JP5456584B2 - toner - Google Patents

Description

  The present invention relates to a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

  To meet the recent demands for speeding up and downsizing, there is a demand for toner that can be fixed at a lower temperature. In order to meet this requirement, a toner using a crystalline resin and an amorphous resin as a binder resin has been proposed. A toner using such a crystalline resin and an amorphous resin has improved low-temperature fixability, but has a tendency to reduce high-temperature offset resistance (maximum fixing temperature) and reduce the fixable width.

  For these problems, the storage elastic modulus at 170 ° C. is 10 to 10,000 Pa, the maximum peak temperature of heat of fusion is 55 to 150 ° C., and the ratio of softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) is 0.6 to There has been proposed a toner containing a crystalline polyester of 1.3, having excellent low-temperature fixability, high image density, and good charge rising properties (see Patent Document 1). In addition, the toner contains a crystalline polyester in which the hexane-insoluble content in the chloroform-soluble content is 50% by weight or more of the chloroform-soluble content, has excellent low-temperature fixability, and has excellent durability even in the one-component development method. Has been proposed (see Patent Document 2). Further, a block copolymer comprising 3 to 50 parts by weight of crystalline polyester and 97 to 50 parts by weight of an ionically crosslinked amorphous vinyl polymer and having a chloroform insoluble content of 3 to 10% by weight. Alternatively, it is shown that a toner containing a graft copolymer as a binder resin is excellent in offset resistance and low-temperature fixability (see Patent Document 3).

JP 2004 197051 A JP 2003-302788 A JP-A-4-81770

  However, for example, a toner layer becomes thicker in an application in which three layers of toner are printed by a full color printer, and these toners improve low-temperature fixability and high-temperature offset resistance to widen the fixable width and increase gloss. Is difficult.

  An object of the present invention is to provide a toner having excellent low-temperature fixability and high-temperature offset resistance, a wide fixable width, and excellent gloss.

  The present invention is a toner comprising a binder resin, wherein the binder resin comprises a crystalline resin and an amorphous resin, and the crystalline resin contains an aliphatic diol having 2 to 10 carbon atoms. A composite resin comprising a polycondensation resin component obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, and a styrene resin component. And a storage elastic modulus at 140 ° C. of the amorphous resin of 360 to 1300 Pa.

  Even when the toner layer is thick, the toner of the present invention has excellent low-temperature fixability and high-temperature offset resistance, a wide fixable width, and excellent gloss effect. The toner of the present invention has an excellent effect even when used in a full-color toner for a non-magnetic one-component developing device, particularly an oilless non-magnetic one-component developing device in which a toner needs to contain a large amount of a release agent.

  The toner of the present invention is a toner containing a binder resin, the binder resin is made of a crystalline resin and an amorphous resin, and the crystalline resin contains an aliphatic diol having 2 to 10 carbon atoms. A composite resin comprising a polycondensation resin component obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, and a styrene resin component. The storage elastic modulus at 100 ° C. is 100 to 8000 Pa, and the amorphous resin has a large storage elastic modulus at 140 ° C. of 360 to 1300 Pa. Even when the toner layer is thick, low temperature fixability In addition, it has excellent high-temperature offset resistance, a wide fixable width, and an excellent gloss effect.

  Generally, when a crystalline resin and an amorphous resin are used, the low-viscosity component increases and the low-temperature fixability improves due to the melting point drop and the glass transition point drop due to the compatibilization of the crystalline resin and the amorphous resin. I think that. On the other hand, the low-viscosity component increased by the compatibilization of the crystalline resin and the amorphous resin causes a high-temperature offset and the like, and deteriorates the fixability at a high temperature.

  The composite resin contained in the toner of the present invention is obtained by polycondensing a styrene resin component, an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms, and a carboxylic acid component containing an aromatic dicarboxylic acid compound. Since the crystalline polycondensation resin component is included, even when the composite resin and the amorphous resin are compatibilized, it is possible to moderately suppress a decrease in the viscosity of the compatible portion. Therefore, compared to the case of using conventional crystalline and amorphous resins, high-temperature offset resistance is exhibited while exhibiting good low-temperature fixability without using a high molecular weight resin, that is, a resin having a high storage elastic modulus. It is thought that it will be possible to keep good.

  Furthermore, compared to the case where conventional crystalline resin and amorphous resin are used, a resin having a high storage elastic modulus is not used, the composite resin has a storage elastic modulus at 140 ° C. of 100 to 8000 Pa, and an amorphous resin of 140 ° C. By setting the storage elastic modulus at 360 to 1300 Pa, it is possible to obtain a high gloss fixed image while improving the low temperature fixability and the high temperature offset resistance.

  In the present invention, the binder resin contains a crystalline resin and an amorphous resin from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner, and the crystalline resin has 2 to 10 carbon atoms. The main component is a composite resin comprising a condensation polymerization resin component obtained by condensation polymerization of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid compound, and a styrene resin component. It is preferable.

  Here, the crystallinity of the resin is represented by the crystallinity index defined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the value of [softening point / maximum endothermic peak temperature]. The crystalline resin has a crystallinity index of 0.6 to 1.4, preferably 0.7 to 1.2, more preferably 0.9 to 1.2, and the amorphous resin is a resin having a value of 1.4 or less than 0.6. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The maximum peak temperature is the melting point if the difference from the softening point is within 20 ° C., and the peak temperature due to the glass transition if the difference from the softening point exceeds 20 ° C.

