JP2006309203A - Toner binder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner binder excellent in both low-temperature fixing property and hot-offset resistance. <P>SOLUTION: The toner binder comprises an aggregate (P) of resin particles (Pi) comprising a resin (A) having one or more right-handed helix polymer units (a) within a molecule and/or a resin (B) having one or more left-handed helix polymer units (b) within a molecule, wherein the resins (A) and (B) are contained in the toner binder and an abundance ratio of a stereo complex of the units (a) and (b) in the toner binder increases after melting. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner binder. More particularly, the present invention relates to a toner binder useful for toner used in electrophotography, electrostatic recording, electrostatic printing, and the like.

The toner binder used in electrophotography, electrostatic recording, electrostatic printing, etc. can fix the toner even when the hot roll temperature is low (low temperature fixability), and the toner does not fuse to the hot roll even at a high hot roll temperature. Satisfying the contradictory performance (hot offset resistance). In recent years, from the viewpoint of energy saving, there has been a demand for further low-temperature fixability than before, and from the viewpoint of miniaturization of apparatuses such as copying machines, further resistance to hot offset has been demanded.
Conventionally, styrene acrylic resins, polyesters, epoxy resins, and the like have been used as toner binders, but cross-linked polyesters are often used because of their excellent low-temperature fixability. As a method for improving the low-temperature fixability and hot offset resistance of polyester, a method of mixing two kinds of polyesters having different molecular weight distributions has been proposed (see Patent Documents 1 to 3).
JP-A-60-214368 JP-A-63-225244 JP-A-4-313760

  However, what is disclosed in these is a powder mixture of polyesters having different softening points, although the balance between low-temperature fixability and hot offset resistance is in an improving trend as compared with conventional polyesters. There is a problem in uniformity, and there is a problem that the pigment cannot be sufficiently dispersed when the toner is kneaded. When the difference between the softening points of the two kinds of polyesters is reduced, the pigment dispersibility is improved, but conversely, there is a problem that the low-temperature fixability and hot offset resistance are not sufficiently improved.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to develop a toner binder excellent in both low-temperature fixability and hot offset resistance.
That is, the present invention relates to a resin (A) having one or more right-handed helical polymer units (a) in the molecule and / or a resin having one or more left-handed helical polymer units (b) in the molecule. A toner binder comprising an aggregate (P) of resin particles (Pi) comprising (B), wherein the toner binder contains (A) and (B), and ( A toner binder characterized in that the stereo complex abundance ratio of a) and (b) is increased.

The toner binder of the present invention has the following effects.
1. Excellent heat melting characteristics and excellent low temperature fixability when used as toner for electrophotography, electrostatic recording, and electrostatic printing.
2. Excellent releasability from heat source when melted, improved hot offset resistance when used as toner for electrophotography, electrostatic recording and electrostatic printing, and widens the temperature range in which toner can be fixed on paper Can do.

  The toner binder of the present invention is an aggregate of resin particles containing a resin (A) having a right-handed helical polymer unit (a) and a resin (B) having a left-handed helical polymer unit (b) in the aggregate. When (P) is used as a toner, it melts in contact with a heat source, so that (a) and (b) are mixed to form a stereo complex of (a) and (b). The pseudo-crosslinked structure formed by the stereocomplex formed at the time of melting increases the viscosity of the toner binder and improves the offset resistance of the electrophotographic toner. In addition, even if the initial melt is low viscosity, thickening due to stereocomplex formation occurs later in the melt, so that while maintaining the hot offset resistance, the molecular weight of the resin (A) and the resin (B) is reduced. It is possible to improve the low-temperature fixability.

The toner binder of the present invention comprises resin particles (Pi) comprising a resin (A) having one or more (a) in the molecule and / or a resin (B) having one or more (b) in the molecule. ) Toner aggregate (P). Even if (A) and (B) are simultaneously contained in one resin particle (Pi), only one of (A) and (B) is contained in one resin particle (Pi). Also good. The number of (Pi) forming (P) varies depending on the method of use and is not particularly limited. From the viewpoint of easy formation of a stereocomplex when the toner binder is melted, it is preferable that (A) and (B) are contained in the same resin particle (Pi). When (A) and (B) are contained in the same resin particle (Pi), they are composite resin particles composed of fine resin particles of (A) and (B), and (a) and (b) are usually It exists in a state where no stereo complex is formed.
The number of (a) in (A) and the number of (b) in (B) are preferably 1 to 10, more preferably 2 to 6, respectively.
The weight ratio of (A) and (B) in the toner binder is preferably (A) :( B) = (20:80) to (80:20), more preferably (A) :( B) = ( 30:70) to (70:30), particularly preferably (A) :( B) = (40:60) to (60:40).

  In the present invention, whether or not a stereocomplex is formed is determined based on a diffraction peak by a wide-angle X-ray diffraction method, specifically, a diffraction peak that appears when a stereocomplex is formed [for example, polylactic acid: flag angle ( 2θ) 11.3-12.3 °, 20.1-12.1 °, and near 23.3-24.3 °], or endothermic peak heat in differential scanning calorimetry (DSC) (endothermic melting heat) Specifically, it can be determined by an endothermic peak that appears when a stereo complex is formed (around + 50 ° C. compared to (A) or (B) alone).

The monomer constituting (a) and (b) is not particularly limited as long as it can form a helical polymer unit. However, since it is easy to introduce the helical polymer unit, it is composed of an optically active monomer (m). Is preferred. (M) includes not only monomers having asymmetric carbon but also monomers that generate asymmetric carbon by polymerization.
(A) and (b) can be produced separately by, for example, homopolymerizing (m) each having a specific optical rotation with a different sign. In order to form a stereo complex, It is preferably in the enantiomeric relationship. (A) and (b) may be a homopolymer of one type of optically active monomer (m), or two or more types of (m), or a combination of one or more types of (m) and other monomers. A polymer may be used, but in the case of a copolymer, since a helical polymer unit can be easily formed, a block copolymer containing one kind of (m) homopolymer portion is preferable. . The degree of polymerization of the homopolymer part (m) in the homopolymer and the block copolymer is preferably 10 to 100,000, more preferably 50 to 8000, from the viewpoint of easy formation of a stereocomplex.
Generally, it is known that a helical polymer is formed by homopolymerizing an optically active monomer having an optical purity of 100%. The structure of the helical polymer unit is confirmed by an X-ray crystal structure analyzer [manufactured by Rigaku Corporation]. , AFC7R, etc.] can be used to distinguish left-handed and right-handed.

