JP6572701B2 - Polyester resin for toner, method for producing polyester resin for toner, toner material, and toner - Google Patents

Description

  The present invention relates to a polyester resin for toner used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method, etc., a method for producing a polyester resin for toner, a toner material, and It relates to toner.

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

  Further, in the heat roller system, the temperature of the fixing unit has been lowered from the viewpoint of energy saving, and the toner has been strongly required to have a capability of fixing onto a paper at a lower temperature, that is, a low temperature fixability. In addition, as the apparatus becomes more compact, a roller that does not apply a release agent is used, and there is an increasing demand for toner to be peelable from the heat roller, that is, offset resistance. In addition, there is a growing demand for toner particle size reduction and glossiness to improve image quality.

  The binder resin for toner has a great influence on the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyamide resin, and the like are known. In particular, a polyester resin which is excellent in fixing property at a low temperature and has a good performance balance has attracted attention.

  As a polyester resin raw material for toner, an aromatic monomer having advantages such as toughness and charging stability is generally used. However, the aromatic diol component has problems such as the health effects of bisphenol A being pointed out and inferior reactivity. Further, when the bisphenol A component is not used as the diol component, although the health effect is reduced, there are problems that the volatile organic component is increased and the health effect in the use environment is likely to increase, and the charging characteristics are weak.

  Use of a polymerization catalyst is effective for improving the reactivity of the polyester resin. In polyester resins for toners, tin compounds, antimony compounds, titanium compounds, germanium compounds and the like are widely used. However, many metal compounds are pointed out in terms of safety, and there are problems such as easy resin coloring when titanium compounds are used although not pointed out in terms of safety.

  In addition, as the polyester resin for the toner, a resin having both low temperature fixability and high temperature hot offset resistance is desired. To achieve this, a trivalent or higher carboxylic acid component or alcohol component is used. In general, the resin is designed to have a branched or crosslinked structure. However, when many trivalent or more monomers are copolymerized, there is a problem that it is difficult to control the polycondensation reaction.

For such complex problems, for example, the prior art document 1 is composed of an acid component mainly composed of dicarboxylic acid and a diol component mainly composed of aromatic diol and / or aliphatic diol, A polyester resin in which a compound composed of a metal element having a work function of 3.4 eV or more is 300 ppm or less based on the total acid component, has a glass transition temperature of 50 to 75 ° C., a softening temperature of 80 to 170 ° C., an acid value It has been reported that a toner having excellent image stability can be obtained without impairing blocking resistance and non-offset property by using a binder resin for toner characterized in that is 25 mg KOH / g or less.
Prior Document 2 discloses a polyester resin for toner, which is a polyester resin containing a non-volatile monocarboxylic acid component, and has a glass transition temperature of 50 ° C. or higher and a softening temperature of 90 to 170 ° C. It has been proposed that both offset width and blocking resistance can be achieved by using.
Prior Document 3 uses an electrostatic latent image developing toner containing a binder resin, a colorant, and calcium atoms, and containing a trace amount of calcium. It has been proposed to improve the charging characteristics and further improve the reproducibility of fine lines.

However, these resins use a titanium catalyst as a catalyst, and have a drawback that they are difficult to use from the viewpoint of resin coloring for color toners and clear toners. In addition, tin and antimony catalysts are used in combination, and there is a possibility that the resin cannot be produced in the future due to usage restrictions. Furthermore, since the acid value is low, the chargeability tends to be insufficient.
In prior art document 2, tin and antimony catalyst are used together, and there is a possibility that the resin cannot be produced in the future due to usage restrictions. If it manufactures only with a titanium catalyst, there exists a subject from a viewpoint of coloring.
In the prior art document 3, since a resin is produced using only a bisphenol A propylene oxide 2-mole adduct using a tin compound as a catalyst, there are problems in that the catalyst cannot be used and coloring.

JP 1998-10777 JP 62-45622 A JP 2006-227288 A

  In view of such circumstances, the present invention provides a toner having excellent storability, fixability, and chargeability in consideration of environmental conservation and safety. It is an object of the present invention to provide a polyester resin for toner having a certain amount or more.

The gist of the present invention is a polyester resin for toner having an acid value of 30 mgKOH / g or more,
The calcium element content in the polyester Ri 1~2000ppm der, among the metal component 100 wt% contained in the polyester resin for toner, calcium element is not less than 80 wt%, a polyester resin for a toner.

  The polyester resin for toner obtained by the production method of the present invention can provide a toner excellent in storage stability, fixing property and charging property in consideration of environmental protection and safety.