  In the present invention, the polycondensation resin component constituting the composite resin includes an alcohol component and an aromatic dicarboxylic acid containing an aliphatic diol having 2 to 10 carbon atoms from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner. A resin obtained by condensation polymerization of a carboxylic acid component containing an acid compound.

  Examples of the condensation polymerization resin component include polyester, polyester / polyamide, and the like. From the viewpoint of improving the low-temperature fixability of the toner, polyester is preferable.

  In the present invention, the alcohol component of the condensation polymerization resin is an aliphatic diol having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 4 to 6 carbon atoms, from the viewpoint of enhancing the crystallinity of the composite resin. contains.

  Examples of the aliphatic diol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 1,4-butenediol, and the like, particularly from the viewpoint of enhancing the crystallinity of the composite resin, α, ω-linear alkanediol is preferred, 1,4-butanediol and 1,6-hexanediol are more preferred, and 1,6-hexanediol is more preferred.

  From the viewpoint of enhancing the crystallinity of the composite resin, the content of the aliphatic diol having 2 to 10 carbon atoms is preferably 70 mol% or more, more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol in the alcohol component. Mol%. In particular, the proportion of the aliphatic diol having 2 to 10 carbon atoms in one alcohol component is preferably 50 mol% or more, more preferably 60 to 100 mol%.

  The alcohol component may contain a polyhydric alcohol component other than the aliphatic diol having 2 to 10 carbon atoms.

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable)
An aromatic diol such as an alkylene oxide adduct of bisphenol A represented by the formula: trivalent or higher alcohols such as glycerin, pentaerythritol, trimethylolpropane, sorbitol, and 1,4-sorbitan.

  In the present invention, the carboxylic acid component of the condensation polymerization resin contains an aromatic dicarboxylic acid compound from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner.

  As the aromatic dicarboxylic acid compound, those having 8 to 12 carbon atoms are preferable. Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, anhydrides of these acids, and alkyls thereof (1 to 8 carbon atoms). ) Esters. In addition, although a dicarboxylic acid compound refers to dicarboxylic acid, its anhydride, and its alkyl (C1-C8) ester, in these, dicarboxylic acid is preferable. Moreover, a preferable carbon number means the carbon number of the dicarboxylic acid part of a dicarboxylic acid compound.

  The content of the aromatic dicarboxylic acid compound is preferably 70 to 100 mol%, more preferably 90 to 100 mol% in the carboxylic acid component, from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner.

  The carboxylic acid component may contain a polyvalent carboxylic acid compound other than the aromatic dicarboxylic acid compound. Examples of the polyvalent carboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, Aliphatic dicarboxylic acids such as itaconic acid, glutaconic acid, succinic acid, adipic acid, succinic acid substituted with an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, and alicyclic rings such as cyclohexanedicarboxylic acid Dicarboxylic acid, trimellitic acid, trivalent or higher aromatic polyvalent carboxylic acid such as 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, etc., and their acid anhydrides and alkyl (C1-8) esters Etc.

  In addition, a monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight.

  In addition, in this specification, the both reactive monomers mentioned later shall not be included in calculation of content of an alcohol component or a carboxylic acid component.

  The ratio of the total number of moles of the aromatic dicarboxylic acid compound and the aliphatic diol having 2 to 10 carbon atoms in the total number of moles of the carboxylic acid component and the alcohol component, which are raw material monomers of the condensation polymerization resin component, is the composite resin From the viewpoint of enhancing crystallinity, it is preferably 75 to 100 mol%, more preferably 85 to 100 mol%, still more preferably 95 to 100 mol%.

  In the molar ratio of the carboxylic acid component to the alcohol component in the condensation polymerization resin component (carboxylic acid component / alcohol component), it is preferable that the amount of alcohol component is larger than that of the carboxylic acid component when increasing the molecular weight of the composite resin. The molar ratio is preferably 0.50 to 0.89, more preferably 0.70 to 0.85.

  The polycondensation reaction of the raw material monomer of the polycondensation resin component is carried out by polycondensation in an inert gas atmosphere at a temperature of about 180 to 250 ° C. in the presence of an esterification catalyst or a polymerization inhibitor, if necessary. Can be done. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate, and esterification that can be used together with the esterification catalyst. Examples of the cocatalyst include gallic acid. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total amount of the alcohol component, carboxylic acid component and both reactive monomers. The amount of the esterification promoter used is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight, with respect to 100 parts by weight of the total amount of the alcohol component, carboxylic acid component and both reactive monomers.

  As a raw material monomer for the styrene resin component, styrene or styrene derivatives such as α-methylstyrene and vinyltoluene (hereinafter, styrene and styrene derivatives are collectively referred to as “styrene derivatives”) is used.

  The content of the styrene derivative is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more in the raw material monomer of the styrene resin component, from the viewpoint of improving the high temperature offset resistance of the toner. .

