JP2007025656A - Toner binder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner binder excellent in transparency and heat resistant preservability. <P>SOLUTION: The toner binder comprises a polyester resin (A) obtained by ring opening polymerization of a cyclic ester (b) to an active hydrogen compound (a), wherein the polyester resin (A) has a haze value of 0.1-40. Alternatively, the toner binder comprises a polyester resin (A) obtained by ring opening polymerization of a cyclic ester (b) to an active hydrogen compound (a), wherein the polyester resin (A) has a light transmittance of 90-100%. <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 used for electrophotography, electrostatic recording, electrostatic printing, and the like.

In recent years, colorization of an electrophotographic system has progressed, and demands for high image quality and high reproducibility are increasing. For full-color electrophotographic toner, toners colored yellow, magenta, and cyan are used. Black toner is also used if necessary. Ordinary toner is obtained by melt-kneading predetermined materials such as toner binder, colorant (dye, pigment, magnetic substance, etc.), charge control agent, etc., solidifying by cooling, and then pulverizing the finely pulverized product. In order to give fluidity to the fine particle powder obtained in this way, an additive (such as ultrafine colloidal silica) is added and mixed by stirring. There is also a method for producing a polymerized toner from a polymerized monomer by a polymerization method, and known polymerization methods include suspension polymerization method, emulsion polymerization method, dispersion polymerization method, seed polymerization method and the like.
In order to obtain a color image by an electrophotographic process, in such a color developer, it is required to use a toner component having higher transparency in order to reproduce all colors of the superimposed toner. Yes.
A method using a colorless charge control agent has been proposed as an aim to provide a toner that does not impair the original color of a colorant by using a toner component having excellent transparency (Patent Literature). 1).
Japanese Patent Laid-Open No. 10-254178

  However, since the toner binder, which is the main component constituting the toner, is not sufficiently transparent, the gloss of the obtained image is not sufficiently satisfactory. Although the coloring of the resin can be reduced by polymerizing at a low temperature when the toner binder resin is polymerized, the toner binder resin obtained under such production conditions has a low molecular weight, and the toner using this is heat-resistant stored. Sex was insufficient.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to develop a toner binder that is excellent in transparency and heat-resistant storage stability.
That is, the present invention comprises (I) a polyester resin (A) obtained by ring-opening polymerization of a cyclic ester (b) on an active hydrogen compound (a), and the haze value of (A) is 0.1 to 40. And (II) a polyester resin (A) obtained by ring-opening polymerization of the cyclic ester (b) on the active hydrogen compound (a), and the light transmittance of (A) is 90-100. % Toner binder.

The toner binder of the present invention has the following effects.
1. Excellent transparency.
2. 2. Excellent heat-resistant storage stability When used as a toner for electrophotography, electrostatic recording, and electrostatic printing, the heat-resistant storage stability is excellent and the gloss of the resulting image is improved.

  The toner binder of the present invention comprises a polyester resin (A) obtained by ring-opening polymerization of a cyclic ester (b) with an active hydrogen compound (a). When (A) is used, the heat resistant storage stability is good and it is easy to obtain a transparent resin.

The active hydrogen compound (a) is not particularly limited as long as the cyclic ester (b) undergoes ring-opening polymerization, and examples thereof include alcohols, carboxylic acids, amines, polyester resins having a hydroxyl group and / or a carboxyl group, and thiols. 2 or more may be used in combination.
As the alcohol, a divalent to hexavalent polyol is preferable from the viewpoint of the degree of freedom in composition design. The following are mentioned as a 2-6 valent polyol.
Examples of the divalent alcohol 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.); alkylene ether glycol having 4 to 100 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol) , Polypropylene glycol, polyethylene polypropylene glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated) Bisphenol A and the like; alkylene oxide (hereinafter abbreviated as AO) of the above alicyclic diol (ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO)) Etc.] Addition (addition mole number 1-30); AO (EO, PO, BO, etc.) addition product (addition mole number 2-30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); polylactone diol (Poly ε-caprolactone diol and the like); vegetable oil-based polyol [divalent castor oil polyol and the like]); and polybutadiene diol and the like.

As the divalent alcohol, in addition to the diol having no functional group other than the above hydroxyl group, a diol having another functional group may be used. For example, a diol having a carboxyl group, a sulfonic acid group, or a sulfamic acid group. And diols having these and neutralized salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [having 6 to 24 carbon atoms, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylol. Heptanoic acid, 2,2-dimethyloloctanoic 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 (alkyl group having 1 to 6 carbon atoms) or an AO adduct thereof (EO as AO). Or PO, such as PO, 1-6 addition moles of AO: for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; (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).

  Examples of 3 to 6-valent polyols include 3 to 6-valent polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, trimethylol ethane, trimethylol propane, penta Erythritol, sorbitol, sorbitan, and polyglycerol; saccharides and derivatives thereof such as glucose and fructose) and AO adducts thereof; AO adducts of trisphenols (such as trisphenol PA) (addition mole number 2 to 100); novolac resin AO adducts of phenol novolac, cresol novolak, etc. (addition mole number 2-30); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers, etc.]; vegetable oil-based polyol [3-6 -Valent castor oil Estriol, etc.]), and the like.