(M) is not particularly limited, but α-alkyl (alkyl group having 1 to 4 carbon atoms) -α-hydroxycarboxylic acid, α-hydrocarbyl (hydrocarbyl group having 1 to 12 carbon atoms) -α. -Amino acid, α-hydrocarbyl (hydrocarbyl group having 1 to 8 carbon atoms) methacrylate, cyclic ester having asymmetric carbon (total carbon number of 3 to 6), α-alkylethylene oxide (total carbon number of 6 to 9) ), Α-alkylethylene sulfide (total carbon number 6 to 9), and the like.
Examples of the alkyl group having 1 to 4 carbon atoms in the α-alkyl-α-hydroxycarboxylic acid include a methyl group, an ethyl group, and an isopropyl group, and specific examples thereof include L-lactic acid and D-lactic acid. The hydrocarbyl group having 1 to 12 carbon atoms in the α-hydrocarbyl-α-amino acid may be any of an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group, such as a methyl group, an ethyl group, and a phenyl group. Group, benzyl group, α-methylbenzyl and the like, and specific examples include γ-benzylglutamic acid and γ-methylglutamic acid. Examples of the hydrocarbyl group in α-hydrocarbyl methacrylate include those described above, and specific examples include α-methylbenzyl methacrylate and methyl methacrylate. Specific examples of the cyclic ester having an asymmetric carbon include L-lactide, D-lactide, α-methyl-α-ethyl-β-propiolactone, and β- (1,1-dichloropropyl) -β-pro. Piolactone is mentioned. Examples of the alkyl group in α-alkylethylene oxide include those described above, and specific examples thereof include t-butylethylene oxide. Examples of the alkyl group in the α-alkylethylene sulfide include those described above, and specific examples thereof include t-butylethylene sulfide.
Of these, L-lactic acid, D-lactic acid, L-lactide, D-lactide, t-butylethylene oxide, t-butylethylene sulfide, α-methyl are preferable from the viewpoint of easy introduction of the helical polymer unit. -Α-ethyl-β-propiolactone, β- (1,1-dichloropropyl) -β-propiolactone, and combinations thereof, more preferably L-lactic acid and D-lactic acid, and / or L-lactide and D-lactide, particularly preferably L-lactide and D-lactide.

  As the polymerization reaction mode of the monomers constituting the right-handed helical polymer unit (a) and the left-handed helical polymer unit (b), any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. However, among these, from the viewpoint of easy stereoregular polymerization necessary for forming a helical polymer unit, a cyclic ester having an asymmetric carbon, α-alkylethylene oxide, α- Ring-opening polymerization of cyclic monomers such as alkylethylene sulfide and dehydration condensation of hydroxycarboxylic acid.

As a catalyst used for ring-opening polymerization and dehydration condensation, a known catalyst is used, and can be appropriately selected in consideration of reactivity and selectivity. For example, base catalysts include hydroxides of alkali metals (Li, Na, K, etc.), alcoholates of alkali metals (Li, Na, K, etc.), and alkylamines (monoalkylamines, dialkylamines, trialkylamines). Examples of acid catalysts include Lewis acid catalysts such as halides and alkoxides of metals (Al, Sb, B, Be, P, Fe, Zn, Ti, Zr, etc.), inorganic acids (HCl, HBr, H ₂ SO ₄ , HClO _4, etc.) and organic acids (acetic acid, oxalic acid, etc.) and the like, and two or more kinds can be used in combination. The amount of the polymerization catalyst used is preferably 0.001 to 5% by weight based on the weight of all monomers to be reacted.

The method for introducing (a) into the resin (A) and the method for introducing (b) into the resin (B) are not particularly limited, but the helical polymer unit (a) or ( b) ring-opening polymerization of the monomer constituting the monomer, a method of graft polymerizing the monomer constituting the helical polymer unit (a) or (b) to the resin, and a method of polymerizing the helical polymer unit (a) or (b) to the resin. The method of combining is mentioned.
Specifically, as a method for subjecting the active hydrogen-containing compound to ring-opening polymerization, the polyols (11) and (12), polycarboxylic acids (13) and (14), polyamine (16) and polythiol (described later) are used. And a ring-opening polymerization reaction for active hydrogen-containing compounds such as 17). In addition, as a method of graft polymerization to the resin, polycondensation reaction to a functional group having active hydrogen in the resin (hydroxyl group, carboxyl group, amino group, etc.), ring-opening polymerization reaction, vinyl polymerizable group in the resin and Vinyl polymerization. In addition, as a method of bonding the helical polymer unit to the resin, the functional group having active hydrogen (hydroxyl group, thiol group, carboxyl group, etc.) in the helical polymer unit and the functional group that reacts with the active hydrogen contained in the resin. Reaction with groups (isocyanate group, thioisocyanate group, epoxy group, etc.), and functional groups with active hydrogen in resin and functional groups with active hydrogen in helical polymer unit react with active hydrogen Examples include a method of bonding using a substance having two or more (isocyanate group, epoxy group, etc.).
The content of the helical polymer unit (a) or (b) contained in the resin (A) or (B) is preferably 10 to 99% by weight, more preferably 30 to 90%, from the viewpoint of easy formation of a stereocomplex. It is 97% by weight, particularly preferably 50 to 95% by weight.

