JP5182487B2 - Polyester resin for electrostatic image developing toner and method for producing the same, electrostatic image developing toner and method for producing the same, electrostatic image developer, image forming method, and image forming apparatus - Google Patents

Description

  The present invention relates to a polyester resin for an electrostatic charge image developing toner and a manufacturing method thereof, an electrostatic charge image developing toner and a manufacturing method thereof, an electrostatic charge image developer, an image forming method, and an image forming apparatus.

In recent years, the garbage problem has become more serious, and there is a strong demand for recycling of various kinds of garbage ranging from paper, bottles and cans to large garbage.
Among these recycled products, particularly for plastics, PET bottles made from polyethylene terephthalate (PET) are collected to some extent, made into fiber, and reused as clothing, carpets, fillers, furniture, and the like.
For recycling plastics, (1) material recycling, (2) chemical recycling, and (3) thermal recycling are known.
In the chemical recycling method, monomer recovery by depolymerization reaction and raw material monomer recovery by chemical decomposition reaction are known.
For example, Patent Document 1 describes a method for recovering a monomer in a low temperature region. Patent Document 2 discloses a method for depolymerizing polylactic acid in which polylactic acid is depolymerized in an organic solvent in the presence of a hydrolase to generate a repolymerizable oligomer.
Furthermore, for depolymerization of polyethylene terephthalate (PET), for example, Patent Document 3 discloses a method of depolymerizing with ethylene glycol using alkali metal, alkaline earth metal, zinc, cobalt and manganese weak acid salts as catalysts. Have been described. Patent Document 4 discloses a method for recovering dimethyl terephthalate from PET.

  As for toner resin using waste PET as a raw material, for example, Patent Document 5 describes a method in which a polyester resin recovered from waste is added to a reaction system and polymerization is performed in the presence of alcohol and / or water. Has been. Patent Document 6 discloses a binder resin for toner obtained by reacting polyethylene terephthalate or modified polyethylene terephthalate (hereinafter referred to as PET) with an alcohol and / or a carboxylic acid compound, followed by depolymerization and condensation polymerization. In addition, a binder resin composition for toner is described in which the intrinsic viscosity number of the PETs is 0.70 to 0.90, and the content of diethylene glycol in the PETs is 3% by weight or less. Further, Patent Document 7 discloses a first stage for producing a depolymerized composition of waste polyester resin; and a polycondensation reaction of the depolymerized composition by adding a polyhydric alcohol to the depolymerized composition to produce an acid value. A second step of producing a polyester polymer of 10 to 150 mg KOH / g; and a polyester polymer obtained in the second step, wherein the acid value of the polyester polymer is 20 mg KOH / g or more, either a solid or liquid polyester resin A third (a) stage for producing one of them; a third polyester (b) for producing a solid polyester resin as it is when the acid value of the polyester polymer obtained in the second stage is less than 20 mg KOH / g. ) Stage, and a method for reclaiming waste polyester resin is described.

Japanese Patent Laying-Open No. 2005-330211 International Publication No. 2004/013217 Pamphlet JP-A-7-2738 JP 2000-218167 A JP-A-8-253596 Japanese Patent Laid-Open No. 2004-163808 JP 2005-517050 A

  An object of the present invention is a recycled polyester resin, and has excellent initial image quality, low-temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity when used as an electrostatic charge image developing toner. It is to provide a polyester resin for an electrostatic charge image developing toner.

The above problems have been solved by the means described in <1>, <3>, <6> to <10> below. It is shown below with <2>, <4> and <5> which are preferable embodiments.
<1> Regenerated polyester resin having an alkylene terephthalate structure as a structural unit, containing a depolymerization catalyst, insoluble in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) at 25 ° C. A polyester resin for electrostatic charge image developing toner, wherein the content is 1 to 30% by weight,
<2> The polyester resin for electrostatic charge image developing toner according to <1>, wherein the depolymerization catalyst is a rare earth catalyst,
<3> including a step of preparing a polyester resin (a) containing an alkylene terephthalate structure as a structural unit, and the polyester resin (a), a polycondensable monomer (b), and a depolymerization catalyst (c). Including a step of obtaining a polyester resin (d) by depolymerizing and polycondensing the composition, and 1,1,1,3,3,3-hexafluoro-2-propanol of the polyester resin (d) at 25 ° C. (HFIP) Method for producing polyester resin for electrostatic charge image developing toner, wherein insoluble content is 1 to 30% by weight,
<4> The method for producing a polyester resin for an electrostatic charge image developing toner according to <3>, wherein the depolymerization catalyst (c) is a rare earth catalyst,
<5> The method for producing a polyester resin for electrostatic charge image developing toner according to <3> or <4>, wherein the polycondensable monomer (b) contains an aliphatic dicarboxylic acid,
<6> The polyester resin for electrostatic charge image developing toner according to <1> or <2>, or the electrostatic charge image produced by the production method according to any one of <3> to <5>. An electrostatic charge image developing toner comprising a polyester resin for developing toner,
<7> The electrostatic charge image developed by the polyester resin for electrostatic image developing toner according to <1> or <2> or the production method according to any one of <3> to <5>. A step of obtaining a resin particle dispersion in which a polyester resin for developing toner is dispersed in an aqueous medium, a step of aggregating the resin particles in a dispersion containing at least the resin particle dispersion to obtain aggregated particles, and the aggregated particles A method for producing an electrostatic image developing toner comprising a step of heating and fusing the toner,
<8> The electrostatic charge image developing toner according to <6> above, or the electrostatic charge image developer comprising the electrostatic charge image developing toner produced by the production method according to <7> and a carrier,
<9> A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image. The developer including a developing step, a transferring step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for fixing the toner image transferred to the surface of the transfer target. The electrostatic image developing toner described in <6> above, the electrostatic image developing toner manufactured by the manufacturing method described in <7>, or the electrostatic image developer described in <8> above is used. Image forming method,
<10> A latent image holding member, a charging unit for charging the latent image holding member, an exposure unit for exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member, and a developer. Developing means for developing the electrostatic latent image to form a toner image, transfer means for transferring the toner image from the latent image holding member to the transfer target, and the toner image transferred to the surface of the transfer target A fixing unit for fixing, and the developer is the electrostatic image developing toner described in <6>, the electrostatic image developing toner manufactured by the manufacturing method described in <7>, or <8 An image forming apparatus using the electrostatic charge image developer described in the above item.

According to the invention described in <1> above, when it is a recycled polyester resin and is used for an electrostatic image developing toner, the initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity It is possible to provide a polyester resin for an electrostatic charge image developing toner having excellent chargeability.
According to the invention described in <2>, when it is a recycled polyester resin and is used for an electrostatic charge image developing toner, initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity It is possible to provide a polyester resin for an electrostatic charge image developing toner having excellent chargeability.
According to the invention described in the above <3>, when it is a recycled polyester resin and is used for an electrostatic charge image developing toner, initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity It is possible to provide a method for producing a polyester resin for an electrostatic charge image developing toner having excellent chargeability.
According to the invention described in the above <4>, when it is a recycled polyester resin and is used for an electrostatic charge image developing toner, initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity It is possible to provide a method for producing a polyester resin for an electrostatic charge image developing toner having excellent chargeability.
According to the invention described in the above <5>, when it is a recycled polyester resin and is used for an electrostatic charge image developing toner, initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity It is possible to provide a method for producing a polyester resin for an electrostatic charge image developing toner having excellent chargeability.
According to the invention described in <6>, an electrostatic charge image developing toner comprising a regenerated polyester resin and excellent in initial image quality, low-temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity. Can be provided.
According to the invention described in <7>, an electrostatic charge image development comprising a regenerated polyester resin and excellent in initial image quality, low temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity. A toner production method can be provided.
According to the invention described in <8>, an electrostatic charge image development comprising a regenerated polyester resin and excellent in initial image quality, low-temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity. An agent can be provided.
According to the invention described in <9>, an electrostatic charge image development comprising a regenerated polyester resin and excellent in initial image quality, low-temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity. An image forming method using toner can be provided.
According to the invention described in <10>, the electrostatic image development includes a regenerated polyester resin and has excellent initial image quality, low temperature fixability, image quality under high temperature and high humidity, and chargeability under high temperature and high humidity. An image forming apparatus using toner can be provided.

  The present invention is described in detail below.

(Polyester resin for electrostatic image developing toner)
The polyester resin for electrostatic image developing toner of the present invention (hereinafter also referred to as “the polyester resin for toner of the present invention” or “the polyester resin of the present invention”) is a recycled polyester resin having an alkylene terephthalate structure as a structural unit. The depolymerization catalyst is contained, and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) insoluble matter at 25 ° C. is 1 to 30% by weight.
The polyester resin of the present invention can be suitably used as a binder resin for an electrostatic charge image developing toner.

The recycled polyester resin is a polyester resin produced using a polyester resin that has been produced once or more as a raw material.
The polyester resin as a raw material is not particularly limited as long as at least a polyester resin having an alkylene terephthalate structure as a constituent unit is used, and once manufactured as a product having a resin is discarded, and then recovered. A polyester resin (hereinafter also referred to as “recovered polyester resin”) is preferable, and recovered polyethylene terephthalate is more preferable.
The recovered polyester resin that can be used in the present invention does not contain a compound that interferes with the performance or polymerization reaction of the toner and has a certain degree of purity. It is not limited. Specific examples include polyester resins recovered from wastes such as PET bottles, clothing, carpets, fillers, furniture, and polyester films. Among them, recycled polyethylene terephthalate recovered from PET bottles and polyester films, or recycled modified polyethylene terephthalate that has been processed once from recovered waste for recycling because it is discarded in large quantities and is easy to recover. Preferably used.
In use, pulverized ones, pellets, and the like are preferably used for ease of handling, dispersion, and decomposition.
Moreover, the polyester resin of this invention may contain the impurity originating in a waste material etc., for example.

