JP2014101429A - Polyester resin and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin for a toner having excellent pulverizing property and a wide fixing temperature range.SOLUTION: A method for producing a polyester resin is provided, comprising polymerization condensation of a polyester resin having a structural unit expressed by formula (1) and an unsaturated double bond with a monomer mixture including a polyvalent carboxylic acid and a polyhydric alcohol. In the method, the monomer mixture includes at least one of a polyvalent carboxylic acid having an unsaturated double bond and a polyhydric alcohol having an unsaturated double bond, and erythritan.

Description

  The present invention relates to a polyester resin and a method for producing the same.

In the method of obtaining an image by the electrophotographic printing method and the electrostatic charge developing method, the electrostatic charge image formed on the photoreceptor is developed with toner charged in advance by friction and then fixed. As for the fixing method, there are a heat roller method in which a toner image obtained by development is fixed using a pressurized and heated roller, and a non-contact fixing method in which fixing is performed using an electric oven or flash beam light. In order to pass through these processes without any problem, the toner needs to maintain a stable charge amount first, and then needs to have good fixability to paper. In addition, the apparatus has a fixing unit which is a heating body, and the temperature in the apparatus rises, so that it is necessary that the toner does not block. Furthermore, it is required that the resin has good grindability during the production of toner.

  In response to recent demands for higher speed, smaller size, and energy saving of printers, the temperature of heat roller type fixing units has been lowered. Therefore, the toner resin is required to be fixed on paper at a lower temperature and to have good fixability in a wide temperature range.

  For example, Patent Document 1 describes a polyester resin for toner obtained by crosslinking a polyester resin having an unsaturated double bond. Patent Document 2 describes a polyester resin excellent in heat resistance and transparency obtained by copolymerizing erythritan.

WO2007 / 034813 JP 2008-239744 A

  However, in the polyester resin described in Patent Document 1, the resin is difficult to break and the grindability is not sufficient. Further, when the polyester resin described in Patent Document 2 is used for toner, fixing at a low temperature is insufficient.

  An object of the present invention is to solve this problem, and to provide a polyester resin for toner that has excellent pulverization properties and a wide fixing temperature range.

The gist of the present invention resides in a structural unit represented by the following general formula (1) and a polyester resin having an unsaturated double bond.

  By using the polyester resin of the present invention, it is possible to provide a toner having excellent pulverization properties and a wide fixing temperature range.

  The polyester resin of the present invention has a structural unit represented by the following general formula (1).

In the present invention, the polyester resin having the structural unit represented by the general formula (1) includes a polyhydric alcohol including a polyhydric alcohol (erythritan) represented by the following general formula (2) and a polycarboxylic acid. Obtained by polycondensation. Erythritan is synthesized, for example, by an intramolecular dehydration reaction of erythritol, which is a natural polysaccharide.

  In the present invention, the pulverizability of the toner using the polyester resin of the present invention is improved by having the structural unit represented by the general formula (1).

Moreover, in this invention, it is preferable to contain 1-45 mol part of structural units represented by the said General formula (1) with respect to 100 mol part of structural units derived from polyhydric carboxylic acid. When the structural unit represented by the general formula (1) is contained in an amount of 1 mol part or more with respect to 100 mol parts of the structural unit derived from the polyvalent carboxylic acid, the grindability is improved. , Low temperature fluidity is improved. From the viewpoint of grindability, it is preferably 10 parts by mole or more, and more preferably 40 parts by mole or less.
Furthermore, the polyester resin of the present invention has an unsaturated double bond.
The position of the unsaturated double bond may be the main chain or the side chain of the polyester resin.

  In the present invention, crosslinking between molecular chains is caused by crosslinking reaction of unsaturated double bonds in the polyester resin, the molecular weight distribution is widened, and the fixing temperature range of the polyester resin for toner is widened.

  The unsaturated double bond is a carbon-carbon double bond and includes at least one of a polyvalent carboxylic acid having an unsaturated double bond and a polyhydric alcohol having an unsaturated double bond. And a polyhydric alcohol monomer mixture.

  The polyvalent carboxylic acid having an unsaturated double bond is preferably 1 to 50 mol parts in 100 mol parts of the polyvalent carboxylic acid in the monomer mixture, and the polyhydric alcohol having an unsaturated double bond is 1-50 mol part is preferable with respect to 100 mol part of polyhydric carboxylic acid in a monomer mixture. Moreover, when using both together, it is preferable that the sum total of both is 1-50 mol part.