  Examples of the carboxylic acid include aliphatic polycarboxylic acids having 2 to 3 or more carbon atoms having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), 2 to 8 carbon atoms having 2 to 8 carbon atoms. And trivalent or higher aromatic polycarboxylic acids (such as terephthalic acid, isophthalic acid, trimellitic acid, and pyromellitic acid).

Examples of the amine include ammonia; examples of the aliphatic amine include alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, isopropanolamine, and aminoethylethanolamine), and alkylamines having 1 to 20 carbon atoms (for example, n- Butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), polyalkylenepolyamines (dialkylenetriamine to hexaalkyleneheptamine having 2 to 6 carbon atoms in the alkylene group), Examples thereof include diethylenetriamine and triethylenetetramine).
C6-C20 aromatic mono- or polyamines (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, and diphenyletherdiamine); C4-C20 alicyclic Examples include amines (isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic amines having 4 to 20 carbon atoms (for example, aminoethylpiperazine).

  As the thiol, those having 2 to 4 thiol groups and having 2 to 18 carbon atoms are preferable. Ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-propanedithiol, 1, 4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate) thiocyanur Examples include acids, and di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and the like.

  Examples of the polyester resin having a hydroxyl group and / or a carboxyl group include the above-mentioned 2 to 6-valent polyol and the above-mentioned polycarboxylic acid (2 to 3 or more aliphatic polycarboxylic acid and / or 2 to 3 or Further polycondensates with aromatic polycarboxylic acids) or acid anhydrides or lower alkyl esters thereof. Further, these lower alkyl esters are preferably those having 1 to 4 carbon atoms, and examples thereof include methyl esters, ethyl esters, and isopropyl esters.

  Preferred among (a) are 2- to 6-valent polyols and polyester resins having a hydroxyl group and / or a carboxyl group, more preferably alkylene glycols having 2 to 36 carbon atoms, diols having a carboxyl group, and bisphenols. AO adduct, C 4-100 alkylene ether glycol, 3-6 valent polyhydric aliphatic alcohol, 3-6 valent polyhydric aliphatic alcohol AO adduct, novolak resin AO adduct, A hexavalent castor oil polyol, a polyester resin having a hydroxyl group and / or a carboxyl group, and a combination thereof. Of these, the most preferable ones are divalent to tetravalent castor oil polyols, hydroxyl value of 1 to 80 (especially 5 to 60) mgKOH / g and / or acid value of 1 to 40 (especially 5 to 25) mgKOH / g. It is a polyester resin. The hydroxyl value and acid value can be measured by the method described in JIS K0070.

  The cyclic ester (b) to be subjected to ring-opening polymerization in (a) is not particularly limited as long as it produces a polyester by ring-opening polymerization, but L-lactide and D-lactide are easy to obtain starting materials. DL-lactide, racemic lactide, glycolide, γ-butyrolactone, δ-valerolactone, and ε-caprolactone are preferred. Among these, L-lactide, D-lactide, DL-lactide, racemic lactide, and mixed lactide thereof are more preferable because a resin having a high Tg and high transparency can be obtained. Therefore, it is a mixed lactide of racemic lactide and other lactide having a racemic lactide ratio of 10 to 30% by weight.

The form of (A) is a block copolymer comprising a polymer of (a) and (b) when (a) is a polymer such as an AO adduct or alkylene ether glycol when heat resistant storage stability is important. It is preferable that If it is a block copolymer, a block having a high Tg is brought close to the surface by appropriately adjusting the difference in physical properties (SP value, HLB, etc.) between the block made of (a) and the block made of the polymer of (b). It becomes possible to orient and heat resistant storage stability is improved.
The method for orienting one block near the surface is not particularly limited. For example, the step of producing a resin solution by dissolving or dispersing (A) in an organic solvent, 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 the resin solution and an aqueous medium, a step of generating resin particles by removing the organic solvent in the particles, There is a method in which the resin particles are separated from the aqueous medium and dried (the details are described in, for example, JP-A-2005-49858).

The number average molecular weight (Mn), melting point, Tg, SP value, hydroxyl value and acid value of the resin (A) may be appropriately adjusted within a preferable range depending on the use conditions.
For example, Mn (measured by gel permeation chromatography) is usually 1,000 to 5,000,000, preferably 2,000 to 500,000. The melting point of (A) (measured by DSC, hereinafter the melting point is measured by DSC) is usually 80 to 130 ° C, preferably 80 to 120 ° C, more preferably 90 to 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) is usually 30 to 80 ° C, preferably 45 to 75 ° C, and more 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) is usually 8 to 16, preferably 9 to 14. The hydroxyl value of (A) is usually 70 mgKOH / g or less, preferably 5 to 50 mgKOH / g, more preferably 10 to 45 mgKOH / g. A smaller hydroxyl value is preferred from the viewpoint of improving environmental stability and charge amount. The acid value of (A) is usually 0 to 40 mgKOH / g, preferably 1 to 30 mgKOH / g, more preferably 10 to 30 mgKOH / g, and particularly preferably 15 to 25 mgKOH / g. The smaller the acid value, the better the environmental stability. However, it is preferable that the acid value has a moderate acid value from the viewpoint of improving the rising of charging.

