JP2019061239A - Toner binder and resin particle - Google Patents

Abstract

To provide a toner binder that, as toner, can achieve both low-temperature fixability and heat-resistant storage stability and excellent in chargeability, and resin particles containing the toner binder.SOLUTION: A toner binder contains an amorphous resin (A) and a crystalline polyester resin (C), and the crystalline polyester resin (C) is a block polymer obtained by bonding a crystalline polyester resin (c1) and a crystalline polyester resin (c2) satisfying the following condition (1) by using a bonding agent. Condition (1): 0.5(cal/cm)≤[absolute value of difference between SP value of said (c1) and SP value of said (c2)]≤2.0(cal/cm).SELECTED DRAWING: None

Description

  The present invention relates to a toner binder and resin particles containing the toner binder.

  In recent years, low temperature fixability of toner has been strongly demanded from the viewpoint of energy saving. In general, the low temperature fixability of the toner and the heat resistant storage stability are in a trade-off relationship, and in order to make them compatible, a toner binder in which a crystalline polyester is introduced into the toner has been proposed (see Patent Document 1).

  From the viewpoint of improving low-temperature fixability, it is desirable that the toner binder and the crystalline resin be compatible with each other by heating, so it has been considered that the smaller the difference between the SP values is, the better. However, when a toner is produced using a toner binder and a crystalline resin having a small difference in SP value, the toner binder and the crystalline resin become compatible with each other before heating at the time of fixing, although the low temperature fixability is excellent. The crystalline resin was exposed on the surface of the toner, and the heat-resistant storage stability of the toner was not sufficient.

Japanese Patent Application Laid-Open No. 2002-287426

  The present invention provides a toner binder which is compatible with low temperature fixability and heat resistant storage stability in the case of toner and is excellent in chargeability (saturated charge amount, charge stability), and resin particles containing the toner binder. With the goal.

The present inventors arrived at the present invention as a result of earnest studies to solve these problems. That is, the present invention is the following two inventions.
A toner binder comprising a noncrystalline resin (A) and a crystalline polyester resin (C), wherein the crystalline polyester resin (C) satisfies the following condition (1): crystalline polyester resin (c1) and crystals Resin binder, which is a block polymer obtained by bonding a polyester resin (c2) with a binder, and resin particles containing the toner binder.
Condition (1): 0.5 (cal / cm ³ ) ^1/2 ≦ [absolute value of difference between SP value of (c1) and SP value of (c2)] ≦ 2.0 (cal / cm ³ ) ^1/2

  In the case of a toner, the toner binder of the present invention and the resin particles containing the toner binder can achieve both low temperature fixability and heat resistant storage stability, and are excellent in chargeability.

The toner binder of the present invention is a toner binder containing an amorphous resin (A) and a crystalline polyester resin (C), and the crystalline polyester resin (C) satisfies the following condition (1): It is a block polymer in which a polyester resin (c1) and a crystalline polyester resin (c2) are bonded using a binder.
Condition (1): 0.5 (cal / cm ³ ) ^1/2 ≦ [absolute value of difference between SP value of (c1) and SP value of (c2)] ≦ 2.0 (cal / cm ³ ) ^1/2

The toner binder of the present invention contains a noncrystalline resin (A) and a crystalline polyester resin (C).
In the present invention, "crystalline" means that the ratio (Tm / Ta) of the softening point (hereinafter abbreviated as Tm) to the maximum peak temperature of heat of fusion (hereinafter abbreviated as Ta) is 0.8 to 1.55. In the differential scanning calorimetry (DSC), it refers to having an endothermic peak maximum. Moreover, "non-crystalline" indicates that (Tm / Ta) is greater than 1.55. Tm and Ta can be measured by the following method.

<Method of measuring Tm>
It measures using a heightening type flow tester {"CFT-500D" [made by Shimadzu Corporation etc.] etc.}.
In (a) used for measurement of Tm, 1 g is used as a measurement sample. While heating the measurement sample at a heating rate of 6 ° C / min, apply a load of 1.96MPa with a plunger and push it out from a nozzle with a diameter of 1 mm and a length of 1 mm to obtain "plunger descent amount (flow value)" Draw a graph “Temperature”, read the temperature corresponding to 1⁄2 of the maximum value of the amount of drop of the plunger, and let this value (temperature at which half of the measurement sample flowed out) be Tm.

<Method of measuring Ta>
It measures using a differential scanning calorimeter {"DSC 210" (manufactured by Seiko Instruments Inc., etc.).
(A) to be subjected to the measurement of Ta is melted at 130 ° C. as a pretreatment, then cooled from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./min, and then 0.50 from 70 ° C. to 10 ° C. Cool at a rate of ° C / min. Here, once by DSC, the temperature rise rate is increased at a temperature increase rate of 20 ° C./min to measure the endothermic change, and a graph of “endothermic value” and “temperature” is drawn and observed at this time 20 to 100 The endothermic peak temperature in ° C. is Ta ′. In the case where there are a plurality of heat sinks, the temperature of the peak having the largest heat absorption is Ta ′. Thereafter, the sample is stored at (Ta′-10) ° C. for 6 hours, and then stored at (Ta′-15) ° C. for 6 hours.
Next, after cooling the above (a) to 0 ° C. at a temperature lowering rate of 10 ° C./min by DSC, the temperature is raised at a temperature rising rate of 20 ° C./min to measure the endothermic change and draw a similar graph Let the temperature corresponding to the maximum peak of the heat quantity be the endothermic peak temperature (Ta) of the heat of fusion.

  As the non-crystalline resin (A), the type of composition of the resin is not particularly limited as long as it is non-crystalline, but in the case of toner, non-crystalline polyester resin (from the viewpoint of low temperature fixability and charging stability) It is preferable that it is a1) and / or a non-crystalline vinyl resin (a2).

The non-crystalline polyester resin (a1) is obtained by polycondensation of a polyol component (xa) and a carboxylic acid component (ya).
Examples of the polyol component (xa) of the non-crystalline polyester resin (a1) include diols and polyols having a valency of 3 or more.
As the diol, alkylene glycol having 2 to 10 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,6 9-nonanediol and 1,10-decanediol etc.), C4-10 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol etc.), C11-36 alkylene glycol (1,12-dodecane) Diols, etc.), C11-C36 alkylene ether glycols (polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, etc.), C6-C36 alicyclic diols (1,4-cyclohexanedimethanol (Hydrogenated bisphenol A etc.), (poly) oxyalkylenes of the above-mentioned alicyclic diols [C 2-4 carbon atoms of alkylene groups (oxyethylene, oxypropylene etc.), the following polyoxyalkylene groups are also the same] ether [oxyalkylenes And polyoxyalkylene ethers of dihydric phenols (monocyclic dihydric phenols (such as hydroquinone) and bisphenols (such as bisphenol A, bisphenol F and bisphenol S)) (AO units) The number of units is 2 to 30), diols having a carboxy group, diols having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Among them, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6- from the viewpoint of coexistence of low temperature fixing property and hot offset resistance in the case of toner. Hexanediol, neopentyl glycol and polyoxyalkylene ether of bisphenol (number 2 to 30 of AO units) are preferred.