  As long as the resin (A) and the resin (B) are resins having a helical polymer unit (a) or (b) in the molecule, the kind and composition thereof are not limited. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyether resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin And polycarbonate resin. As the resin (A) and the resin (B), two or more of the above resins may be used in combination. Of these, vinyl resins, polyester resins, polyurethane resins, polyether resins, epoxy resins and combinations thereof are preferred from the viewpoint of good heat melting properties, and more preferably polyester resins, polyether resins and It is a combination of them.

Hereinafter, vinyl resin, polyester resin, polyurethane resin, polyether resin and epoxy resin, which are preferable resins, will be described in detail.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).

(1) Carboxyl group-containing vinyl monomer and salts thereof:
C3-C20 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride, such as (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, etc. Carboxyl group-containing vinyl monomer.

(2) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropanesulfonic acid, 2- ( T) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-C18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, Propylene, butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and Sulfate ester or sulfonic acid group-containing monomers represented by general formulas (3-1) to (3-3); and salts thereof.

O- (AO) nSO ₃ H
｜
_{CH 2 = CHCH 2 -OCH 2 CHCH} 2 O-Ar-R (3-1)

CH = CH-CH ₃
｜
R-Ar-O- (AO) nSO 3 H (3-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (3-3)

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl (C1 to C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) Phosphonic acids, such as 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (1), (3), and (4) include those exemplified as the neutralized salt of the carboxyl group. Preferred are alkali metal salts and amine salts, and more preferred are sodium salts and salts of tertiary monoamines having 3 to 20 carbon atoms.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N -Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof (6-2) amide Containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic acid Amides, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc. (6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, Cyanostyrene, cyanoacrylate, etc. (6-4) Quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide Diethylaminoethyl (meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomers: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomers:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (Two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, Tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide (hereinafter abbreviated as EO) ) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] (9-2) vinyl (thio) ether, for example vinyl methyl ether , Vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2-butoxy ethyl Ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as vinyl methyl ketone , Vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  Examples of the vinyl monomer copolymer excluding the portion that becomes the helical polymer unit (a) or (b) include polymers obtained by copolymerizing any of the above monomers (1) to (10) at an arbitrary ratio. For example, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-butadiene- (meth) acrylic acid copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene- Acrylonitrile- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer And a salt of such a copolymer or a copolymer thereof.

  As a method of introducing (a) or (b) into the vinyl resin, (i) at the time of polymerization of the vinyl monomer, the hydroxyl group-containing vinyl monomer (5), the epoxy group-containing vinyl monomer (7), etc. Then, after polymerizing a monomer containing a vinyl monomer having a functional group capable of reacting with the monomer (m) to synthesize a vinyl resin having a functional group capable of reacting with (m), the monomer containing (m) is reacted. (Ii) vinyl resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) And a functional group (isocyanate group, epoxy) which reacts with active hydrogen. How binding using sheet material having group) two or more [later the polyisocyanate (15) and below the polyepoxides, such as hexamethylene diisocyanate (19), etc.] and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

Examples of polyester resins include polycondensates of polyols with polycarboxylic acids or acid anhydrides or lower alkyl esters thereof, and metal salts of these polycondensates. The polyol is a diol (11) and a polyol having a valence of 3 to 8 or more (12), and the polycarboxylic acid or its acid anhydride or its lower alkyl ester is a dicarboxylic acid (13) and a valence of 3 to 6 or more. The above polycarboxylic acid (14) and these acid anhydrides or lower alkyl esters are mentioned.
The ratio of polyol and polycarboxylic acid is preferably 2/1 to 1/5, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ˜¼, particularly preferably from 1 / 1.3 to ３.

  Examples of the diol (11) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, Decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Alkylene oxides (hereinafter abbreviated as AO) [EO, propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1-30); bisphenols (bisphenols) A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (addition mole number 2-30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol.

As the diol, in addition to the diol having no functional group other than the hydroxyl group, a diol (11a) having another functional group may be used. Examples of (11a) include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid and 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the polyol (12) having 3 to 8 or more valences include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside; AO adducts of trisphenols (such as trisphenol PA) 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers, etc.]; Etc.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Examples of the dicarboxylic acid (13) include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acids (dodecenyl succinic acid, Pentadecenyl succinic acid, octadecenyl succinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [dimer acid (dimerized linoleic acid), etc.], alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid) Acid, fumaric acid, citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the tricarboxylic acid having a valence of 3 to 6 or more (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
As the dicarboxylic acid (13) or the polycarboxylic acid (14) having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester) Etc.) may be used.

As a method of introducing the helical polymer unit (a) or (b) into the polyester resin, (i) (m) starting from a hydroxyl group and / or carboxyl group present as a terminal functional group of the polyester resin (Ii) a polyester resin having a functional group having an active hydrogen (hydroxyl group, carboxyl group, etc.) and a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) A substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen, the polymer (m) or the block copolymer containing a homopolymerized part of (m) [hexamethylene diisocyanate, etc. Later-described polyisocyanate (15) and later-described polyepoxide (19), etc.] Binding method and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.
In addition, as a polyester resin having a helical polymer unit (a) or (b), ring-opening polymerization of a cyclic ester (total carbon number 3 to 6) having an asymmetric carbon in (m) is added to the active hydrogen-containing compound. What was made to use may be used, and the polyester resin obtained by doing in this way is also preferable.

  Polyurethane resins include polyisocyanate (15) and active hydrogen-containing compounds {water, polyol [including diol (11) [including diol (11a) having a functional group other than hydroxyl group], and 3 to 8 or more valences] Polyol (12)], polycarboxylic acid [dicarboxylic acid (13), and polycarboxylic acid (14) having 3 or more valences or more], polyester polyol obtained by polycondensation of polyol and polycarboxylic acid, active hydrogen A polyether polyol having a structure in which an alkylene oxide is added to a compound having an atom, a ring-opening polymer of a lactone having 6 to 12 carbon atoms, a polyamine (16), a polythiol (17), and a combination thereof, etc.} And a terminal isocyanate group formed by reacting (15) with an active hydrogen-containing compound. And polymers obtained by reacting an equivalent amount of primary and / or secondary monoamine (18) to isocyanate groups of the prepolymer, and amino group-containing polyurethane resins.