  In the first invention, the haze value of the polyester resin (A) constituting the toner binder can be measured using a haze meter obtained by forming the resin into a film (thickness: 2 mm) (JIS K7136). The smaller the haze value of (A), the more transparent the toner binder, and when used as an electrophotographic, electrostatic recording, or electrostatic printing toner, the gloss of the resulting image is improved. The haze value of (A) is 0.1 to 40, preferably 0.3 to 30, more preferably 0.5 to 20, and most preferably 1 to 15.

  The light transmittance (A) in the second invention can be measured by using a haze meter for the resin (film thickness 2 mm) (JIS K7361-1). The smaller the light transmittance of (A), the higher the transparency of the toner binder, and when used as an electrophotographic, electrostatic recording, or electrostatic printing toner, the gloss of the resulting image is improved. The light transmittance of (A) is 90 to 100%, preferably 92 to 100%, more preferably 94 to 100%.

  In (A), either the haze value or the light transmittance satisfies the above range, but preferably satisfies the above range at the same time.

The polymerization catalyst (c) used for the synthesis of (A) is not particularly limited as long as it can polymerize the active hydrogen compound (a) with the cyclic ester (b) as a main constituent unit, but it is not limited. In that at least one atom (m) selected from the group of atoms belonging to Group 4, Group 7, Group 8, Group 9, Group 12 and Group 13 of the Periodic Table of Elements is obtained, A metal catalyst coordinated with the polycarboxylic acid ligand (n) having at least two or more carboxyl groups represented by the general formula (1) is preferable.
(COOH) z
｜
(Z) x-Ar- (COO-) y (1)

[In the general formula (1), Z is a monovalent organic group represented by R-, RO-, RS-, ROCO-, RCOO-, RNHCO- or RCONH- (R is a hydrogen atom, a cyano A monovalent hydrocarbon group which may be substituted with a group and / or a nitro group), a halogen atom, a cyano group or a nitro group. Ar represents an aromatic ring; y represents an integer of 1 to 6; z represents an integer of 0 to 5; x represents an integer of 0 to 6. x + y + z is 6 or less. ]

As the atom (m) of the present invention, group 4 atoms (titanium, zirconium, hafnium, etc.), group 7 atoms (manganese, etc.), group 8 atoms (iron, ruthenium, osmium, etc.), group 9 atoms (cobalt, rhodium and Indium, etc.), group 12 atoms (such as zinc and cadmium), and group 13 atoms (such as boron and aluminum).
Of these, titanium, zirconium, hafnium, manganese, iron, cobalt, zinc, boron and aluminum are preferable, and titanium, zirconium, manganese and cobalt are more preferable. Particularly preferred are titanium and zirconium, and most preferred is titanium. The group means a group of the periodic table of elements.

  In the general formula (1), Z represents a monovalent organic group represented by R-, RO-, RS-, ROCO-, RCOO-, RNHCO-, RCONH-, a halogen atom, a cyano group or a nitro group. It is. Here, R is a monovalent hydrocarbon group in which the hydrogen atom may be substituted with a halogen atom, a cyano group, or a nitro group. These may be independently substituted.

  The monovalent hydrocarbon group represented by R can be a hydrocarbon group having 1 to 30 carbon atoms, and includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Some hydrogen atoms may be substituted with halogen (fluorine, chlorine, bromine, etc.), cyano group, or nitro group.

Aliphatic hydrocarbon groups include methyl, ethyl, isopropyl, t-butyl, octyl, 2-ethylhexyl, octadecanyl, vinyl, propenyl, octenyl, octadecenyl, monofluoromethyl, trifluoromethyl, pentafluoroethyl, chlorooctyl, cyanoethyl And nitrooctadecanyl and the like.
As the alicyclic hydrocarbon, a saturated alicyclic hydrocarbon and an unsaturated alicyclic hydrocarbon can be used.
As the saturated alicyclic hydrocarbon, a saturated alicyclic hydrocarbon having 5 to 20 carbon atoms (preferably 5 to 15 and more preferably 5 to 10) is used. Specific examples include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, dodecylcyclohexyl, 2,3,4-tripropylcyclohexyl, 2-methylcyclohexyl, 3,5-dimethylcyclohexyl, 2 , 4,6-trimethylcyclohexyl, dichlorocyclopentyl, perfluorocyclohexyl, cyanotrimethylcyclohexyl and nitrocyclopentyl.
As the unsaturated alicyclic hydrocarbon, an unsaturated alicyclic hydrocarbon having 5 to 20 carbon atoms (preferably 5 to 15 and more preferably 5 to 10) is used. Specific examples include cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl, dodecylcyclohexenyl, cyclooctenyl, 2,3,4-trimethylcyclohexenyl, dinitrocyclopentyl and the like.
As the aromatic hydrocarbon, an aromatic hydrocarbon having 6 to 20 carbon atoms (preferably 6 to 20 and more preferably 6 to 10) is used. Specific examples include phenyl, tolyl, xylyl, cumenyl, mesityl, ethylphenyl, propylphenyl, butylphenyl, t-butylphenyl, 1,3,5-trimethylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, Nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, p-cumylphenyl, α-naphthyl, β-naphthyl, pentafluorophenyl, heptylfluoronaphthyl, trifluoromethylphenyl, trifluoromethylnaphthyl, par Fluoromethylphenyl, 3-methyltetrafluorophenyl, p-trifluoromethyltetrafluorophenyl, 3,5-dimethyltrifluorophenyl, 2,4,5-trifluoro Methylphenyl, 3,5-di [t-butyl] phenyl, 2,3,5-trimethylphenyl, indenyl, azulenyl, fluorenyl, phenanthrenyl, anthracenyl, acenaphthylenyl, biphenylenyl, cyanonaphthacenyl, nitropyrenyl, triphenylenyl and perfluoro-3 , 4,5-tripropylphenyl and the like.