Examples of the trivalent or higher polyols include aliphatic polyhydric alcohols having 3 to 36 carbon atoms and having 3 to 36 carbon atoms or more [alkane polyols and intramolecular or intermolecular dehydrated products thereof (glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol etc.], sugars and esters thereof (sucrose and methyl glucoside etc.), (poly) oxyalkylene ethers (the number of AO units) of the aliphatic polyhydric alcohol 30), polyoxyalkylene ethers of trisphenol (such as trisphenol PA) (numbers of AO units 2 to 30), polyoxyalkylene ethers of novolak resins (such as phenol novolak and cresol novolac, average degree of polymerization 3 to 60) (AO) Number of units 2 30), and the like.
Among these, aliphatic polyhydric alcohols having 3 to 8 or more valences and polyoxyalkylene ethers of novolak resins (number 2 to 30 of AO units) are preferable.

  In order to obtain an amorphous resin, the content of the linear diol is preferably 70 mol% or less, more preferably 60 mol% or less of the diol component used. Moreover, in the polyol component (xa) which comprises amorphous polyester resin (a1), it is preferable that a diol component is 90-100 mol%.

Examples of the carboxylic acid component (ya) of the non-crystalline polyester resin (a1) include dicarboxylic acids, trivalent or higher polycarboxylic acids and monocarboxylic acids.
As dicarboxylic acids, aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.), alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, etc.) ), Alicyclic dicarboxylic acid having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid), etc.), alkene dicarboxylic acid having 4 to 36 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, etc.), maleic acid, fumaric acid, citraconic And acids and the like, and ester forming derivatives thereof.

  Here, ester-forming derivatives mean acid anhydrides, alkyl (C1-C24 methyl, ethyl, butyl, stearyl etc., preferably C1-C4) esters and partial alkyl esters. The same applies to the following ester-forming derivatives.

  Among these carboxylic acid components (ya), aromatic dicarboxylic acids having 8 to 36 carbon atoms and alkanedicarboxylic acids having 4 to 36 carbon atoms are preferable from the viewpoint of achieving both the low temperature fixability of the resin particles and the hot offset resistance. And alkene dicarboxylic acids having 4 to 36 carbon atoms and ester-forming derivatives thereof, and still more preferably phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, maleic acid, fumaric acid and / or their compounds. It is an ester forming derivative.

  Examples of trivalent or higher (preferably 3- to 6-valent) polycarboxylic acids include aromatic carboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatics having 6 to 36 carbon atoms (alicyclic And carboxylic acid (including hexane tricarboxylic acid and decane tricarboxylic acid) and ester forming derivatives thereof. Among these, trimellitic acid, pyromellitic acid and ester-forming derivatives thereof are preferable.

  Examples of monocarboxylic acids include aliphatic (including alicyclic) monocarboxylic acids having 1 to 30 carbon atoms and aromatic monocarboxylic acids having 7 to 36 carbon atoms.

  The non-crystalline polyester resin (a1) in the present invention can be produced in the same manner as known polyester production methods. For example, the reaction temperature of the polyol component (xa) and the carboxylic acid component (ya) is preferably 150 to 280 ° C., more preferably 170 to 260 ° C., particularly preferably in an inert gas (nitrogen gas etc.) atmosphere. It can carry out by making it react at 190-240 degreeC. The reaction time is preferably 30 minutes or more, particularly 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure to improve the reaction rate at the end of the reaction.

  The reaction ratio between the polyol component (xa) and the polycarboxylic acid component (ya) is preferably 2/1 to 1/2, more preferably 1 as the molar ratio [OH] / [COOH] of hydroxy group and carboxy group. It is preferably from 5/1 to 1 / 1.3, particularly preferably from 1.3 / 1 to 1 / 1.2.

  At this time, an esterification catalyst can be used as needed. As the esterification catalyst, tin-containing catalysts (such as dibutyltin oxide), antimony trioxide, titanium-containing catalysts [titanium alkoxide, potassium oxalate titanate, titanium terephthalate, catalyst described in JP-A-2006-243715 [titanium dihydroxy Bis (triethanol aminate), titanium monohydroxy tris (triethanol aminate), intramolecular polycondensed products thereof, etc.] and catalysts described in JP-A-2007-11307 (titanium tributoxy terephthalate, titanium triisopropoxy) Terephthalate and titanium diisopropoxy diterephthalate etc.], zirconium-containing catalysts (zirconyl acetate etc) and zinc acetate etc. may be mentioned. Among these, preferred is a titanium-containing catalyst.

Examples of the non-crystalline vinyl resin (a2) include polymers obtained by homopolymerizing or copolymerizing radical polymerizable monomers using a radical polymerization initiator. As a radically polymerizable monomer, the following monomers (w1)-(w9) etc. are mentioned.
The polymerization can be carried out by known methods such as solution polymerization, bulk polymerization, suspension polymerization and emulsion polymerization.
As radical polymerization initiators, azo polymerization initiators (azobisisobutyronitrile, azobisvaleronitrile, azobiscyanovaleric acid, etc.) and organic peroxide polymerization initiators [benzoyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane etc.] and the like can be mentioned. Among these, di-t-butyl peroxide or 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane is preferred.
The amount of the radical polymerization initiator used is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, and particularly preferably 0.1 to 6% by weight, based on the total amount of monomers. is there.

(W1) Hydrocarbons having a polymerizable double bond:
The following (w11) aromatic hydrocarbon etc. which have an aliphatic hydrocarbon which has a polymerizable double bond, and (w12) a polymerizable double bond etc. are mentioned.
(W11) Aliphatic hydrocarbon having a polymerizable double bond:
Examples of the chain hydrocarbon having a polymerizable double bond include alkenes having 2 to 30 carbon atoms (such as ethisoprene, 1,4-pentadiene, 1,5-hexadiene and 1,7-octadiene).
Examples of cyclic hydrocarbons having a polymerizable double bond include mono- or dicycloalkenes having 6 to 30 carbon atoms (such as cyclohexene, vinylcyclohexene and ethylidenebicycloheptene) and mono or dicycloalkadienes having 5 to 30 carbon atoms. (Di) cyclopentadiene etc.] and the like.

(W12) Aromatic hydrocarbon having a polymerizable double bond:
Styrene, a hydrocarbyl (C1-C30 alkyl, cycloalkyl, aralkyl and / or alkenyl) substituent of styrene (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl Examples thereof include styrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene and the like), vinyl naphthalene and the like.

(W2) Monomers having a carboxy group and a polymerizable double bond and salts thereof:
C 3-15 unsaturated monocarboxylic acid {(meth) acrylic acid ["(meth) acrylic" means acrylic or methacrylic], crotonic acid, isocrotonic acid, cinnamic acid, etc.}, 3 to 30 carbon atoms Unsaturated dicarboxylic acid and its anhydride [(anhydride) maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc] and monoalkyl (C1-C10) of C3-C10 unsaturated dicarboxylic acid Ester (monomethyl maleate, monodecyl maleate, monoethyl ester of fumaric acid, monobutyl ester of itaconic acid, monodecyl ester of citraconic acid, etc.) and the like can be mentioned.

