JP2017048389A - Polyester resin for toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin for a toner which has sufficiently reduced TVOC and high productivity and to provide a toner containing the polyester resin for a toner.SOLUTION: There is provided a polyester resin for a toner which is a polycondensation product of a monomer mixture including an acid component and 90 to 150 pts.mol of an alcohol component based on 100 pts.mol of the acid component, wherein the polyester resin contains a constitutional unit derived from an alkylene oxide adduct of bisphenol A and a constitutional unit derived from ethylene glycol and the total amount of volatile organic compounds is 380 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyester resin for toner and a toner.

In a method for obtaining an image by an electrophotographic printing method or an electrostatic charge developing method, usually, an electrostatic charge image formed on a photoreceptor is developed with toner charged in advance by friction and then fixed. When the toner is heated at the time of fixing or the like, a volatile organic compound (VOC: Volatile Organic Compound) may be generated.
The occurrence of VOC may affect the health and environment of the user. Therefore, in recent years, in consideration of health and environmental protection, reduction of the total amount of VOC (TVOC: Total Volatile Organic Compound) is required, and reduction of TVOC (lower TVOC) is also required for toner.

As a method for reducing TVOC of toner, for example, a toner in which particulate allophane is blended with toner particles has been proposed (Patent Document 1).
In Patent Document 1, TVOC is reduced by adsorbing VOC to particulate allophane, but the binder resin contained in the toner is not reduced in TVOC.

  As a method for reducing the TVOC of the binder resin, for example, a method in which volatile components are distilled off after polymerization in the production of the binder resin (Patent Document 2), and a reduced pressure reaction time during the production of the binder resin is increased. There have been proposed a method (Patent Document 3) for removing residual monomers from a resin and a method (Patent Documents 4 and 5) for adjusting the amount of a volatile component (aliphatic diol component) resulting from a polyester resin.

Japanese Patent Laying-Open No. 2015-75743 JP 2012-128127 A JP 2008-40286 A JP 2000-305315 A JP 2000-305316 A

However, the methods described in Patent Documents 2 and 3 are inferior in productivity.
As described in Patent Documents 4 and 5, the method of adjusting the amount of the aliphatic diol component has a limit in reducing the TVOC of the polyester resin.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyester resin for toner having a sufficiently reduced TVOC and a high productivity, and a toner containing the polyester resin for toner.

The present invention has the following aspects.
[1] A polyester resin for toner, which is a polycondensate of a monomer mixture containing an acid component and 90 to 150 mol parts of an alcohol component with respect to 100 mol parts of the acid component, the addition of alkylene oxide of bisphenol A A polyester resin for a toner comprising a structural unit derived from a product and a structural unit derived from ethylene glycol, wherein the total amount of volatile organic compounds is 380 ppm or less.
[2] The polyester resin for toner according to [1], which satisfies at least one of the following conditions (a), (b), and (c).
Condition (a): a polycondensate obtained in the presence of a titanium-based catalyst, wherein the structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.
Condition (b): The structural unit derived from the alkylene oxide adduct of bisphenol A is 30 mol parts or less and the structural unit derived from terephthalic acid is 70 mol parts or less with respect to 100 mol parts of the acid component.
Condition (c): a polycondensate of a monomer mixture in which the ratio of the number of carboxy groups derived from the acid component to the number of hydroxyl groups derived from the alcohol component (hydroxyl group / carboxy group) is 1.09 or less, The structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.
[3] A toner containing the polyester resin for toner according to [1] or [2].

  According to the present invention, it is possible to provide a polyester resin for toner having a sufficiently reduced TVOC and high productivity, and a toner containing the polyester resin for toner.

"Polyester resin for toner"
The polyester resin for toner of the present invention (hereinafter, also simply referred to as “polyester resin”) is a weight of a monomer mixture containing an acid component and 90 to 150 mol parts of an alcohol component with respect to 100 mol parts of the acid component. It is a condensate.
Such a polyester resin is produced using an acid component and at least an alkylene oxide adduct of bisphenol A and ethylene glycol as raw materials as an alcohol component.