  When the content of the monomer having an unsaturated double bond is 1 mol part or more, the low-temperature fixing width of the toner tends to be widened, and when the content of the unsaturated double bond is 50 mol part or less, The storage stability of the toner tends to be good. From the viewpoint of grindability, it is more preferably 5 mol parts or more and 30 mol parts or less.

  Examples of the polyvalent carboxylic acid having an unsaturated double bond include fumaric acid, maleic acid, maleic anhydride, citraconic acid, itaconic acid, tetrahydrophthalic acid and ester derivatives thereof, acrylic acid, crotonic acid, methacrylic acid and These ester derivatives are exemplified. Examples of the polyhydric alcohol having an unsaturated double bond include 1,4-dihydroxy-2-butene. Among these, fumaric acid, maleic acid, and maleic anhydride are preferable from the viewpoint of reactivity.

In addition, examples of the structural unit derived from a polyhydric alcohol other than those described above and the structural unit derived from a polyvalent carboxylic acid included in the polyester resin of the present invention include those derived from a polyhydric alcohol and a polycarboxylic acid described later.
In addition, the content of the structural unit represented by the general formula (1) contained in the polyester resin of the present invention is a copolymer determined from 1H-NMR (nuclear magnetic resonance apparatus) and the integral ratio of the spectrum by 13C-NMR measurement. It can be determined from the composition. In particular, by using two types of nuclear probes, analysis with high accuracy becomes possible.
The polyester resin of the present invention preferably further has a structural unit derived from a bisphenol A derivative. By containing a bisphenol A derivative as a structural unit, blocking resistance and durability are improved. Examples of the bisphenol A derivative include polyoxypropylene- (2.0) -2,2-bis (4-hydroxy). Phenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene ( 3.3) Alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane.

  Furthermore, the glass transition temperature (Tg) of the polyester resin of the present invention is preferably 75 ° C. or lower. When Tg is 75 ° C. or lower, low-temperature fluidity, grindability, and storage stability are good. 45 ° C. or higher is preferable from the viewpoint of storage stability, and 73 ° C. or lower is preferable from the viewpoint of low-temperature fixability. In addition, glass transition temperature (Tg) is the value which measured the polyester resin using the differential scanning calorimeter.

  Moreover, as for the softening temperature (T4) of the polyester resin of this invention, 80-140 degreeC is preferable. If the softening temperature is 80 ° C. or higher, the storage stability of the toner is good, and if it is 140 ° C. or lower, the low-temperature fluidity is good.

  Furthermore, the acid value of the polyester resin of the present invention is preferably 1 to 50 mgKOH / g. If the acid value is 1 mgKOH / g or more, the chargeability is good, and if it is 50 mgKOH / g or less, moisture absorption can be suppressed.

Moreover, as for the peak molecular weight (Mp) in the gel permeation chromatography (GPC) of the polyester resin of this invention, 500-9000 are preferable. If the Mp is 500 or more, the storage stability is good, and if it is 9000 or less, the grindability is good. Furthermore, 2000 or more are more preferable from the point of grindability, and 7000 or less are more preferable. Next, the manufacturing method of the polyester resin of this invention is demonstrated.

  The polyester resin of the present invention can be produced by a method of polycondensing a monomer mixture containing a polyvalent carboxylic acid and a polyhydric alcohol, wherein the monomer mixture has a polyvalent carboxylic acid having an unsaturated double bond and an unsaturated group. It can be obtained by polycondensing a monomer mixture containing at least one of a polyhydric alcohol having a double bond and a polyhydric alcohol represented by the formula (2).

  The erythritan represented by the formula (2) is preferably contained in an amount of 1 to 50 mol parts per 100 mol parts of the polyvalent carboxylic acid. When 1 mol part or more of the erythritan is contained with respect to 100 mol parts of the polyvalent carboxylic acid, the grindability is good, and when 50 mol parts or less is contained, the grindability and the low temperature fluidity are good. In view of grindability, the amount is preferably 10 parts by mole or more, and preferably 45 parts by mole or less.

  Furthermore, in this invention, it is preferable that a bisphenol A derivative is included in the said monomer mixture as polyhydric alcohols other than Formula (2). As the bisphenol A derivative, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) Propane, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2- Scan (4-hydroxyphenyl) bisphenol A alkylene oxide adducts such as propane.