  The organic group represented by RO- is an alkyloxy, alkenyloxy, cycloalkyloxy group, cycloalkenyloxy group, aryloxy group or the like having 1 to 30 carbon atoms, a part of which is a halogen atom, It may be substituted with a cyano group or a nitro group.

  Examples of the organic group represented by RS- include an alkylthio group having 1 to 30 carbon atoms, an alkenylthio group, a cycloalkylthio group, a cycloalkenylthio group, an arylthio group, and the like. Group and nitro group may be substituted.

  As the organic group represented by ROCO-, an organic group having 1 to 30 carbon atoms can be used, and an alkyloxycarbonyl group, an alkenyloxycarbonyl group, a cycloalkyloxycarbonyl group, a cycloalkenyloxycarbonyl group, an aryloxycarbonyl group. And some of the hydrogen atoms may be substituted with a halogen atom, a cyano group, or a nitro group.

  Examples of the organic group represented by RCOO- include an alkylcarbonyloxy group having 1 to 30 carbon atoms, an alkenylcarbonyloxy group, a cycloalkylcarbonyloxy group, a cycloalkenylcarbonyloxy group, and arylcarbonyloxy. The hydrogen atom may be substituted with a halogen atom, a cyano group, or a nitro group.

  Examples of the organic group represented by RNHCO- include an alkylaminocarbonyl group having 1 to 30 carbon atoms, an alkenylaminocarbonyl group, a cycloalkylaminocarbonyl group, a cycloalkenylaminocarbonyl group, an arylaminocarbonyl group, and the like. The hydrogen atom may be substituted with a halogen atom, a cyano group or a nitro group.

  Examples of the organic group represented by RCONH- include alkylcarbonylamino, alkenylcarbonylamino, cycloalkylcarbonylamino, cycloalkenylcarbonylamino, arylcarbonylamino, and the like, and some of the hydrogen atoms are halogen atoms, cyano groups, nitro groups, and the like. It may be substituted with a group.

  Among these examples of the organic group Z, halogen, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alkyloxy, aryloxy, alkylthio, arylthio, alkyloxycarbonyl, aluleoxycarbonyl, alkylcarbonyloxy, Arylcarbonyloxy is preferred. More preferably halogen, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alkyloxy, aryloxy, alkyloxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, arylcarbonyloxy, particularly preferably halogen, Aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alkyloxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy. More particularly preferred are halogen, aliphatic hydrocarbon, aromatic hydrocarbon, alkyloxy, aryloxy, alkylcarbonyloxy and arylcarbonyloxy, and most preferred are halogen, aliphatic hydrocarbon and aromatic hydrocarbon.

In addition, it is not desirable that Z has a substituent having a high coordination ability with respect to the atom (m) because the activity of the catalyst is easily lowered.
Such undesirable substituents include sulfino groups (—SO ₂ H), sulfo groups (—SO ₃ ), cyanato groups (—OCN), isocyanate groups (—NCO), thiocyanato groups (—SCN), hydrazino Examples include a group (H ₂ N—NH—), a phosphono group (—P (OH) ₃ ), a phosphino group (—PR ₂ ), an amino group (—NR ₂ ), and the like.

  In the general formula (1) of the polycarboxylic acid ligand (n), the aromatic ring represented by Ar represents an aromatic ring having 3 to 50 carbon atoms, and is a monocyclic aromatic ring (S) or polycyclic. Ring assembly aromatic ring (T), condensed polycyclic aromatic ring (U), monocyclic aromatic heterocycle (V), polycyclic ring assembly aromatic heterocycle (W) and condensed polycyclic aromatic Heterocycle (X) etc. are mentioned. Among these aromatic rings, monocyclic aromatic rings (S), condensed polycyclic aromatic rings (U), and monocyclic aromatic heterocyclic rings (V) are preferable, and (S) and ( U), most preferably (S).