  Hereinafter, the polyester resin for toner of the present invention will be described.

  The polyester resin for toner of the present invention is a polyester resin for toner having an acid value of 30 mgKOH / g or more, and the calcium element content in the polyester is 1 to 2000 ppm.

<Calcium element>
The calcium element (component) contained in the toner polyester resin of the present invention is not particularly limited, but calcium compounds such as calcium acetate, calcium acetate monohydrate, calcium acetate hydrate, calcium formate, calcium lactate, calcium Acrylate, calcium methacrylate, diethoxycalcium, dimethoxycalcium, dimethoxyethoxycalcium, 2-ethylhexylcalcium, calcium silicate, calciumgluconate, calcium trifluoromethanesulfonate, calcium undecylenate, calcium 2,4-pentanedionate complex, etc. Is mentioned. Preferred materials include calcium acetate, calcium acetate monohydrate, calcium formate, calcium lactate, calcium acrylate, calcium methacrylate, diethoxycalcium, calcium 2,4-pentandionate complex, and particularly preferred is calcium acetate. , Calcium acetate monohydrate, calcium acetate hydrate and other catalyst-derived components.
When the amount of the calcium element is 1 ppm or less, the catalytic ability is not exhibited and the polymerization stability becomes low. On the other hand, if the amount of calcium element is more than 2000 ppm, the dispersion of calcium agent is poorly distributed, which makes it difficult to carry out a uniform reaction and impairs the polymerization stability or causes insoluble matter after dissolution of the resin solvent. From the above viewpoint, the amount of calcium element is preferably in the range of 1 to 1800 ppm, more preferably in the range of 1 to 1500 ppm.

The calcium component used in the polyester resin for toner of the present invention is preferably contained in 80 wt% of 100 wt% of the metal (component) contained in the resin. The metal component other than the calcium component contained in the polyester resin for toner of the present invention is preferably a titanium-based compound, specifically, a titanium alkoxide compound having an alkoxy group, titanium carboxylate, titanyl carboxylate, titanyl carboxylate, and The at least 1 titanium compound which consists of a titanium chelate compound is mentioned.
Examples of the titanium alkoxide compound having an alkoxy group include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetrapentoxy titanium, tetraoctoxy titanium and the like.
Titanium carboxylate compounds include titanium formate, titanium acetate, titanium propionate, titanium octoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, titanium isooctanetricarboxylate , Titanium octane tetracarboxylate, titanium decane tetracarboxylate, titanium benzoate, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalenedicarboxylate, titanium 4,4-biphenyldicarboxylate, 2,5 -Titanium dicarboxylate, anthracene dicarboxylate, trimellitic acid titanium, 2,4,6-naphthalene tricarboxylic acid titanium, pyromellitic acid titanium, 2,3,4,6-naphthalene tetracarboxylic acid titanium, etc. It is.
Examples of the titanyl carboxylate compound include titanyl benzoate, titanyl phthalate, titanyl terephthalate, titanyl isophthalate, titanyl 1,3-naphthalenedicarboxylate, titanyl 4,4-biphenyldicarboxylate, titanyl 2,5-toluenedicarboxylate, Anthracene dicarboxylic acid titanyl, trimellitic acid titanyl, 2,4,6-naphthalene tricarboxylic acid titanyl, pyromellitic acid titanyl, 2,3,4,6-naphthalene tetracarboxylic acid titanyl, etc. are mentioned.
The titanyl carboxylate compound is not particularly limited, and examples thereof include alkali metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, barium, etc.) salts for the above-mentioned titanyl carboxylate. .
Among these, tetrabutoxy titanium and tetrapropoxy titanium are preferable from the viewpoints of reactivity and the particle size of the aqueous dispersion. When a titanium chelate compound is used, the ligand is preferably selected from acetylacetone, ethyl acetoacetate, octylene glycol, triethanolamine, lactic acid, and ammonium lactate.
When the amount of the titanium-based material exceeds 20 wt%, coloring becomes strong, which is not preferable.