  The bisphenol A derivative is preferably contained in an amount of 5 to 70 mol parts per 100 mol parts of the polyvalent carboxylic acid. If it is 5 mol parts or more, the fixing strength of the toner is good, and if it is 70 mol parts or less, thermal decomposition during polymerization can be prevented.

  The polyhydric alcohol other than the above contained in the monomer mixture includes ethylene glycol, neopentyl glycol, propylene glycol, hexanediol, polyethylene glycol, 1,2-propanediol, 1,4-butanediol, Diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, D-isosorbide, L-isosorbide, isomannide, 1,4-dihydroxy-2-butene, sorbitol, 1,2,3,6-hexatetralol, 1, 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2- Mechi 1,2,4-butane triol, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  Among these, ethylene glycol, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2 from the viewpoint of low-temperature fluidity, storage stability and grindability. .3) -2,2-bis (4-hydroxyphenyl) propane is preferred.

  These polyhydric alcohols may be used alone or in combination of two or more.

  From the viewpoint of the balance between the glass transition temperature (Tg) and the softening temperature (T4), the total amount of the polyhydric alcohol is preferably 150 mol parts or less, more than 60 mol parts, based on 100 mol parts of the polyvalent carboxylic acid. 140 mol parts or less are more preferable, 70 mol parts or more and 130 mol parts are more preferable, and 80 mol parts or more and 120 mol parts or less are particularly preferable.

  When this content is 80 mol parts or more, the production stability of the polyester resin tends to be good. When the amount is 120 mol parts or less, Tg tends to be high with respect to T4, and the storage stability tends to be good.

  Examples of the polyvalent carboxylic acid contained in the monomer mixture include divalent terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate. Carboxylic acids, or esters or anhydrides thereof, fats such as phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, succinic acid, or esters or anhydrides thereof Group dicarboxylic acid, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid Acid, 1,2,7,8-octanetetracarbo Acid or the like of these ester or acid anhydride may be mentioned. These can be used alone or in combination of two or more.

  Furthermore, a monovalent carboxylic acid or alcohol may be included for the purpose of adjusting the number of terminal functional groups and improving the dispersibility of other toner materials within a range not impairing the object of the present invention.

  Examples of monovalent carboxylic acid compounds include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid, aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid, and cinnamon. Examples thereof include unsaturated carboxylic acids having one or more unsaturated double bonds in the molecule, such as acid, oleic acid, linoleic acid, and linolenic acid.

  Examples of the monovalent alcohol compound include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol, and aliphatic alcohols having 30 or less carbon atoms such as oleyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. It is done.

  For polycondensation of polyester resin, for example, a titanium catalyst such as titanium tetrabutoxide, a tin catalyst such as dibutyltin oxide, tin acetate, tin disulfide, etc., a catalyst such as zinc acetate, antimony trioxide, germanium oxide, etc. Can do. From the viewpoint of reducing environmental burden, a titanium-based catalyst is preferable.

  The polycondensation reaction temperature is preferably in the range of 180 ° C to 280 ° C. When the reaction temperature is 180 ° C. or higher, productivity tends to be good. When the reaction temperature is 280 ° C. or lower, decomposition of the resin and by-product of volatile components that cause odor tend to be suppressed. The lower limit of the reaction temperature is more preferably 200 ° C. or higher, and the upper limit is more preferably 270 ° C. or lower.

  Moreover, as a method of determining the glass transition temperature (Tg) of the obtained polyester resin, the resin may be sampled during the reaction, Tg measurement may be performed, and the reaction may be terminated when a predetermined Tg is reached. The term “stopping the reaction” means that stirring of the reaction apparatus is stopped, the inside of the apparatus is brought to normal pressure, the inside of the apparatus is pressurized with nitrogen, the reaction product is taken out from the lower part of the apparatus, and cooled to 100 ° C. or lower.

  Furthermore, in this invention, a polyester resin can also be superposed | polymerized by adding a mold release agent component with said component in the range which does not impair the effect of this invention as needed. By adding a release agent component and polymerizing, the toner fixing property and wax dispersibility tend to be improved.

  A stabilizer may be added for the purpose of obtaining polymerization stability of the polyester resin. Examples of the stabilizer include hydroquinone, methyl hydroquinone, hindered phenol compounds and the like.