  The alkylene terephthalate structure in the polyester resin of the present invention is a structure represented by the following formula (A).

（式（Ａ）中、Ａは二価のアルキレン基を表す。）

(In the formula (A), A represents a divalent alkylene group.)

The divalent alkylene group in A may be a linear alkylene group or a branched alkylene group. Further, preferably an alkylene group having 2 to 8 carbon atoms, an ethylene group - particularly preferably (-CH ₂ CH _2).
That is, the alkylene terephthalate structure in the polyester resin of the present invention is particularly preferably an ethylene terephthalate structure.
In the present invention, the description “A to B” represents not only a range between A and B but also a range including A and B at both ends thereof. For example, if “A to B” is a numerical value range, “A or more and B or less” or “B or more and A or less” is represented.

The depolymerization catalyst contained in the polyester resin of the present invention is preferably a metal catalyst, more preferably a titanium catalyst, a hafnium catalyst or a rare earth catalyst, and even more preferably a rare earth catalyst.
The rare earth catalyst is preferably a rare earth catalyst having a rare earth element selected from the group consisting of Y, Sc, Yb and Sm as its constituent component, more preferably a scandium catalyst.
The rare earth catalyst is preferably a rare earth metal triflate (rare earth metal trifluoromethanesulfonate), a rare earth metal trifurylimide (rare earth metal bis (trifluoromethanesulfonyl) imide), or a rare earth metal alkylsulfate. More preferred is triflate or rare earth metal trifurylimide.
Specifically, it is raised as a triflate of metal elements of Sc (OSO ₂ CF ₃ ) ₃ , Y (OSO ₂ CF ₃ ) ₃ , Yb (OSO ₂ CF ₃ ) ₃ , Sm (OSO ₂ CF ₃ ) ₃ . Moreover, these rare earth elements may be used individually by 1 type, or may be used in combination of 2 or more types, and the combination in particular does not restrict | limit this invention.
As content of the depolymerization catalyst in the polyester resin of this invention, it is preferable that it is 0.01 to 5.0 weight%, and it is more preferable that it is 0.1 to 2.0 weight%. Within the above range, a resin having physical properties suitable for the toner can be easily produced, and the depolymerization catalyst itself is not affected as a compound in the toner evaluation.

The polyester resin of the present invention has a 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) insoluble content at 25 ° C. of 1 to 30% by weight, and 2 to 25% by weight. Is preferable, and it is more preferable that it is 3 to 20 weight%. Within the above range, both offset resistance, storage stability and fixing property are excellent.
1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is a polar solvent. The polyester resin of the present invention has a specific insoluble content with respect to this HFIP.
For example, the solubility of polyalkylene terephthalate such as PET in HFIP is usually low and depends on the molecular weight, but the insoluble content at 25 ° C. is 50% by weight or more and often 80% by weight or more. Further, a conventionally known polyester resin for toner produced from only a monomer without using the recovered polyester resin as a raw material has an insoluble content in HFIP of less than 1% by weight.
In general, when a high molecular weight component resin typified by PET is used as a binder resin for a toner, it is known that the high temperature offset resistance is improved, but the low temperature fixability is deteriorated. For example, when the depolymerization of the polyester resin used as a raw material is insufficient, the insoluble content of the obtained polyester resin in HFIP exceeds 30% by weight. When such a polyester resin is used as a polyester resin for toner, it is difficult to obtain appropriate fixing properties.
The content of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) insoluble matter at 25 ° C. of the polyester resin is not very clear, but one of them is A resin component having a molecular weight exceeding 100,000 can be exemplified.

As a measuring method of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) insoluble matter of polyester resin at 25 ° C., it can be measured with reference to a known insoluble matter measuring method. However, it can be particularly preferably measured by the method shown below.
The resin sample was finely pulverized, and 5.0 g of sample powder that passed through a 42 mesh (opening: 355 μm) sieve was collected and placed in a 150 ml container together with 5.0 g of filter aid radiolite (# 700). 100 g of HFIP is poured into the container, placed on a ball mill stand and rotated for 5 hours or more to sufficiently dissolve the sample. On the other hand, a filter paper (No. 2) having a diameter of 7 cm is placed in a pressure filter, radiolite is uniformly precoated thereon, and a small amount of HFIP is added to bring the filter paper into close contact with the filter. The contents of are poured into the filter. Further, thoroughly wash with 100 ml of HFIP and pour into the filter so that no deposits remain on the vessel wall of the container. Thereafter, the upper lid of the filter is closed and filtration is performed. Filtration is performed under a pressure of 4 kg / cm ³ or less. After the HFIP outflow stops, washing with 100 ml of HFIP is followed by pressure filtration. These operations are performed in an atmosphere at 25 ° C. After completion of the above operation, the weight of the dried product obtained by placing the filter paper, the residue on the filter paper, and all of the radiolite on an aluminum foil in a vacuum dryer and drying at a temperature of 85 ° C. and a pressure of 100 mmHg for 10 hours. Is measured, and the weight ratio of insoluble matter is calculated.

The polyester resin of the present invention has at least an alkylene glycol unit (the following formula (A-1)) and a terephthalate unit (the following (A-2)) as monomer units, but has other monomer units. Preferably it is.
The polyester resin of the present invention preferably has a total of 1 to 85% by weight of alkylene glycol units and terephthalate units, and more preferably has a total of 3 to 70% by weight. Within the above range, the cost is excellent and the reaction control during production is easy.

  A in Formula (A-1) has the same meaning as A in Formula (A), and the preferred range is also the same.

Preferred examples of the other monomer units include monomer units derived from a polycondensable monomer described later. The other monomer unit is preferably a monomer unit derived from a polycarboxylic acid and a monomer unit derived from a polyol, more preferably a monomer unit derived from a dicarboxylic acid and a monomer unit derived from a diol, More preferred are a monomer unit derived from an aliphatic dicarboxylic acid and a monomer unit derived from a diol.
Moreover, it is preferable that the polyester resin of this invention has a monomer unit represented by a following formula (Z-1) and / or a formula (Z-2) as said other monomer unit.

Wherein Z ¹ in (Z-1) represents a group containing an alkylene group or bisphenol skeleton having 3 or more divalent atoms, divalent alkylene group having 3 to 12 carbon atoms, or, of bisphenols or bisphenols A group obtained by removing hydrogen atoms of two hydroxy groups from an alkylene oxide adduct is preferable.
Z ² in the formula (Z-2) is a single bond, a divalent alkylene group or a divalent alkenylene group, a divalent alkenylene divalent alkylene group or 2 to 8 carbon atoms having 2 to 8 carbon atoms It is preferably a group.
The alkylene group may be linear, branched or a ring structure.
Moreover, the polyester resin of this invention is a monomer unit represented by the said Formula (A-1), Formula (A-2), Formula (Z-1), and / or Formula (Z-2), All monomer units. In this case, it is preferably 80% by weight or more, and preferably 90% by weight or more.
The terminal structure of the polyester resin of the present invention varies depending on the substrate, production conditions, quenching conditions, and the like, and examples thereof include a carboxyl group, a hydroxy group, and an alkoxycarbonyl group.

The polyester resin of the present invention preferably uses, as a raw material, a polycondensable monomer such as a polyvalent carboxylic acid, a polyhydric alcohol, or a hydroxycarboxylic acid in addition to the polyester resin.
Examples of the polycondensable monomer that can be used in the present invention include polyvalent carboxylic acids, polyhydric alcohols, and hydroxycarboxylic acids. The polycarboxylic acid or hydroxycarboxylic acid may be a lower ester compound, an acid anhydride, or an acid halide.
In addition, a lower ester shows that the carbon number of the alkoxy part of ester is 1-8. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, and isobutyl ester.
Moreover, the oligomer and / or prepolymer of the said polycondensable monomer can also be used as a polycondensable monomer.
The polyester resin of the present invention can take any form such as amorphous (amorphous) polyester resin (non-crystalline polyester resin), crystalline polyester resin, or a mixed form thereof.

  The polyvalent carboxylic acid that can be used in the present invention is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid , Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalate Acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenyldiacetic acid, diphenyl-p , P′-dicarboxylic acid, naphthalene-1,4-dica Bon acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and anthracene dicarboxylic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Furthermore, the lower ester, acid anhydride, acid halide, etc. of the said polyhydric carboxylic acid can also be mentioned. These may be used alone or in combination of two or more.

  The polyhydric alcohol (polyol) that can be used in the present invention is a compound containing two or more hydroxyl groups in one molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule, and examples thereof include ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, and dodecanediol. Can do. Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine. These may be used alone or in combination of two or more.

In addition, an amorphous resin or a crystalline resin can be easily obtained by using the amount or combination of these polycondensable monomers.
For example, the polyvalent carboxylic acid suitably used for obtaining the crystalline polyester resin includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, azelaic acid, sebacic acid, maleic acid. Acid, fumaric acid, citraconic acid, itaconic acid, glutamic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, these Examples thereof include acid anhydrides, lower esters thereof, and acid halides thereof.
Further, for example, as a polyol suitably used for obtaining a crystalline polyester resin, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol 1,4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol Polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A and the like can also be mentioned.

  Also, for example, polyvalent carboxylic acids preferably used for obtaining an amorphous polyester resin include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid and the like. Examples thereof include aromatic dicarboxylic acids such as dibasic acids, and these lower esters are not limited thereto. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and anhydrides thereof. Examples include, but are not limited to, sodium 2-sulfoterephthalate, sodium 5-sulfoisophthalate, sodium sulfosuccinate and lower esters thereof.