In the general formula (1), the number y of divalent oxycarbonyl groups (—COO—) is an integer of 1 to 6, preferably an integer of 2 to 5, and more preferably 2 or 3. This oxycarbonyl group is covalently bonded to the aromatic ring and further coordinated to the atom (m).
The number z of monovalent carboxyl groups (—COOH) is an integer of 0 to 5, preferably 0 to 2. This carboxyl group is covalently bonded only to the aromatic ring and is not coordinated to the atom (m). y + z is an integer of 2-6. The number x of Z is an integer of 0-6, preferably 0-4, more preferably 0-2. Moreover, x + y + z is 6 or less.

The polycarboxylic acid ligand (n) represented by the general formula (1) has y divalent oxycarbonyl groups (—COO—), z monovalent carboxyl groups (—COOH) and x number. The organic group Z is covalently bonded to the aromatic ring. The oxycarbonyl group (—COO—) is further coordinated to the same or different metal atom (m) to form a complex as a polymerization catalyst.
The oxycarbonyl group and the carboxyl group are derived from one or more polycarboxylic acids.

  Examples of the polycarboxylic acid include monocyclic aromatic polycarboxylic acid, polycyclic ring assembly aromatic polycarboxylic acid, condensed polycyclic aromatic polycarboxylic acid, monocyclic aromatic heterocyclic polycarboxylic acid, polycyclic And a ring-assembled aromatic heterocyclic polycarboxylic acid and a condensed polycyclic aromatic heterocyclic polycarboxylic acid.

  As the monocyclic aromatic polycarboxylic acid, a monocyclic aromatic polycarboxylic acid having a structure in which at least two carboxys are bonded to the monocyclic aromatic ring (S) can be used. In addition, the number r in () represents the number (p + q) of the carboxyl group of polycarboxylic acid.

  As the polycyclic ring assembly aromatic polycarboxylic acid, a polycyclic ring assembly aromatic polycarboxylic acid in which at least two carboxy groups are bonded to the polycyclic ring assembly aromatic ring (T) can be used. Aggregated aromatic dicarboxylic acids (r = 2), polycyclic ring assembled aromatic tricarboxylic acids (r = 3) and polycyclic ring assembled aromatic poly (tetra-, penta- or hexa-) carboxylic acids (r = 4) ~ 6) etc. are used.

  As the condensed polycyclic aromatic polycarboxylic acid, a condensed polycyclic aromatic polycarboxylic acid in which at least two carboxyls are bonded to the condensed polycyclic aromatic ring (U) can be used, and the condensed polycyclic aromatic dicarboxylic acid can be used. Acid (r = 2), condensed polycyclic aromatic tricarboxylic acid (r = 3), condensed polycyclic aromatic poly (tetra-, penta- or hexa-) carboxylic acid (r = 4-6), etc. are used. Be

  As the monocyclic aromatic heterocyclic polycarboxylic acid, a monocyclic aromatic heterocyclic polycarboxylic acid in which at least two carboxyl groups are bonded to the monocyclic aromatic heterocyclic ring (V) can be used. Aromatic heterocyclic dicarboxylic acid (r = 2), monocyclic aromatic heterocyclic tricarboxylic acid (r = 3) and monocyclic aromatic heterocyclic poly (tetra-, penta- or hexa-) carboxylic acid (r = 4) ~ 6) etc. are used.

  As the polycyclic ring assembly aromatic heterocyclic polycarboxylic acid, a polycyclic ring assembly aromatic heterocyclic polycarboxylic acid in which at least two carboxy groups are bonded to the polycyclic ring assembly aromatic heterocyclic ring (W) can be used. Polycyclic ring assembly aromatic heterocyclic dicarboxylic acid (r = 2), polycyclic ring assembly aromatic heterocyclic tricarboxylic acid (r = 3) and polycyclic ring assembly aromatic heterocyclic poly (tetra-, penta -Or hexa-) carboxylic acid (r = 4 to 6) or the like is used.

  As the condensed polycyclic aromatic heterocyclic polycarboxylic acid, a condensed polycyclic aromatic heterocyclic polycarboxylic acid in which at least two carboxyls are bonded to the condensed polycyclic aromatic heterocyclic ring (X) can be used. Cyclic aromatic heterocyclic dicarboxylic acid, condensed polycyclic aromatic heterocyclic tricarboxylic acid, condensed polycyclic aromatic heterocyclic poly (tetra-, penta-) carboxylic acid and the like are used.

  Of these polycarboxylic acids, monocyclic aromatic polycarboxylic acids, polycyclic ring-assembled aromatic polycarboxylic acids, and condensed polycyclic aromatic polycarboxylic acids are preferred, and monocyclic aromatic dicarboxylic acids are more preferred. A monocyclic aromatic tricarboxylic acid, a polycyclic ring assembly aromatic dicarboxylic acid, a polycyclic assembly aromatic tricarboxylic acid, a condensed polycyclic aromatic dicarboxylic acid and a condensed polycyclic aromatic tricarboxylic acid. Particularly preferred are monocyclic aromatic dicarboxylic acids, monocyclic aromatic tricarboxylic acids, polycyclic ring-assembled aromatic dicarboxylic acids and polycyclic ring-assembled aromatic tricarboxylic acids, and even more preferred monocyclic aromatic Dicarboxylic acids and monocyclic aromatic tricarboxylic acids. Most preferred is a monocyclic aromatic dicarboxylic acid, and specific examples include terephthalic acid.