The polyester resin of the present invention may be used alone as a binder resin for toner. However, after mixing the polyester resin of the present invention with another polyester resin, the unsaturated double bond of the polyester resin of the present invention is subjected to a crosslinking reaction. It is preferable to use a polyester resin for toner. By causing the unsaturated double bond to undergo a crosslinking reaction, the fixing temperature range is widened.
When the polyester resin of the present invention is subjected to a crosslinking reaction, a part thereof is changed to a crosslinking component having a high crosslinking density that is not dissolved in THF (THF insoluble component), and a part thereof is converted to a crosslinking component having a low crosslinking density that is dissolved in THF. Change and the rest remains unreacted. As a result, the resin obtained by the crosslinking reaction has a THF insoluble content (crosslinking component not dissolved in THF) and a THF soluble content (crosslinking component dissolved in THF, unreacted polyester resin (1), and unreacted resin). Polyester resin (2)).
Of the THF soluble component, the unreacted polyester resin (2) has an effect of imparting low-temperature fixability to the toner. Of the THF soluble component, the unreacted polyester resin (1) has an effect of imparting elasticity to the toner. Further, since the THF-insoluble matter is highly crosslinked, the toner has an effect of imparting a higher elastic modulus to the toner.
As a result, the polyester resin for toner obtained by the crosslinking reaction exhibits high high-temperature offset resistance while maintaining good low-temperature fixability, and a wide fixing temperature range. The change in the fixing temperature range due to the crosslinking reaction can be judged by the fact that the molecular weight distribution (Mw / Mn) after the crosslinking reaction is larger than the molecular weight distribution before the crosslinking reaction.

As another polyester resin to be mixed with the polyester resin of the present invention, a polyester resin having a peak molecular weight of 10,000 or more and 1,000,000 or less in gel permeation chromatography is preferable and contains an unsaturated double bond. May be.
The Tg of other polyester resins is preferably 40 to 80 ° C. When the temperature is 40 ° C. or higher, the storage stability of the toner tends to be good, and when the temperature is 80 ° C. or lower, the low-temperature fixability of the toner tends to be good. Further, the acid value is preferably 50 mgKOH / g or less. When the acid value is 50 mgKOH / g or less, the fixed image density of the toner tends to be good. The other polyester resin can be obtained by polycondensing a monomer mixture containing a known polycarboxylic acid and a polyhydric alcohol.

  In addition, it is preferable that 60 mass% or more of the polyester resin of this invention is mixed.

  Examples of the crosslinking reaction method include a reaction in which an unsaturated double bond is reacted by a radical addition reaction, a cation addition reaction, an anion addition reaction, or the like to generate an intermolecular carbon-carbon bond. The radical addition reaction used is particularly preferred.

  The radical reaction initiator is not particularly limited, and an azo compound or an organic peroxide is used. Among them, an organic peroxide is preferable because it has high initiator efficiency and does not generate a cyanide byproduct.

Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2, 5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, Acetyl peroxide, isobutyryl peroxide, octaninoroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylpero 2-ethylhexanoate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, t -Butyl peroxy acetate etc. are mentioned.

  Among these, a radical reaction initiator having a high hydrogen abstraction ability is particularly preferred because the crosslinking reaction proceeds efficiently and the amount used is small. Preferred examples of the radical initiator having a high hydrogen abstraction ability include benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t-butylperoxy ) Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide and the like.

  As for the usage-amount of a radical reaction initiator, 0.01-20 mass parts is preferable with respect to 100 mass parts of polyester resins. When the amount of radical reaction initiator used is 0.01 parts by mass or more, the crosslinking reaction tends to proceed, and when it is 20 parts by mass or less, the odor tends to be good.

  Moreover, it is preferable to dilute and use a crosslinking reaction initiator with a diluent. By adding the radical reaction initiator diluted with a diluent, it tends to suppress the self-induced degradation of the radical reaction initiator, ensuring safety during the production of the polyester resin, and the radical reaction initiator by self-induced degradation. Wasteful consumption can be suppressed, and the amount of radical reaction initiator used can be reduced.

  As the diluent, a mold release agent is preferable, and a diluent that does not inhibit the crosslinking reaction of the unsaturated double bond is preferably used. As those that do not inhibit the crosslinking reaction of unsaturated double bonds, hydrocarbon-based release agents are preferred, for example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; Examples thereof include oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block compounds thereof.