<Acid component>
Examples of the acid component include divalent carboxylic acids and trivalent or higher carboxylic acids. Hereinafter, divalent carboxylic acid and trivalent or higher carboxylic acid are collectively referred to as “polyvalent carboxylic acid”.
Examples of the divalent carboxylic acid include isomers of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid (specifically, 1,4-, 1,5-, 1,6-, 1,7-, 2,5 -, 2,6-, 2,7-, 2,8-), and lower alkyl esters thereof; succinic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, adipic acid, furandicarboxylic acid, and These monomethyl, monoethyl, dimethyl, diethyl esters and acid anhydrides thereof; fumaric acid, maleic acid, maleic anhydride, citraconic acid, itaconic acid, tetrahydrophthalic acid, and ester derivatives thereof; acrylic acid, crotonic acid, Examples thereof include methacrylic acid and ester derivatives thereof.
Examples of lower alkyl esters of terephthalic acid and isophthalic acid include dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate.
Among these, as the divalent carboxylic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of excellent storage stability, handling property and cost of the toner, and isophthalic acid is more preferable from the viewpoint of excellent reactivity.
These may be used individually by 1 type and may use 2 or more types together. Moreover, you may use together with the below-mentioned trivalent or more carboxylic acid.

Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, , 2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and acid anhydrides and lower alkyl esters thereof.
Among these, as the trivalent or higher carboxylic acid, trimellitic acid, trimellitic acid anhydride, pyromellitic acid, and pyromellitic acid anhydride are preferable from the viewpoint of excellent handleability and cost.

<Alcohol component>
As the alcohol component, at least an alkylene oxide adduct of bisphenol A and ethylene glycol are used. Hereinafter, the alkylene oxide adduct of bisphenol A, ethylene glycol, and other dihydric or higher alcohols are collectively referred to as “polyhydric alcohol”.
Ethylene glycol corresponds to VOC. Therefore, when only ethylene glycol is used as the alcohol component, the productivity of the polyester resin is excellent, but a polyester resin having a high TVOC is easily obtained.
However, according to the present invention, since the alkylene oxide adduct of bisphenol A is used in combination as the alcohol component, the TVOC of the polyester resin can be reduced.

  Examples of the alkylene oxide adduct of bisphenol A include compounds represented by the following general formula (i).

In formula (i), R ¹ O and R ² O are each an alkylene oxide.
R ¹ and R ² are the same or different and each is an alkylene group having 2 or 3 carbon atoms.
x and y are numbers indicating the average number of added moles of alkylene oxide, and both x and y are 1 or more. Moreover, x + y = 2-6 is preferable and 2-3 is more preferable.

Specific examples of the compound represented by the general formula (i) include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.3)- 2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.3) -2,2- Bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2, 2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2 4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane.
These may be used individually by 1 type and may use 2 or more types together.

  As an alkylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A may be used alone, a propylene oxide adduct of bisphenol A may be used alone, or an ethylene oxide adduct of bisphenol A And a propylene oxide adduct of bisphenol A may be used in combination. In addition, when using the ethylene oxide adduct of bisphenol A independently, it is preferable to use 2 or more types of polyhydric carboxylic acid.

As the alcohol component, an alkylene oxide adduct of bisphenol A and a polyhydric alcohol other than ethylene glycol (other polyhydric alcohols) may be used in combination.
Examples of other polyhydric alcohols include neopentyl glycol, propylene glycol, hexanediol, polyethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, and 1,4-cyclohexanedimethanol. , D-isosorbide, L-isosorbide, isomannide, erythritan, 1,4-dihydroxy-2-butene and other dihydric alcohols; sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, penta Erythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2 , 4-bu Ntorioru, trimethylolpropane, 1,3,5-trihydroxy methyl benzene, and the like trihydric alcohols such as glycerin. Of these, trimethylolpropane and neopentyl glycol are preferred.
These may be used individually by 1 type and may use 2 or more types together.