  As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanate, aromatic aliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or mixtures thereof; diaminodiphenylmethane and minor amounts (eg 5-20%] )) With a trifunctional or higher functional polyamine]]: phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p -Isocyanatophenylsulfonyl isocyanate Etc., and the like.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate And aliphatic polyisocyanates.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate and the like.
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the polyamine (16) include aliphatic polyamines (C2 to C18): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) , Polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1-C4 ) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hex Methylenediamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5, 5] Undecane etc.]; [4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3- Heterocyclic polyamines (C4 to C15) such as diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylpiperazine, 1,4- Aromatics such as diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine Polyamines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4'- and 4,4'-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', Aromatic polyamines having 4 ″ -triamine, naphthylenediamine, etc .; nucleus-substituted alkyl groups (C1-C4 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, etc.), such as 2,4- and 2,6 -Tolylenediamine, Crudetolylenediamine, Diethyltolylenediamine Amine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4-diaminobenzene, 1 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2, , 3-Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetra Methyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodi Phenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4 , 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone, etc.], and mixtures of these isomers in various proportions; [3] nuclear substitution electron withdrawing Aromatic polyamines having groups (halogens such as Cl, Br, I, F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc.) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro 1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro- , 4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3, , 3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone Bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxy) Phenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2 -Bromoaniline), 4,4'-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; [4] Aromatic polyamines having secondary amino groups [above [1] to [3] In the aromatic polyamine, a part or all of —NH ₂ is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (Methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamines (the above alkylene Low molecular weight polyamide polyamine obtained by condensation with diamine, polyalkylene polyamine, etc.) Examples thereof include hydrides of cyanoethylated products of all (polyalkylene glycol and the like).

  Examples of the polythiol (17) include alkanedithiols having 2 to 36 carbon atoms (ethylene dithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (18) include alkylamines having 2 to 24 carbon atoms (such as ethylamine, n-butylamine, and isobutylamine).

  As a method for introducing (a) or (b) into a polyurethane resin, (i) a block copolymer of a monomer containing (m) starting from a hydroxyl group and / or an isocyanate group present as a terminal functional group of the polyurethane resin (Ii) a polyurethane resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having an active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) (m ) Or a block copolymer containing a homopolymerized portion of (m) and a substance having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen [the above polymethylene such as hexamethylene diisocyanate Isocyanate (15) and polyepoxide (19) and the like described later] And the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

Polyether resins include compounds having active hydrogen atoms (for example, diol (11), 3 to 8 or more polyol (12), dicarboxylic acid (13), 3 to 6 or more polycarboxylic acid. (14) compounds having a structure in which an alkylene oxide is added to a primary and / or secondary monoamine (18) and the like and mixtures thereof. Examples of the alkylene oxide added to the active hydrogen atom-containing compound include EO, PO, 1,2-, 1,3-, 1,4-, 2,3-butylene oxide, styrene oxide, and the like, and two or more kinds thereof. In combination (block and / or random addition). Among the polyether polyols, those having a polyoxypropylene chain and those having a polyoxypropylene chain and a polyoxyethylene chain (EO content of 25% by weight or less) are preferable. The polyether polyol is obtained by adding PO to the active hydrogen atom-containing compound; and PO and other alkylene oxides (hereinafter abbreviated as AO , preferably EO) in the order of 1) PO- AO . obtained by adding (Chippudo), 2) PO- AO -PO- obtained by adding in the order of AO (balanced), 3) obtained by adding in the order of AO -PO- AO, 4) PO- AO sequence of -PO A block adduct such as those added in (5) (active secondary), etc .; 5) a random adduct in which PO and AO are mixed and added; and 6) those added in the order described in JP-A-57-209920, 7 ) Random / block adducts such as those added in the order described in JP-A-53-13700. These may be used in combination.

As a method for introducing the helical polymer unit (a) or (b) into the polyether resin, (i) a monomer containing (m) starting from a hydroxyl group present as a terminal functional group of the polyether resin is blocked. (Ii) a polyether resin having a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) and a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.) A substance [hexamethylene diisocyanate] having two or more functional groups (isocyanate group, epoxy group, etc.) that react with active hydrogen, the (m) polymer or the block copolymer containing the homopolymer part of (m) And the like using the polyisocyanate (15), etc.]. Among these methods, the method (i) is preferable because the number of reaction steps is small.
Further, as the polyether resin having the helical polymer unit (a) or (b), the active hydrogen-containing compound is subjected to ring-opening polymerization of α-alkylethylene oxide (total carbon number of 6 to 9) in (m). Can also be used.

  Examples of the epoxy resin include ring-opened polymer of polyepoxide (19), polyepoxide (19) and active hydrogen group-containing compound {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid (13 ) Or a polyaddition product of a trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17) or the like}, or a polyepoxide (19) and a dicarboxylic acid (13) or a trivalent or higher polycarboxylic acid ( 14) a cured product with an acid anhydride.

  The polyepoxide (19) is not particularly limited as long as it has two or more epoxy groups in the molecule. A thing preferable as a polyepoxide (19) has 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material. The epoxy equivalent of the polyepoxide (19) (molecular weight per epoxy group) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the cross-linked structure becomes dense and the cured product has good physical properties such as water resistance, chemical resistance and mechanical strength. When the epoxy equivalent is 65 or more, synthesis is easy.