  Note that the melting point of the release agent is preferably 120 ° C. or less because mixing with a crosslinking reaction initiator is easy and the low-temperature fixability of the toner can be further enhanced. As the mold release agent having a melting point of 120 ° C. or less, paraffin wax is most preferable.

  The method of diluting a crosslinking reaction initiator with a mold release agent is a method of mixing a liquid crosslinking reaction initiator into a mold release agent liquefied by heating, or dissolving and mixing a solid crosslinking reaction initiator in a liquid mold release agent. And a method of impregnating a solid mold release agent with a liquid crosslinking reaction initiator. Among them, from the viewpoint of uniformity and dispersibility of the crosslinking reaction initiator, a method of mixing a liquid crosslinking reaction initiator with a liquefied release agent or a solid crosslinking reaction initiator with a liquefied release agent. The method of dissolving is preferred.

  About the apparatus which performs a crosslinking reaction, a melt mixing apparatus is preferable from a viewpoint of mixing a polyester resin and a crosslinking reaction initiator uniformly in a short time.

  Examples of the melt mixing apparatus include a single screw extruder, a twin screw extruder, a continuous closed mixer, a gear extruder, a disk extruder and a roll mill extruder, a continuous melt mixing apparatus such as a static mixer, a Banbury mixer, a Brabender mixer, Examples thereof include a batch closed type melt mixing apparatus such as a haake mixer.

  Among these, a continuous melt mixing apparatus is preferable because a crosslinking reaction initiator can be efficiently dispersed in a polyester resin in a short time.

  Next, a toner using the polyester resin of the present invention will be described. The toner of the present invention is obtained by blending the polyester resin of the present invention with known colorants, charge control agents, mold release agents, flow modifiers and other additives, magnetic materials, and the like.

  Colorants include carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo, disazo, Examples thereof include condensed azo dyes and pigments. The content of the colorant is not particularly limited, but is preferably 2 to 10% by mass in the toner from the viewpoint of the toner color tone, image density, and thermal characteristics.

  Examples of the charge control agent include a quaternary ammonium salt as a positive charge control agent and a basic or electron donating organic substance, and as a negative charge control agent, a metal chelate, a metal-containing dye, an acid or electron withdrawing property. Organic materials and the like. In the case of a color toner, it is preferable that the charge control agent is colorless to light color and does not cause a color tone hindrance to the toner. A metal salt of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, a metal complex, an amide compound, a phenol compound, A naphthol compound etc. are mentioned. Furthermore, a vinyl polymer having a styrene, acrylic acid, methacrylic acid or sulfonic acid group may be used as the charge control agent.

  The content of the charge control agent is preferably 0.5 to 5% by mass in the toner. When the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be a sufficient level, and when the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. It tends to be.

  As the mold release agent, carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, taking into account the toner releasability, storage stability, fixability, color developability, etc. Fatty acid amides, silicone waxes and the like can be appropriately selected and used. The content of the release agent is not particularly limited, but is preferably 0.3 to 15% by mass in the toner.

  Other additives include fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive fine titanic inorganic powder, styrene resin, acrylic resin, etc. Agents, lubricants and the like. The content of these additives in the toner is preferably 0.05 to 10% by mass.

  Further, as the binder resin, a binder resin other than the polyester resin of the present invention may be used. For example, a polyester resin other than the polyester resin of the present invention, a styrene resin, a styrene-acrylic resin, a cyclic olefin resin, or a methacrylic acid resin. An epoxy resin etc. can be mentioned and 2 or more types can be mixed and used.

  The toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.

  The toner containing the polyester resin for toner of the present invention can be produced by a known method. For example, after mixing the above-mentioned binder resin and compound, melt-kneading with a twin-screw extruder or the like, coarsely pulverizing, finely pulverizing, and classifying, and performing external addition treatment of inorganic particles as necessary Method (pulverization method), the above-mentioned binder resin and compound are dissolved and dispersed in a solvent, granulated in an aqueous medium, then the solvent is removed, washed and dried to obtain toner particles, and if necessary Examples include a method (chemical method) in which inorganic particles are externally added and manufactured.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Moreover, evaluation was performed by the following method.