  Raw material monomers for styrene resin components used other than styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; ethylenic monocarboxylic esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N-vinyl pyrrolidone N-vinyl compounds such as

  The raw material monomer of the styrene resin component used in addition to the styrene derivative can be used in combination of two or more. In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  Among the raw material monomers of the styrene resin component used other than the styrene derivative, (meth) acrylic acid alkyl ester is preferable from the viewpoint of improving the low-temperature fixability of the toner. 1-22 are preferable from said viewpoint, and, as for carbon number of the alkyl group in (meth) acrylic-acid alkylester, 8-18 are more preferable. In addition, carbon number of this alkyl ester means carbon number derived from the alcohol component which comprises ester.

  Specific examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary ) Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like. Here, “(iso or tertiary)” and “(iso)” mean that both of these groups are present and not present, and when these groups are not present Indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  The content of the (meth) acrylic acid alkyl ester is preferably 30% by weight or less, more preferably 20% by weight or less in the raw material monomer of the styrenic resin component, from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner. Preferably, it is more preferably 10% by weight or less.

  A resin obtained by addition polymerization of a raw material monomer containing a styrene derivative and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  The addition polymerization reaction of the raw material monomer of the styrenic resin component can be carried out by a conventional method, for example, in the presence of a polymerization initiator such as dicumyl peroxide, a crosslinking agent, etc., in the presence of an organic solvent or in the absence of a solvent. The temperature condition is preferably 110 to 200 ° C, more preferably 140 to 170 ° C.

  When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone or the like can be used. The amount of the organic solvent used is preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the raw material monomer of the styrene resin component.

  The glass transition point (Tg) of the styrenic resin component is preferably 60 to 130 ° C, more preferably 80 to 120 ° C, and still more preferably 90 to 110 ° C, from the viewpoint of improving the high temperature offset resistance of the toner.

Tg of styrene resin component is the empirical formula that predicts Tg called thermoadditive formula in the case of polymer, Fox formula (TGFox, Bull. Am. Physics Soc., Volume 1, No. 3, page 123 ( 1956)), the value obtained by calculation from the following formula (1) is used from the Tgn of the homopolymer of each monomer constituting the polymer.
1 / Tg = Σ (Wn / Tgn) (1)
(In the formula, Tgn is Tg represented by the absolute temperature of the homopolymer of each monomer component, and Wn is the weight fraction of each monomer component.)

  In the present specification, both reactive monomers described later are not included in the calculation of the content of the styrene resin component, and are not used in the calculation of Tg of the styrene resin component.

  For the calculation of the glass transition point (Tg) of the Fox formula used in the examples of the present invention, Tgn of styrene: 373 K (100 ° C.) and Tgn of 2-ethylhexyl acrylate: 223 K (-50 ° C.) are used.

  In the composite resin, the condensation polymerization resin component and the styrene resin component are preferably bonded directly or via a linking group. Examples of the linking group include a compound derived from an amphoteric monomer and a chain transfer agent described later, other resins, and the like.

  The composite resin is preferably in a state where the polycondensation resin component and the styrene resin component are dispersed in each other, and the dispersion state is determined by the following Tg of the composite resin measured by the method described in Examples. It can be evaluated by the difference from the calculated value of the Fox equation.

  That is, the composite resin in the present invention is a crystalline resin, but has an amorphous part derived from a styrene resin component and a condensation polymerization resin component, and has a Tg and a shrinkage derived from the styrene resin component. It has Tg derived from the polymerization resin component. The Tg of the styrene resin component and the Tg of the condensation polymerization resin component in the composite resin are values measured separately. As the degree of dispersion between the condensation polymerization resin component and the styrene resin component increases, When Tg approaches each other and the polycondensation resin component and the styrene resin component are dispersed to a substantially uniform state, both Tgs overlap and the measured value becomes almost one.

  Therefore, in a state where the styrene resin component and the condensation polymerization resin component are mutually dispersed, the Tg of the composite resin measured under the measurement conditions described later is different from the Tg calculated by the Fox equation of the styrene resin component. Value. Specifically, the absolute value of the difference between the glass transition point of the composite resin and the glass transition point calculated by the Fox formula of the styrene resin component in the composite resin is preferably 10 ° C or higher, more preferably 30 ° C or higher. Preferably, it is 50 ° C. or higher, more preferably 70 ° C. or higher. Generally, since the Tg of the condensation polymerization resin component is lower than the Tg of the styrene resin component, the measured value of Tg of the composite resin is often lower than the calculated Tg of the styrene resin component.

  Such a composite resin includes, for example, (1) a method in which a raw material monomer of a polycondensation resin component is polycondensed in the presence of a styrene resin having a carboxy group or a hydroxyl group, and the carboxy group or hydroxyl group has both reactivity described later. The thing derived from a monomer, a chain transfer agent, etc. can be used. (2) It can be obtained by a method such as addition polymerization of a raw material monomer of a styrene resin component in the presence of a condensation polymerization resin having a reactive unsaturated bond.