  Examples of the polyepoxide (19) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, tetramethylbiphenyl diglycidyl ester Ter, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, dinaphthyltriol triglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl -Tret-butyl-butylhydroxymethane triglycidyl ether, 9,9'-bis (4-hydroxyphenyl) furorange glycidyl ether, 4,4'-oxybis (1,4-phenylethyl) tetracresol glycidyl ether, 4 , 4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether, Of glycol ether of enolic or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, phenol and glyoxal, glutaraldehyde, or formaldehyde Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reactions, polyglycidyl ethers of polyphenols obtained by condensation reactions of resorcin and acetone, and the like. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Furthermore, in the present invention, the aromatic system is obtained by reacting a polyol with the above-mentioned two reactants, such as triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol. The glycidyl group-containing polyurethane (pre) polymer and an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A are also included. Heterocyclic polyepoxy compounds include trisglycidyl melamine; alicyclic polyepoxy compounds include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl). Ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) Methyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine, dimer acid diglycidyl ester, and the like. The alicyclic group also includes a hydrogenated product of the aromatic polyepoxide compound; examples of the aliphatic polyepoxy compound include polyglycidyl ethers of polyvalent aliphatic alcohols and polyglycidyl esters of polyvalent fatty acids. Body, and glycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Can be mentioned. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. In the present invention, the aliphatic type also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more of the polyepoxides of the present invention may be used in combination.

  As a method for introducing the helical polymer unit (a) or (b) into the epoxy resin, (i) a functional group having an active hydrogen such as a hydroxyl group present in the epoxy resin is included as a starting point (m). (Ii) a method of block copolymerizing monomers, (ii) an epoxy resin having a functional group having an active hydrogen such as a hydroxyl group, and a functional group having an active hydrogen (a hydroxyl group, a carboxyl group, an amino group, etc.) A substance having two or more functional groups (isocyanate group, epoxy group, etc.) that reacts with active hydrogen from a polymer or a block copolymer containing a homopolymerized portion of (m) [the polyisocyanate such as hexamethylene diisocyanate ( 15) and the above polyepoxide (19) etc.] and the like. Among these methods, the method (i) is preferable because the number of reaction steps is small.

The number average molecular weight (Mn), melting point, melting start temperature, Tg, SP value, hydroxyl value, and acid value of the resin (A) and the resin (B) can be appropriately adjusted within a preferable range depending on the use conditions when the toner is used. Good.
For example, Mn (measured by gel permeation chromatography) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (A) and (B) (measured by DSC, hereinafter the melting point is measured by DSC) is preferably 80 to 130 ° C, more preferably 85 to 120 ° C, particularly preferably 90 to 110 ° C. is there. 80 ° C. or higher is preferable from the viewpoint of heat-resistant storage stability, and 130 ° C. or lower is preferable from the viewpoint of low-temperature fixability. (A) and (B) melting start temperature (measured with a flow tester, hereinafter melting start temperature is measured with a flow tester) is preferably 80 to 130 ° C, more preferably 85 to 120 ° C, particularly preferably. 90-110 ° C. 80 ° C. or higher is preferable from the viewpoint of heat-resistant storage stability, and 130 ° C. or lower is preferable from the viewpoint of low-temperature fixability. Tg of (A) and (B) is preferably 30 to 80 ° C, more preferably 45 to 75 ° C, and particularly preferably 50 to 70 ° C. A Tg of 30 ° C. or higher is preferable from the viewpoint of heat resistant storage stability, and a Tg of 80 ° C. or lower is preferable from the viewpoint of low temperature fixability. The SP value of (A) and (B) is preferably 8 to 16, more preferably 9 to 14. The hydroxyl value of (A) and (B) is preferably 70 mgKOH / g or less, more preferably 5 to 50 mgKOH / g, and particularly preferably 10 to 45 mgKOH / g. A hydroxyl value of 70 mgKOH / g or less is preferable from the viewpoint of improving environmental stability and charge amount. The acid value of (A) and (B) is preferably 0 to 40 mgKOH / g, more preferably 1 to 30 mgKOH / g, particularly preferably 10 to 30 mgKOH / g, and most preferably 15 to 25 mgKOH / g. A smaller acid value improves environmental stability, but a more suitable acid value is preferable in terms of improving the rising of charging.

When the toner binder of the present invention is an aggregate (P) of resin particles (Pi) containing only one of the resin (A) and the resin (B) in one resin particle, the resin (A) alone Alternatively, the particles consisting of the resin (B) alone are (i) a method of coarsely pulverizing (A) or (B) obtained by monomer polymerization, and finally making fine particles using a jet pulverizer or the like; ii) a step of producing a resin solution by dissolving or dispersing (A) or (B) obtained by monomer polymerization in an organic solvent, and the resin solution and the aqueous medium in the presence of an emulsifier and / or a dispersion stabilizer. A step of producing an aqueous dispersion in which particles of the resin solution are dispersed in the aqueous medium by mixing, a step of generating resin particles by removing an organic solvent in the particles, and the resin particles in the aqueous medium Or It can be separated, and a method of obtaining a sequentially subjected to fine the drying step, may be used to select from commonly known methods used.
The toner binder of the present invention can be obtained by powder-mixing particles comprising (A) alone and particles comprising (B) alone, and can be mixed with ordinary mixing conditions and mixing equipment. The mixing conditions for mixing the powder are not particularly limited, but the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. Although it does not specifically limit as mixing time, Preferably it is 3 minutes or more, More preferably, it is 5 to 60 minutes. Although it does not specifically limit as a mixing apparatus, For example, a Henschel mixer, a Nauter mixer, a Banbury mixer, etc. are mentioned. A Henschel mixer is preferable. In the aggregate (P) of resin particles (Pi) obtained by powder mixing, unlike the case of melt mixing, the stereocomplex of (a) and (b) is not formed.