  Further, as the polycondensable monomer, a hydroxycarboxylic acid containing a carboxyl group and a hydroxy group in one molecule can also be used. For example, malic acid, tartaric acid, 2,2-dimethylolbutanoic acid, citric acid, mucic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxytridecanoic acid , Hydroxyhexadecanoic acid, hydroxypentadecanoic acid, hydroxystearic acid and the like.

The polyester resin of the present invention is preferably an amorphous resin.
Moreover, it is preferable that the glass transition temperature of the polyester resin of this invention is 45-80 degreeC, It is more preferable that it is 50-75 degreeC, It is further more preferable that it is 50-70 degreeC. By selecting one having a glass transition temperature in such a range, it is possible to obtain further excellent low-temperature fixability, smoothness of the fixing surface, and blocking resistance.
In addition, the glass transition temperature of resin in this invention is measured as follows. That is, using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the sample was heated to 200 ° C., allowed to stand at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 ° C./min. When measured at a rate of temperature increase of 10 ° C./min, the temperature at the intersection of the base line extension below the glass transition temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex The transition temperature (Tg) is assumed.

In addition, for the measurement of the melting point of the resin, a differential scanning calorimeter (DSC) was used, and the input compensation shown in JIS K-7121: 87 when measuring from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be determined as the melting peak temperature of differential scanning calorimetry. A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.
“Crystallinity” as shown in the above “crystalline resin” means that in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 6 ° C. On the other hand, a resin having an endothermic peak with a half-value width exceeding 6 ° C. or a resin having no clear endothermic peak means non-crystalline (amorphous).

The softening point of the polyester resin of the present invention is preferably 75 to 170 ° C, and more preferably 80 to 160 ° C. When the softening point is 75 ° C. or higher, the offset resistance and the blocking resistance are excellent. Further, when the softening point is 170 ° C. or less, the low-temperature fixability is excellent.
Specifically, the softening point of the resin is measured as follows.
While a 1 cm ³ sample was heated at a heating rate of 6 ° C./min using a Koka flow tester (manufactured by Shimadzu Corporation), a load of 20 kg / cm ² was applied by a plunger, a diameter of 1 mm, and a length A nozzle of 1 mm is pushed out, thereby drawing a plunger descending amount (flow value) -temperature curve, and when the height of the S-shaped curve is h, the temperature corresponding to h / 2 (half of the resin is The temperature that flows out is the softening point.

In addition, the chloroform-insoluble content of the polyester resin of the present invention at 25 ° C. is preferably 1% by weight or more and less than 40% by weight, more preferably 1% by weight or more and less than 30% by weight from the viewpoint of fixability. . When the chloroform-insoluble content is in the above range, the toner has sufficient fixing strength and excellent fixability.
The method for measuring the insoluble matter in chloroform at 25 ° C. is preferably carried out in the same manner as the method for measuring the insoluble matter in HFIP at 25 ° C.

Furthermore, the polyester resin of the present invention preferably has an acid value of less than 60 mgKOH / g, more preferably less than 40 mgKOH / g, from the viewpoint of maintaining the charge amount of the toner under high temperature and high humidity. Moreover, it is preferable that an acid value is 5.0 mgKOH / g or more. Within the above range, the chargeability is excellent under high temperature and high humidity.
Further, when the polyester resin of the present invention is used for a positively chargeable toner, the acid value is preferably 20 mgKOH / g or less.

In the present invention, the method for measuring the acid value of the polyester resin is as follows.
The acid value refers to the number of mg of potassium hydroxide in the ethanolic potassium hydroxide solution required to neutralize the acidic groups or free fatty acids of the resin contained in 1.0 g of the polyester resin.
The acid value is measured by taking 1.0 g of polyester resin, dissolving it in 50 mL of toluene, preparing a solution to which 1% of phenolphthalein indicator solution is added, stirring with a stirrer for 2 hours or more, and then using a burette. And titrating with a 0.1 mol / L ethanolic potassium hydroxide solution.
The acid value at this time is as follows: Acid value (mgKOH / g) = A × 5.611 × f ÷ Sample collection weight (g)
It is represented by
Here, A is the amount (mL) of a 0.1 mol / L ethanolic potassium hydroxide solution required for titration, and f is a factor of the ethanolic potassium hydroxide solution used.

In the present invention, in order to set the softening point, glass transition temperature, acid value, etc. of the resin within the above-mentioned ranges, it is possible to adjust the type and composition ratio of raw material monomers, the type and amount of catalyst used, or the selection of reaction conditions. It can be done easily.
Further, the polyester resin of the present invention may contain a known additive such as a known additive in the resin and a coloring agent in the electrostatic image developing toner described later, if necessary.

(Method for producing polyester resin for electrostatic image developing toner)
The method for producing a polyester resin for an electrostatic charge image developing toner of the present invention (hereinafter also referred to as “the method for producing a polyester resin for a toner of the present invention” or “the method for producing a polyester resin of the present invention”) has an alkylene terephthalate structure. A step of preparing a polyester resin (a) containing as a structural unit (hereinafter also referred to as “resin preparation step”), the polyester resin (a), a polycondensable monomer (b), and a depolymerization catalyst A step of obtaining a polyester resin (d) by depolymerizing and polycondensing the composition containing (c) (hereinafter, also referred to as “depolymerization-polycondensation step”), and 25 of the polyester resin (d). The 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) insoluble matter at 1 ° C. is 1 to 30% by weight.
The polyester resin produced by the method for producing a polyester resin of the present invention can be suitably used as a binder resin for an electrostatic charge image developing toner.
Moreover, it is preferable that the said polyester resin of this invention is manufactured by the manufacturing method of the polyester resin of this invention.
In the method for producing a polyester resin of the present invention, when it is a recycled polyester resin and is used for an electrostatic charge image developing toner, the initial image quality, low temperature fixability, image quality under high temperature and high humidity, and charging under high temperature and high humidity. A polyester resin for electrostatic charge image developing toner having excellent properties can be easily obtained. Further, in the method for producing a polyester resin of the present invention, the raw material cost can be reduced by using a regenerated polyester resin without complicating the production process, and even when used for an electrostatic charge image developing toner, The total production cost can be made lower than the conventional method while maintaining the toner performance.

The method for producing a polyester resin for toner according to the present invention uses a polyester resin that has been produced once or more as a raw material, and performs polycondensation while decomposing the polyester resin in the presence of a depolymerization catalyst.
By adding a polycondensable monomer (b) and a depolymerization catalyst (c) to the polyester resin (a), a transesterification reaction or a hydrolysis reaction is promoted, and the depolymerization of the polyester resin (a). A carboxylic acid or ester thereof is produced. Further, the depolymerization catalyst (c) also functions as a polycondensation catalyst, and the polycondensation of the polyester resin (a) and the polycondensable monomer (b) proceeds, and is suitable for use in electrostatic image developing toners. A polyester resin (d) that can be used for the above can be obtained.
The HFIP insoluble content of the polyester resin (d) obtained by the method for producing a polyester resin of the present invention is 1 to 30% by weight and 2 to 25% by weight from the viewpoint of compatibility between offset resistance, storage stability and fixability. %, And more preferably 3 to 20% by weight.

Moreover, it is preferable that the weight average molecular weights of the said polyester resin (d) are 1,500-60,000, and it is more preferable that it is 3,000-40,000. When the weight average molecular weight is 1,500 or more, the cohesive strength of the resin does not decrease and the hot offset property is good. Further, when the weight average molecular weight is 60,000 or less, the hot offset property is good and the rise in the minimum fixing temperature can be suppressed.
In addition, the polyester resin (d) may have partial branching or crosslinking depending on selection of the valence of the polycondensable monomer (b).

<Resin preparation process>
The method for producing a polyester resin for an electrostatic charge image developing toner according to the present invention includes a step of preparing a polyester resin (a) containing an alkylene terephthalate structure as a structural unit (resin preparation step).
The polyester resin (a) is not particularly limited as long as at least a polyester resin having an alkylene terephthalate structure as a constituent unit is used, and is preferably a recovered polyester resin, more preferably recovered polyethylene terephthalate. As the recovered polyester resin that can be used in the present invention, those described above can be suitably used.
Moreover, there is no restriction | limiting in particular about the shape of the said polyester resin (a), However, For ease of handling, dispersion | distribution, decomposition | disassembly, etc., it is preferable that it is chip shape, a powder form, or a pellet form, and it is a chip form. Is more preferable.
The polyester resin (a) may contain impurities derived from wastes, for example, but when using a recovered polyester resin recovered from the wastes, for example, a paint film or a laminate film adhered to the product surface In addition, it is preferable that impurities such as various additives contained in the resin, foreign matters mixed at the time of recovery, dirt, etc. adhering to the waste are removed as necessary. The method for removing impurities is not particularly limited and may be performed by a known method.

The HFIP insoluble content of the polyester resin (a) is preferably more than 30% by weight, more preferably 50% by weight or more, and further preferably 75% by weight or more. In general, the HFIP insoluble matter at 25 ° C. of polyalkylene terephthalate such as PET is 50% by weight or more.
The weight average molecular weight of the polyester resin (a) is preferably 6,000 to 60,000, and more preferably 10,000 to 30,000.
The proportion of the alkylene terephthalate structure in the polyester resin (a) is preferably 50% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more.
The glass transition point of the polyester resin (a) is preferably 50 to 75 ° C, and more preferably 55 to 70 ° C.
The HFIP insoluble matter control of the polyester resin (d) adjusts the reaction conditions such as the type and ratio of the polycondensable monomer (b) and the depolymerization catalyst (c), the reaction time, the degree of pressure reduction, and the reaction temperature. Thus, it can be carried out by decreasing the high molecular weight.