As a salt which comprises the salt of the monomer which has a carboxy group and a polymerizable double bond, alkali metal salts (sodium salt and potassium salt etc.), alkaline earth metal salts (calcium salt and magnesium salt etc.), ammonium salt And amine salts and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound, but primary amine salts (ethylamine salt, butylamine salt and octylamine salt etc.), secondary amines (diethylamine salt and dibutylamine salt etc), tertiary amine (triethylamine) Salts and tributylamine salts etc.). Examples of quaternary ammonium salts include tetraethyl ammonium salt, triethyl lauryl ammonium salt, tetrabutyl ammonium salt and tributyl lauryl ammonium salt.

  As salts of monomers having a carboxy group and a polymerizable double bond, sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples thereof include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate and aluminum acrylate.

(W3) monomers having a sulfo group and a polymerizable double bond, and salts thereof:
Alkene sulfonic acid having 2 to 14 carbon atoms (vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, etc.), styrene sulfonic acid and alkyl thereof (2 to 24 carbon atoms) (α-methyl styrene sulfonic acid, etc.) , C 5-18 sulfo (hydroxy) alkyl- (meth) acrylate (sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid, 2- (meth) acryloyloxyethane sulfonic acid And 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, etc., sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid , 2- (Meth) acrylamido-2-methylpropanesul Acid and 3- (meth) acrylamido-2-hydroxypropane sulfonic acid etc.], alkyl (C3-C18) allyl sulfosuccinic acid (propyl allyl sulfosuccinic acid, butyl allyl sulfosuccinic acid and 2-ethylhexyl-allyl sulfosuccinic acid etc) , Polyoxyalkylenes having a polymerization degree of 2 to 30 (oxyethylene, oxypropylene, oxybutylene etc. Oxyalkylene may be used alone or in combination, and when used in combination, the addition form may be random addition or block addition), mono (mono) Examples thereof include sulfuric acid esters of meta) acrylate [polyoxyethylene monomethacrylate sulfuric acid esters having a polymerization degree of 5 to 15 and polyoxypropylene monomethacrylate sulfuric acid esters having a polymerization degree of 5 to 15], salts thereof and the like.

  In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has a carboxy group and a polymerizable double bond by said (w2) is mentioned.

(W4) a monomer having a phosphono group and a polymerizable double bond and a salt thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoester having 1 to 24 carbon atoms in alkyl group (such as 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), carbon number in alkyl group is (Meth) acryloyloxyalkyl phosphonic acid (such as 2-acryloyl oxyethyl phosphonic acid) which is 1 to 24 can be mentioned.
In addition, as a salt, what was illustrated as a salt which comprises the monomer which has a carboxy group and a polymerizable double bond by said (w2) is mentioned.

(W5) a monomer having a hydroxyl group and a polymerizable double bond:
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-hydroxyethyl propenyl ether, sucrose allyl ether and the like can be mentioned.

(W6) Nitrogen-containing monomer having a polymerizable double bond:
(W 61) a monomer having an amino group and a polymerizable double bond, (w 62) a monomer having an amide group and a polymerizable double bond, and (w 63) a carbon number having a nitrile group and a polymerizable double bond Monomers of 10 to 10, monomers of 8 to 12 carbon atoms having a (w 64) nitro group and a polymerizable double bond, and the like can be mentioned.
(W61) a monomer having an amino group and a polymerizable double bond:
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-acetoaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole And aminothiazoles, aminoindoles, aminopyrroles, aminoimidazoles, aminomercaptothiazoles and salts thereof.

(W62) a monomer having an amide group and a polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid amide, N, N -Dimethyl acrylamide, N, N- dibenzyl acrylamide, methacryl formamide, N- methyl- N- vinyl acetamide, N- vinyl pyrrolidone, etc. are mentioned.
(W63) a monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond:
Examples include (meth) acrylonitrile, cyanostyrene and cyanoacrylate.
(W64) a monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc. are mentioned.

(W7) a monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate, p-vinylphenyl phenyl oxide, etc. are mentioned.

(W8) a monomer having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond:
Examples thereof include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene and chloroprene.

(W9) Esters having a polymerizable double bond, ethers having a polymerizable double bond, ketones having a polymerizable double bond, and sulfur-containing compounds having a polymerizable double bond:
(W91) an ester having 2 to 24 carbon atoms having a polymerizable double bond, (w 92) an ether having 3 to 16 carbon atoms having a polymerizable double bond, and (w 93) a carbon having 4 to 4 carbon atoms having a polymerizable double bond Examples thereof include 12 ketones, (w94) sulfur-containing compounds having 2 to 16 carbon atoms having a polymerizable double bond, and the like.
(W91) ester having 2 to 24 carbon atoms having a polymerizable double bond:
Vinyl acetate, 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, (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) acrylate , Etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleates (two alkyl groups have carbon number 2-8 linear, branched or alicyclic groups), poly (meth) alyloxyalkanes (diaryloxyethanes, triaryloxyethanes, tetraaryloxyethanes, tetraaryloxypropanes, tetraaryloxypropanes) Monomers [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) monoacrylate having a polyalkylene glycol chain and a polymerizable double bond such as roxybutane and tetramethalyloxyethane etc.) Methyl alcohol EO 10 moles adduct (meth) acrylate and lauryl alcohol EO 30 moles adduct (meth) acrylate Lilate etc], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohol: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri ( Meta) acrylate and polyethylene glycol di (meth) acrylate etc] etc are mentioned.
(W92) Ethers having 3 to 16 carbon atoms having a polymerizable double bond:
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-butoxyethyl ether, 3,4-dihydro Examples include -1, 2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, acetoxystyrene and phenoxystyrene.
(W93) ketone having 4 to 12 carbon atoms having a polymerizable double bond:
And vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone.
(W94) a sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond:
Divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like can be mentioned.

  Among these radically polymerizable monomers, preferred as the non-crystalline vinyl resin (a2) of the present invention is styrene, having 3 to 15 carbon atoms, from the viewpoint of low temperature fixability and charge stability of resin particles. Saturated monocarboxylic acid, (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms, and acrylonitrile are preferable, and styrene, (meth) acrylic acid, butyl (meth) acrylate and acrylonitrile are more preferable.

  The toner binder of the present invention contains a crystalline polyester resin (C), and the crystalline polyester resin (C) is a block of a unit composed of a crystalline polyester resin (c1) and a unit composed of a crystalline polyester resin (c2) It is a polymer.

  The crystalline polyester resin (c1) and the crystalline polyester resin (c2) are obtained by polycondensation of a polyol component (xc) and a carboxylic acid component (yc).

  Examples of the polyol component (xc) of the crystalline polyester resin (c1) and the crystalline polyester resin (c2) include aliphatic diols and the like. Aliphatic diols include linear aliphatic diols, aliphatic diols having secondary hydroxy groups, and branched aliphatic diols.