  From the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner, the composite resin is used in addition to the raw material monomer of the condensation polymerization resin component and the raw material monomer of the styrene resin component, and further, the raw material monomer of the condensation polymerization resin component and A resin (hybrid resin) obtained by using both reactive monomers capable of reacting with any of the raw material monomers of the styrene resin component is preferable. Therefore, when polymerizing the raw material monomer of the condensation polymerization resin component and the raw material monomer of the styrene resin component to obtain a composite resin, the condensation polymerization reaction and / or the addition polymerization reaction should be performed in the presence of both reactive monomers. Is preferred. As a result, the composite resin becomes a resin (hybrid resin) in which a condensation polymerization resin component and a styrene resin component are bonded via a structural unit derived from both reactive monomers, and the condensation polymerization resin component and the styrene resin component Becomes more finely and uniformly dispersed.

  From these, the composite resin is (a) a raw material monomer of a polycondensation resin component containing an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms and a carboxylic acid component containing an aromatic dicarboxylic acid compound, ( (B) A resin obtained by polymerizing a bifunctional monomer capable of reacting with either a raw material monomer of a styrene resin component, and (c) a raw material monomer of a condensation polymerization resin component and a raw material monomer of a styrene resin component. It is preferable.

  As the both reactive monomers, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or in the molecule. A compound having a carboxyl group, more preferably a carboxyl group, and an ethylenically unsaturated bond is preferred, and by using such a bireactive monomer, the dispersibility of the resin that becomes the dispersed phase can be further improved. The both reactive monomers are preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, but from the viewpoint of the reactivity of the condensation polymerization reaction and the addition polymerization reaction. Therefore, acrylic acid, methacrylic acid or fumaric acid is more preferable. However, when used with a polymerization inhibitor, a polyvalent carboxylic acid such as fumaric acid may function as a raw material monomer for the condensation polymerization resin component.

  The use amount of both reactive monomers increases the dispersibility of the styrene resin component and the condensation polymerization resin component, and improves the low temperature fixability and high temperature offset resistance of the toner from the viewpoint of the alcohol component of the condensation polymerization resin component. 1 to 30 mol is preferable, 2 to 25 mol is more preferable, 2 to 20 mol is more preferable, and the total amount of raw material monomers of the styrenic resin component (not including the polymerization initiator) is 100 2-30 mol is preferable with respect to mol, 5-25 mol is more preferable, and 10-20 mol is still more preferable.

  Specifically, the hybrid resin obtained using the both reactive monomers is preferably produced by the following method. Both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomer of the styrenic resin component from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner.

(i) A method in which the step (B) of the addition polymerization reaction with the raw material monomer and the both reactive monomers of the styrene resin component is performed after the step (A) of the condensation polymerization reaction with the raw material monomer of the condensation polymerization resin component. The step (A) is performed under a reaction temperature condition suitable for the condensation polymerization reaction, the reaction temperature is lowered, and the step (B) is performed under a temperature condition suitable for the addition polymerization reaction. It is preferable that the raw material monomer and the both reactive monomers of the styrene resin component are added to the reaction system at a temperature suitable for the addition polymerization reaction. Both reactive monomers react with the condensation polymerization resin component together with the addition polymerization reaction.
After the step (B), the reaction temperature is raised again, and if necessary, a raw material monomer of a polycondensation resin component such as a trivalent or higher that becomes a cross-linking agent is added to the polymerization system, and the polycondensation in the step (A). The reaction and reaction with both reactive monomers can be further advanced.

(ii) Method of performing the step (A) of the condensation polymerization reaction with the raw material monomer of the condensation polymerization resin component after the step (B) of the addition polymerization reaction with the raw material monomer of the styrene resin component and the amphoteric monomer. The step (B) is carried out under the reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is raised, and the condensation polymerization reaction in the step (A) is carried out under the temperature conditions suitable for the condensation polymerization reaction. Both reactive monomers are involved in the condensation polymerization reaction as well as the addition polymerization reaction.
The raw material monomer of the condensation polymerization resin component may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the condensation polymerization reaction. In the former case, the progress of the condensation polymerization reaction can be controlled by adding an esterification catalyst at a temperature suitable for the condensation polymerization reaction.

(iii) A method in which the step (A) of the condensation polymerization reaction using the raw material monomer of the condensation polymerization resin component and the step (B) of the addition polymerization reaction using the raw material monomer and both reactive monomers of the styrene resin component are performed in parallel. In the method, the step (A) and the step (B) are carried out under reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is increased, and a crosslinking agent is optionally added under temperature conditions suitable for the condensation polymerization reaction. It is preferable to add a raw material monomer of a polycondensation resin component having a valence of 3 or more to the polymerization system and further perform the polycondensation reaction in step (A). At that time, under a temperature condition suitable for the condensation polymerization reaction, a radical polymerization inhibitor can be added to advance only the condensation polymerization reaction. Both reactive monomers are involved in the condensation polymerization reaction as well as the addition polymerization reaction.

  In the above method (i), a prepolymerized polycondensation resin may be used in place of the step (A) of performing the polycondensation reaction. In the method (iii), when the step (A) and the step (B) are performed in parallel, the raw material monomer of the styrene resin component is contained in the mixture containing the raw material monomer of the condensation polymerization resin component. It is also possible to carry out the reaction by dropping the prepared mixture.

  The methods (i) to (iii) are preferably performed in the same container.