<Depolymerization-polycondensation step>
The method for producing a polyester resin for an electrostatic charge image developing toner of the present invention comprises depolymerizing and polymerizing a composition comprising the polyester resin (a), a polycondensable monomer (b), and a depolymerization catalyst (c). It includes a step of obtaining a polyester resin (d) by condensation (depolymerization-polycondensation step).
As the polycondensable monomer (b), the above-mentioned polycondensable monomer can be suitably used, and even if the polycondensable monomer is used alone, two or more kinds can be used. May be used in combination.
The polycondensable monomer (b) preferably uses a polyvalent carboxylic acid and a polyhydric alcohol in combination, and the number of moles Cm of the carbonyl group in the polyvalent carboxylic acid and the number of moles Hm of the hydroxy group in the polyhydric alcohol. It is more preferable to use together so that the ratio of Cm: Hm = 0.9: 1.1 to 1.1: 0.9.
The polyvalent carboxylic acid used as the polycondensable monomer (b) is preferably a divalent or trivalent carboxylic acid, more preferably a divalent carboxylic acid, and a divalent fat. More preferred are group carboxylic acids. Moreover, it is preferable that carbon number of polyhydric carboxylic acid is 2-20, it is more preferable that it is 2-12, and it is further more preferable that it is 2-10.
The polyhydric alcohol used as the polycondensable monomer (b) is preferably a diol, and more preferably an aliphatic diol or an alkylene oxide adduct of bisphenols. Moreover, it is preferable that carbon number of a polyhydric alcohol is 2-30, and it is more preferable that it is 2-24.
The amount of the polyester resin (a) used is preferably 1.0 to 600.0 parts by weight, and 3.0 to 500.0 parts by weight with respect to 100 parts by weight of the polycondensable monomer (b). Part is more preferable, and 5.0 to 200 parts by weight is further preferable. Within the above range, cost is excellent and reaction control is easy.

As the depolymerization catalyst (c), the above-described depolymerization catalyst can be suitably used, and the depolymerization catalyst may be used alone or in combination of two or more.
In addition, as the depolymerization catalyst (c), a depolymerization catalyst and a catalyst that also functions as a normal polycondensation catalyst may be used in combination, but a depolymerization catalyst having catalytic ability for both depolymerization and polycondensation is used. It is preferable to use it.
The depolymerization catalyst (c) is preferably a metal catalyst, and is a titanium catalyst, a hafnium catalyst, or a rare earth catalyst from the viewpoint of depolymerization and polycondensation at low energy (low temperature) and environmental load. Is more preferable, and a rare earth catalyst is more preferable.
The rare earth catalyst is preferably a rare earth catalyst having a rare earth element selected from the group consisting of Y, Sc, Yb and Sm as its constituent component, more preferably a scandium catalyst.
In addition, the rare earth catalyst is a rare earth metal triflate (rare earth metal trifluoromethanesulfonate), rare earth metal trifurylimide (rare earth metal bis (trifluoromethanesulfonyl) imide), or rare earth metal, from the viewpoint of achieving polycondensation at a low temperature. Alkyl sulfate is preferable, and rare earth metal triflate or rare earth metal trifurylimide is more preferable.
The amount of the depolymerization catalyst (c) used is preferably 0.01 to 5.0 parts by weight, and 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the polyester resin (a). Preferably there is. It is excellent in the efficiency which transesterifies and / or hydrolyzes a polyester resin (a) as it is the said range, and physical property control of the obtained polyester resin (d) is easy.

The depolymerization reaction and polycondensation reaction in the depolymerization-polycondensation step can be carried out by methods such as bulk polymerization, solution polymerization, and interfacial polymerization, and bulk polymerization is preferably used. Moreover, although reaction is possible under atmospheric pressure, general conditions, such as pressure reduction and nitrogen stream, can be widely used.
The depolymerization reaction and polycondensation reaction are preferably performed at a temperature lower than the temperature in the conventional depolymerization reaction and polycondensation reaction, the reaction temperature is more preferably 70 to 200 ° C, and 80 to 180 ° C. More preferably it is. Within the above range, the solubility of the monomer and the catalytic activity are excellent, the reactivity is sufficient, the process is a low energy process, and coloring of the resin due to high temperature can be suppressed.

The depolymerization reaction and polycondensation reaction in the depolymerization-polycondensation step may be performed using an organic solvent.
Specific examples of organic solvents that can be used in the present invention include hydrocarbon solvents such as toluene, xylene, mesitylene, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane, p. -Halogen solvents such as chlorotoluene, ketone solvents such as 3-hexanone, acetophenone, benzophenone, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, dibenzyl ether, benzylphenyl Ether solvents such as ether, methoxynaphthalene and tetrahydrofuran, thioether solvents such as phenyl sulfide and thioanisole, ethyl acetate, butyl acetate, pentyl acetate, methyl benzoate, methyl phthalate, ethyl phthalate, Ester solvents such as acid cellosolve, diphenyl ether, or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether, 3-phenoxytoluene, 4-bromophenyl ether, 4-chlorophenyl ether, 4-bromodiphenyl ether, Halogen-substituted diphenyl ether such as 4-methyl-4'-bromodiphenyl ether, 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, alkoxy-substituted diphenyl ether such as 4-methyl-4'-methoxydiphenyl ether, or dibenzofuran Examples thereof include diphenyl ether solvents such as cyclic diphenyl ether such as xanthene, and these may be used as a mixture.

  Furthermore, dehydration and demonomer may be added in the depolymerization reaction and polycondensation reaction. Specific examples of the dehydration and demonomer include, for example, molecular sieves such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, alumina, silica gel, calcium chloride, calcium sulfate, diphosphorus pentoxide, concentrated Examples include sulfuric acid, magnesium perchlorate, barium oxide, calcium oxide, potassium hydroxide, sodium hydroxide, metal hydrides such as calcium hydride, sodium hydride, lithium aluminum hydride, or alkali metals such as sodium. It is done. Of these, molecular sieves are preferable because of easy handling and regeneration.

In the depolymerization-polycondensation step, it is preferable to carry out a depolymerization reaction and a polycondensation reaction in one-pot, that is, in the same reaction vessel or reaction vessel.
The addition timing of the polyester resin (a), the polycondensable monomer (b), the depolymerization catalyst (c), and other additives is not particularly limited, and an arbitrary amount is added at an arbitrary timing. Thus, it is sufficient that the polyester resin (d) is finally obtained. For example, the polyester resin (a) may be preliminarily mixed in the polycondensable monomer (b), and includes a polycondensable monomer (b) and a depolymerization catalyst (c). It may be added during the polycondensation reaction. Further, for example, the polycondensable monomer (b) may be added after the depolymerization reaction has proceeded to some extent with the composition containing the polyester resin (a) and the depolymerization catalyst (c).

Furthermore, in the depolymerization reaction and the polycondensation reaction in the depolymerization-polycondensation step, the polymerization may be performed in the presence of a monohydric alcohol and / or water. In the presence of monohydric alcohol and / or water, the polyester resin (a) is decomposed by transesterification, hydrolysis, etc. to produce carboxylic acid and / or its alkyl ester, It can be polycondensed with the condensable monomer (b).
Although there is no restriction | limiting in particular as monohydric alcohol, It is preferable that it is C1-C8 monohydric alcohol. Further, as the monohydric alcohol, for example, it may be a monohydric alcohol generated in the reaction system when a polyvalent carboxylic acid ester is used as the polycondensable monomer (b), and different from that. A monohydric alcohol may be added separately.
The amount of the monovalent alcohol and / or water is preferably 10.0 to 100.0 parts by weight with respect to 100 parts by weight of the polyester resin (a), and 15.0 to 80.0 parts by weight. More preferably, it is a part. It is excellent in the efficiency which transesterifies and / or hydrolyzes a polyester resin (a) as it is the said range, and the physical property control of the obtained polyester resin (d) is easy.
Further, for example, when the polyester resin (a) is recovered polyethylene terephthalate, by performing depolymerization and polycondensation while removing ethylene glycol generated by depolymerization of the added polyester resin (a) from the reaction system, A polyester resin (d) which does not contain a monomer unit derived from ethylene glycol or has a small amount thereof can be suitably obtained. Examples of the method for removing ethylene glycol from the reaction system include a method for azeotropic distillation with water and a method for distilling ethylene glycol from the reaction system under reduced pressure.

In the depolymerization-polycondensation step, a rosin resin may be added for adjusting the viscosity. Preferred examples of the rosin resin include gum rosin, hydrogenated rosin, rosin ester and the like.
The addition amount of the rosin resin is preferably 1 to 80 parts by weight, and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the polyester resin (a).

  Moreover, in each process in the manufacturing method of the polyester resin of this invention, you may add well-known additives, such as a well-known additive in resin and the coloring agent in the below-mentioned electrostatic charge image developing toner, as needed.

(Resin particle dispersion and production method thereof)
The method for producing the resin particle dispersion of the present invention is not particularly limited as long as the polyester resin of the present invention or the polyester resin produced by the method of producing the polyester resin of the present invention is used. Can be manufactured.
Further, the resin particle dispersion of the present invention can be suitably used as a resin particle dispersion for an electrostatic charge image developing toner.
In the present invention, the dispersion medium of the resin particle dispersion is preferably an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

Examples of the method for producing the resin particle dispersion of the present invention include a method including a dispersion step in which a polyester resin-containing material is dispersed in an aqueous medium to obtain a resin particle dispersion.
In the dispersion step, it is preferable to carry out dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.
Examples of the surfactant that can be used in the present invention include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents: Nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based, and acids having surface-active effects. Among these, it is preferable to use an acid having a surface active effect. Surfactant may be used individually by 1 type and may use 2 or more types together.
Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol. Sodium 6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, Examples include sodium caprylate, sodium caproate, potassium stearate, calcium oleate and the like.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Nonionic surfactants include, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene. Examples include oxide esters and sorbitan esters.