<Acid value of polyester resin for toner>
The acid value of the polyester resin for toner of the present invention is 30 mgKOH / g or more. When the acid value is less than 30 mgKOH / g, the charge of the toner is hardly improved and the image density tends to become unstable. The upper limit of the acid value of the polyester resin is preferably less than 70 mgKOH / g. If it is less than 70 mgKOH / g, the fall of the storage stability of a toner can be suppressed and generation | occurrence | production of the defect | deletion of an image can be reduced.
In order to make the acid value of the resin 30 mgKOH / g or more, it can be achieved by adjusting the amount of the acid component and the alcohol component at the time of preparation. Specifically, the polyhydric alcohol component is preferably 120 mol parts or less, more preferably 70 mol parts or more and 110 mol parts or less, and 80 mol parts or more and 105 mol parts with respect to 100 mol parts of the polycarboxylic acid. Particularly preferred. If the polyhydric alcohol component is 120 mol parts or more, the acid value tends to be low. On the other hand, when the amount is less than 70 parts by mole, the amount of alcohol in the system is reduced and a uniform polymerization reaction becomes difficult.

<Bisphenol A alkylene oxide adduct>
The bisphenol A alkylene oxide adduct that can be used in the toner polyester resin of the present invention is not particularly limited, and examples thereof include a propylene oxide adduct or an ethylene oxide adduct of bisphenol A, and the addition mole number is preferably 2-6. Specifically, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane , Polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Propylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxy) Eniru) propane.

  The amount of the alkylene oxide adduct of bisphenol A in the polyester resin for toner of the present invention is preferably 80 mol% or less from the viewpoints of reactivity and coloring, with the total acid component being 100 mol%.

<Polyhydric alcohol>
Moreover, aliphatic diol etc. can be used as a polyhydric alcohol in the polyester resin for toners of this invention. Aliphatic diols include ethylene glycol, neopentyl glycol, propylene glycol, dipropylene glycol, butanediol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4- Examples include cyclohexanedimethanol, isosorbide, and erysultane. These can be used alone or in combination of two or more, and can also be used in combination of aliphatic diol and aromatic diol.

  In addition to these diols, trihydric or higher polyhydric alcohols can be used as long as the effects of the present invention are not impaired. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3,5-trihydroxymethyl Examples include benzene and glycerin. These can be used alone or in combination of two or more. Among these, pentaerythritol, trimethylolpropane, and glycerin are particularly preferable.

  The amount of the aliphatic alcohol in the polyester resin for toner of the present invention is preferably in the range of 20 mol% to 120 mol% from the viewpoints of reactivity and coloring, with the total acid component being 100 mol%. From the viewpoint of reactivity and raw material adjustment, the range of 40 to 100 mol% is more preferable.

<Acid component>
The polyester resin for toner of the present invention may contain a trivalent or higher acid component. By including a trivalent or higher acid component, the fixability and hot offset resistance of the obtained toner tend to be good. The amount of the trivalent or higher acid component relative to 100 mol parts of the total acid component is preferably 0.1 to 30 mol%. When the amount is 0.1 mol or more, the fixability and hot offset resistance of the obtained toner are improved, and when the amount is 30 mol% or less, the preservability is improved and the gelation reaction during the polycondensation reaction is improved. This is because it becomes easier to control. The upper limit of the amount of trivalent or higher acid component relative to 100 mol% of all acid components is more preferably 25 mol% or less.

  The trivalent or higher acid component that can be used in the present invention includes trimellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1, Examples include 2,5-hexanetricarboxylic acid or esters or acid anhydrides thereof, pyromellitic acid, 1,2,7,8-octanetetracarboxylic acid, or esters or acid anhydrides thereof. Trimellitic acid or its acid anhydride is preferred because it is easily available industrially.

  As the polyvalent carboxylic acid in the polyester resin for toner of the present invention, terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, or these Aromatic dicarboxylic acid components such as acid anhydrides; aliphatic dicarboxylic acid components such as succinic acid, adipic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, or esters or acid anhydrides thereof Can be used.

  Although the usage-amount of aromatic dicarboxylic acid is not restrict | limited in particular, It is preferable to use 60-90 mol part in 100 mol part of all the acid components. When the amount of aromatic dicarboxylic acid used is 60 mol parts or more, the storage stability of the toner tends to be good and the resin strength tends to be improved. As for the lower limit of the usage-amount of aromatic dicarboxylic acid, 70 mol part or more is more preferable. Terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost.

<Softening temperature>
The softening temperature of the polyester resin for toner of the present invention is preferably 80 to 150 ° C. The fixability and storage stability of the toner obtained when the softening temperature is 80 ° C. or higher tend to be good. In addition, when the softening temperature is 150 ° C. or lower, the fixability of the toner tends to be good, and 140 ° C. or lower is more preferable.

  The polyester resin for toner of the present invention is preferably amorphous in consideration of performance as a binder resin. Therefore, it is important to appropriately adjust the type and ratio of each raw material component.