  In the composite resin, the weight ratio of the condensation polymerization resin component to the styrene resin component [condensation polymerization resin component / styrene resin component] (in the present invention, the raw material monomer of the condensation polymerization resin component is the raw material of the styrene resin component The weight ratio with respect to the monomer), that is, [the total amount of the raw material monomer of the condensation polymerization resin component / the total amount of the raw material monomer of the styrene resin component] is that the continuous phase is the condensation polymerization resin and the dispersed phase is the styrene type. From the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner by being a resin, 50/50 to 95/5 is preferable, 55/45 to 90/10 is more preferable, and 60/40 to 85/15 Is more preferable. In the above calculation, the amount of both reactive monomers is included in the total amount of the raw material monomers of the condensation polymerization resin component. The amount of the polymerization initiator does not include the total amount of raw material monomers of the styrene resin component.

  In order to obtain a high molecular weight composite resin, the molar ratio of the carboxylic acid component and the alcohol component is adjusted as described above, the reaction temperature is increased, the amount of the catalyst is increased, the dehydration reaction is performed for a long time under reduced pressure, etc. The reaction conditions may be selected. Although a high-power motor can be used to stir the reaction raw material mixture to produce a high molecular weight crystalline resin, when the production equipment is not particularly selected, the raw material monomer is not used. A method of reacting with a reactive low-viscosity resin or a solvent is also an effective means.

  The storage elastic modulus at 140 ° C. of the composite resin is 100 Pa or more, preferably 140 Pa or more, more preferably 200 Pa or more, and further preferably 250 Pa or more, from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, it is 8000 Pa or less, preferably 5000 Pa or less, more preferably 2000 Pa or less, and even more preferably 1000 Pa or less. Taking these viewpoints together, the storage elastic modulus of the composite resin at 140 ° C. is 100 to 8000 Pa, preferably 140 to 5000 Pa, more preferably 200 to 2000 Pa, and further preferably 250 to 1000 Pa.

  In the present invention, when the composite resin is composed of two or more resins, the storage elastic modulus at 140 ° C. of the composite resin is a weighted average value of the storage elastic modulus at 140 ° C. of each composite resin.

  Control of the storage elastic modulus at 140 ° C of the composite resin is to increase the chain length of the alcohol component, increase the amount of styrene, increase the valence of the carboxylic acid component, and control the aromatic system in the carboxylic acid component. The storage elastic modulus can be increased by increasing the monomer amount and the reaction time.

  The softening point of the composite resin is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, it is preferably 160 ° C. or lower, more preferably 130 ° C. or lower, and even more preferably 115 ° C. or lower. Taking these viewpoints together, the softening point of the composite resin is preferably 80 to 160 ° C, more preferably 90 to 130 ° C, and even more preferably 100 to 115 ° C.

  The melting point of the composite resin (= maximum endothermic peak temperature) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher, from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, 150 ° C. or lower is preferable, 130 ° C. or lower is more preferable, and 115 ° C. or lower is further preferable. Taking these viewpoints together, the melting point of the composite resin is preferably 80 to 150 ° C, more preferably 90 to 130 ° C, and still more preferably 100 to 115 ° C.

  The softening point and melting point can be adjusted by adjusting the raw material monomer composition, polymerization initiator, molecular weight, catalyst amount, etc., or by selecting reaction conditions.

  The Tg of the composite resin is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, and still more preferably 0 ° C. or higher, from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and further preferably 30 ° C. or lower. Taking these viewpoints together, the Tg of the composite resin is preferably −10 to 50 ° C., more preferably −5 to 40 ° C., and still more preferably 0 to 30 ° C.

  In the present invention, the crystalline resin may contain crystalline polyester or the like, but from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner, the content of the composite resin in the crystalline resin is In the crystalline resin, 80% by weight or more is preferable, 90% by weight or more is more preferable, and 95% by weight or more is more preferable.

  The content of the composite resin in the binder resin is preferably 7% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more from the viewpoint of improving the low-temperature fixability and gloss of the toner. Further, from the viewpoint of improving the high temperature offset resistance of the toner, it is preferably 50% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less. Taking these viewpoints together, the content of the composite resin in the binder resin is preferably 7 to 50% by weight, more preferably 10 to 30% by weight, and even more preferably 15 to 25% by weight.

  As the amorphous resin in the present invention, polyester, vinyl resin, epoxy resin, polycarbonate, polyurethane and the like are used. From the viewpoint of improving the low-temperature fixability of the toner, a polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component is preferable.

  As with the polycondensation resin component of the composite resin, the amorphous polyester also contains an alcohol component and a carboxylic acid component in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, a polymerization inhibitor, etc. , And can be produced by condensation polymerization at a temperature of about 180 to 250 ° C.

  However, in order to obtain an amorphous polyester, when a monomer that promotes crystallization of a resin such as an aliphatic diol having 2 to 6 carbon atoms or an aliphatic carboxylic acid compound having 2 to 8 carbon atoms is used, Two or more monomers are used in combination to suppress crystallization, that is, in both the alcohol component and the carboxylic acid component, one of these monomers is 10 to 70 mol%, preferably 20 to 60 mol in each component. It is preferable that 2 or more, preferably 2 to 4 of these monomers are used.

  In addition, in order to obtain an amorphous polyester, a monomer that promotes the amorphization of the resin, that is, the alcohol component is an alkylene oxide adduct of bisphenol A, and the carboxylic acid component is a succinic acid substituted with an alkyl group or an alkenyl group. It is preferable to use an acid or terephthalic acid.