As the linear aliphatic diol, linear aliphatic diol having 2 to 36 carbon atoms (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,20-eicosanediol) and the like. And as an aliphatic diol which has a secondary hydroxy group, the aliphatic diol (for example, 1, 2- propylene glycol etc.) etc. which have a C2-36 secondary hydroxy group are mentioned.
Examples of branched aliphatic diols include branched aliphatic diols having 2 to 36 carbon atoms (for example, neopentyl glycol and 2,2-diethyl-1,3-propanediol).

  Among the polyol components (xc), from the viewpoint of low-temperature fixability and heat resistant storage stability, it is preferably an aliphatic diol, more preferably a linear aliphatic diol, and particularly preferably 2 to 20 carbon atoms. It is a linear aliphatic diol.

As the polyol component (xc) of the present invention, polyol components other than the above-mentioned aliphatic diols described below can be used within the range not affecting the effect of the present invention.
Examples of aliphatic diols other than the above aliphatic diols include alkylene ether glycols having 4 to 36 carbon atoms (eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol), 4 to 36 alicyclic diols (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A), alkylene oxides of the above-mentioned alicyclic diols (hereinafter abbreviated as AO) [ethylene oxides (hereinafter abbreviated as EO) And propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), and the like] adducts (additional mole number: 1 to 30) and polybutadiene diol and the like.

  As an aromatic diol, AO (EO, PO, BO, etc.) adduct of bisphenol (bisphenol A, bisphenol F, bisphenol S, etc.) etc. (additional mole number 2-30) etc. are mentioned.

The trifunctional or higher (trivalent to trivalent or higher) polyols include trivalent to trivalent or higher polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrated products thereof, for example, Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin; sugars and their esters such as sucrose and methylglucoside; AO adducts of trisphenol (such as trisphenol PA) AO adduct of novolak resin (phenol novolac, cresol novolac, etc.) (additional mole number 2-30); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomer, etc.] Etc.
Among these, trihydric or higher trihydric or higher polyhydric aliphatic alcohols and AO adducts of novolak resins are preferable.

  In the polyol component (xc), the content of the linear aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more of the polyol component (xc). If it is 80 mol% or more, the crystallinity of the resin is improved and the melting point is increased, so that the heat resistant storage stability is improved.

Examples of the polycarboxylic acid component (yc) of the crystalline polyester resin (c1) and the crystalline polyester resin (c2) include dicarboxylic acids and trivalent or higher polycarboxylic acids.
Examples of dicarboxylic acids include aliphatic dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); Dicarboxylic acid (dimer acid (dimerized linoleic acid etc.)), alkene dicarboxylic acid having 4 to 36 carbon atoms (dodecenyl succinic acid, pentadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid etc.); carbon number 8 to 36 Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, etc.) and the like.

Examples of trivalent or higher (3 to 6 or more) polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.).
In addition, as a dicarboxylic acid and polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a C1-C4 lower alkyl ester (a methyl ester, an ethyl ester, isopropyl ester etc.).

  Among the polycarboxylic acid components (yc), from the viewpoint of heat-resistant storage stability, preferred are aliphatic dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, and more preferably linear aliphatic dicarboxylic acids and Aromatic dicarboxylic acids, particularly preferably adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, terephthalic acid and isophthalic acid.

  Each end of the crystalline polyester resin (c1) and the crystalline polyester resin (c2) may be a hydroxy group or a carboxy group, and may be the same or different.

  As a manufacturing method of crystalline polyester resin (c1) and crystalline polyester resin (c2), the manufacturing method similar to said (a1) is mentioned.

The crystalline polyester resin (C) of the present invention is a block polymer in which a crystalline polyester resin (c1) satisfying the following condition (1) and a crystalline polyester resin (c2) are bonded using a binder. In addition, SP value of (c1) and (c2) is calculated including the carboxy group and hydroxy group of polyester terminal.
Condition (1): 0.5 (cal / cm ³ ) ^1/2 ≦ [absolute value of difference between SP value of (c1) and SP value of (c2)] ≦ 2.0 (cal / cm ³ ) ^1/2
If the absolute value of the difference between the SP value of (c1) and the SP value of (c2) is less than 0.5 (cal / cm ³ ) ^1/2 , the (A) may occur before the heating at the time of fixing. And (c1) are compatible with each other, or the crystalline polyester resin (C) is exposed on the surface of the resin particles, resulting in deterioration of the heat resistant storage stability. When the absolute value of the difference between the SP value of (c1) and the SP value of (c2) exceeds 2.0 (cal / cm ³ ) ^1/2 , the reaction in producing the crystalline polyester resin (C) The sex is bad.

Furthermore, it is preferable that the above (c1) and the above (c2) satisfy the following conditions (2) and (3) from the viewpoint of coexistence of low temperature fixability and heat resistant storage stability.
Condition (2): [absolute value of difference between the SP value of (A) and the SP value of (c1)] ≦ 1.0 (cal / cm ³ ) ^1/2
Condition (3): [absolute value of difference between the SP value of (A) and the SP value of (c2)]> 1.0 (cal / cm ³ ) ^1/2
When the absolute value of the difference between the SP value of (A) and the SP value of (c1) is less than 1.0 (cal / cm ³ ) ^1/2 , the low temperature fixability is improved. When the absolute value of the difference between the SP value of (A) and the SP value of (c2) is 1.0 (cal / cm ³ ) ^1/2 or more, the heat resistant storage stability is improved.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147-154)"

  The SP value of (A) is appropriately selected from the type and weight of the component, and the SP value of (c1) and (c2) is the type and weight of the diol and dicarboxylic acid which are the respective components. By appropriately selecting, it can be adjusted to a value satisfying the conditions (1), (2) and (3).

  The crystalline polyester resin (C) of the present invention is a block polymer in which a crystalline polyester resin (c1) and a crystalline polyester resin (c2) are bonded with a binder, and the crystalline polyester resin (c1) and the crystalline polyester resin (c1) It can be obtained by bonding the crystalline polyester resin (c2) by the method described later, etc.

  It is a block polymer which can be obtained by combining the crystalline polyester resin (c1) and the crystalline polyester resin (c2). The binder species which were in the terminal functional groups of the crystalline polyester resin (c1) and the crystalline polyester resin (c2) were selected, and the crystalline polyester resin (c1) and the crystalline polyester resin (c2) were selected. A block polymer can be obtained by a method such as bonding.