The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons.
Examples of acids having a surface-active effect include alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acids, alkyl disulfonic acids, alkylphenol sulfonic acids, alkyl naphthalene sulfonic acids, and alkyls. Higher fatty acid sulfates such as tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfate, dibutyl phenyl phenol sulfate dodecyl sulfate, higher Alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkyl Sulfuric acid ester, naphthenyl alcohol sulfuric acid, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfuric acid, naphthenic acid, paratoluenesulfonic acid, and these Examples include all salt compounds, and a plurality of them may be combined as necessary. Of these, alkylbenzenesulfonic acid or a salt thereof is preferable.

Further, a polymer dispersant or a stabilizing aid may be added to the resin particle dispersion of the present invention.
Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate.
Further, in order to prevent the Ostwald Ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizing aid. It is also possible.

The method for dispersing and granulating the polyester resin in the aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability of the obtained emulsion, stability, and the like.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer (CMC Publishing)”. As the polar group used for self-emulsification, a carboxyl group, a sulfo group and the like can be used, and a carboxyl group is preferably used.

When an organic solvent is used in the dispersion step, the method for producing a resin particle dispersion of the present invention may include a step of removing at least a part of the organic solvent and a step of forming resin particles.
For example, after emulsifying the binder resin-containing material, it is preferable to solidify as particles by removing a part of the organic solvent. As a specific method of solidification, after the polycondensation resin-containing material is emulsified and dispersed in an aqueous medium, while stirring the solution, an inert gas such as air or nitrogen is fed into the organic solvent at the gas-liquid interface. A method of drying (waste wind drying method), a method of drying while maintaining a reduced pressure and bubbling an inert gas as necessary (a reduced pressure topping method), and further a polycondensation resin-containing material in an aqueous medium There is a method in which an emulsified dispersion liquid emulsified and dispersed or an emulsion liquid containing a polycondensation resin is discharged from the pores in a shower-like manner and dropped into a dish-shaped receiver and dried while repeating this (shower-type solvent removal method). . It is preferable to remove the solvent by selecting or combining these methods as appropriate based on the evaporation rate of the organic solvent to be used, the solubility in water, and the like.

The center diameter (median diameter) of the resin particles in the resin particle dispersion of the present invention is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm, More preferably, it is 1.0 μm.
When the median diameter of the resin particles is 0.05 μm or more, the cohesiveness at the time of particle formation is good, free resin particles are not generated, the viscosity of the system does not increase, and the particle size can be easily controlled. Therefore, it is preferable. When the median diameter of the resin particles is 2.0 μm or less, coarse powder is not generated, the particle size distribution is good, and the release agent such as wax is not liberated, and the releasability at fixing and the offset generation temperature. Is preferable because it does not decrease.
It is also important that not only the center diameter of the resin particles in the resin particle dispersion but also the generation of ultrafine powder or ultracoarse powder, and the ratio of particles of 0.01 μm or less or 5.0 μm or more is 10% or less. It is preferable that it is 5% or less.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

(Electrostatic image developing toner and method for producing the same)
The electrostatic image developing toner of the present invention (also simply referred to as “toner”) is the polyester resin for electrostatic image developing toner of the present invention or the electrostatic image developing toner produced by the method for producing the polyester resin of the present invention. As long as it is an electrostatic charge image developing toner containing a polyester resin, a resin particle dispersion is produced using a polyester resin, even if it is produced by a mechanical production method such as a melt-kneading pulverization method. You may manufacture a toner by what is called a chemical manufacturing method which manufactures a toner from a dispersion liquid.

When the pulverized toner is manufactured by the kneading and pulverization method, it is preferable that the binder resin manufactured as described above is mixed with other toner raw materials in advance by stirring with a Henschel mixer, a super mixer, or the like before melt-kneading. At this time, a combination of the agitator capacity, the rotation speed of the agitator, the agitation time, and the like must be selected.
Next, the agitated product of the binder resin and the other toner raw materials is kneaded in a molten state by a known method. Kneading with a single-screw or multi-screw extruder is preferable because dispersibility is improved. At this time, the number of kneading screw zones of the kneading apparatus, the cylinder temperature, the kneading speed, etc. must all be set to appropriate values and controlled. Among the control factors at the time of kneading, the number of rotations of the kneader, the number of kneading screw zones, and the cylinder temperature have a particularly great influence on the kneading state. In general, the number of revolutions is preferably 300 to 1,000 rpm, and the kneading screw zone number is kneaded better by using a multi-stage zone such as a two-stage screw rather than a single stage. For example, when the main component of the binder resin is an amorphous polyester resin, the cylinder set temperature is determined from the softening temperature of the amorphous polyester resin, and is preferably −20 to + 100 ° C. than the softening temperature. . The above range is preferable because sufficient kneading and dispersion can be obtained, aggregation hardly occurs, kneading share is applied, and sufficient dispersion and cooling after kneading can be easily performed.
The melt-kneaded kneaded product is sufficiently cooled and then pulverized by a known method such as a mechanical pulverization method such as a ball mill, a sand mill, or a hammer mill, or an airflow pulverization method. If cooling by a conventional method is not sufficient, a cooling or freeze pulverization method can also be selected.

  For the purpose of controlling the particle size distribution of the toner, the pulverized toner may be classified. By eliminating particles having an inappropriate diameter by classification, there is an effect of improving toner fixing property and image quality.

  The method for producing the electrostatic image developing toner of the present invention is not particularly limited, but the electrostatic image produced by the polyester resin for an electrostatic image developing toner of the present invention or the polyester resin of the present invention is produced. A step of obtaining a resin particle dispersion in which a polyester resin for developing toner is dispersed in an aqueous medium (hereinafter also referred to as “resin particle dispersion preparation step”), and the resin particles in a dispersion containing at least the resin particle dispersion It is preferable to include a step of agglomerating particles to obtain aggregated particles (hereinafter also referred to as “aggregation step”) and a step of fusing the aggregated particles by heating (hereinafter also referred to as “fusion step”). .

In the resin particle dispersion preparation step, the resin particle dispersion may be prepared in the same manner as in the method for producing the resin particle dispersion of the present invention described above.
Using a resin particle dispersion, so-called latex, it is possible to produce a toner in which the toner particle diameter and distribution are controlled using an aggregation (association) method. Specifically, the produced latex is mixed with a colorant particle dispersion, a release agent particle dispersion, etc., if necessary, and an aggregating agent is further added to cause heteroaggregation, whereby aggregated particles having a toner diameter are formed. After forming, the aggregated particles are fused by heating to a temperature above the glass transition point or the melting point of the resin particles, washed and dried. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

In the aggregation step, it is possible to mix the resin particle dispersion other than the resin particle dispersion of the present invention and the resin particle dispersion of the present invention, and perform the steps after the aggregation. At that time, after the resin particle dispersion of the present invention is aggregated in advance and the first aggregated particles are formed, the resin particle dispersion of the present invention or another resin particle dispersion is further added to form a second shell on the surface of the first particles. It is also possible to make the particles multi-layered, such as forming a layer. Of course, it is also possible to produce multilayer particles in the reverse order of the above example.
Further, for example, in the aggregation step, the resin particles of the resin particle dispersion of the present invention and the colorant particles of the colorant particle dispersion are previously aggregated, and after the formation of the first aggregated particles, the resin particle dispersion of the present invention is further dispersed. It is also possible to form a second shell layer on the first particle surface by adding a liquid or another resin particle dispersion. In this example, the colorant dispersion is separately adjusted, but naturally, a colorant may be blended in advance with the resin particles.

  After completing the coalesced particle fusion step, desired toner particles are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of the charging property, the washing step is sufficiently substituted and washed with ion-exchanged water. It is preferable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  As the flocculant, a compound having a monovalent or higher charge is preferable, and specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, oxalic acid Examples thereof include aliphatic acids such as sodium, sodium phthalate and potassium salicylate, metal salts of aromatic acids, and metal salts of phenols such as sodium phenoxide.

In consideration of the stability of the aggregated particles, the stability of the coagulant with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the coagulant in terms of performance and use. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.
The amount of these flocculants added varies depending on the valence of the charge, but they are all small, 3% or less for monovalent, 1% or less for divalent, 0 for trivalent. .5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

  In addition, magnetic materials such as metals, alloys such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese, or compounds containing these metals as internal additives, or quaternary ammonium salt compounds as charge control agents, Various commonly used charge control agents such as nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used, but ions that affect aggregation and temporary stability From the viewpoint of strength control and reduction of wastewater contamination, a material that is difficult to dissolve in water is suitable.

Specific examples of the release agent that can be used in the present invention include, for example, various ester waxes, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that show a softening point by heating, oleic acid amide, and erucic acid amide. , Fatty acid amides such as ricinoleic acid amide and stearic acid amide, plant wax such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal wax such as beeswax, montan Examples thereof include mineral and petroleum waxes such as wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, and Fischer-Tropsch wax, and modified products thereof.
These waxes are hardly dissolved in a solvent such as toluene at room temperature or very little even if dissolved.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, heated above the melting point, and have a strong shearing ability and pressure discharge type dispersers. (Gorin homogenizer, manufactured by Gorin Co., Ltd.) can be dispersed in the form of fine particles to prepare a dispersion of particles of 1 μm or less.

The release agent is preferably added in the range of 5 to 25% by weight with respect to the total weight of the toner constituting solids in order to secure the peelability of the fixed image in the oilless fixing system.
The particle size of the obtained release agent particle dispersion can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). In addition, when using a release agent, after the resin particles, colorant particles, and release agent particles are aggregated, it is possible to add resin particle dispersion to adhere the resin particles to the surface of the aggregated particles. From the viewpoint of securing the property.

Examples of the surfactant used for pigment dispersion, release agent dispersion, aggregation, or stabilization thereof can include those described above.
As the dispersing means, a general means such as a rotary shear type homogenizer, a ball mill having a media, a sand mill, a dyno mill or the like can be used.

  Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that have already been widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

The toner of the present invention preferably contains a colorant.
As the colorant, known ones can be used, and may be arbitrarily selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.
Specifically, carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, balkan orange, watch young red, permanent red, brilliantamine 3B, brilliantamine 6B, depon Oil red, pyrazolone red, risor red, rhodamine B rake, lake red C rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalelate, titanium black, etc. Pigment, acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindine Examples include various dyes such as benzene, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, and xanthene. it can.

  Specific examples of the colorant include carbon black, nigrosine dye (CI No. 50415B), aniline blue (CI No. 50405), calco oil blue (CI No. azoic Blue 3), chrome yellow (CI No.14090), Ultramarine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160) ), Malachite green oxalate (CI No. 42000), lamp black (CI No. 77266), rose bengal (CI No. 45435), and mixtures thereof can be preferably used.

The amount of the colorant used is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner. Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.
Moreover, when using a magnetic body as a black coloring agent, unlike other coloring agents, 12 to 240 weight% can be added.
The blending amount of the colorant is a necessary amount for securing the color developability at the time of fixing. Moreover, OHP transparency and color developability can be ensured by setting the center diameter (median diameter) of the colorant particles in the toner to 100 to 330 nm.
The center diameter of the colorant particles can be measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).
As a method for dispersing the colorant, an arbitrary method, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill can be used, and the method is not limited at all. These colorant particles may be added to the mixed solvent at the same time as other particle components, or may be divided and added in multiple stages.

Further, when used as a magnetic toner, magnetic powder may be included. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used.
When the toner is obtained in the aqueous phase in the present invention, it is necessary to pay attention to the water phase transferability of the magnetic material. Preferably, the surface of the magnetic material is modified in advance and subjected to, for example, a hydrophobic treatment. Is preferred.

When the toner of the present invention is produced, an addition polymerization type resin particle dispersion prepared by using conventionally known emulsion polymerization or the like can be used together.
Examples of addition polymerization monomers that can be used for the preparation of addition polymerization resins include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, and vinyl propionate. , Vinyl esters such as vinyl benzoate and vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate , Α-chloromethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other methylene aliphatic carboxylic acid esters; acrylonitrile, methacrylonitrile, and other acrylonitriles; acrylamide, methacrylamide, and other acrylamides Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; methacrylic acid, acrylic acid and cinnamon Examples thereof include vinyl carboxylic acids such as acid and carboxyethyl acrylate. Further, the addition polymerization resin may be a homopolymer or a copolymer of these addition polymerization monomers, and various waxes can be used together.
In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to create a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, dissolve the resin in those solvents, disperse it in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heat or reduce the pressure. A resin particle dispersion can be obtained by evaporating the solvent.

In addition, the toner of the present invention is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, vinyl resin, polyester, silicone and the like. The resin particles can be used by being added to the surface of the toner particles while being sheared in a dry state.
In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

The electrostatic charge image developing toner of the present invention has a volume average particle diameter (D _50v ) of preferably 2 μm or more and 10 μm or less, more preferably 3 μm or more and 8 μm or less, and further preferably 5 μm or more and 7 μm or less.
Further, it is preferable that the toner particle size distribution is narrower. More specifically, the ratio of the 16% diameter (D _16p ) and the 84% diameter (D _84p ) in terms of the smaller number particle size of the toner is expressed as a square root. (GSDp), that is, GSDp represented by the following formula is preferably 1.40 or less, more preferably 1.31 or less, and particularly preferably 1.15 or more and 1.27 or less. preferable.
_{GSDp = {(D 84p) /} (D 16p)} 0.5
If the volume average particle size and GSDp are both in the above ranges, extremely small particles do not exist, and therefore, it is possible to suppress a decrease in developability due to an excessive charge amount of the small particle size toner.

A Coulter counter TA-II type (manufactured by Coulter, Inc.) can be used to measure the average particle size of particles such as resin particles and toner particles. In this case, measurement can be performed using an optimum aperture depending on the particle size level of the particles. The particle diameter of the measured particle represents a volume average particle diameter unless otherwise specified.
When the particle size is about 5 μm or less, the particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).
Further, when the particle size is on the order of nanometers, it can be measured using a BET specific surface area measuring device (Flow Sorb II 2300, manufactured by Shimadzu Corporation).
The volume average primary particle size, number average particle size distribution index, volume average particle size distribution index, and the like of the produced aggregated particles are, for example, Coulter Counter TA-II (Coulter), Multisizer II (Coulter), etc. It can be measured with the measuring instrument. A cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided based on the particle size distribution, and the particle size that becomes 16% cumulative is the volume D _16v , the number D _16P , and the cumulative 50%. The particle diameter to be defined is defined as volume D _50v and number D _50P , and the particle diameter to be accumulated 84% is defined as volume D _84v and number D _84P . Using these, the volume average particle size distribution index (GSDv) can be calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) can be calculated as (D _84P / D _16P ) ^1/2 .

SF1 which is the shape factor of the electrostatic image developing toner is preferably in the range of 110 to 145, more preferably in the range of 120 to 140.
The shape factor SF1 is a shape factor indicating the degree of unevenness on the particle surface, and is calculated by the following equation.

In the formula, ML indicates the maximum length of the particle, and A indicates the projected area of the particle.
As a specific measurement method of SF1, for example, first, an optical microscope image of toner or carrier dispersed on a slide glass is taken into an image analysis apparatus through a video camera, SF1 is calculated for 50 toners or carriers, and an average is calculated. There is a method for obtaining the value.

(Electrostatic image developer)
The electrostatic image developing toner of the present invention can be used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development according to an electrostatic latent image can be applied.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually preferably 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
The electrostatic image developing toner of the present invention and the electrostatic image developer of the present invention can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system).
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for fixing the toner image transferred to the surface of the transfer target. In addition, the electrostatic image developing toner of the present invention or the electrostatic image developer of the present invention is used.
Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.
The latent image forming step is a step of forming an electrostatic latent image on the surface of the latent image holding member.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention.
The transfer step is a step of transferring the toner image onto a transfer target.
The fixing step is a step of forming a copy image by fixing a toner image on a transfer medium such as paper by a heating roller fixing device in which the temperature of the heating roller is set to a constant temperature.
The cleaning step is a step of removing the electrostatic charge image developer remaining on the latent image holding member. In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable.
The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

(Image forming device)
The image forming apparatus of the present invention includes a latent image holding member, charging means for charging the latent image holding member, and exposure for exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member. Developing means for developing the electrostatic latent image with a developer to form a toner image; transfer means for transferring the toner image from the latent image holding member to the transfer member; and transferring the toner image to the surface of the transfer member. In addition, the image forming apparatus has fixing means for fixing the toner image, and uses the electrostatic image developing toner of the present invention or the electrostatic image developer of the present invention.
In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member.

As the latent image holding member and each of the above-described units, the configurations described in the respective steps of the image forming method can be preferably used.
Any of the above-described means can be a known means in the image forming apparatus. Further, the image forming apparatus of the present invention may include means and devices other than the above-described configuration. Further, the image forming apparatus of the present invention may simultaneously perform a plurality of the above-described means.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

<Method for measuring weight average molecular weight and number average molecular weight of resin>
For the measurement of the weight average molecular weight and the number average molecular weight of the resin, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) was flowed at a flow rate of 1.2 ml / min, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml was injected as a sample weight for measurement. In measuring the molecular weight of the sample, the measurement conditions included in the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear are selected with several monodisperse polystyrene standard samples having a molecular weight of the sample. .
In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed.
Further, as the GPC column, TSK-GEL, GMH (manufactured by Tosoh Corporation), etc. satisfying the above conditions were used.

<Method for measuring acid value of resin>
The acid value is measured by taking 1.0 g of polyester resin, dissolving it in 50 mL of toluene, preparing a solution to which 1% of phenolphthalein indicator solution is added, stirring with a stirrer for 2 hours or more, and then using a burette. Titration was carried out with a 0.1 mol / L ethanolic potassium hydroxide solution.
The acid value at this time is as follows: Acid value (mg · KOH / g) = A × 5.611 × f ÷ Sample weight (g)
It is represented by
Here, A is the amount (mL) of a 0.1 mol / L ethanolic potassium hydroxide solution required for titration, and f is a factor of the ethanolic potassium hydroxide solution used.

<Measurement of glass transition temperature of resin>
Using a differential scanning calorimeter (DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.), the sample was heated to 200 ° C., allowed to stand at that temperature for 3 minutes, and then cooled to room temperature at a cooling rate of 10 ° C./min. Measurement was performed at a temperature rate of 10 ° C./min. In the measurement results, the temperature at the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope between the peak rising portion and the peak apex was defined as the glass transition temperature (Tg).

<Measurement method of softening point of resin>
While a 1 cm ³ sample was heated at a heating rate of 6 ° C./min using a Koka flow tester (manufactured by Shimadzu Corporation), a load of 20 kg / cm ² was applied by a plunger, a diameter of 1 mm, and a length A nozzle of 1 mm is pushed out, thereby drawing a plunger descending amount (flow value) -temperature curve, and when the height of the S-shaped curve is h, the temperature corresponding to h / 2 (half of the resin is The temperature that flowed out was taken as the softening point.