  Further, in each of the alcohol component or the carboxylic acid component, at least one of the components, preferably in each of the two components, more preferably 30 to 100 mol%, and even more preferably 50 to 100 mol% is used. .

  The alkylene oxide adduct of bisphenol A is preferably used in the alcohol component in an amount of 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 95 to 100 mol%.

  Succinic acid substituted with an alkyl group or alkenyl group is preferably used in a carboxylic acid component of 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

  The terephthalic acid is preferably 30 to 100 mol%, more preferably 40 to 95 mol%, still more preferably 50 to 95 mol% in the carboxylic acid component.

  From the viewpoint of improving the transferability of the toner, the acid value of the amorphous polyester is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and further preferably 20 mgKOH / g or less.

  In the present invention, the amorphous polyester having a polyester component obtained by condensation polymerization of an alcohol component and a carboxylic acid component includes not only the polyester but also a modified resin thereof.

  Examples of the polyester-modified resin include urethane-modified polyester in which polyester is modified with a urethane bond, epoxy-modified polyester in which polyester is modified with an epoxy bond, and a hybrid resin in which a polyester component and other resin components are combined. .

  The softening point of the amorphous resin is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 105 ° C. or higher, from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, it is preferably 160 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower. Taking these viewpoints together, the softening point of the amorphous resin is preferably 70 to 160 ° C, more preferably 90 to 140 ° C, and further preferably 105 to 130 ° C.

  The maximum endothermic peak temperature of the amorphous resin is preferably 50 ° C. or higher, preferably 55 ° C. or higher, and more preferably 60 ° C. or higher from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, 90 ° C. or less is preferable, 80 ° C. or less is preferable, and 75 ° C. or less is more preferable. When these viewpoints are put together, the maximum peak temperature of the endotherm of the amorphous resin is preferably 50 to 90 ° C, more preferably 55 to 80 ° C, and further preferably 60 to 75 ° C.

  The Tg of the amorphous resin is preferably 45 ° C. or higher and more preferably 55 ° C. or higher from the viewpoint of improving the high temperature offset resistance of the toner. Further, from the viewpoint of improving the low-temperature fixability and gloss of the toner, it is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower. Taking these viewpoints together, the Tg of the amorphous resin is preferably 45 to 80 ° C, more preferably 55 to 75 ° C. In addition, Tg is a physical property peculiar to an amorphous phase, and is distinguished from the highest endothermic peak temperature.

  In the present invention, the amorphous resin has a softening point of preferably 3 ° C. or higher, more preferably 5 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of improving the high temperature offset resistance of the toner. An amorphous resin may be contained. Among the two or more types of amorphous resins, the softening point of the resin having the lowest softening point is preferably 80 to 135 ° C, more preferably 95 to 120 ° C, and still more preferably, from the viewpoint of low-temperature fixability of the toner. The softening point of the resin having the highest softening point is preferably from 100 to 150 ° C, more preferably from 110 to 135 ° C, and even more preferably from 120 to 130, from the viewpoint of improving high-temperature offset resistance. ° C. When two or more types of amorphous resins are contained, two types are preferable from the viewpoint of improving toner productivity.

  When two types of amorphous resins are used, the weight ratio of the high softening point resin to the low softening point resin (high softening point resin / low softening point resin) is preferably 1/9 to 9/1, 8 to 8/2 is more preferable.

  The storage elastic modulus at 140 ° C. of the amorphous resin is 360 Pa or more, preferably 500 Pa or more, more preferably 700 Pa or more, and further preferably 800 Pa or more, from the viewpoint of improving the high-temperature offset resistance of the toner. Further, from the viewpoint of improving the low-temperature fixability and gloss of the toner, it is 1300 Pa or less, preferably 1200 Pa or less, more preferably 1100 Pa or less, and even more preferably 1000 Pa or less. When these viewpoints are put together, the storage elastic modulus at 140 ° C. of the amorphous resin is 360 to 1300 Pa, preferably 500 to 1200 Pa, more preferably 700 to 1100 Pa, and further preferably 800 to 1000 Pa.

  When the amorphous resin is composed of two or more resins, the storage elastic modulus at 140 ° C. of the amorphous resin is such that the weighted average value of the storage elastic modulus at 140 ° C. of each amorphous resin is within the above range. .

  When the amorphous resin is composed of two or more kinds of resins, the storage elastic modulus at 140 ° C. of each amorphous resin is preferably 50 Pa or more, and preferably 60 Pa or more from the viewpoint of improving the high temperature offset resistance of the toner. More preferably, 70 Pa or more is more preferable, and 80 Pa or more is more preferable. Further, from the viewpoint of improving low-temperature fixability and gloss of the toner, 1300 Pa or less is preferable, 1200 Pa or less is more preferable, 1100 Pa or less is more preferable, and 1000 Pa or less is even more preferable. Taking these viewpoints together, the storage elastic modulus at 140 ° C. of each amorphous resin when the amorphous resin is composed of two or more resins is preferably 50 to 1300 Pa, more preferably 60 to 1200 Pa, and 70 to 1100 Pa is more preferable, and 80 to 1000 Pa is more preferable.