The toner binder of the present invention may be composed of resin particles (Pi) containing (A) and (B) at the same time, and (A) and (B) are contained in the same resin particles (Pi). In the case, the aqueous dispersion of (A) and the aqueous dispersion of (B) are separately prepared by the above method (ii), the organic solvent is removed after mixing, and the fineness of (A) and (B) A method of producing composite resin particles composed of various resin particles is preferable. In the composite resin particles obtained in this manner, (a) and (b) are present in a state where a stereocomplex is not formed.
Furthermore, it is preferable not to have a heating (humidification) step of 90 ° C. or higher, and to have a heating (humidification) step of 80 ° C. or higher after the composite resin particles are prepared and used as a toner component for fixing. More preferably not. As a result, the formation of a stereo complex before use can be minimized, and the low-temperature fixability is improved.

The toner binder of the present invention includes at least one release agent selected from the group consisting of carnauba wax (C1), Fischer-Tropsch wax (C2), paraffin wax (C3), and polyolefin wax (C4), if necessary. C) can be included.
Although it does not specifically limit as (C1), For example, natural carnauba wax, de-free fatty acid type carnauba wax, etc. are mentioned.
(C2) is not particularly limited. For example, petroleum-based Fischer-Tropsch wax (such as Paraflint H1, Paraflint H1N4 and Paraflint C105 manufactured by Schumann-Sasol), natural gas-based Fischer-Tropsch wax (FT100 manufactured by Shell MDS, etc.) And those obtained by purifying these Fischer-Tropsch waxes by a method such as fractional crystallization [Nippon Seiwa Co., Ltd. MDP-7000, MDP-7010, etc.].
Although it does not specifically limit as (C3), For example, petroleum wax type paraffin wax [Nippon Seiwa Co., Ltd. paraffin wax HNP-5, HNP-9, HNP-11 etc.] etc. are mentioned.
Although it does not specifically limit as (C4), For example, polyethylene wax [Sanyo Chemical Industries Co., Ltd. sun wax 171P, sun wax LEL400P, etc.], Polypropylene wax [Sanyo Chemical Industries Co., Ltd. Viscol 550P, biscol 660P etc.] etc. Is mentioned.
Of these waxes, carnauba wax and Fischer-Tropsch wax are preferred, and carnauba wax and petroleum Fischer-Tropsch wax are more preferred. By using these waxes as release agents, the low-temperature fixability in the case of a toner is further improved.
When the mold release agent (C) is contained, the content of (C) is preferably 0.01 to 20%, more preferably based on the total weight of the resins (A) and (B) and (C). Is 0.1% to 15%, especially 0.5 to 10%. When the content of the release agent is in the range of 0.01 to 20%, the hot offset resistance when the toner is used becomes better.

The toner binder of the present invention can contain a charge control agent (D) if necessary.
(D) is not particularly limited. For example, nigrosine dye, quaternary ammonium salt compound, quaternary ammonium base-containing polymer, metal-containing azo dye, salicylic acid metal salt, sulfonic acid group-containing polymer, fluorine-containing polymer, and halogen-substituted polymer. An aromatic ring containing polymer etc. are mentioned.
The content of (D) when the charge control agent (D) is contained in the toner binder of the present invention is not particularly limited, but based on the total weight of the resins (A) and (B) and (D), Preferably it is 0.01 to 5%, More preferably, it is 0.02 to 4%.

Further, in the toner binder of the present invention, other resins than (A) and (B) can be contained as necessary. Although it does not specifically limit as other resin, In each said resin, resin etc. which do not contain helical polymer unit (a) and (b) are mentioned.
Other resin may be contained in the same resin particle (Pi) as (A) and / or (B), or may exist as another resin particle.
Other resins preferably have the same ranges of Mn, melting point, melting start temperature, Tg, SP value, hydroxyl value and acid value as in (A) and (B).
The content of the other resin in the toner binder is preferably 30% or less, more preferably 20% or less, based on the total weight of (A) and (B).
When the toner binder of the present invention contains (C), (D), and / or other resins, the mixing method of (A) and (B) and these components is as follows. The method is not particularly limited as long as the stereocomplex (b) is not formed, but powder mixing may be performed in advance by the same method as described above, or may be mixed at the time of toner formation. In addition, as a method of containing other resin in the same resin particles (Pi) as (A) and / or (B), the resin particles (Pi) containing (A) and (B) at the same time are used. A method similar to the creation method can be mentioned.

  The toner binder of the present invention can be used as toner for electrophotography, electrostatic recording, electrostatic printing, etc. When used as toner, colorant, filler, antistatic agent, colorant, release agent, charge control. Additives such as an agent, magnetic powder, ultraviolet absorber, antioxidant, antiblocking agent, heat stabilizer, and flame retardant may be mixed. An example of producing an electrophotographic toner using the toner binder of the present invention is shown below.

  The content of the toner binder in the toner is not particularly limited, but when using a dye or pigment as a colorant, it is preferably 70 to 98%, more preferably 74 to 96%, and when using magnetic powder. , Preferably 20 to 85%, more preferably 35 to 65%.

Although it does not specifically limit as a coloring agent, For example, dye, a pigment, magnetic powder, etc. can be used. Specifically, Carbon Black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Varanitoaniline Red, Toluidine Red, Carmine, Pig FB Mention 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 OP, Magnetite and Iron Black .
The content of the colorant in the toner is not particularly limited. For example, when a dye or a pigment is used, it is preferably 2 to 15%, and when a magnetic powder is used, preferably 15 to 70%. Preferably it is 30 to 60%.

Although it does not specifically limit as a mold release agent (C), For example, the above-mentioned thing is mentioned, In use, it may be the same as that of the above-mentioned mold release agent, or may differ.
The amount of (C) in the toner is not particularly limited, but is preferably 0 to 10%, and more preferably 1 to 7%.

Although it does not specifically limit as a charge control agent (D), For example, the above-mentioned thing is mentioned.
The content of (D) in the toner is not particularly limited, but is preferably 0 to 5%, more preferably 0.01 to 4%.

The fluidizing agent is not particularly limited, and examples thereof include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.
The content of the fluidizing agent in the toner is preferably 0 to 5%.