As a raw material for the polyester resin, in addition to the polyvalent carboxylic acid and the polyhydric alcohol, a monovalent carboxylic acid or a monovalent alcohol may be used in combination.
Examples of monovalent carboxylic acids include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid; aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid; cinnamic acid, Examples thereof include unsaturated carboxylic acids having one or more unsaturated double bonds in the molecule, such as oleic acid, linoleic acid, and linolenic acid.
Examples of the monovalent alcohol include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol; aliphatic alcohols having 30 or less carbon atoms such as oleyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol.

<Method for producing polyester resin>
It does not restrict | limit especially as a manufacturing method of a polyester resin, It can manufacture using the manufacturing method of a well-known polyester resin. For example, a monomer mixture containing an acid component, an alcohol component, and the like is charged into a reaction vessel, heated to a temperature, an esterification reaction or a transesterification reaction is performed, and water or alcohol generated by the reaction is removed. Subsequently, the polycondensation reaction is carried out. At this time, the pressure in the reactor is gradually reduced, and the polycondensation is carried out while distilling off the diol component under a vacuum of 150 mmHg (20 kPa) or less, preferably 15 mmHg (2 kPa) or less. .

  Catalysts used for esterification, transesterification and polycondensation include titanium-based catalysts, dibutyltin oxide, calcium acetate, calcium acetate hydrate, tin acetate, tin disulfide, tin oxide, and 2-ethylhexanetin. Examples include catalysts, zinc acetate, antimony trioxide, and germanium dioxide. Among these, as the catalyst, a titanium-based catalyst is preferable because a polyester resin with reduced TVOC is easily obtained.

Examples of the titanium-based catalyst include titanium alkoxide compounds having an alkoxy group, titanium carboxylates, titanyl carboxylates, titanyl carboxylates, and titanium chelate compounds.
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.
Examples of titanium carboxylate compounds include titanium formate, titanium acetate, titanium propionate, titanium octoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, titanium sebacate, titanium hexanetricarboxylate, and isooctanetricarboxylic acid. Titanium, octanetetracarboxylic acid titanium, decanetetracarboxylic acid titanium, benzoic acid titanium, phthalic acid titanium, terephthalic acid titanium, isophthalic acid titanium, 1,3-naphthalenedicarboxylic acid titanium, 4,4-biphenyldicarboxylic acid titanium, 2, 5-toluene dicarboxylic acid titanium, anthracene dicarboxylic acid titanium, trimellitic acid titanium, 2,4,6-naphthalene tricarboxylic acid titanium, pyromellitic acid titanium, 2,3,4,6-naphthalene tetracarboxylic acid titanium And the like. Of these, tetrabutoxy titanium is preferred.
A titanium-type catalyst may be used individually by 1 type, and may use 2 or more types together.

In addition to the structural unit derived from the alkylene oxide adduct of bisphenol A and the structural unit derived from ethylene glycol, the polyester resin of the present invention has a molar number of alcohol component of 90 to 100 parts by mole. It is a polycondensate of a monomer mixture mixed at a ratio of 150 mole parts (molar ratio of 0.9 to 1.5). As described above, ethylene glycol, which is an essential component in the polyester resin of the present invention, is VOC, but if the number of moles of the alcohol component relative to 100 mole parts of the acid component is 150 mole parts or less, the amount of unreacted ethylene glycol is reduced. This can reduce the TVOC. On the other hand, if the number of moles of the alcohol component relative to 100 mole parts of the acid component is 90 mole parts or more, the polyester resin can be obtained with high productivity.
Considering the physical properties of the resulting polyester resin, it is preferable to combine the acid component and the alcohol component within the above ratio range.
The molar ratio is a molar ratio represented by alcohol component / acid component.

Moreover, it is preferable that the polyester resin of the present invention satisfies at least one of the following conditions (a), (b), and (c).
Condition (a): a polycondensate obtained in the presence of a titanium-based catalyst, wherein the structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.
Condition (b): The structural unit derived from the alkylene oxide adduct of bisphenol A is 30 mol parts or less and the structural unit derived from terephthalic acid is 70 mol parts or less with respect to 100 mol parts of the acid component.
Condition (c): a polycondensate of a monomer mixture in which the ratio of the number of carboxy groups derived from the acid component to the number of hydroxyl groups derived from the alcohol component (hydroxyl group / carboxy group) is 1.09 or less, The structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.