<Polymerization reaction>
As a method for the polymerization reaction in the polyester resin for toner of the present invention, a monomer mixture containing a polyhydric alcohol, a polyvalent carboxylic acid, and a lower alkyl ester thereof is put into a reaction vessel, and subjected to esterification reaction or transesterification reaction. There is a method in which water or lower alkyl alcohol is distilled off, and then the degree of polymerization is increased while removing glycol by a polycondensation reaction to obtain a resin.

  In the polyester resin for toner of the present invention, the esterification reaction or transesterification temperature is preferably 220 ° C. to 280 ° C. It is because productivity improves by setting it as 220 degreeC or more, and 245 degreeC or more is more preferable. Moreover, when it is 280 degrees C or less, it exists in the tendency which can suppress decomposition | disassembly of resin and the by-product of the volatile matter which becomes a factor of an odor, and 270 degrees C or less is more preferable.

The temperature of the polycondensation reaction is preferably 220 ° C to 250 ° C. This is because when the temperature of the polycondensation reaction is 220 ° C. or higher, the productivity tends to be good. When the temperature is 250 ° C. or lower, the decomposition of the resin can be suppressed, and the productivity can be improved. This is because there is a tendency to suppress the by-product of volatile matter that is a factor.
In the above temperature range, it is preferable to set the polycondensation reaction temperature in consideration of the raw material composition ratio and the like. In the case of a composition ratio with a superior reactivity such as a small amount of bisphenol A alkylene oxide adduct, a large amount of trivalent acid component, and a small number of hydroxyl groups when the number of carboxyl groups is 1, In the case where the composition ratio is low and the reactivity is inferior, it is effective to set the polycondensation reaction temperature high.

<Glass transition temperature>
The glass transition temperature (hereinafter referred to as Tg) of the polyester resin for toner of the present invention is not particularly limited, but is preferably 40 to 75 ° C. When Tg is 45 ° C. or higher, the toner has a tendency to improve blocking resistance, and when Tg is 75 ° C. or lower, the toner has a tendency to improve fixability. As for the lower limit of Tg, 45 degreeC or more is more preferable.

<Toner>
Next, a toner using the polyester resin for toner of the present invention will be described.
The polyester resin for toner of the present invention can be used as a main component of a toner binder or blended with other toner binder resins. When a binder resin other than the polyester resin of the present invention is used as the binder resin, for example, a polyester resin other than the polyester resin of the present invention, a styrene resin, a styrene-acrylic resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy Resin etc. can be mentioned, and can be used individually or in mixture of 2 or more types in the range which does not impair the effect of this invention.

  As a colorant at the time of toner formation, carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, Examples thereof include monoazo, disazo, condensed azo dyes and pigments. These dyes and pigments can be used alone or in admixture of two or more. In the case of a full-color toner, yellow includes benzidine yellow, monoazo dyes, condensed azo dyes, magenta, quinacridone, rhodamine dyes, monoazo dyes, cyan, phthalocyanine blue, and the like.

  The content of the colorant is preferably 2 to 10% by mass in the toner from the viewpoint of the color tone, image density, and thermal characteristics of the toner.

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

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

  Examples of the release agent to be added to the toner include carnauba wax, rice wax, montan wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, and silicone wax. Each can be used alone or in combination of two or more.

  The content of the releasing agent is preferably 0.3 to 15% by mass in the toner because it affects the releasing effect of the toner, storage stability, fixing property, color developing property and the like. The lower limit of the content of the release agent is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Further, the upper limit value of the content of the release agent is more preferably 13% by mass or less, and particularly preferably 10% by mass or less.

  Further, additives such as flow modifiers include fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive fine titanic inorganic powder, styrene resin, Examples thereof include resistance adjusting agents such as acrylic resins, lubricants, and the like, and these are used as an internal additive or an external additive.

  The content of these additives is not particularly limited, but is preferably 0.05 to 10% by mass in the toner. When the content of these additives is 0.05% by mass or more, a toner performance-modifying effect tends to be sufficiently obtained, and when it is 10% by mass or less, the image stability of the toner tends to be good. is there.