  Controlling the storage modulus of amorphous resin at 140 ° C increases the chain length of the alcohol component, increases the valence of the carboxylic acid component, and increases the amount of aromatic monomers in the carboxylic acid component. In addition, the storage elastic modulus can be increased by increasing the reaction time.

  The ratio of the storage elastic modulus of the composite resin at 140 ° C. to the storage elastic modulus of the amorphous resin at 140 ° C. [the storage elastic modulus of the composite resin at 140 ° C./the storage elastic modulus of the amorphous resin at 140 ° C.] From the viewpoint of improving low-temperature fixability and gloss, 4.5 or less is preferable, 2.0 or less is more preferable, 1.5 or less is more preferable, and 1.0 or less is even more preferable. Further, from the viewpoint of improving the high temperature offset resistance of the toner, 0.16 or more is preferable, 0.25 or more is more preferable, 0.30 or more is more preferable, and 0.40 or more is more preferable. Taking these viewpoints together, the ratio [storage elastic modulus of composite resin at 140 ° C./storage elastic modulus of amorphous resin at 140 ° C.] is preferably 0.16 to 4.5, more preferably 0.25 to 2.0, and 0.30 to 1.5. Is more preferable, and 0.40 to 1.0 is even more preferable. However, when the amorphous resin is composed of two or more resins, the storage elastic modulus at 140 ° C. of the amorphous resin used in the above calculation is the weighted average of the storage elastic modulus at 140 ° C. of each amorphous resin. The same applies to the composite resin.

  The content ratio of the crystalline resin and the amorphous resin (crystalline resin / amorphous resin) improves the low-temperature fixability and high-temperature offset resistance of the toner to widen the fixable width and improve the gloss. Therefore, the weight ratio is preferably 7/93 to 50/50, more preferably 10/90 to 30/70, and further preferably 15/85 to 25/75.

  In addition to the binder resin, the toner may contain a colorant, a release agent, a charge control agent, and the like.

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Isoindoline, Disazo Yellow and the like can be used. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The toner of the present invention may be either black toner or color toner.

  As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples thereof include montan wax, sazol wax and their deoxidized wax, ester waxes such as fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These may be used alone or in admixture of two or more.

  The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoint of improving the low-temperature fixability and high-temperature offset resistance of the toner.

  The content of the release agent is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, more preferably 7 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of preventing filming of the toner on the photoreceptor. The following is more preferable. Further, from the viewpoint of improving the high temperature offset resistance of the toner, 0.5 part by weight or more is preferable, 1.0 part by weight or more is more preferable, and 1.5 part by weight or more is further preferable. Therefore, taking these viewpoints together, 0.5 to 10 parts by weight is preferable, 1.0 to 8 parts by weight is more preferable, and 1.5 to 7 parts by weight is even more preferable. Further, from the viewpoint of oilless fixing of the toner, 3 parts by weight or more is preferable, 3.5 parts by weight or more is more preferable, and 4 parts by weight or more is more preferable. Therefore, taking these viewpoints together, it is preferably 3 to 10 parts by weight, more preferably 3.5 to 8 parts by weight, and even more preferably 4 to 7 parts by weight.

  The charge control agent is not particularly limited. Examples of the negative charge control agent include metal-containing azo dyes such as “Bontron S-28” (manufactured by Orient Chemical Co., Ltd.), “T-77” (Hodogaya Chemical Co., Ltd.). , "Bontron S-34" (Orient Chemical Co., Ltd.), "Eisenspiron Black TRH" (Hodogaya Chemical Co., Ltd.), etc .; copper phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, such as "Bontron" E-81 ”,“ Bontron E-84 ”,“ Bontron E-304 ”(manufactured by Orient Chemical Industry Co., Ltd.), etc .; Nitroimidazole derivatives; Boron benzylate complex, for example,“ LR-147 ”(manufactured by Nippon Carlit) Non-metallic charge control agents such as “Bontron F-21”, “Bontron E-89” (manufactured by Orient Chemical Co., Ltd.), “T-8” (Hodogaya Chemical Co., Ltd.), “FCA- 2521NJ '', `` FCA-2508N '' (Fujikura Kasei Co., Ltd.) I can get lost.

  Examples of positively chargeable charge control agents include nigrosine dyes such as `` Bontron N-01 '', `` Bontron N-04 '', `` Bontron N-07 '' (above, manufactured by Orient Chemical Industries), `` CHUO CCA-3 '' ( Chuo Gosei Co., Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains; Quaternary ammonium salt compounds such as “Bontron P-51” (Orient Chemical Industries), “TP-415” And Tetsuya Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, “COPYCHARGEPXVP435” (manufactured by Clariant), and the like.

  The content of the charge control agent is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more with respect to 100 parts by weight of the binder resin, from the viewpoint of suppressing toner fog. Further, from the viewpoint of improving the developability by appropriately adjusting the charge amount of the toner, the amount is preferably 5 parts by weight or less, more preferably 3 parts by weight or less with respect to 100 parts by weight of the binder resin. That is, taking these viewpoints together, the content of the charge control agent is preferably 0.1 to 5 parts by weight and more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the binder resin.