Since the alkylene oxide adduct of bisphenol A is a component that does not easily volatilize, the more the amount used, that is, the polyester resin contains more constituent units derived from the alkylene oxide adduct of bisphenol A, in order to reduce TVOC. It is advantageous. However, since the alkylene oxide adduct of bisphenol A has low reactivity, it may be disadvantageous in the production of the polyester resin, and there is a concern about the influence on the health of the human body.
In any of the conditions (a), (b), and (c), the amount of the alkylene oxide adduct of bisphenol A used is not more than a predetermined amount, and ethylene glycol that is a component corresponding to VOC is in an unreacted state. Each requirement for making it difficult to remain in the polyester resin is shown. If the polyester resin satisfies at least one of the above conditions (a), (b), and (c), TVOC is further reduced despite the small number of components derived from the alkylene oxide adduct of bisphenol A (specifically, In this case, the TVOC can be 380 ppm or less) and the health of the human body is sufficiently taken into consideration.

(Condition (a))
Condition (a) is a polycondensate obtained in the presence of a titanium-based catalyst, and the structural unit derived from an alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.
Under the condition (a), the polycondensate is obtained by polycondensing a monomer mixture in the presence of a titanium-based catalyst. When a titanium-based catalyst is used during polycondensation, the reactivity between the acid component and the alcohol component is improved. As a result, even if a large amount of ethylene glycol is used as the alcohol component, ethylene glycol reacts sufficiently with the polyvalent carboxylic acid, and the proportion of unreacted ethylene glycol decreases, so that TVOC tends to be further lowered.

(Condition (b))
In condition (b), the structural unit derived from the alkylene oxide adduct of bisphenol A is 30 mole parts or less and the structural unit derived from terephthalic acid is 70 mole parts or less with respect to 100 mole parts of the acid component.
Among polyvalent carboxylic acids, terephthalic acid is inferior in reactivity. By setting the amount of terephthalic acid as the polyvalent carboxylic acid to 70 mol parts or less, the reactivity can be increased and the TVOC of the polyester resin can be reduced. As the polyvalent carboxylic acid other than terephthalic acid, isophthalic acid, trimellitic acid and its anhydride are preferable in consideration of reactivity and performance.

(Condition (c))
Condition (c) is a polycondensate of a monomer mixture in which the ratio of the number of carboxy groups derived from the acid component to the number of hydroxyl groups derived from the alcohol component (hydroxyl group / carboxy group) is 1.09 or less. The structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.
As described above, since ethylene glycol is a component corresponding to VOC, it is important to make it difficult for unreacted ethylene glycol to remain in order to reduce TVOC. If the polyester resin is a polycondensate of a monomer mixture containing an acid component and an alcohol component such that the ratio (hydroxyl group / carboxy group) is 1.09 or less, the surplus of hydroxyl groups is reduced. Unreacted ethylene glycol can be made difficult to remain, and TVOC can be reduced.

The polymerization temperature in the esterification reaction, transesterification reaction or polycondensation reaction is preferably 180 to 280 ° C. If the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and if it is 280 ° C. or lower, the polyester resin tends to be decomposed and volatile by-products that cause odors can be suppressed. Reduce more. The lower limit of the polymerization temperature is more preferably 200 ° C. or higher, and the upper limit is more preferably 270 ° C. or lower.
In addition, the shorter the time of the polycondensation step (the total of the polycondensation reaction time and the take-out time), the more likely the decomposition of the polyester resin and the by-product of volatile components that cause odors are suppressed.

The polycondensation may be performed in the presence of a release agent (wax). By performing polycondensation in the presence of a release agent, the fixability and wax dispersibility of the toner tend to be further improved.
As a mold release agent, the thing similar to what is mentioned as another component mentioned later is mentioned, Any 1 type may be used independently and 2 or more types may be used together.
The amount of the release agent added during the polycondensation can be appropriately set within a range not impairing the effects of the present invention.
However, from the viewpoint of reducing TVOC, it is more advantageous to perform polycondensation without using a release agent.