<Glass transition temperature (Tg)>
Using a differential differential calorimeter (DSC-60, manufactured by Shimadzu Corporation), measurement was performed from the intersection of the base line of the chart and the tangent line of the endothermic curve at a heating rate of 5 ° C./min. The sample to be measured was 10 mg ± 0.5 mg weighed in an aluminum pan, melted at 100 ° C. for 10 minutes, and then rapidly cooled using dry ice.

<Softening temperature (T4)>
Using a flow tester (CFT-500D manufactured by Shimadzu Corporation), 4 mm out of 1.0 g of the resin sample flowed out at a constant temperature of 1 mmφ × 10 mm, a load of 294 N, and a temperature increase rate of 3 ° C./min. When the temperature was measured.

<Acid value>
About 0.2 g of the sample was precisely weighed in a branch Erlenmeyer flask (A (g)), 10 ml of benzyl alcohol was added, and the mixture was heated with a heater at 230 ° C. for 15 minutes in a nitrogen atmosphere to dissolve the resin. After cooling to room temperature, 10 ml of benzyl alcohol, 20 ml of chloroform and a few drops of a phenolphthalein solution were added and titrated with a 0.02N KOH solution (titrate = B (ml), titer of KOH solution = p). . A blank measurement was performed in the same manner (titer amount = C (ml)), and calculation was performed according to the following formula.
Acid value (mgKOH / g) = (BC) × 0.02 × 56.11 × p ÷ A
<Molecular weight: number average molecular weight (Mn), mass average molecular weight (Mw), peak molecular weight (Mp)>
It measured by GPC method on the following conditions. The peak molecular weight (Mp) was determined by standard polystyrene conversion from the retention time corresponding to the peak value of the obtained elution curve. The peak value of the elution curve is a point where the elution curve shows a maximum, and when there are two or more maximum values, the elution curve gives the maximum value.
Apparatus: Toyo Soda Industry Co., Ltd., HLC8020
Column: Toyo Soda Industry Co., Ltd., TSKgelGMHXL (column size: 7.8 mm (ID) x 30.0 cm (L)) connected in series Oven temperature: 40 ° C
Eluent: THF
Sample concentration: 4 mg / 10 mL
Filtration conditions: Filter sample solution with 0.45 μm Teflon membrane filter Flow rate: 1 mL / min Injection amount: 0.1 mL
Detector: RI
Standard polystyrene sample for preparing calibration curve: TSK standard manufactured by Toyo Soda Industry Co., Ltd.
, A-500 (molecular weight 5.0 × 10 ² ), A-2500 (molecular weight 2.74 × 10 ³ ), F-2 (molecular weight 1.96 × 10 ⁴ ), F-20 (molecular weight 1.9 × 10) ⁵ ), F-40 (molecular weight 3.55 × 10 ⁵ ), F-80 (molecular weight 7.06 × 10 ⁵ ), F-128 (molecular weight 1.09 × 10 ⁶ ), F-288 (molecular weight 2.89) × 10 ⁶ ), F-700 (molecular weight 6.77 × 10 ⁶ ), F-2000 (molecular weight 2.0 × 10 ⁷ ).

<Compositional analysis of structural units of polyester resin>
Analysis was performed using a superconducting nuclear magnetic resonance apparatus.
Device: JEOL Excalibur 270 Superconducting FT-NMR
Magnet: JNM-GSX270 type Superconducting magnet spectrometer: JNM-EX270 type Observation frequency: 1H 270MHz, 13C 67MHz
Solvent: Deuterated chloroform temperature: 35 ° C
Number of integrations: 1H: 16 times, 13C: 1024 times 1 H-NMR and 13-NMR were measured, and the ratios of polycarboxylic acid and polyol were determined from the integral ratio of the assigned peaks derived from the respective structural units.
(Assigned peak range of 1 H-NMR)
Derived from terephthalic acid structure: 8.0-8.1 ppm
Derived from fumaric acid structure: 6.8 to 6.9 ppm
Origin of ethylene glycol structure: 4.0-5.0 ppm
Derived from erythritan structure: 3.9 to 4.2 ppm, 5.2 ppm to 5.7 ppm
Bisphenol A ethylene oxide 2-mole adduct structure origin: 4.2-4.3, 4.6-4.7, 6.8-6.9, 7.1-7.2 ppm
Bisphenol A propylene oxide 2.3 mol adduct structure origin: 1.5-1.6, 4.6-4.7, 5.6-5.7, 6.8-6.9, 7.1-7 .2ppm
(Assigned peak range of 13 C-NMR)
Derived from carbonyl carbon of terephthalic acid structure: 165.4-165.6 ppm
Derived from benzene ring carbon with terephthalic acid structure: 129.5-133.8ppm
Derived from carbonyl carbon of fumaric acid structure: 165.4 to 165.6 ppm
Derived from (-C = C-) carbon of the fumaric acid structure: 133.4-133.8 ppm
Origin of ethylene glycol structure: 63.0-63.1 ppm
Origin of the erythritan structure:
{-(C = O) -O-CH-}: 7.4 to 7.5 ppm
(—CH 2 —O—): 7.0 ppm to 7.1 ppm
Bisphenol A ethylene oxide 2-mole adduct structure origin:
(-O-CH2-CH2-O-): 6.8 to 6.9 ppm
(-O-C6H4-O-): 114.1, 127.7, 143.6, 156.2 ppm
(-C (CH3) 2-): 31.1, 41.8 ppm
In addition, the attribution of each absorption in a NMR spectrum was performed according to the chemical domain extra number 141 NMR-review and experiment guide [I], p.132-133.