  Preferable specific examples of the polymerization catalyst (c) include a combination of the above preferred atom (m) and the above preferred polycarboxylic acid ligand (n), more preferably titanium terephthalate, and terephthalate. Zirconate and particularly preferably titanium terephthalate.

  The method of obtaining the polyester resin (A) by ring-opening polymerization of the cyclic ester (b) to the active hydrogen compound (a) can be carried out by the same method as the usual esterification reaction. For example, (B) A mixture of the polymerization catalyst (c) and, if necessary, a solvent can be placed in a reaction vessel equipped with a stirrer at a time to produce heating and stirring at a reaction temperature in a nitrogen atmosphere. The initial reaction pressure may be any of pressurization, normal pressure, and slight pressure reduction. The catalyst may be added in the whole amount required for the reaction at once, or may be added in the middle of the reaction in several times.

  The ratio of the number of moles of (a) to the number of moles of (b) is appropriately adjusted according to the purpose of using the polyester to be produced. The larger the ratio (a), the lower the molecular weight of the polyester. The molar ratio (b) / (a) is preferably 1 to 10000, more preferably 5 to 5000, and particularly preferably 10 to 3000.

  The amount of the polymerization catalyst (c) used is preferably from 0.0005 to 0.05 mol%, more preferably from 0.001 to 0.04, as the concentration of atoms (m) based on the number of moles of (b) to be reacted. Mol%, most preferably 0.005 to 0.03 mol%. Within this concentration range, there is little coloring at the time of polymerization, and a transparent polyester having no haze is easily obtained. Moreover, 2 or more types of (c) can be used together in a polymerization reaction.

  When performing a polymerization reaction, a solvent can be used if necessary. As a solvent, what is used for normal esterification and transesterification can be used as it is. Examples thereof include benzene, toluene, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), xylene, carbon tetrachloride and chloroform. When using a solvent, the amount of solvent used (% by weight) is preferably 0 to 80, more preferably 10 to 60, and particularly preferably 30 to 50, based on the weight of the carboxylic acid component to be reacted.

  The reaction temperature (° C.) of the polymerization reaction is preferably 120 to 300, more preferably 140 to 280, and particularly preferably 160 to 250.

In the toner binder of the present invention, other resins may be used in addition to (A). Other resins include polyester resins other than those of the present invention (polyester resin not containing (A) in the structural unit), styrene resins (a copolymer of styrene and alkyl (meth) acrylate, and styrene and a diene monomer). Copolymer, etc.], epoxy resin (cured product of addition condensate of bisphenol A and epichlorohydrin, etc.), urethane resin (polyaddition product of diol and diisocyanate, etc.) and the like. The Mn of other resins is preferably 1,000 to 2,000,000.
The content (% by weight) of these other resins is preferably 0 to 80, more preferably 0 to 50, and particularly preferably 0 to 30 based on the weight of the toner binder.

The toner binder of the present invention is used as a dry toner by mixing a colorant and, if necessary, various additives such as a release agent and a charge control agent.
Known dyes, pigments and magnetic powders can be used as the colorant. Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Varanitoaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Examples include rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, prilliant green, phthalocyanine green, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, magnetite, iron black and the like.
The content of the colorant in the toner is preferably 2 to 15% by weight when using a dye or pigment, and preferably 20 to 70% by weight when using magnetic powder.
Known release agents can be used, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing wax (carnauba wax, Montan wax, distearyl ketone, etc.).
The content of the release agent in the toner is preferably 0 to 10% by weight, and more preferably 1 to 7% by weight.
As the charge control agent, known ones, that is, 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, halogen-substituted aromatic Examples thereof include a ring-containing polymer.
The content of the charge control agent in the toner is preferably 0 to 5% by weight.
Furthermore, a fluidizing agent can also be used. As the fluidizing agent, known materials such as colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder can be used.
The toner may be produced by a commonly used method. (I) The components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally used a jet pulverizer or the like. Examples of the method include obtaining a toner by mixing the fluidizing agent after the particles are finely divided and further classified to obtain particles having a volume average particle diameter (D50) of preferably 5 to 20 microns. And (ii) a step of producing a resin solution by dissolving or dispersing components constituting the toner excluding the fluidizing agent 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 The toner is obtained by sequentially performing the steps of separating and drying the toner and then mixing the fluidizing agent. Since a block having a high Tg can be oriented on the surface, it is preferable to prepare a toner by the method (ii). Details of the method (ii) are described in, for example, JP-A-2005-49858.

The dry toner using the toner binder of the present invention is 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. And used as a developer of an electric latent image. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.
Next, the recording material is fixed to a support (paper, polyester film, etc.) by a known hot roll fixing method.