<Measurement method of HFIP insoluble matter>
The resin sample was finely pulverized, and 5.0 g of sample powder that passed through a 42 mesh (opening: 355 μm) sieve was collected and placed in a 150 ml container together with 5.0 g of filter aid radiolite (# 700). 100 g of HFIP was poured into the container, placed on a ball mill mount and rotated for 5 hours or more to sufficiently dissolve the sample. On the other hand, a filter paper (No. 2) having a diameter of 7 cm is placed in a pressure filter, radiolite is uniformly precoated thereon, and a small amount of HFIP is added to bring the filter paper into close contact with the filter. Was poured into the filter. Further, it was thoroughly washed with 100 ml of HFIP and poured into a filter so that deposits did not remain on the wall of the container. Thereafter, the upper lid of the filter was closed and filtration was performed. Filtration was performed under a pressure of 4 kg / cm ³ or less, and after HFIP outflow stopped, washing with 100 ml of HFIP was followed by further pressure filtration. These operations were performed in an atmosphere at 25 ° C. After completion of the above operation, the weight of the dried product obtained by placing the filter paper, the residue on the filter paper, and all of the radiolite on an aluminum foil in a vacuum dryer and drying at a temperature of 85 ° C. and a pressure of 100 mmHg for 10 hours. Was measured, and the weight ratio of insoluble matter was calculated.

<Measurement of volume average particle diameter of particles>
A Coulter counter TA-II type (manufactured by Coulter, Inc.) was used for measuring the volume average particle diameter of the particles. In this case, measurement was performed using an optimum aperture depending on the particle size level of the particles. The particle diameter of the measured particle is expressed by a volume average particle diameter.
When the particle size of the particles was about 5 μm or less, the measurement was performed using a laser diffraction / scattering particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
Furthermore, when the particle size was on the order of nanometers, measurement was performed using a BET specific surface area measuring device (Flow Sorb II 2300, manufactured by Shimadzu Corporation).

(Polyester resin example 1)
In a reactor equipped with a stirrer, reflux condenser, separator, thermometer, and nitrogen inlet, 400 parts of a chip obtained by pulverizing waste PET, 200 parts of gum rosin, and 0.3 parts of scandium triflate are placed, and the mixture is mixed. Heated to 180 ° C. and maintained at that temperature for 2 hours. When the waste PET chip began to dissolve, the mixture was stirred. After the above mixture became clear, the reactor was cooled to 150 ° C. and then 180 parts of maleic anhydride was added. When the temperature of the mixture reached the point at which the ring-opening reaction was completed, the mixture was reheated to 180 ° C. and maintained for 3 hours for depolymerization reaction. 200 parts of bisphenol A ethylene oxide 2-mole adduct (that is, a compound in which 1 mol of ethylene oxide is added to each hydroxyl group end of bisphenol A) is added to the reactor, heated to 150 ° C., and maintained at that temperature for 5 hours. Then, polycondensation with dehydration reaction was carried out.
The obtained polyester resin (A1) had an acid value of 39 mgKOH / g, a weight average molecular weight of 11,000, a softening point of 80 ° C., and an HFIP insoluble content of 5.4%.

(Preparation of resin particle dispersion (A1))
While adding 0.5 parts by weight of soft sodium dodecylbenzenesulfonate as a surfactant to 100 parts by weight of the polyester resin (A1), adding 300 parts by weight of ion-exchanged water, heating to 90 ° C. and heating In a round glass flask, the mixture was sufficiently mixed and dispersed with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the pH of the system was further adjusted to 7.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 95 ° C. while stirring with a homogenizer was continued. Furthermore, the reaction was continued at 90 ° C. for 5 hours to obtain a resin particle dispersion. A resin particle dispersion (A1) having a resin particle central diameter of 280 nm and a solid content of 20% was obtained.

(Preparation of release agent particle dispersion (W1))
30 parts by weight of dodecyl sulfate, 852 parts by weight of ion-exchanged water, 188 parts by weight of palmitic acid, 25 parts by weight of pentaerythritol, mixed and heated to 250 ° C., and then poured into the aqueous dodecyl sulfate solution. Emulsified for 5 minutes. Thereafter, the mixture was further emulsified in an ultrasonic bath for 5 minutes, and then the emulsion was maintained at 70 ° C. in a flask while stirring and held for 15 hours. Thus, a release agent particle dispersion (W1) having a release agent particle center diameter of 310 nm, a melting point of 72 ° C., and a solid content of 20% was obtained.

(Preparation of colorant particle dispersion (P1))
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3)
50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight The above ingredients are mixed and dissolved, and a homogenizer (IKA, Ultra Tarrax) is used for 5 minutes. Dispersion was carried out with an ultrasonic bath for 10 minutes to obtain a cyan colorant particle dispersion (P1) having a center diameter of 190 nm and a solid content of 21.5%.

(Toner Example 1)
<Preparation of toner particles>
210 parts by weight of resin particle dispersion (A1) (42 parts by weight of resin)
Colorant particle dispersion (P1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.0 parts by weight)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Tarrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and held at 42 ° C. for 60 minutes, and then 50 parts by weight (21 parts by weight of resin) of the resin particle dispersion (A1) was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 80 ° C. while continuing stirring.
During the temperature rise to 80 ° C., the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did. After completion of the reaction, the reaction mixture was cooled to 55 ° C., kept at this temperature for 3 hours, and then cooled again to room temperature. Further, after filtration and sufficient washing with ion exchange water, solid-liquid separation was performed by Nutsche suction filtration. Then, it was redispersed in 3 liters of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration and then vacuum drying for 12 hours to obtain toner particles (toner 1).
When the particle size of the toner particles was measured with a Coulter counter, the cumulative volume average particle size D ₅₀ was 5.9 μm, and the volume average particle size distribution index GSDv was 1.17. Further, the shape factor SF1 of the toner particles obtained by shape observation with Luzex was 135 potato shapes.

<Preparation of external toner>
This is a reaction product of silica (SiO ₂ ) particles having an average primary particle size of 40 nm subjected to surface hydrophobization treatment with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane. Metatitanic acid compound particles having an average primary particle diameter of 20 nm were added in an amount of 1% by weight and mixed with a Henschel mixer to prepare a cyan externally added toner.

<Creation of carrier>
A methanol solution containing 0.1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of Cu—Zn ferrite particles having a volume average particle diameter of 40 μm, and after coating with a kneader, the methanol was distilled off, and further 120 The silane compound was completely cured by heating at 0 ° C. for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene is added, and perfluorooctylethyl methacrylate-methyl is added using a vacuum reduced pressure kneader. A resin-coated carrier was prepared so that the coating amount of the methacrylate copolymer was 0.5% by weight.

<Production of developer>
5 parts by weight of the external toner prepared as described above was mixed with 100 parts by weight of the obtained resin-coated carrier for 20 minutes using a V blender to prepare an electrostatic charge image developer. This was used as a developer in the following evaluation.

(Evaluation of toner)
Using the above developer, Fuji Xerox Co., Ltd. DocuCentreColor500 remodeling machine uses Fuji Xerox Co., Ltd. J-coated paper as the transfer paper, and the process speed is adjusted to 180 mm / sec to fix the toner. The oilless fixability of the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) tube fixing roll is good, and the fixing temperature (this temperature is caused by image rubbing due to cloth rubbing of the image). (Determination) was 120 ° C. or higher, and the image showed sufficient fixability. Both developability and transferability were good, and there was no image defect and high quality and good initial image quality (◯) were exhibited.

<Evaluation criteria for chargeability under high temperature and high humidity>
The charge amount of the developer under high temperature and high humidity was measured by the following method. That is, the produced developer was allowed to stand for 20 hours in a high-temperature and high-humidity environment at 30 ° C. and 80%, and the amount of reverse polarity toner was measured with a toner charge distribution measuring device (Espert Analyzer: manufactured by Hosokawa Micron Corporation). .
○: The amount of the reverse polarity toner is less than 5%.
Δ: The amount of reverse polarity toner is 5% or more and less than 10%.
X: The amount of reverse polarity toner is 10% or less.
○ was accepted.

<Toner fixability evaluation criteria>
The minimum fixing temperature of the toner was evaluated by the following method.
In the modified DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd., J-coated paper manufactured by Fuji Xerox Co., Ltd. is used as the transfer paper, the process speed is adjusted to 180 mm / sec, and the fixing roll temperature is increased from 90 ° C. to 5 ° C. And the minimum fixing temperature was measured. The evaluation of the minimum fixing temperature of the toner is as follows.
○: The minimum fixing temperature is less than 120 ° C.
(Triangle | delta): The minimum fixing temperature is 120 to 140 degreeC.
X: The minimum fixing temperature is 140 ° C. or higher.
○ was accepted.

<Initial image quality evaluation criteria>
Images were formed under the above conditions, and the initial image quality was evaluated according to the following criteria.
○: Image density, background stain, and fine line reproducibility are extremely good (no image defects).
Δ: Slightly inferior in image density, background stain, and fine line reproducibility, but no problem in use (slight image defects)
X: Inferior in any of image density, background stain, and fine line reproducibility (with image defects).
○ was accepted.

<Image quality evaluation criteria under high temperature and high humidity (Long-term image quality maintenance evaluation under high temperature and high humidity)>
In the above-mentioned modified machine, a continuous print test of 50,000 sheets was performed under conditions of high temperature and high humidity of 30 ° C. and 80%, but the initial good image quality was maintained until the end, and filming on the photoconductor also occurred. None (image quality evaluation under high temperature and high humidity: ○).
In addition, the evaluation criteria are as follows.
○: Good image quality maintenance and no filming on the photoreceptor.
Δ: Image quality maintenance is good in the range of continuous printing of 50,000 sheets. However, slight filming on the photoreceptor is observed.
X: Image quality degradation is observed. In addition, filming on the photoconductor is also observed.

(Polyester resin example 2)
In a reactor equipped with a stirrer, reflux condenser, separator, thermometer and nitrogen inlet, 400 parts of chips obtained by pulverizing waste PET, 200 parts of hydrogenated rosin, 0.3 parts of monobutyltartaric acid, 150 parts of trimellitic anhydride 200 parts of glycerin and 0.3 part of scandium trifluoromethanesulfonate (scandium triflate) were added. About others, the polyester resin was manufactured similarly to Example 1.
The obtained polyester resin (A2) had an acid value of 19 mgKOH / g, a weight average molecular weight of 17,000, a softening point of 95 ° C., and an HFIP insoluble content of 11.9%.