As the binder, various binders can be used. A dehydration reaction or an addition reaction can be performed using a polyvalent carboxylic acid, a polyhydric alcohol, a polyvalent isocyanate, a polyfunctional epoxy, an acid anhydride or the like.
Examples of the polyvalent carboxylic acid and the acid anhydride include the same as the dicarboxylic acid component. Examples of the polyhydric alcohol include the same as the diol component.
As the polyvalent isocyanate, aromatic diisocyanates (such as diphenylmethane diisocyanate) having 6 to 20 carbon atoms (excluding carbon in NCO groups, the same applies hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms (such as hexamethylene diisocyanate), carbon Alicyclic diisocyanate having 4 to 15 carbon atoms, aromatic aliphatic diisocyanate having 8 to 15 carbon atoms, and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretimine group, And isocyanurate groups, oxazolidone group-containing modified products and the like) and mixtures of two or more of these.
As polyfunctional epoxy, bisphenol A type or -F type epoxy compound (bisphenol A type or -F type diglycidyl ether etc.), phenol novolac type epoxy compound, cresol novolac type epoxy compound, hydrogenated bisphenol A type epoxy compound, bisphenol Diglycidyl ether of AO adduct of A or -F, diglycidyl ether of AO adduct of hydrogenated bisphenol A, diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexane dimethanol, polyethylene glycol) And polypropylene glycols), trimethylolpropane di- or triglycidyl ether, pentaerythritol tri- or tetraglycidyl ether Ter, sorbitol hepta or hexaglycidyl ether, resorcinol diglycidyl ether, dicyclopentadiene phenol addition type glycidyl ether, methylene bis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, polybutadiene diglycidyl Ether etc. are mentioned.
The binder is preferably a polyisocyanate and a polyfunctional epoxy from the viewpoint of reactivity, and more preferably a polyisocyanate.

In the non-crystalline resin (A), the crystalline polyester resin (c1) and the crystalline polyester resin (c2) of the present invention, the respective hydrophilic-lipophilic balance (HLB value) [according to Oda method] satisfies the following conditions (4 It is preferable to satisfy
Condition (4): HLB value (c1)> HLB value (A)> HLB value (c2)
Here, the HLB (Hydrophile-Lipophile Balance) value is a scale indicating the balance of inorganicity / organicity, and means that the higher the HLB value, the higher the inorganicity. The calculation is calculated by the following equation using the Oda method. In addition, the HLB value of (c1) and (c2) is calculated including the carboxy group and hydroxy group of polyester terminal.
HLB value 10 10 × inorganic / organic (Reference: “Introduction to surfactants” 2007 issued by Sanyo Chemical Industries, Ltd. P212)

  The HLB value can be adjusted by the composition, the amount of use, etc. of the respective raw materials (A), (c1) and (c2).

  In the toner binder of the present invention, the weight ratio (c1 / c2) of the crystalline polyester resin (c1) to the crystalline polyester resin (c2) is preferably 25/75 to 75/25. When the weight ratio (c1 / c2) is 25/75 to 75/25, the low temperature fixability and the heat resistant storage stability are further improved. In addition, the weight of (c1) and (c2) is calculated including the carboxy group and hydroxy group of polyester terminal.

  In the toner binder of the present invention, the weight ratio (A / C) of the noncrystalline resin (A) to the crystalline polyester resin (C) is preferably 99/1 to 60/40. When the weight ratio (A / C) is 99/1 to 60/40, the low temperature fixability and the heat resistant storage stability are further improved.

The crystalline polyester resin (c1) and the method for producing the crystalline polyester resin (c2) can be produced in the same manner as the method for producing the amorphous polyester resin (a1) in the same manner as the known polyester production method.
At this time, an esterification catalyst can be used as needed. As the esterification catalyst that can be used, one similar to that used in the method for producing the amorphous polyester resin (a1) can be used.

  The manufacturing method of crystalline polyester resin (C) is demonstrated. The crystalline polyester resin (C) is formed by bonding the crystalline polyester resin (c1) and the crystalline polyester resin (c2) with a binder. As for (c1) and (c2), a binder type which is present at each of the terminal functional groups can be selected, and (c1) and (c2) can be bonded to form a block polymer.

Methods of combining (c1) and (c2) include a dehydration reaction and an addition reaction.
As a dehydration reaction, both are both terminal alcohol resin, reaction etc. which couple | bond these with a binder (polyvalent carboxylic acid etc.), etc. are mentioned. In this case, the reaction is carried out at a reaction temperature of 180 ° C. to 230 ° C. in the absence of a solvent to obtain a block polymer.
As the addition reaction, both of them are resins having a hydroxy group at the end, and reactions in which these are bound with a binder (polyvalent isocyanate etc.) can be mentioned. In this case, both (c1) and (c2) are dissolved in a soluble solvent, a binder is added thereto, and the reaction is carried out at a reaction temperature of 80 ° C. to 150 ° C. to obtain a block polymer. In the other case, either (c1) or (c2) is reacted with the binder, and then either (c1) or (c2) is charged and reacted to obtain a block polymer. Be In addition, in the case of a resin having a carboxy group at both ends, a reaction in which these are bound with a binder (polyvalent epoxy or the like) can be mentioned. In this case, both (c1) and (c2) are dissolved in a soluble solvent, a binder is added thereto, and the reaction is carried out at a reaction temperature of 80 ° C. to 150 ° C. to obtain a block polymer.

The resin particles of the present invention may contain, in addition to the toner binder of the present invention, a colorant, a release agent, a charge control agent, and the like.
As the colorant, all dyes, pigments and the like used as colorants for toner can be used. Specifically, carbon black, iron black, sudan black SM, fast yellow G, benzidine yellow, solvent yellow (21, 77 and 114 etc.), pigment yellow (12, 14, 17 and 83 etc.), indofirst orange, Irgacin red, paranitroaniline red, toluidine red, solvent red (17, 49, 128, 5, 13, 22 and 48.2 etc.), disperse red, carmine FB, pigment orange R, lake red 2G, rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60 and 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, La tetrazole brown B and oil pink OP, and the like. These may be used alone or in admixture of two or more. If necessary, magnetic powders (powders of ferromagnetic metals such as iron, cobalt and nickel, and compounds such as magnetite, hematite and ferrite) can be contained as well as the function as a colorant.

As a mold release agent, one having a softening point of 50 to 170 ° C. is preferable, and polyolefin wax, natural wax (carnauba wax, montan wax, paraffin wax, rice wax, etc.), aliphatic alcohol having 30 to 50 carbon atoms Contanol etc.), C30-C50 fatty acid (triacontan carboxylic acid etc.), and these mixtures etc. are mentioned.
Examples of polyolefin waxes include (co) polymers obtained by (co) polymerization of olefins (ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and mixtures thereof, etc.) and (co) polymers Thermally-deformed polyolefins], oxides of (co) polymers of olefins with oxygen and / or ozone, maleic acid-modified products of (co) polymers of olefins [maleic acid and its derivatives (maleic anhydride, maleic acid Monomethyl, monobutyl maleate and dimethyl maleate etc.)), olefin and unsaturated carboxylic acid [(meth) acrylic acid, itaconic acid, maleic anhydride etc] and / or unsaturated carboxylic acid alkyl ester [(meth) acrylic acid] Alkyl (alkyl C 1-18) ester and maleic acid Copolymers with alkyl (C1-18 alkyl ester) etc., etc., polymethylene (Fischer Tropsch wax etc. such as Sazole wax etc.), fatty acid metal salt (eg calcium stearate) and fatty acid ester (behenic acid behenyl etc.) Etc.

  As a charge control agent, nigrosine dye, triphenylmethane dye having tertiary amine as a side chain, quaternary ammonium salt, polyamine resin, imidazole, quaternary ammonium base-containing polymer, metal-containing azo dye, copper phthalocyanine dye, salicylic acid Metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of alkyl esters of salicylic acid, cetyltrimethylammonium bromide and the like can be mentioned.