<Physical properties of polyester resin>
The TVOC of the polyester resin is 380 ppm or less, preferably 330 ppm or less, and more preferably 300 ppm or less. A binder resin such as a polyester resin is usually contained in the toner by about 90% by mass or less. If the TVOC of the polyester resin is 380 ppm or less, the TVOC of the toner containing the polyester resin is approximately 300 ppm or less, so that a toner having a sufficiently reduced TVOC can be obtained.
The TVOC of the polyester resin can be measured using a gas chromatograph mass spectrometer (GC-MS).

The glass transition temperature (Tg) of the polyester resin is preferably 40 to 85 ° C, and more preferably 45 to 75 ° C. If the glass transition temperature is 40 ° C. or higher, the storage stability of the toner is improved, and if it is 85 ° C. or lower, the low-temperature fixability of the toner is more excellent.
The glass transition temperature of the polyester resin is determined as follows. That is, using a differential differential calorimeter, the temperature at the intersection of the low-temperature baseline of the chart when measured at a heating rate of 5 ° C./min and the tangent to the endothermic curve near the glass transition temperature is obtained. Is Tg.

The softening temperature (T4) of the polyester resin is preferably 80 to 170 ° C, more preferably 85 to 160 ° C. When the softening temperature is 80 ° C. or higher, the hot offset resistance is good. On the other hand, when the softening temperature is 170 ° C. or lower, the low-temperature fixability is good.
The softening temperature of the polyester resin can be measured using a flow tester.

The acid value of the polyester resin is preferably from 0.1 to 60 mgKOH / g, more preferably from 0.1 to 50 mgKOH / g, still more preferably from 1 mgKOH / g to less than 30 mgKOH / g. If the acid value is 0.1 mgKOH / g or more, the productivity of the polyester resin tends to be improved, and if it is 60 mgKOH / g or less, the moisture resistance of the polyester resin is improved, and the toner is affected by the use environment. It becomes difficult.
The acid value of the polyester resin is the amount of potassium hydroxide required to neutralize 1 g of the sample, expressed in milligrams.

<Effect>
The polyester resin of the present invention is a polycondensate of a monomer mixture containing a specific amount of an acid component and an alcohol component, and uses an alkylene oxide adduct of bisphenol A and ethylene glycol as the monomer component (polyhydric alcohol). The TVOC was manufactured to be 380 ppm or less. Therefore, the polyester resin of the present invention has a sufficiently reduced TVOC.
Moreover, if the polyester resin of the present invention is used, it is necessary to distill off the volatile components after polymerization in the production of the resin as in the past, or to remove the residual monomer by extending the reduced pressure reaction time during the production of the resin. In addition, since highly reactive ethylene glycol is used, productivity is high.
In particular, if the polyester resin satisfies at least one of the conditions (a), (b), and (c), sufficient consideration is given to the health of the human body.
The polyester resin of the present invention is suitable as a binder resin for toner, and if the polyester resin of the present invention is used, a toner having a sufficiently reduced TVOC can be obtained.

[toner]
The toner of the present invention contains the above-described polyester resin for toner of the present invention.
The content of the polyester resin of the present invention is preferably 5 to 90% by mass in 100% by mass of the toner.

  In addition, the toner of the present invention may contain a compound such as a colorant, a charge control agent, a release agent, a flow modifier, a magnetic material, and a resin (other binder resin) other than the polyester resin of the present invention as necessary. May be included.

Colorants include carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo, disazo, Examples include condensed azo dyes or pigments. These may be used individually by 1 type and may use 2 or more types together.
When the toner is used as a color toner, examples of yellow colorants include benzidine yellow, monoazo dyes, and condensed azo dyes, and examples of magenta colorants include quinacridone, rhodamine dyes, and monoazo dyes. Examples of cyan colorants include phthalocyanine blue.
The content of the colorant is not particularly limited, but is preferably 2 to 10% by mass in 100% by mass of the toner from the viewpoint of excellent toner color tone, image density, and thermal characteristics.