The method for producing the toner using the toner binder of the present invention is not particularly limited as long as the stereocomplex of (a) and (b) is not formed during toner production, and a commonly used known method can be applied, for example, The components constituting the toner excluding the fluidizing agent consisting of only the resin (A) or only the resin (B) are powder mixed by the above method, then melt-kneaded, then coarsely pulverized, and finally a jet pulverizer, etc. And then further classifying to make particles having a volume average particle diameter (D50) of preferably 5 to 20 microns, and then mixing with a fluidizing agent to obtain a toner. (A) Toner comprising only And (B) a toner composed of a single powder by the above method.
Also, a step of producing a resin solution by dissolving or dispersing components constituting the toner excluding the fluidizing agent in an organic solvent, and mixing the resin solution and an aqueous medium in the presence of an emulsifier and / or a dispersion stabilizer. A step of producing an aqueous dispersion in which particles of the resin solution are dispersed in the aqueous medium, a step of generating resin particles by removing an organic solvent in the particles, and separating the resin particles from the aqueous medium. There is a method in which, after sequentially performing the drying step, a toner is obtained by mixing a fluidizing agent (for example, see JP-A-2005-49858). In this method, the aqueous dispersion consisting of (A) and the aqueous dispersion consisting of (B) are prepared separately, and the organic solvent is removed after mixing, thereby simultaneously containing (A) and (B). Toner particles can be obtained.
The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

The toner binder of the present invention is electrically mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic resin, silicone resin, etc.) as necessary. Used as a latent image developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0.
In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electric latent image.

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

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this. Hereinafter, “parts” means “parts by weight” unless otherwise specified.
<Example 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries, Ltd.), 1000 parts of L-lactide and 1 part of tin octylate were charged, and after nitrogen substitution Polymerization was conducted at 160 ° C. for 6 hours to obtain [Resin 1]. [Resin 2] was obtained in the same manner except that L-lactide was changed to D-lactide. As a result of X-ray crystal structure analysis (manufactured by Rigaku Corporation, using AFC7R, the same applies below), it was found that [Resin 1] contained a left-handed helical structure and [Resin 2] contained a right-handed helical structure. . [Resin 1] 100 parts, Colorant [carbon black MA-100, manufactured by Mitsubishi Chemical Corporation] 2 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 2 parts Was melt-mixed by a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain [Resin Particles 1] having a particle size (D50) of about 9 μm. A similar operation was performed except that [Resin 1] was changed to [Resin 2] to obtain [Resin Particle 2] having a particle size (D50) of about 9 μm. 100 parts of [Resin Particle 1] and 100 parts of [Resin Particle 2] were mixed with powder using a Henschel mixer (30 ° C., 60 minutes) to obtain a toner (T1) comprising the toner binder of the present invention.

<Example 2>
In a beaker, 100 parts of [Resin 1] and 40 parts of ethyl acetate were mixed, 500 parts of water and 3 parts of sodium dodecylnaphthalene sulfonate were added, and then a TK homomixer (made by Tokushu Kika) was used. An aqueous dispersion 1 was obtained by mixing at 12,000 rpm for 1 minute at 25 ° C. [Aqueous dispersion 2] was obtained in the same manner except that [Resin 1] was changed to [Resin 2]. 100 parts of [Aqueous Dispersion 1], 100 parts of [Aqueous Dispersion 2], 4 parts of a colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Corporation], and a mold release agent [Biscol 550P (softening point 150) ° C); Sanyo Chemical Industries Co., Ltd.] [Aqueous Dispersion 3] consisting of 4 parts and 50 parts of water was mixed, and TK homomixer (manufactured by Tokushu Kika) was used. The mixture was stirred for minutes to obtain [Aqueous dispersion 4]. After stirring [Aqueous Dispersion 4] at 50 ° C. for 3 hours, the process of centrifuging, adding 100 parts of water and solid-liquid separation is repeated three times, and the toner of the present invention having a particle size (D50) of about 5 μm A toner (T2) comprising a binder was obtained.

<Example 3>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 1 part of glycerin, 1000 parts of L-lactide and 1 part of tin octylate were charged, and after substitution with nitrogen, polymerization was performed at 160 ° C. for 6 hours to obtain [Resin 3]. It was. [Resin 4] was obtained in the same manner except that L-lactide was changed to D-lactide. As a result of X-ray crystal structure analysis (manufactured by Rigaku Corporation, using AFC7R, the same applies below), it was found that [Resin 3] contained a left-handed helical structure and [Resin 4] contained a right-handed helical structure. . [Resin 1] 100 parts, Colorant [carbon black MA-100, manufactured by Mitsubishi Chemical Corporation] 2 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 2 parts Was melt-mixed by a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain [Resin Particles 3] having a particle size (D50) of about 9 μm. A similar operation was performed except that [Resin 3] was changed to [Resin 4] to obtain [Resin Particle 4] having a particle size (D50) of about 9 μm. 100 parts of [Resin Particle 3] and 100 parts of [Resin Particle 4] were mixed with powder using a Henschel mixer (30 ° C., 60 minutes) to obtain a toner (T3) comprising the toner binder of the present invention.

<Comparative Example 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries), 1000 parts of racemic-lactide and 1 part of tin octylate were added, and after nitrogen substitution And polymerized at 160 ° C. for 6 hours to obtain [Resin 5]. As a result of X-ray crystal structure analysis, it was found that [Resin 5] has a random structure and does not contain a helical structure. [Resin 5] 100 parts, colorant [carbon black MA-100, manufactured by Mitsubishi Chemical Corporation] 4 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); manufactured by Sanyo Chemical Industries, Ltd.] 4 The parts were melt-mixed with a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain a toner (CT1) comprising a comparative toner binder having a particle size (D50) of about 9 μm.

