phase s1] was obtained. 600 parts of [Aquatic phase s1] is added to this [Oil phase s1], and a TK homomixer (manufactured by Tokushu Kagaku Kogyo Co., Ltd.) is used to carry out a dispersion operation at 25 ° C. for 1 minute at a rotation speed of 12000 rpm, and further a film. The solvent was removed with an evaporator under the conditions of a reduced pressure of −0.05 MPa (gauge pressure), a temperature of 40 ° C., and a rotation speed of 100 rpm for 30 minutes to obtain an aqueous colored polymer dispersion (X-1).
・ Centrifuge 100 parts of classification (X-1), add 60 parts of water, centrifuge and separate into solid and liquid twice, and then dry at 35 ° C for 1 hour, and then use an elbow as a classification machine. With a jet classifier [made by Matsubo Co., Ltd., EJ-L-3 (LABO) type], the amount of fine powder of 3.17 μm or less is 12% by volume or less, and the amount of coarse powder of 8.0 μm or more is 3% by volume or less. , Fine powder and coarse powder were removed to obtain colored polymer particles [Cs-1].
-External treatment Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] was added to 100 parts of the colored polymer particles [Cs-1] of the obtained colored powder, and the peripheral speed was increased. Was mixed for 30 seconds at 15 m / sec, and paused for 1 minute for 5 cycles to obtain toner (Ts-1).

<Manufacturing of toners (Ts-2) to (Ts-16) and (Ts'-1) to (Ts'-5) by the dissolution / suspension method>
The procedure is the same as that of the toner (Ts-1) except that (D-2) to (D-16) and (D'-1) to (D'-5) are used instead of the toner binder (D-1). [Oil phase s2] to [Oil phase s16] and [Oil phase s'1] to [Oil phase s'5] are obtained, respectively, and the toners (Ts-2) have the compositions shown in Tables 3 and 4, respectively. -(Ts-16) and (Ts'-1)-(Ts'-5) were obtained.

[Manufacturing of toner (Tf-1) by kneading and crushing method]
The polymer (A-11) obtained in Production Example 11 was used as a toner binder (D-17) to obtain a toner (Tf-1) by the method described below.
・ Kneading (D-17) 85 parts, pigment carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 6 parts, mold release agent carnauba wax 4 parts, charge control agent [T-77, Hodogaya Chemical Industry Co., Ltd.] Manufactured by Co., Ltd.] 4 parts were made into toner by the following method. First, each raw material was premixed using a Henschel mixer [FM10B manufactured by Nippon Coke Industries Co., Ltd.] and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikekai Co., Ltd.].
・ After crushing and classification, finely crushed using a supersonic jet crusher Lab Jet [LJ type manufactured by Nippon Pneumatic Industries Co., Ltd.], and then classified by an air flow classifying machine [MDS-I manufactured by Nippon Pneumatic Industries Co., Ltd.]. Then, colored resin particles (FP-1) were obtained.
-External treatment Next, 100 parts of colored resin particles (FP-1) were mixed with 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent with a sample mill, and toner (Tf-) was mixed. 1) was obtained.

Toners (Ts-1) to (Ts-16) and (Tf-1) obtained in Examples 1 to 17 and comparative toners (Ts'-1) to (Ts') obtained in Comparative Examples 1 to 5 Regarding -5), the low temperature fixability, the storage stability under high temperature and high humidity, and the hydrolysis resistance were evaluated by the following methods. The results are shown in Tables 3 and 4.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so as to have a concentration of 1.00 mg / cm ^2. At this time, as a method of placing the powder on the paper surface, a printer with the heat fixing machine removed was used. This paper was passed through a soft roller in a fixing speed (peripheral speed of a heating roller) of 213 mm / sec and a heating roller temperature range of 90 to 200 ° C. in 5 ° C. increments. Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which the cold offset occurred was measured.
The lower the temperature at which the cold offset is generated, the better the low temperature fixability. Under these evaluation conditions, it is generally preferable that the temperature is 125 ° C. or lower.

<Preservation under high temperature and high humidity>
1 g of toner and 0.01 g of hydrophobic silica (Aerosil R8200, manufactured by Evonik Japan Co., Ltd.) were mixed with a shaker for 1 hour. The mixture was placed in a glass container without a lid and allowed to stand in an atmosphere of a temperature of 40 ° C. and a humidity of 80% for 48 hours, the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated according to the following criteria.
⊚: No blocking has occurred and there is no change in visual fluidity. ○: Blocking has occurred, but when the container is shaken, the agglutination is unraveled and the container flows.

<Hydrolysis resistance>
1 g of toner is placed in a glass container without a lid and allowed to stand in an atmosphere of temperature 95 ° C. and humidity 95% for 10 days, and the weight average molecular weight and storage elastic modulus (Pa) at 100 ° C. are measured by GPC measurement before and after the test. The change in weight average molecular weight and the change in storage elastic modulus were confirmed, and whether or not hydrolysis had occurred was evaluated. The GPC measurement and the storage elastic modulus (Pa) at 100 ° C. were measured by the same method as that of the polymer (A).
⊚: Changes in weight average molecular weight and storage elasticity are both less than ± 5% ○: Changes in molecular weight are ± 5% or more, but changes in storage elasticity are less than ± 5% ×: Both molecular weight and elasticity are ± 5% or more change of

As is clear from the evaluation results in Tables 3 and 4, the toners (Ts-1) to (Ts-16) and (Tf-1) containing the toner binder of the present invention have low temperature fixability and high temperature and high humidity. Good storage stability and hydrolysis resistance.
On the other hand, the toners (Ts'-1) to (Ts'-5) containing the toner binder for comparison are at least one of the low temperature fixability, the storage stability under high temperature and high humidity, and the hydrolysis resistance. The evaluation result was inferior.

The toner binder of the present invention has excellent low-temperature fixability, storage stability under high temperature and high humidity, and hydrolysis resistance, and is suitably used as a toner for static charge image development used in electrophotographic, electrostatic recording, electrostatic printing, etc. it can.
Further, it is suitable for applications such as paint additives, adhesive additives, and electronic paper particles.

Claims (4)

A monomer (a) which is a (meth) acrylate having 18 to 24 carbon atoms of a chain hydrocarbon group and
A toner binder containing a polymer (A) having a monomer (x) satisfying the following relational expression (1) as a constituent monomer.
A toner binder in which the polymer (A) has a crosslinked structure and the polymer (A) satisfies the following relational expression (2).
Relational expression (1): {(dP) ² + (dH) ² } ^0.5 ≧ 8.3
[In the relational expression (1), (dP) is the polar term of the Hansen solubility parameter (HSP) of the monomer (x), and (dH) is the Hansen solubility parameter (HSP) of the monomer (x). It is a hydrogen bond term of. ]
Relational expression (2): Tm-Tg ≧ 10
[In the relational expression (2), Tm is the peak top temperature (° C.) of the endothermic peak measured by DSC, and Tg is the glass transition temperature (° C.) measured by DSC. ] The toner binder according to claim 1, wherein the glass transition temperature of the polymer (A) measured by DSC is 45 ° C. or lower. The toner binder according to claim 1 or 2, wherein the polymer (A) satisfies the relational expression (3).
Relational expression (3): 8.0 × 10 ⁵ ≦ G'(40) ≦ 1.5 × 10 ⁸
[In the relational expression (3), G'(40) is the storage elastic modulus (Pa) at 40 ° C. as measured by viscoelasticity. ] The toner binder according to any one of claims 1 to 3, wherein the xylene insoluble content of the polymer (A) is 7 to 50% by weight.