(Preparation of resin particle dispersion (A2))
Resin particle dispersion with a central particle diameter of 260 nm and a solid content of 20%, similar to the preparation of the resin particle dispersion (A1) except that the polyester resin (A2) is used instead of the polyester resin (A1) (A2) was obtained.

(Toner Example 2)
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A2). A developer was prepared in the same manner as in Example 1. The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Polyester resin example 3)
In a reactor equipped with a stirrer, reflux condenser, separator, thermometer and nitrogen inlet, 400 parts of a chip obtained by pulverizing waste PET, 200 parts of rosin ester, 0.3 part of tetrabutoxy titanium, 150 parts of fumaric acid, 100 parts of neopentyl glycol and 100 parts of ethylene glycol were added. About others, the polyester resin was manufactured similarly to Example 1.
The obtained polyester resin (A3) had an acid value of 18 mgKOH / g, a weight average molecular weight of 12,000, a softening point of 105 ° C., and an HFIP insoluble content of 22.6% by weight.

(Preparation of resin particle dispersion (A3))
Resin particle dispersion in which the center diameter of the resin particles is 290 nm and the solid content is 20%, except that the polyester resin (A3) is used instead of the polyester resin (A1). (A3) was obtained.

(Toner Example 3)
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A3). The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Toner Example 4)
Polyester resin (A1) 500 parts by weight Carbon black (# 4000, Mitsubishi Chemical Co., Ltd.) 10 parts by weight is premixed with a Henschel mixer (Mitsui Mine Co., Ltd.), melt-kneaded with a twin screw extruder, and cooled. After coarse pulverization, the mixture was pulverized by a jet mill and further classified using an air classifier to obtain particles having an average particle size of 5.9 μm and GSDv = 1.30. Using these particles, a developer was prepared in the same manner as in Example 1. The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Polyester resin example 4)
In a reactor equipped with a stirrer, reflux condenser, separator, thermometer, and nitrogen inlet, 400 parts of waste PET crushed chips and 0.3 parts of scandium triflate are placed, and the mixture is heated to 175 ° C. And kept at that temperature for 2 hours. When the waste PET chip began to dissolve, the mixture was stirred. After the mixture became clear, the reactor was cooled to 150 ° C. and then 180 parts of fumaric acid was added. When the temperature of the mixture reached the point at which the ring-opening reaction was completed, the mixture was reheated to 180 ° C. and maintained for 3 hours for depolymerization reaction. 200 parts of a 2-mole ethylene oxide 2-mole adduct of bisphenol A was added to the reactor, heated to 150 ° C., maintained at that temperature for 5 hours, and polycondensation with dehydration reaction was carried out.
The obtained polyester resin (A4) had an acid value of 29 mgKOH / g, a weight average molecular weight of 15,000, a softening point of 95 ° C., and an HFIP insoluble content of 9.9%.

(Toner Example 5)
A resin particle dispersion (A4) was prepared in the same manner as the resin particle dispersion (A1) except that the polyester resin (A4) was used instead of the polyester resin (A1).
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A4). The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Polyester resin example 5)
A reactor equipped with a stirrer, reflux condenser, separator, thermometer, and nitrogen inlet is charged with 400 parts of a chip obtained by pulverizing waste PET and 0.2 part of yttrium triflate, and the mixture is heated to 180 ° C. And kept at that temperature for 2 hours. When the waste PET chip began to dissolve, the mixture was stirred. After the mixture became clear, the reactor was cooled to 150 ° C. and then 120 parts of maleic acid was added. When the temperature of the mixture reached the point at which the ring-opening reaction was completed, the mixture was reheated to 180 ° C. and maintained for 3 hours for depolymerization reaction. 200 parts of a 2-mole ethylene oxide 2-mole adduct of bisphenol A was added to the reactor, heated to 150 ° C., maintained at that temperature for 5 hours, and polycondensation with dehydration reaction was carried out.
The obtained polyester resin (A5) had an acid value of 18 mgKOH / g, a weight average molecular weight of 17,000, a softening point of 101 ° C., and an HFIP insoluble content of 15.6%.

(Toner Example 6)
A resin particle dispersion (A5) was prepared in the same manner as the resin particle dispersion (A1) except that the polyester resin (A5) was used instead of the polyester resin (A1).
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A5). The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Polyester resin comparative example 1)
A reactor equipped with a stirrer, reflux condenser, separator, thermometer, and nitrogen inlet was charged with 400 parts of chips from waste PET, and the mixture was heated to 250 ° C. and maintained at that temperature for 2 hours. . When the waste PET chip began to dissolve, the mixture was stirred. After the mixture became clear, the reactor was cooled to 200 ° C. and then 150 parts of terephthalic acid was added. Further, the mixture was reheated to 230 ° C. and maintained for 3 hours to cause a depolymerization reaction. To the reactor, 200 parts of bisphenol A propylene oxide 2-mole adduct was added and heated to 240 ° C., maintained at that temperature for 5 hours, and polycondensation with dehydration reaction was carried out.
The obtained polyester resin (A6) had an acid value of 9 mgKOH / g, a weight average molecular weight of 29,000, a softening point of 80 ° C., and an HFIP insoluble content of 51%.

(Preparation of resin particle dispersion (A6))
Resin particle dispersion in which the center diameter of the resin particles is 490 nm and the solid content is 20%, except that the polyester resin (A6) is used instead of the polyester resin (A1). (A6) was obtained.

(Toner Comparative Example 1)
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A6). The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

(Polyester resin comparative example 2)
A reactor equipped with a stirrer, reflux condenser, separator, thermometer, and nitrogen inlet is charged with 400 parts of a chip obtained by pulverizing waste PET and 0.5 part of p-toluenesulfonic acid, and the mixture was heated to 180 ° C. Heated and maintained at that temperature for 2 hours. When the waste PET chip began to dissolve, the mixture was stirred. After the mixture became clear, the reactor was cooled to 120 ° C. and then 150 parts of maleic anhydride was added. Further, the mixture was reheated to 150 ° C. and maintained for 3 hours for depolymerization reaction. 200 parts of a 2-mole propylene oxide adduct of bisphenol A was added to the reactor, heated to 180 ° C., maintained at that temperature for 5 hours, and polycondensation with dehydration reaction was carried out.
The obtained polyester resin (A7) had an acid value of 19 mgKOH / g, a weight average molecular weight of 9,000, a softening point of 80 ° C., and an HFIP insoluble content of 80%.

(Preparation of resin particle dispersion (A7))
Resin particle dispersion in which the center diameter of the resin particles is 490 nm and the solid content is 20%, as in the preparation of the resin particle dispersion (A1), except that the polyester resin (A7) is used instead of the polyester resin (A1). (A7) was obtained.

(Toner Comparative Example 2)
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion (A1) described in Toner Example 1 was changed to Resin Particle Dispersion (A7). The toner was evaluated in the same manner as in Toner Example 1. The results are shown in Table 1.

  As is apparent from the results in Table 1, the electrostatic image developing toner of the present invention contains initial image quality, low temperature fixability, image quality under high temperature and high humidity, and high temperature and high humidity, despite containing the regenerated polyester resin. Excellent chargeability.

Claims (9)

Obtaining a resin particle dispersion in which a polyester resin for electrostatic charge image developing toner is dispersed in an aqueous medium;
A step of aggregating the resin particles in a dispersion containing at least the resin particle dispersion to obtain aggregated particles; and
Heating and aggregating the aggregated particles,
The polyester resin for electrostatic charge image developing toner is a regenerated polyester resin having an alkylene terephthalate structure as a structural unit, containing a depolymerization catalyst, and 1,1,1,3,3,3-hexafluoro at 25 ° C. A process for producing an electrostatic charge image developing toner , characterized in that the insoluble content of 2-propanol (HFIP) is 1 to 30% by weight. The method for producing an electrostatic charge image developing toner according to claim 1, wherein the depolymerization catalyst is a rare earth catalyst. Preparing a polyester resin (a) containing an alkylene terephthalate structure as a structural unit; and
The polyester resin (a), polycondensable monomer (b), and further comprises the step of obtaining a polyester resin (d) by depolymerization and polycondensation of a composition comprising a depolymerization catalyst (c),
Static according to claim 1 or 2 1,1,1,3,3,3 hexafluoro-2-propanol (HFIP) insoluble matter is 1 to 30 wt% in the 25 ° C. of the polyester resin (d) A method for producing a charge image developing toner. The process for producing an electrostatic charge image developing toner according to claim 3, wherein the depolymerization catalyst (c) is a rare earth catalyst. The method for producing an electrostatic charge image developing toner according to claim 3 or 4, wherein the polycondensable monomer (b) contains an aliphatic dicarboxylic acid. Electrostatic image developing toner produced by the method according to any one of claims 1乃 optimum 5. An electrostatic charge image developing toner according to claim 6 or an electrostatic charge image developer comprising the electrostatic charge image developing toner produced by the production method according to any one of claims 1 to 5 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target; and
Including a fixing step of fixing the toner image transferred to the surface of the transfer target,
As the developer, an electrostatic image developing toner according to claim 6, any one to electrostatic charge image developing toner produced by the method of claims 1 to 5, or, according to claim 7 An image forming method using an electrostatic charge image developer. Latent image carrier,
Charging means for charging the latent image holding member;
Exposure means for exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member;
Developing means for developing the electrostatic latent image with a developer to form a toner image;
Transfer means for transferring the toner image from the latent image holding member to a transfer target; and
Having fixing means for fixing the toner image transferred to the surface of the transfer material;
As the developer, an electrostatic image developing toner according to claim 6, any one to electrostatic charge image developing toner produced by the method of claims 1 to 5, or, according to claim 7 An image forming apparatus using an electrostatic charge image developer.