It is preferable that the content rate of each component which comprises the resin particle of this invention is as follows.
The content of the toner binder is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and particularly preferably 45 to 92% by weight, based on the weight of the resin particles.
The content of the colorant is preferably 0 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.5 to 50% by weight, based on the weight of the resin particles.
The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight, based on the weight of the resin particles.
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, particularly preferably 0.5 to 7.5% by weight, based on the weight of the resin particles. .

There is no restriction | limiting in particular about the manufacturing method of the resin particle of this invention, A well-known kneading method can be used. Specifically, it can be obtained by dry-blending the constituents of the resin particles and then melt-kneading it with a twin-screw extruder or the like.
In addition, the resin particles of the present invention may be mixed with carrier particles [iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite coated on the surface with resin (such as acrylic resin and silicone resin)], if necessary. Thus, it can be used as a developer for an electric latent image, but it can also be obtained in the process of this particle formation (e.g. emulsion phase inversion method, polymerization method, etc.).
Specifically, after the components of the resin particles are dissolved or dispersed in an organic solvent, the resin particles can be emulsified by adding water or the like, and then separated and classified. You may manufacture by the method of using the organic particulates as described in Unexamined-Japanese-Patent No. 2002-284881.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

  The NCO content in the present invention was measured according to JIS K 6806: 2003. However, toluene was used as a titration solvent as a solvent capable of dissolving the sample.

  The epoxy equivalent in the present invention was measured according to JIS K 7236: 2001.

<Production Example 1> [Synthesis of Crystalline Polyester Resin (c0-1)]
348 parts by weight of ethylene glycol, 843 parts by weight of sebacic acid, and 2 parts by weight of tetrabutoxytitanate as a polymerization catalyst are put in a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe, nitrogen introducing pipe and pressure reducing device, The temperature is raised to 180 ° C., and reaction is allowed to proceed for 10 hours while distilling off water generated under nitrogen stream at the same temperature, and then while gradually rising to 220 ° C. while distilling off water generated under nitrogen stream The reaction is carried out for 4 hours, and then the reaction is carried out while distilling off water under a reduced pressure of 0.007 to 0.026 MPa, and when the acid value becomes 0.1 [mg KOH / g] or less, the crystalline polyester resin ( c0-1) was obtained.

<Production Example 2> [Synthesis of Crystalline Polyester Resin (c0-2)]
A crystalline polyester resin was prepared in the same manner as in Preparation Example 1 except that 348 parts by weight of ethylene glycol was changed to 643 parts by weight of 1,6-hexanediol and 843 parts by weight of sebacic acid to 737 parts by weight of adipic acid. (C0-2) was obtained.

<Production Example 3> [Synthesis of Crystalline Polyester Resin (c0-3)]
A crystalline polyester resin (c0) was prepared in the same manner as in Preparation Example 1 except that in Preparation Example 1, 348 parts by weight of ethylene glycol was changed to 614 parts by weight of 1,12-dodecanediol and 843 parts by weight of sebacic acid to 466 parts by weight. -3) was obtained.

Preparation Example 4 Synthesis of Crystalline Polyester Resin (c0-4)
A crystalline polyester was prepared in the same manner as in Preparation Example 1 except that 348 parts by weight of ethylene glycol was changed to 529 parts by weight of 1,9-nonanediol and 843 parts by weight of sebacic acid to 675 parts by weight of dodecanedioic acid. Resin (c0-4) was obtained.

<Production Example 5> [Synthesis of Crystalline Polyester Resin (c0-5)]
A crystalline polyester was prepared in the same manner as in Preparation Example 1 except that 348 parts by weight of ethylene glycol was changed to 596 parts by weight of 1,12-dodecanediol and 843 parts by weight of sebacic acid to 595 parts by weight of dodecanedioic acid. Resin (c0-5) was obtained.

<Production Example 6> [Synthesis of Crystalline Polyester Resin (c0-6)]
A crystalline polyester resin (c0-6) was prepared in the same manner as in Preparation Example 1 except that in Preparation Example 1, 348 parts by weight of ethylene glycol was changed to 554 parts by weight and 843 parts by weight of sebacic acid was changed to 850 parts by weight of succinic acid. Obtained.

<Production Example 7> [Production of Crystalline Polyester Block Resin (C-1)]
Crystalline polyester resin (c0-1) 42.2 parts by weight while introducing nitrogen into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe, crystalline polyester resin (c0- 3) Add 52.8 parts by weight and 100 parts by weight of ethyl acetate, raise the temperature to 60 ° C, dissolve uniformly, and then introduce 5 parts by weight of hexamethylene diisocyanate (HDI) as a binder while introducing nitrogen did.
Next, the temperature is raised to 90 ° C., and the urethanation reaction is carried out over 10 hours to obtain an ethyl acetate solution of the crystalline polyester block resin (C-1), and then ethyl acetate is distilled off to obtain a crystalline polyester block resin (C -1) was obtained. The NCO content of the crystalline polyester block resin (C-1) was 0%.

<Production Examples 8, 9, 12 to 14> [Production of Crystalline Polyester Block Resin (C-2), (C-3) and (C-6) to (C-8)]
The crystalline polyester block resins (C-2), (C-3) and (C-6) to (C-8) were prepared in the same manner as in Production Example 7 except that the raw materials listed in Table 2 below were used. Obtained. The NCO content of each of the crystalline polyester block resins (C-2), (C-3) and (C-6) to (C-8) was 0%.

<Production Example 10> [Production of Crystalline Polyester Block Resin (C-4)]
A crystalline polyester resin (c0-1), 19.0 parts by weight of a crystalline polyester resin (c0-2) while introducing nitrogen into a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling pipe and a nitrogen introducing pipe. 5) 76.0 parts by weight and 100 parts by weight of ethyl acetate were added, the temperature was raised to 60 ° C., and dissolved uniformly, and then 5 parts by weight of bisphenol A diglycidyl ether was introduced while introducing nitrogen as a binder .
Next, the temperature is raised to 90 ° C., and an addition reaction is carried out over 10 hours to obtain an ethyl acetate solution of crystalline polyester block resin (C-4), and then ethyl acetate is distilled off to obtain crystalline polyester block resin (C- I got 4). The epoxy equivalent of crystalline polyester block resin (C-4) was 0.

<Production Example 11> [Production of Crystalline Polyester Block Resin (C-5)]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introducing pipe, 42.2 parts by weight of crystalline polyester resin (c0-2) and 100 parts by weight of ethyl acetate are introduced while introducing nitrogen. The temperature was raised to 60 ° C. to be homogeneously dissolved, and then 5 parts by weight of isophorone diisocyanate (IPDI) as a binder was introduced while introducing nitrogen.
Next, the temperature is raised to 90 ° C., and the urethanation reaction is carried out for 10 hours, and then 52.8 parts by weight of the crystalline polyester resin (c0-4) is added, and the urethane formation reaction is carried out for further 10 hours to After an ethyl acetate solution of polyester block resin (C-5) was obtained, ethyl acetate was distilled off to obtain crystalline polyester block resin (C-5). The NCO content of the crystalline polyester block resin (C-5) was 0%.