Charge control agents include quaternary ammonium salts and positively chargeable charge control agents such as basic or electron donating organic substances; metal chelates, metal-containing dyes, acidic or electron withdrawing organic substances, etc. Examples include a negatively chargeable charge control agent.
When the toner is used as a color toner, a charge control agent that is colorless or light in color and has less color disturbance to the toner is suitable. Examples of such a charge control agent include salicylic acid or alkylsalicylic acid chromium, zinc, Examples thereof include metal salts with aluminum and the like, metal complexes, amide compounds, phenol compounds, naphthol compounds and the like. 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 100% by mass of the toner. If 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 if it is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. It tends to be.

As the mold release agent, carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, taking into account the toner releasability, storage stability, fixability, color developability, etc. Fatty acid amides, silicone waxes and the like can be appropriately selected and used. These may be used individually by 1 type and may use 2 or more types together.
The melting point of the release agent may be appropriately determined in consideration of the toner performance.
The content of the release agent is not particularly limited, but is preferably 0.3 to 15% by mass in 100% by mass of the toner because it affects the toner performance. 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 12% by mass or less.

Additives such as flow modifiers include flow improvers such as fine powdered silica, alumina, titania; inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, conductive titania; styrene resin, acrylic Resistance control agents such as resins; lubricants and the like are used, and these are used as an internal additive or an external additive.
The content of these additives is preferably 0.05 to 10% by mass in 100% by mass of the toner. If the content of these additives is 0.05% by mass or more, the effect of improving the performance of the toner tends to be sufficiently obtained, and if it is 10% by mass or less, the image stability of the toner tends to be good. is there.

  Examples of other binder resins include polyester resins (excluding the polyester resin of the present invention), styrene resins, cyclic olefin resins, and epoxy resins. These may be used individually by 1 type and may use 2 or more types together.

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

When the toner of the present invention is used as a magnetic one-component developer, the toner contains a magnetic substance. Examples of magnetic materials include ferromagnetic alloys containing ferrite, magnetite, iron, cobalt, nickel, etc .; alloys that do not contain compounds or ferromagnetic elements, but become ferromagnetic when appropriately heat-treated (for example, manganese) -So-called Heusler alloy, chromium dioxide, etc. containing manganese and copper such as copper-aluminum and manganese-copper-tin.
The content of the magnetic material is not particularly limited, but is preferably 3 to 70% by mass in 100 masses of the toner because it greatly affects the pulverizability of the toner. If the content of the magnetic material is 3% by mass or more, the charge amount of the toner tends to be a sufficient level, and if it is 70% by mass or less, the fixability and grindability of the toner tend to be good. The upper limit of the content of the magnetic material is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

When the toner of the present invention is used as a two-component developer, the toner of the present invention is used in combination with a carrier.
Examples of the carrier include magnetic substances such as iron powder, magnetite powder, and ferrite powder, those having a surface coated with a resin coating, and magnetic carriers. Examples of the coating resin for the resin coating carrier include styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, and mixtures of these resins.
The amount of the carrier used is preferably 500 to 3000 parts by mass with respect to 100 parts by mass of the toner. If the amount of carrier used is 500 parts by mass or more, fog and the like tend not to occur, and if it is 3000 parts by mass or less, the density of the fixed image tends to be sufficient.

  The method for producing the toner of the present invention is not particularly limited, but the polyester resin of the present invention and the above-mentioned compound are mixed, and then melt-kneaded with a twin screw extruder or the like, followed by coarse pulverization, fine pulverization, and classification. A method of producing by performing external addition treatment of inorganic particles and the like as necessary (pulverization method); after dissolving and dispersing the polyester resin and the compound of the present invention in a solvent and granulating in an aqueous medium Removal of the solvent, washing and drying to obtain toner particles, and if necessary, the inorganic particles are externally added and manufactured, or the polyester resin of the present invention is emulsified in water and atomized Examples include a method (chemical method) in which toner particles are aggregated and fused in water together with products, washed and dried to obtain toner particles, and if necessary, inorganic particles are externally added.

  The average particle size of the toner of the present invention is not particularly limited, but is preferably 3 to 15 μm, more preferably 5 to 10 μm. If the average particle size of the toner is 3 μm or more, the productivity tends to be good, and the problem of pneumoconiosis tends not to occur. On the other hand, when the average particle diameter of the toner is 15 μm or less, a high-quality image tends to be stably formed.