<Crushability>
The resin powder is passed through a sieve to obtain a resin powder that passes through 16 mesh and does not pass through 22 mesh. Thereafter, the mixture was passed through a 30-mesh sieve, and the weight (A) g of the resin that did not pass through was precisely weighed. The resin residual ratio was obtained by the following formula, and this operation was performed three times, and the average value was evaluated.
{(A) g / resin weight before grinding (10.00 g)} × 100 = resin remaining rate (%)
The grindability was evaluated as follows from the obtained resin residual ratio.
◎ (Very good): Resin residual rate is less than 60% ○ (Good): Resin residual rate is 60% or more and less than 70% △ (Available): Resin residual rate is 70% or more and less than 85% x (Inferior): Resin residual rate is 85% or more
About 5 g of the toner was weighed and put into a sample bottle, which was left in a drier kept at 45 ° C. for about 24 hours, and the degree of toner aggregation was evaluated as an index of storage stability. The evaluation criteria were as follows.
○ (Good): Dispersed when the sample bottle is inverted and tapped 1-3 times x (Inferior): Dispersed when the sample bottle is inverted and tapped four or more times <Fixing temperature range>
90 parts by mass of a release agent (SP-0160 manufactured by Nippon Seiki Co., Ltd.) is heated to 75 ° C. and melted, and 10 parts by mass of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane. And the resulting mixture was cooled and pulverized to prepare a crosslinking initiator diluted with a release agent.

  Polyester resin 1 (77 parts by mole of terephthalic acid, 20 parts by mole of isophthalic acid, 3 parts by mole of adipic acid, 1,4-cyclohexane) using a twin-screw extruder (PCM-29 manufactured by Ikegai Co., Ltd .: L / D = 30) 15 parts by weight of dimethanol, 105 parts by mole of ethylene glycol, Tg: 64 ° C., T4: 185 ° C., acid value: 2 mg KOH / g, Mn: 8000, Mw: 52000, Mp: 50000) After 85 parts by mass of the obtained polyester resin was melt-kneaded, 0.2 part by mass of the crosslinking initiator was supplied to an extruder, and a crosslinking reaction was performed at an external temperature setting of 180 ° C. and a residence time of 3 minutes.

The molecular weight of the obtained resin was measured according to the above-described molecular weight measurement procedure, and the molecular weight distribution after the crosslinking reaction was compared with the molecular weight distribution before the crosslinking reaction, and used as an index of the fixing temperature range. The evaluation criteria were as follows.
○ (Wide fixing temperature range): The molecular weight distribution after the crosslinking reaction is larger than the molecular weight distribution before the crosslinking reaction.
× (Narrow fixing temperature range): The molecular weight distribution after the crosslinking reaction is not different from the molecular weight distribution before the crosslinking reaction.