Although the Example of this invention is shown below, the embodiment of this invention is not limited to this. In addition, the resin and toner production methods and evaluation methods shown in this example are as follows.
A polycarboxylic acid, a polyhydric alcohol, and a catalyst having the charging composition shown in Table 1 were charged into a reaction vessel equipped with a distillation column. Next, the temperature was raised and heated so that the temperature in the reaction system became 265 ° C., this temperature was maintained, and the esterification reaction was carried out until no water was distilled from the reaction system. Subsequently, the temperature in the reaction system was set to 235 ° C., the pressure in the reaction vessel was reduced, and a condensation reaction was carried out while distilling the polyalcohol from the reaction system.
For the polymerization end point, the condensation reaction was carried out until the torque of the stirring blade reached a value indicating the desired softening temperature. Next, stirring of the reaction apparatus was stopped, the inside of the apparatus was brought to normal pressure, the inside of the apparatus was pressurized with nitrogen, the reaction product was taken out from the lower part of the apparatus, and cooled to 100 ° C. or less to obtain a polyester resin. Polymerization stability was evaluated from the above esterification reaction behavior and condensation reaction behavior, and the evaluation results are shown in Table 1. The resin obtained with good polymerization stability was evaluated for characteristic values and shown in Table 1.

Evaluation method of resin (1) Glass transition temperature (Tg)
The temperature at the intersection of the base line of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured at a heating rate of 5 ° C./min using a differential differential calorimeter DSC-60 manufactured by Shimadzu Corporation Asked.

(2) Softening temperature When measured using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm under a constant temperature increase with a load of 294 N (30 Kgf) and a temperature increase rate of 3 ° C./min, The temperature at which 1/2 of 1.0 g of sample flowed out was determined.

(3) About 0.2 g of acid value sample is precisely weighed in a Erlenmeyer flask with branches (A (g)), 20 ml of benzyl alcohol is added, and the resin is dissolved by heating in a nitrogen atmosphere for 15 minutes with a heater at 230 ° C. did. After allowing to cool to room temperature, 20 ml of chloroform and a few drops of cresol red solution as an indicator were added, and titrated with 0.02 N KOH solution (titrate = B (ml), titer of KOH solution = p). A blank measurement was performed in the same manner (titer amount = C (ml)), and calculation was performed according to the following formula.
Acid value (mgKOH / g) = (BC) × 0.02 × 56.11 × p ÷ A

(4) About 5 g of resin pulverized to a colorability of 3 mm or less was placed in a petri dish CM-A128 and a spectrophotometer CM-5 (manufactured by Konica Minolta) equipped with a petri dish target mask φ30 mm (CM-A203). , SCE method, field of view: 2 °, main light source: C was selected for measurement. The following evaluation criteria were set for color and clear toner from the obtained L and b values.
○ (Good): L ≧ 50, b: −3 to 5
Δ (available): 40 ≦ L <50, b: 5-25
X (Inferior): L <40, b> 25

(5) Storage stable resin 1:93 parts by mass, 3 parts by mass of quinacridone pigment (E02 manufactured by Clariant) as a colorant, and 1 part by mass of negatively chargeable charge control agent LR-147 (manufactured by Nihon Cartrit), carnauba 3 parts by weight of wax (manufactured by Toyo Petrolide Co., Ltd.) is mixed with powder, melt-kneaded using a twin screw extruder (PCM-29: Ikegai Co., Ltd.) at an external temperature setting of 120 ° C. and a residence time of 1 minute, and coarsely pulverized Thereafter, it was finely pulverized by a jet mill type pulverizer, and a fine powder having an average particle diameter of 5 μm was obtained by a classifier. Using this finely pulverized toner not subjected to external addition, the storage stability was evaluated. The evaluation results are shown in Table 1.
About 5 g of the toner was weighed and put into a sample bottle, which was left in a drier kept at 50 ° C. for 24 hours, and the degree of toner aggregation was evaluated as an index of blocking resistance. The evaluation criteria were as follows.
◎ (Very good): Disperse just by inverting the sample bottle.
○ (Good): Dispersed when the sample bottle is turned upside down and tapped 2-3 times.
Δ (Available): The sample bottle is turned upside down and dispersed by tapping 4 to 5 times.
X (Inferior): The sample bottle is inverted and does not disperse when tapped 5 times.