  Since the toner of the present invention contains the above-described polyester resin of the present invention, TVOC is sufficiently reduced.

Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the following examples.
The evaluation method of the polyester resin shown in the present example is as follows.

[Measurement / Evaluation]
<Measurement of glass transition temperature (Tg)>
The glass transition temperature of the polyester resin is determined from the intersection of the base line of the chart and the tangent line of the endothermic curve at a heating rate of 5 ° C./min using a differential differential calorimeter (“DSC-60” manufactured by Shimadzu Corporation). It was measured. The measurement sample was 10 mg ± 0.5 mg weighed in an aluminum pan, melted at 100 ° C. above the glass transition temperature for 10 minutes, and then rapidly cooled using dry ice.

<Measurement of softening temperature (T4)>
The softening temperature of the polyester resin was determined by using a flow tester (manufactured by Shimadzu Corporation, “CFT-500D”) with a 1 mmφ × 10 mm nozzle, a load of 294 N, and a uniform heating rate of 3 ° C./min. The temperature when ½ amount in 1.0 g of the sample flowed out was measured, and this was taken as the softening temperature.

<Measurement of acid value>
The acid value of the polyester resin was measured as follows.
About 0.2 g of the measurement sample was precisely weighed in a branch Erlenmeyer flask (a (g)), 20 mL of benzyl alcohol was added, and the measurement sample was dissolved by heating with a heater at 230 ° C. for 15 minutes under a nitrogen atmosphere. After allowing to cool to room temperature, 20 mL of chloroform and a few drops of cresol red solution were added, and titrated with 0.02 N KOH solution (titrate = b (mL), titer of KOH solution = p). Blank measurement was performed in the same manner (titrated amount = c (mL)), and the acid value was calculated according to the following formula.
Acid value (mgKOH / g) = {(bc) × 0.02 × 56.11 × p} / a

<Measurement of TVOC>
The TVOC of the polyester resin was measured as follows.
About 10 mg (9.9 mg or more, less than 10.1 mg) of a measurement sample is precisely weighed, and volatile components are extracted from the measurement sample by heating and extracting at 130 ° C. for 10 minutes in a heat desorption apparatus, and then trapped (concentrated) by a cooling module. did. Next, after rapid heating, the sample was subjected to GC-MS to quantify TVOC. The measurement apparatus, measurement conditions, and quantification method are as follows.

(measuring device)
・ Heat desorption apparatus: manufactured by GUSTER Co., Ltd., “Heat Desorption Introduction System TDS A / TDS 2 / CIS 4”
GC-MS: “GC / MS 6890N / 5975” manufactured by Agilent Technologies, Inc.

(Heat desorption conditions)
Sample heating temperature: 50 ° C. (0.5 min) → 50 ° C./min→130° C. (10 min)
-Cryofocus and rapid heating conditions: -30 ° C (0.5 min)-> 12 ° C / sec-> 130 ° C (10 min)
・ Interface: 130 ℃
・ Carrier gas: Helium ・ Desorbtopn Mode: Splitless

(GC condition)
Column: “UA-5 (30 min × 0.25 mm ID, film thickness 0.25 μm), manufactured by Frontier Laboratories
Column temperature: 35 ° C. (3 min) → 10 ° C./min→330° C. (7 min)
Carrier gas: helium (flow rate 1.0 ml / min)
Inlet mode: Solvent vent (injected at a vent flow rate of 50 ml / min and split vent line flow rate of 30 min / min over 0.02 min.)
・ Transfer line temperature: 280 ℃

(MS conditions)
・ Ionization method: EI
・ Ionization voltage: 70V
・ Ionization current: 300 μA
・ Scan range: 29-550amu

(Quantitative method of TVOC)
In the obtained chromatogram, the total peak area of each component excluding ethylene glycol (EG) was previously prepared for the components detected during the peak elution time of n-hexane and n-hexadecane. From the measurement result (peak area) (1000 ppm, injection amount 1 μl under the above GC conditions and MS conditions), the concentration was calculated as the toluene equivalent concentration.
For EG, the peak area of EG was calculated as the EG concentration from the measurement result (peak area) of a previously prepared EG solution (1000 ppm, injection amount 1 μl under the above GC conditions and MS conditions).
TVOC was defined as the total area density of each component excluding EG and the sum of EG density values.