<Production Example 15> [Synthesis of Amorphous Polyester Resin (A-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe, 235 parts by weight of bisphenol A · PO2 molar adduct, 196 parts by weight of bisphenol A · PO3 adduct, 243 parts by weight of bisphenol A · EO adduct, Add 9 parts by weight of trimethylolpropane, 226 parts by weight of terephthalic acid, 40 parts by weight of adipic acid and 2 parts by weight of titanium diisopropoxy bis triethanolaminate as a condensation catalyst, and then gradually increase the temperature to 230 ° C, 0.5 The reaction was carried out for 10 hours under a reduced pressure of -2.5 kPa. Subsequently, it cooled to 180 degreeC, 28 weight parts of trimellitic acid anhydrides were added, and it took out after reaction for 1 hour, sealing under normal pressure, and obtained the non-crystalline polyester resin (A-1).

<Production Example 16> [Synthesis of Amorphous Polyester Resin (A-2)]
In Production Example 15, 235 parts by weight of bisphenol A · PO2 mole adduct, 196 parts by weight of bisphenol A · PO3 adduct, 243 parts by weight of bisphenol A · EO adduct, 9 parts by weight of trimethylolpropane, 226 parts by weight of terephthalic acid A crystalline polyester resin (A) was prepared in the same manner as in Production Example 15, except that 40 parts by weight of adipic acid was changed to 826 parts by weight of propylene glycol, 27 parts by weight of trimethylolpropane, 584 parts by weight of terephthalic acid, and 87 parts by weight of adipic acid. -2) was obtained.

Production Example 17 Synthesis of Amorphous Polyvinyl Resin (A-3)
250 parts by weight of xylene is charged into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel and nitrogen introducing pipe, and 395 parts by weight of styrene and 105 parts by weight of n-butyl acrylate are contained in another glass beaker A monomer solution was prepared by adding 5 parts by weight of di-t-butyl peroxide and stirring at 40 ° C. to prepare a monomer solution, which was then charged into the dropping funnel. After the gas phase part of the reaction vessel was replaced with nitrogen, the monomer solution was dropped at 70 ° C. for 2 hours under closed condition, and aged at 70 ° C. for 6 hours from the end of the dropping to obtain non-crystalline polyvinyl resin (A- 3) After obtaining a solution, xylene was distilled off to obtain a non-crystalline polyvinyl resin (A-3).

<Production Example 18> [Production of Fine Particle Dispersion (O-1)]
690.0 parts by weight of water, a sodium salt of polyoxyethylene monomethacrylate sulfate, "Eleminol RS-30" [Sanyo Chemical Industries, Ltd.] in a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introducing pipe 9.0 parts by weight, 90.0 parts by weight of styrene, 90.0 parts by weight of methacrylic acid, 110.0 parts by weight of butyl acrylate and 1.0 parts by weight of ammonium persulfate, 350 revolutions / minute After stirring for 15 minutes, a white emulsion was obtained.
Then, the temperature was raised to 75 ° C., and reaction was carried out at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous solution of ammonium persulfate is added, and the mixture is aged at 75 ° C. for 5 hours to obtain a vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfuric acid ester) A fine particle dispersion (O-1) was obtained.
The volume average particle size of the particles dispersed in the fine particle dispersion is 0.1 μm when measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” [manufactured by Horiba, Ltd.]. there were. When a part of the fine particle dispersion (O-1) was taken out and the Tg and the Mw were measured, the Tg was 65 ° C., and the Mw was 150,000.

<Production Example 19> [Production of Colorant Dispersion (P-1)]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introducing pipe, 557 parts by weight of propylene glycol, 569 parts by weight of terephthalic acid dimethyl ester, 184 parts by weight of adipic acid and tetrabutoxytitanate 3 as a condensation catalyst The parts by weight were charged, and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off generated methanol. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off propylene glycol and water generated under a nitrogen stream, and further for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight.
Next, the reaction solution is cooled to 180 ° C., 121 parts by weight of trimellitic anhydride is added, and reaction is performed under normal pressure sealing for 2 hours, and then the reaction is performed until the softening point becomes 180 ° C. at 220 ° C. under normal pressure. , 500).
In a beaker, 20 parts by weight of phthalocyanine blue, 4 parts by weight of colorant dispersant "Solspaz 28000" (manufactured by Avicia Co., Ltd.), 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate are added and stirred uniformly. After dispersion, phthalocyanine blue was finely dispersed by a bead mill to obtain a colorant dispersion (P-1). The volume average particle size measured by “LA-920” of the colorant dispersion (P-1) was 0.2 μm.

<Production Example 20> [Production of Wax (w-1)]
454 parts by weight of xylene, heat-deformed polyolefin (low molecular weight polyethylene) "San wax LEL-400" [softening point: 128 ° C, Sanyo Chemical Industries, Ltd.] 150 parts by weight (manufactured by Kogyo Co., Ltd.) is introduced, and after nitrogen substitution, the temperature is raised to 170 ° C. with stirring, 595 parts by weight of styrene and 255 parts by weight of methyl methacrylate at the same temperature, di-t-butylperoxyhexahydroterephthalate A mixed solution of 34 parts by weight and 119 parts by weight of xylene was added dropwise over 3 hours, and then kept at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax (w-1).
The SP value of the graft chain of the modified wax (w-1) was 10.35 (cal / cm ³ ) ^1/2 , the Mn was 1,900, the Mw was 5,200, and the Tg was 56.9 ° C.

<Production Example 21> [Production of Release Agent Dispersion (W-1)]
Paraffin wax "HNP-9" (maximum heat of fusion heat: 73 ° C, manufactured by Nippon Seiso Co., Ltd.) 10 parts by weight, denatured wax, in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer (W-1) 1 part by weight and 33 parts by weight of ethyl acetate were charged, the temperature was raised to 78 ° C. with stirring, and after stirring for 30 minutes at the same temperature, cooling to 30 ° C. over 1 hour to make paraffin wax into fine particles The resultant was further crystallized by using an ultravisco mill (manufactured by Imex Co., Ltd.) to obtain a releasing agent dispersion (W-1). The volume average particle size of the obtained paraffin wax microparticles was 0.25 μm.

Example 1
10 parts by weight of the crystalline polyester block resin (C-1) and 90 parts by weight of the non-crystalline polyester resin (A-1) were dry-blended to obtain a toner binder (R-1).
In a reaction vessel equipped with a stirrer and a thermometer, 30 parts by weight of the colored dispersion (P-1), 140 parts by weight of the releasing agent dispersion (W-1), 100 parts by weight of the toner binder (R-1) and acetic acid After charging 153 parts by weight of ethyl and stirring, the toner binder was uniformly dissolved to obtain a resin solution (D-1). In a beaker, 170.2 parts by weight of ion exchanged water, 0.3 parts by weight of fine particle dispersion, 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate "Eleminol MON-7" [Sanyo Chemical Industries, Ltd. 36 parts by weight of Co., Ltd. and 15.3 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, 63.8 parts by weight of the resin solution (D-1) was added and stirred for 2 minutes while the TK autohomomixer was stirred at 10,000 rpm. Next, this mixture is transferred to a reaction vessel equipped with a stirrer, heating and cooling device, a condenser and a thermometer, and ethyl acetate is distilled off until the ethyl acetate concentration in the mixture becomes 0.5% by weight or less at 50 ° C. To obtain an aqueous resin dispersion of resin particles. Then, the resin particles were washed, separated by filtration, and dried at 40 ° C. for 18 hours to obtain volatile resin content of 0.5% by weight or less to obtain resin particles (S-1).