(6) About 10 mg (9.9 mg or more and less than 10.1 mg) of an environmental pollutant sample is precisely weighed, and volatile components are extracted from the sample by heating and extraction at 130 ° C and 160 ° C for 10 minutes in a heat desorption device, and then in a cooling module Once trapped (concentrated), then rapidly heated and subjected to GC-MS.
Equipment: GC / MS 6890N / 5975 made by Agilent Technology, heat desorption introduction system made by GERSTEL TDS A / TDS 2 / CIS 4
Sample heating temperature:
130 ° C (normal): 50 ° C (0.5min) → 50 ° C / min → 130 ° C (10min)
160 ℃: 50 ℃ (0.5min) → 50 ℃ / min → 160 ℃ (10min)
Cryofocus and rapid heating conditions
130 ℃ (normal): -30 ℃ (0.5min) → 12 ℃ / sec → 130 ℃ (10min)
160 ℃: -30 ℃ (0.5min) → 12 ℃ / sec → 180 ℃ (10min)
The interface
130 ° C (normal): 130 ° C
160 ℃: 180 ℃
Carrier gas: He
Desorption Mode Splitless <GC condition>
Column: UA-5 manufactured by FRONTER LAB (30min × 0.25mmI.D. Film thickness 0.25μm)
Column temperature: 35 ℃ (3min) → 10 ℃ / min → 330 ℃ (7min)
Carrier gas: He (flow rate: 1.0ml / min)
Inlet mode: Solvent vent (bent flow rate: 50ml / min, flexible bent line flow rate: 30min/min@0.02min)
Transfer line temperature: 280 ° C
<MS conditions>
Ionization method EI
Ionization voltage 70V
Ionization current 300μA
Scan range 29-550amu
<Quantitative method>
In the chromatogram of each sample, for the components detected during the peak elution time of n-hexane and n-hexadecane, the total peak area of each component excluding ethylene glycol (EG) was determined as the toluene solution (1000 ppm, GC / The concentration in terms of toluene was calculated from the measurement result (peak area) of the injection amount (1 μl) under MS conditions. For EG, the concentration of EG peak area was calculated from the measurement result (peak area) of the EG solution (1000 ppm, injection amount 1 μl under the above GC / MS conditions). The concentration of the total area of each component excluding EG and the sum of the concentrations of EG were defined as the amount of volatile components. The amount of volatile components contained in the toner was evaluated by the method described above, and the environmental contamination was evaluated according to the following evaluation criteria.
○ (Good): Volatile component amount is less than 300ppm
X (Inferior): Volatile component amount is 300 ppm or more

(7) Hot offset resistant resin 1: 92.5 parts by mass, 3 parts by mass of quinacridone pigment (E02 made by Clariant) as a colorant and 1 part by mass of a negative charge control agent LR-147 (made by Nippon Carlit) Parts, 3 parts by weight of carnauba wax (Toyo Petrolide Co., Ltd.), 0.5 parts by weight of polyglycidyl methacrylate (softening temperature: 139 ° C., P-1900 manufactured by Mitsubishi Rayon Co., Ltd.) are mixed with powder, and a twin screw extruder (PCM- 29: Ikegai Co., Ltd.) was used to set the external temperature: 120 ° C., and the residence time was 1 minute. Offset resistance is a rotational rheometer (TA Instruments, AR-2000ex, geometry: 25 mmφ parallel plate, GAP: 1 mm, frequency: 1 Hz, strain: 0.01, measurement temperature: 80 to 240 ° C. (3 ° C. The temperature was evaluated from the G ′ of the toner at 200 ° C. obtained by
○ (Good): G ′ is 800 Pa or more × (Inferior): G ′ is less than 800 Pa

About the Example and comparative example which were described in Table 1, the material described below was used.
BPP: polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane BPE: polyoxyethylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane

  From the results of Examples 1 to 8, the polyester resin having an acid value of 30 mgKOH / g or more and a calcium element content of 1 to 2000 ppm is excellent in colorability, has a small amount of volatile organic components, and has polymerization stability. It was confirmed that the storage stability, coloring property, offset resistance and the like were also excellent. On the other hand, from the result of Comparative Example 1, it was confirmed that when the acid value was 30 mgKOH / g, the environmental pollution property and the hot offset resistance were poor.

Claims (5)

Acid value is a polyester resin for a toner of the above 30 mgKOH / g, calcium element content of the polyester is Ri 1~2000ppm der, among the metal component 100 wt% contained in the polyester resin for toner, the calcium element A polyester resin for toner that is 80 wt% or more . The polyester resin for toner according to claim 1 , wherein the amount of the aliphatic alcohol is in the range of 20 mol% to 120 mol% when the total acid components are 100 mol%.
The method for producing a resin according to claim 1, wherein the polymerization is performed using a calcium compound as a polymerization catalyst. A method for producing a toner material, comprising mixing and / or reacting the polyester resin for toner according to claim 1 or 2 with polyglycidyl methacrylate. A toner comprising 30 to 95 wt% of the polyester resin for toner according to claim 1.