[Examples 1 to 5, Comparative Examples 1 and 2]
The acid component, the alcohol component, and the polymerization catalyst having the charging composition shown in Table 1 were charged into a reaction vessel equipped with a distillation tower. In addition, the quantity of a polymerization catalyst is the quantity (ppm) with respect to an acid component.
Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, the temperature increase was started, the temperature in the reaction system was heated to 265 ° C., and the esterification reaction was performed while maintaining this temperature. After the distillation of water from the reaction system ceases and the esterification reaction is completed, the temperature in the reaction system is lowered and maintained at 240 ° C., the pressure in the reaction vessel is reduced over about 40 minutes, and the degree of vacuum is set to 133 Pa. A polycondensation reaction was carried out while distilling off the alcohol component from the system.
The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase in viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. And stirring was stopped when the predetermined torque was shown, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reaction product was taken out (discharged) from the reaction vessel to obtain a polyester resin.
The physical properties (glass transition temperature, softening temperature, acid value, TVOC) of the obtained polyester resin were measured. These results are shown in Table 1.

Abbreviations in Table 1 are as follows.
Diol A: propylene oxide derivative of bisphenol A (polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane (PO 2.3 mol adduct))
-Diol B: ethylene oxide derivative of bisphenol A (polyoxyethylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, (EO 2.3 mol adduct))

  In Table 1, “OH group / COOH group” is a ratio represented by the number of carboxy groups (COOH groups) derived from the acid component / number of hydroxyl groups (OH groups) derived from the alcohol component. “Alcohol component / acid component” is a molar ratio represented by alcohol component / acid component.

Examples 1 to 3 satisfy the condition (a), Example 4 satisfies the condition (b), and Examples 2, 4, and 5 satisfy the condition (c).
As is clear from the results of Table 1, the polyester resins obtained in Examples 1 to 5 had a lower TVOC than the polyester resins obtained in Comparative Examples 1 and 2.
Although Comparative Example 1 contained 56 mole parts of a structural unit derived from the alkylene oxide adduct of bisphenol A with respect to 100 mole parts of the acid component, TVOC was high due to insufficient consideration for VOC reduction. It was.
Comparison between Example 5 and Comparative Example 2 shows that the ratio of the number of carboxy groups derived from the acid component to the number of hydroxyl groups derived from the alcohol component (hydroxyl group / carboxy group) of the polyester resin is 1.09 or less. It was shown that TVOC tends to decrease when the polycondensate is a monomer mixture obtained by mixing an acid component and an alcohol component.

Claims (3)

A polyester resin for toner, which is a polycondensate of a monomer mixture containing an acid component and 90 to 150 mol parts of an alcohol component with respect to 100 mol parts of the acid component,
A polyester resin for toner, comprising a structural unit derived from an alkylene oxide adduct of bisphenol A and a structural unit derived from ethylene glycol, wherein the total amount of volatile organic compounds is 380 ppm or less. The polyester resin for toner according to claim 1, wherein at least one of the following conditions (a), (b), and (c) is satisfied.
Condition (a): a polycondensate obtained in the presence of a titanium-based catalyst, wherein the structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component. Polyester resin for toner.
Condition (b): The structural unit derived from the alkylene oxide adduct of bisphenol A is 30 mole parts or less and the structural unit derived from terephthalic acid is 70 mole parts or less with respect to 100 mole parts of the acid component.
Condition (c): a polycondensate of a monomer mixture in which the ratio of the number of carboxy groups derived from the acid component to the number of hydroxyl groups derived from the alcohol component (hydroxyl group / carboxy group) is 1.09 or less, The structural unit derived from the alkylene oxide adduct of bisphenol A is 45 mol parts or less with respect to 100 mol parts of the acid component.   A toner comprising the toner polyester resin according to claim 1.