(Synthesis of erythritan)
A 300 ml four-necked flask equipped with a Claisen tube wrapped with a heat insulating material and a thermometer was charged with 214.0 g (1.75 mol) of erythritol and 23.1 g (0.2 mol) of an 85 mass% phosphoric acid aqueous solution. Furthermore, a Liebig condenser, a thermometer, a bifurcated adapter, a flask, a pressure gauge, a trap that was not blocked by frozen water, a vacuum pump, and a pressure regulator were connected. The flask was heated in an oil bath while stirring with a magnetic stirrer. After the internal temperature reached 135 ° C., the vacuum pump was started to start depressurization. Erythritan and a part of the water produced and distilled by the reaction were condensed in a Liebig condenser, and collected in a flask attached to a bifurcated adapter. Water that was not condensed in the Liebig condenser was collected in a trap cooled with liquid nitrogen. When 50 ml of the distillate was collected in the flask, the pressure reduction was stopped, 72.5 g (0.59 mol) of erythritol was supplied, and then the vacuum pump was started to resume the collection of erythritan. Thereafter, the supply of erythritol was repeated 13 times by the same operation, and then the reaction was continued until no distillation of erythritan occurred. The total amount of erythritol used was 1229.0 g (10.1 mol). The temperature of the reaction solution was 135 to 150 ° C., and the pressure was finally 150 Pa.

  The erythritan collected in the flask was analyzed by gas chromatography to analyze the purity of erythritan. The obtained amount of erythritan containing water was 1001.7 g, the purity was 96% by mass, the water content was 3% by mass, and the yield was 92%. The weight of the residue remaining in the 300 ml flask was 62.8 g.

(Example 1)
1000 ppm of tetra-n-butoxytitanium with respect to the polyvalent carboxylic acid, polyhydric alcohol, and polyvalent carboxylic acid having the charging composition shown in Table 1 was charged into a reaction vessel equipped with a distillation column. Next, the temperature was raised and heated so that the temperature in the reaction system became 265 ° C., this temperature was maintained, and the esterification reaction was carried out until no water was distilled from the reaction system. Subsequently, the temperature in the reaction system was set to 235 ° C., the pressure in the reaction vessel was reduced, and a polycondensation reaction was carried out while distilling the polyalcohol from the reaction system.

  At the end of the reaction, about 2 g of resin was sampled during the reaction, Tg measurement was performed, and when the predetermined Tg described in Table 1 was reached, the suspension of stirring was stopped, the reaction system was returned to normal pressure by introducing nitrogen, The reaction product was taken out under pressure and cooled to 100 ° C. or lower to obtain a polyester resin. Table 1 shows the characteristic values of the obtained resin.

  Next, 93 parts by weight of resin, 3 parts by weight of quinacridone pigment (E02 manufactured by Clariant) as a colorant, 1 part by weight of a negatively chargeable charge control agent LR-147 (manufactured by Nippon Carlit), carnauba wax (Toyo Petrolide) 3 parts by mass) were mixed with powder, melt-kneaded using a twin screw extruder (PCM-29: Ikegai Co., Ltd.) at an external temperature setting of 120 ° C. and a residence time of 1 minute, coarsely pulverized, and then jet milled The toner was finely pulverized with a mold pulverizer, and a toner having an average particle diameter of 5 μm was obtained with a classifier. Storage stability was evaluated using this toner. The evaluation results are shown in Table 1.

(Examples 2-8 and Comparative Examples 1-2)
A polyester resin was obtained using the same method as in Example 1 except that the charged composition was changed as shown in Table 1. The characteristic values of the obtained polyester resin are shown in Table 1. The results evaluated in the same manner as in Example 1 are shown in Table 1.

比較例１では、一般式（１）で表される構造単位を含んでいないため、粉砕性が不十分であった。
比較例２では、不飽和二重結合を含有していないため定着温度幅が不十分であった。

In Comparative Example 1, since the structural unit represented by the general formula (1) was not included, the grindability was insufficient.
In Comparative Example 2, since the unsaturated double bond was not contained, the fixing temperature range was insufficient.

Claims (5)

A polyester resin having a structural unit represented by formula (1) and an unsaturated double bond.

A method for producing a polyester resin in which a monomer mixture containing a polyvalent carboxylic acid and a polyhydric alcohol is polycondensed, wherein the monomer mixture comprises a polyvalent carboxylic acid having an unsaturated double bond and an unsaturated diester. The method for producing a polyester resin according to claim 1, comprising at least one of a polyhydric alcohol having a heavy bond and a polyhydric alcohol represented by the formula (2).

A method for producing a polyester resin in which the polyester resin according to claim 1 is subjected to a crosslinking reaction using a crosslinking reaction initiator. A polyester resin obtained by the method according to claim 3. A toner containing the polyester resin according to claim 1.