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”.
<Example 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of polypropylene glycol (Newpol PP-2000 manufactured by Sanyo Chemical Industries, Ltd.), 500 parts of L-lactide and 1 part of titanium terephthalate were charged. For 6 hours to obtain [Resin 1].
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. The mixture was mixed at a rotational speed of 12000 rpm at 25 ° C. for 1 minute to obtain [Aqueous Dispersion 1]. [Aqueous dispersion 1] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (manufactured by Tokushu Kika), the mixture was stirred at 12000 rpm at 25 ° C. for 1 minute to obtain [Aqueous Dispersion 2]. [Aqueous Dispersion 2] is stirred at 50 ° C. for 3 hours, and then centrifuged, and the process of adding 100 parts of water and solid-liquid separation is repeated three times. The toner of the present invention having a particle size (D50) of about 5 μm A toner (P1) comprising a binder was obtained.

<Example 2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 701 parts (1,8 mol) of 1,2-propylene glycol, 716 parts (7.5 mol) of dimethyl terephthalate, 180 parts of adipic acid ( 2.5 mol), and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the produced methanol. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the 1,2-propylene glycol produced and water under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it reached 150 ° C., it was taken out. The recovered 1,2-propylene glycol was 316 parts (8.5 mol). The taken-out resin was cooled to room temperature and then pulverized into particles to obtain [Polyester a1]. [Polyester a1] had Mn of 2000, a hydroxyl value of 43 mgKOH / g, and an acid value of 19 mgKOH / g.
In addition, the number of moles in () means a relative molar ratio.
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Polyester a1], 500 parts of L-lactide and 1 part of titanium terephthalate were charged, and after substitution with nitrogen, polymerization was carried out at 160 ° C. for 6 hours. ] Was obtained.
In a beaker, 100 parts of [Resin 2] 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 (manufactured by Tokushu Kika) was used. The mixture was mixed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm to obtain [Aqueous Dispersion 3]. [Aqueous dispersion 3] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (manufactured by Tokushu Kika), the mixture was stirred at 12000 rpm at 25 ° C. for 1 minute to obtain [Aqueous Dispersion 4]. [Aqueous Dispersion 4] is stirred at 50 ° C. for 3 hours, and then centrifuged, and the process of adding 100 parts of water and solid-liquid separation is repeated three times. The toner of the present invention having a particle size (D50) of about 5 μm Toner (P2) comprising a binder was obtained.

<Example 3>
Into an autoclave reaction vessel equipped with a thermometer and a stirrer, 15 parts of [castor oil polyol HS 3P-255 (manufactured by Toyokuni Seiyaku Co., Ltd.)], 500 parts of L-lactide and 1 part of titanium terephthalate are charged and replaced with nitrogen. Thereafter, polymerization was carried out at 160 ° C. for 6 hours to obtain [Resin 3].
In a beaker, 100 parts of [Resin 3] 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 (manufactured by Tokushu Kika) was used. The mixture was mixed at a rotational speed of 12000 rpm at 25 ° C. for 1 minute to obtain [Aqueous Dispersion 5]. [Aqueous dispersion 5] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (manufactured by Tokushu Kika), the mixture was stirred at 12000 rpm for 1 minute at 25 ° C. to obtain [Aqueous Dispersion 6]. [Aqueous Dispersion 6] is stirred at 50 ° C. for 3 hours, then centrifuged, and the process of 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 (P3) comprising a binder was obtained.

<Example 4>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Polyester a1] described in Example 2, 400 parts of L-lactide, 100 parts of racemic lactide and 1 part of titanium terephthalate were added, and after substitution with nitrogen, 160 ° C. For 6 hours to obtain [Resin 4].
In a beaker, 100 parts of [Resin 4] 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. The mixture was mixed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm to obtain [Aqueous Dispersion 7]. [Aqueous dispersion 7] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (made by Tokushu Kika), the mixture was stirred at 25 ° C. for 1 minute at a rotational speed of 12000 rpm to obtain [Aqueous Dispersion 8]. After stirring [Aqueous Dispersion 8] at 50 ° C. for 3 hours, the process of centrifuging, adding 100 parts of water and solid-liquid separation is repeated 3 times, and the toner of the present invention having a particle size (D50) of about 5 μm A toner (P4) comprising a binder was obtained.

<Example 5>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 100 parts of [Polyester a1] described in Example 2, 400 parts of D-lactide, 100 parts of racemic lactide and 1 part of titanium terephthalate were charged, and after substitution with nitrogen, 160 ° C. For 6 hours to obtain [Resin 5].
In a beaker, 100 parts of [Resin 5] 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 (manufactured by Tokushu Kika) was used. The mixture was mixed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm to obtain [Aqueous Dispersion 9]. [Aqueous dispersion 9] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (manufactured by Tokushu Kika), the mixture was stirred at 12000 rpm for 1 minute at 25 ° C. to obtain [Aqueous Dispersion 10]. After stirring [Aqueous Dispersion 10] 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 (P5) comprising a binder was obtained.