<Comparative Example 2>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polyoxyethylene glyceryl ether (Newpol PE-600 manufactured by Sanyo Chemical Industries, Ltd.), 333 parts of racemic-lactide and 1 part of tin octylate are charged, and after nitrogen substitution Polymerization was conducted at 160 ° C. for 6 hours to obtain [Resin 6]. [Resin 7] was obtained in the same manner except that 333 parts of racemic-lactide was changed to 1666 parts of racemic-lactide. As a result of X-ray crystal structure analysis, it was found that [Resin 6] and [Resin 7] had a random structure and did not contain a helical structure. [Resin 6] 50 parts, [Resin 7] 50 parts, Colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Co., Ltd.] 4 parts, and mold release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries [Made by Co., Ltd.] was melt-mixed with a twin-screw kneader [Ikegai PCM-30]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] The toner (CT2) made of a comparative toner binder having a particle size (D50) of about 9 μm was obtained.

<Comparative Example 3>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 1 part of glycerin, 1000 parts of racemic-lactide and 1 part of tin octylate were charged, and after substitution with nitrogen, polymerization was performed at 160 ° C. for 6 hours to obtain [Resin 8]. It was. As a result of X-ray crystal structure analysis, it was found that [Resin 8] has a random structure and does not contain a helical structure. [Resin 8] 100 parts, Colorant [Carbon Black MA-100, manufactured by Mitsubishi Chemical Co., Ltd.] 4 parts, and Mold Release Agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 The parts were melt-mixed with a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. The kneaded product is cooled, coarsely pulverized, and finely pulverized using a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then an airflow classifier [MDS-I, manufactured by Nippon Pneumatic Industry Co., Ltd.] ] To obtain a toner (CT3) made of a comparative toner binder having a particle size (D50) of about 9 μm.

The physical properties of the toners (T1), (T2), (T3), (CT1), (CT2), and (CT3) obtained as described above were confirmed and evaluated. The results are shown in Tables 1 and 2.
(1) Number average molecular weight measurement The THF soluble content of only the resin was measured by gel permeation chromatography (GPC).
The conditions for molecular weight measurement by GPC are as follows.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: Two TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 25 ° C
Sample solution: 0.25 wt% tetrahydrofuran (THF) solution Injection amount: 200 μl
Detector: Refractive index detector The molecular weight calibration curve was prepared using TSK standard polystyrene [manufactured by Tosoh Corporation].

(2) Stereocomplex formation and stereocomplex abundance ratio About “DSC-60” manufactured by Shimadzu Corporation was used to melt about 5% each of the resin before melting and the sample obtained by slow cooling after melting only the resin. 0 mg is put in an aluminum sample container, the sample is placed on a holder unit, and is heated from 20 ° C. to 250 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and appears when a stereo complex is formed. The area of the endothermic peak was defined as before C and after C, respectively.
If the stereo complex is not formed before melting and is formed by melting, the value before C is zero. When a new peak appears about 50 ° C. above the resin before melting and is slightly before melting, the formation of a stereocomplex can be confirmed by increasing the peak area after melting.

(3) Melting characteristics The melting start temperature of the toner was measured with a flow tester (measuring device: constant-heavy extrusion type capillary rheometer flow tester CFT-500D (manufactured by Shimadzu Corporation), measurement conditions: plunger 1 cm ² , die diameter 1 mm, (Load 20 KgF, preheating temperature 50 to 80 ° C., preheating time 300 sec, temperature rising time 6 ° C./min). The lowering start temperature of the plunger was taken as the melting start temperature.

(4) Minimum fixing temperature (MFT) and hot offset generation temperature (HOT)
A non-fixed image developed with a commercial copier [AR5030, manufactured by Sharp Corporation] using the above toner is modified with a fixing unit of a commercial full-color copier [LBP-2160, manufactured by Canon Inc.] to adjust the heat roller temperature. Fixing is performed at a process speed of 80 mm / sec using a variable fixing machine. The heat roller temperature at which the residual ratio of the image density after rubbing the fixed image with the cloth pad becomes 70% or more is defined as the minimum fixing temperature (MFT). Further, the temperature at which hot offset starts to occur by visual determination is defined as hot offset generation temperature (HOT).

  The toner binder of the present invention is extremely useful as a toner binder used for toners used in electrophotography, electrostatic recording, electrostatic printing, and the like because of excellent heat melting characteristics and hot offset resistance.

Claims (8)

The resin (A) having one or more right-handed helical polymer units (a) in the molecule and / or the resin (B) having one or more left-handed helical polymer units (b) in the molecule A toner binder comprising an aggregate (P) of resin particles (Pi), wherein the toner binder contains (A) and (B), and (a) and (b) in the toner binder before and after melting at the time of melting. And a stereocomplex abundance ratio of the toner binder. 2. The toner binder according to claim 1, wherein (A) and (B) are one or more resins selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, polyether resins and epoxy resins. The toner binder according to claim 1 or 2, wherein the monomer constituting (a) and (b) comprises the optically active monomer (m). (M) is α-alkyl (C1-4) -α-hydroxycarboxylic acid, α-hydrocarbyl (C1-12) -α-amino acid, α-hydrocarbyl (C1-8). ) 1 selected from the group consisting of methacrylate, cyclic ester having asymmetric carbon (3 to 6 carbon atoms), α-alkylethylene oxide (6 to 9 carbon atoms) and α-alkylethylene sulfide (6 to 9 carbon atoms). The toner binder according to claim 3, wherein the toner binder is a seed or more. The toner binder according to claim 3 or 4, wherein (m) is L-lactic acid and D-lactic acid, and / or L-lactide and D-lactide. The toner binder according to claim 1, wherein (A) and (B) comprise an aggregate (P) of resin particles (Pi) contained in the same particle. The toner binder according to claim 1, further comprising at least one release agent selected from the group consisting of carnauba wax, Fischer-Tropsch wax, paraffin wax and polyolefin wax. The toner binder according to claim 1, further comprising a charge control agent.