<Examples 2 to 7, Comparative Examples 1 to 2>
Resin particles (S-2) to (S-7) and (S'-1) to (S'-2) are obtained in the same manner as in Example 1 except that the raw materials listed in Table 4 below are used. The

  The volume average particle size of the resin particles (S-1) to (S-7) and (S'-1) to (S'-2) is measured by the following method to evaluate the heat resistant storage stability and low temperature fixability. did. The results are shown in Table 4.

[1] Volume Average Particle Size The resin particles (S-1) to (S-7) and (S'-1) to (S'-2) are dispersed in water, and Coulter Counter "Multisizer III" (Beckman) The volume average particle size was measured by Coulter.

[2] Heat-resistant storage stability Resin particles (S-1) to (S-7) and (S'-1) to (S'-2) are allowed to stand in an atmosphere at 40 ° C for 1 day, and the degree of blocking is determined Judging visually, the heat resistant storage stability was evaluated according to the following criteria.
[Evaluation criteria]
○: no blocking occurred
X: Blocking has occurred.

[3] Low temperature fixing property Resin particles (S-1) to (S-7), (S'-1) are uniformly obtained on the paper so as to be 0.6 mg / cm ² using a printer from which the heat fixing device is removed. ~ (S'-2) was loaded. The temperature of the cold offset was measured by passing the paper through a heat fixing device having a pressure roller at a fixing speed (heat roller circumferential speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² . . The lower the cold offset occurrence temperature, the better the low temperature fixability.

[4] Saturated Charge Amount 0.5 g of resin particles and 20 g of ferrite carrier (F-150, manufactured by Powder Tech Co., Ltd.) were placed in a 50 ml glass bottle, and this was charged at 23 ° C., 50% R.H. H. After adjusting the humidity for at least 8 hours, friction stirring was carried out at 50 rpm × 10 minutes with a Tumbler shaker mixer (manufactured by Willy A. Bashofen), and the charge amount was measured. For the measurement, a blow-off charge amount measuring apparatus [manufactured by Toshiba Chemical Co., Ltd.] was used. The charge amount for 10 minutes of friction time was taken as the saturated charge amount. When the toner is used for toners, the higher the negative charge amount, the better the charging characteristics, and if it is −25 μC / g or less, it is judged that the charging characteristics are good.

[5] Charge stability In the measurement of the saturated charge amount, the same operation is performed except that the humidity control conditions are changed from (1) temperature 23 ° C. and humidity 50% to (2) temperature 40 ° C. and humidity 85%. The charge amount (μC / g) of the resin particles was measured. Calculate the ratio [Q (40 ° C, 85%) / Q (23 ° C, 50%)] of the charge amount under the humidity control condition (2) to the charge amount under the humidity control condition (1) and charge it It is an indicator of stability.
[Evaluation criteria]
○: 0.5 or more Δ: 0.3 or more and less than 0.5 ×: less than 0.3

In addition, the raw material used for the manufacture example and the Example is as follows.
・ Ethylene glycol [Nippon Catalyst]
・ 1,6-Hexanediol [made by Ube Industries]
・ 1,9-nonanediol [made by Kuraray]
・ 1,12-dodecanediol [made by Ube Industries]
・ Sebacic acid (made by Toyokuni Oil Co., Ltd.)
・ Adipic acid [Asahi Kasei]
・ Dodecanedioic acid [made by Ube Industries]
Succinic acid (Mitsui Chemical Co., Ltd.)
-Hexamethylene diisocyanate (HDI) [Asahi Kasei]
・ Diphenylmethane diisocyanate (MDI) [made by Tosoh]
・ Isophorone diisocyanate (IPDI) [made by Tokyo Chemical Industry]
-Bisphenol A diglycidyl ether [made by Tokyo Chemical Industry]
-Bisphenol A · PO 2 molar adduct (BP-2P) [manufactured by Sanyo Chemical Industries, Ltd.]
· Bisphenol A · PO 3 mol adduct (BP-3P) [manufactured by Sanyo Chemical Industries, Ltd.]
-Bisphenol A · EO 2 molar adduct (BPE-20) [manufactured by Sanyo Chemical Industries]
・ Trimethylolpropane (TMP) (Mitsubishi Gas Chemical Co., Ltd.)
-Terephthalic acid [Mitsui Chemical]
-Titanium diisopropoxy bis triethanolaminate [manufactured by Sanyo Chemical Industries, Ltd.]
Anhydrous trimellitic acid (made by Hyakukawa Chemical Co., Ltd.)

  In the case of a toner, the toner binder of the present invention and the resin particles containing the toner binder can be compatible in low temperature fixability and heat resistant storage stability, and are excellent in chargeability. Therefore, they are useful as resin particles and toner binders for toners for electrostatic charge image development used in electrophotography, electrostatic recording, electrostatic printing and the like.

Claims (7)

A toner binder comprising a noncrystalline resin (A) and a crystalline polyester resin (C), wherein the crystalline polyester resin (C) satisfies the following condition (1): crystalline polyester resin (c1) and crystals Toner binder which is a block polymer bound with a water-soluble polyester resin (c2) using a binder.
Condition (1): 0.5 (cal / cm ³ ) ^1/2 ≦ [absolute value of difference between SP value of (c1) and SP value of (c2)] ≦ 2.0 (cal / cm ³ ) ^1/2 The toner binder according to claim 1, wherein the crystalline polyester resin (c1) and the crystalline polyester resin (c2) satisfy the following conditions (2) and (3).
Condition (2): [absolute value of difference between the SP value of (A) and the SP value of (c1)] ≦ 1.0 (cal / cm ³ ) ^1/2
Condition (3): [absolute value of difference between the SP value of (A) and the SP value of (c2)]> 1.0 (cal / cm ³ ) ^1/2 The hydrophilic-lipophilic balance (HLB value) [according to the Oda method] of the non-crystalline resin (A), the crystalline polyester resin (c1) and the crystalline polyester resin (c2) satisfies the following condition (4): Or 2. The toner binder as described in 2).
Condition (4): HLB value (c1)> HLB value (A)> HLB value (c2) The toner binder according to any one of claims 1 to 3, wherein a weight ratio (c1 / c2) of the crystalline polyester resin (c1) to the crystalline polyester resin (c2) is 25/75 to 75/25. The toner binder according to any one of claims 1 to 4, wherein the weight ratio (A / C) of the noncrystalline resin (A) to the crystalline polyester resin (C) is 99/1 to 60/40. The toner binder according to any one of claims 1 to 5, wherein the binder is a polyvalent isocyanate and / or a polyfunctional epoxy. The resin particle containing the toner binder of any one of Claims 1-6.