<Example 6>
Into an autoclave reaction vessel equipped with a thermometer and a stirrer, 15 parts of castor oil polyol HS 3P-255 (manufactured by Toyokuni Oil Co., Ltd.), 400 parts of L-lactide, 100 parts of racemic lactide and 1 part of titanium terephthalate are charged. After substitution with nitrogen, polymerization was carried out at 160 ° C. for 6 hours to obtain [Resin 6].
In a beaker, 100 parts of [Resin 6] and 40 parts of ethyl acetate were mixed, 500 parts of water and 3 parts of sodium dodecylnaphthalenesulfonate were added, and then a TK homomixer (manufactured by Tokushu Kika) was used. The mixture was mixed at 25 ° C. for 1 minute at a rotational speed of 12000 rpm to obtain [Aqueous Dispersion 11]. [Aqueous Dispersion 11] 100 parts, colorant [copper phthalocyanine] 4 parts, release agent [Biscol 550P (softening point 150 ° C.); Sanyo Chemical Industries, Ltd.] 4 parts, and water 50 parts are mixed, Using a TK homomixer (manufactured by Tokushu Kika), the mixture was stirred for 1 minute at 25 ° C. at a rotation speed of 12000 rpm to obtain [Aqueous Dispersion 12]. After stirring [Aqueous Dispersion 12] 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 Toner (P6) comprising a binder was obtained.

<Comparative Example 1>
A toner (CP1) comprising a comparative toner binder was obtained in the same manner as in Example 1 except that the titanium terephthalate was changed to tin octylate.

<Comparative example 2>
In a four-necked flask, a reflux condenser, a distillation tower, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were installed in the usual manner. 15 parts of phthalic anhydride, 170 parts of dimethyl terephthalate, 1,4- 66 parts of cyclohexanedimethanol, 22 parts of ethylene glycol, 49 parts of neopentyl glycol and 0.2 part of titanium tetrabutoxide were charged, and an esterification reaction was carried out at 180 ° C. while distilling water and methanol produced from the distillation column. The esterification reaction was completed when water and methanol no longer distilled from the distillation column. Furthermore, the inside of the system was depressurized to 5 mmHg or less, and the free diol produced by the condensation reaction was distilled out of the system at 200 ° C. and a stirring rotational speed of 150 rpm to obtain [Resin 7]. A toner (CP2) made of a comparative toner binder was obtained in the same manner as in Example 1 except that [Resin 1] was changed to [Resin 7].

The physical properties of the toners (P1) to (P6) and (CP1) to (CP2) obtained as described above were confirmed and their performance was evaluated. The results are shown in Table 1.
(1) Haze value A film having a thickness of 2 mm was prepared using only a toner binder, and measured using a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136.
(2) Light transmittance A film having a thickness of 2 mm was prepared using only a toner binder, and a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) was used in accordance with JIS K7361-1. It was measured.
(3) Gloss Evaluation Fixation evaluation was performed using a modified machine in which the oil supply device was removed from the fixing device of a commercially available color copying machine (CLC-1; manufactured by Canon) and the oil on the fixing roll was removed. The fixing roll temperature at which the 60 ° gloss of the fixed image was 10% or more was defined as the gloss development temperature. A glossy toner has a lower gloss development temperature.
(4) Heat-resistant storage stability After storing the toner at 50 ° C. for 8 hours, the toner was sieved with a 42-mesh sieve for 2 minutes, and the residual ratio (% by weight) on the wire mesh was regarded as heat-resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio.

  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-resistant storage stability and transparency.

Claims (6)

A toner binder comprising a polyester resin (A) obtained by ring-opening polymerization of a cyclic ester (b) on an active hydrogen compound (a), wherein the haze value of (A) is 0.1 to 40. A toner binder comprising a polyester resin (A) obtained by ring-opening polymerization of a cyclic ester (b) on an active hydrogen compound (a), wherein the light transmittance of (A) is 90 to 100%. The toner binder according to claim 1 or 2, wherein the active hydrogen compound (a) is at least one selected from a divalent to hexavalent polyol and a polyester resin having a hydroxyl group and / or a carboxyl group. The cyclic ester (b) is one or more selected from L-lactide, D-lactide, DL-lactide, racemic lactide, glycolide, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. The toner binder according to any one of the above. The polyester resin (A) has at least one atom (m) selected from the group of atoms belonging to Group 4, Group 7, Group 8, Group 9, Group 12, Group 13 of the periodic table of elements, and a general formula ( The toner binder according to any one of claims 1 to 4, which is a resin obtained by polymerization in the presence of a polymerization catalyst for polyester (c) comprising the polycarboxylic acid ligand (n) represented by 1). .
(COOH) z
｜
(Z) x-Ar- (COO-) y (1)
[In the general formula (1), Z is a monovalent organic group represented by R-, RO-, RS-, ROCO-, RCOO-, RNHCO- or RCONH- (R is a hydrogen atom, a cyano A monovalent hydrocarbon group which may be substituted with a group and / or a nitro group), a halogen atom, a cyano group or a nitro group. Ar represents an aromatic ring; y represents an integer of 1 to 6; z represents an integer of 0 to 5; x represents an integer of 0 to 6. x + y + z is 6 or less. ] 6. The toner binder according to claim 5, wherein the atom (m) of the polymerization catalyst (c) is at least one selected from the group consisting of titanium, zirconium, manganese, iron, cobalt, zinc, aluminum and boron.