  The toner of the present invention further includes additives such as magnetic powders, fluidity improvers, conductivity modifiers, extender pigments, reinforcing fillers such as fibrous substances, antioxidants, anti-aging agents, and cleaning improvers. May be appropriately contained.

  In the present invention, the toner particles can be produced by a known method such as a kneading and pulverizing method, a spray drying method, or a polymerization method. However, since the binder resin is excellent in pulverizing properties, the pulverized toner obtained by the kneading and pulverizing method is used. preferable. According to a general method of kneading and pulverization, for example, a raw material containing a binder resin and, if necessary, various additives such as a colorant is mixed with a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded. After cooling, coarsely pulverize using a hammer mill, etc., and further finely pulverize using a fine pulverizer or mechanical pulverizer using a jet stream, The toner particles are obtained by classification to a desired particle size.

  Melting and kneading of raw materials can be performed using a known kneader such as a closed kneader, a single or twin screw extruder, a continuous open roll kneader, etc., but repeated kneading and use of a dispersion aid The continuous open roll type kneader equipped with a supply port and a kneaded product discharge port provided along the axial direction of the roll can efficiently and highly disperse the additive in the binder resin without the need for Is preferably used.

  The toner raw material is preferably mixed in advance using a Henschel mixer, a super mixer, etc., and then supplied to an open roll type kneader, and may be supplied to the kneader from one supply port. However, from the viewpoint of ease of operation and simplification of the apparatus, it is preferable to supply the kneader from one supply port.

  The continuous open roll type kneader refers to an open kneading unit that is not sealed, and can easily dissipate the kneading heat generated during kneading. Further, the continuous open roll type kneader is preferably a kneader equipped with at least two rolls, and the continuous open roll type kneader used in the present invention comprises two rolls having different peripheral speeds, That is, the kneading machine includes two rolls, a high rotation side roll having a high peripheral speed and a low rotation side roll having a low peripheral speed. In the present invention, from the viewpoint of dispersibility, it is desirable that the high rotation side roll is a heating roll and the low rotation side roll is a cooling roll.

  The temperature of the roll can be adjusted by, for example, the temperature of the heat medium passed through the inside of the roll, and each roll may be divided into two or more and the heat medium having different temperatures may be passed through each roll.

  The raw material charging side end temperature of the high rotation side roll is preferably 100 to 160 ° C, and the raw material charging side end temperature of the low rotation side roll is preferably 35 to 100 ° C.

  The high rotation side roll preferably has a set temperature difference between the raw material charging side end and the kneaded product discharge side end of 20 to 60 ° C. from the viewpoint of preventing detachment of the kneaded product from the roll. More preferably, it is 50 degreeC, and it is further more preferable that it is 30-50 degreeC. In the low rotation side roll, the difference in set temperature between the raw material charging side end and the kneaded product discharge side end is preferably 0 to 50 ° C., and 0 to 40 ° C. from the viewpoint of dispersibility of the release agent. It is more preferable that the temperature is 0 to 20 ° C.

  The peripheral speed of the high rotation side roll is preferably 2 to 100 m / min, more preferably 5 to 75 m / min. The peripheral speed of the low rotation side roll is preferably 1 to 90 m / min, more preferably 2 to 60 m / min, and further preferably 4 to 50 m / min. Further, the ratio of the peripheral speeds of the two rolls (low rotation side roll / high rotation side roll) is preferably 1/10 to 9/10, more preferably 3/10 to 8/10.

  The structure, size, material, etc. of the roll are not particularly limited, and the roll surface may be any of smooth, corrugated, uneven, etc., but in order to increase the kneading share, a plurality of roll surfaces are provided on the surface of each roll. It is preferable that the spiral groove is cut.

The volume median particle size (D ₅₀ ) of the toner is preferably 3 to 15 μm and more preferably 4 to 12 μm from the viewpoint of improving the image quality. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  An external additive treatment may be performed in which an external additive is attached to the toner particles, and the external additive may be externally added to the toner particles.

  Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles. Of these, silica is preferably used in combination, and silica having an average particle size of less than 20 nm and silica of 20 nm or more are more preferably used in combination.

  The toner of the present invention is suitable for speeding up and downsizing of the apparatus, and can be fixed at low temperature even when used in an image forming apparatus for printing with overlapping toner layers in a full-color printer or full-color copying machine, and has good resistance to resistance. High temperature offset and gloss can be maintained. Therefore, the toner of the present invention can be suitably used for an image forming method using a color developing device. Furthermore, the toner of the present invention can be suitably used for an oilless non-magnetic one-component developing device. The oilless fixing is a method using a fixing device having a heat roll fixing device that does not include an oil supply device. The oil supply device has an oil tank and has a mechanism for quantitatively applying oil to the surface of the heat roll, as well as a device having a mechanism for bringing a roll pre-impregnated with oil into contact with the heat roll, etc. including.

[Resin storage modulus G '(140)]
Measurement is performed using a viscoelasticity measuring device (rheometer) ARES (TA Instruments) (Strain: 0.05%, Frequency: 6.28 rad / sec). The measurement equipment conditions are set as follows. Heat / stand a parallel plate with a diameter of 8mm to 140 ° C, melt the sample at 140 ° C and place it on the parallel plate so that the gap is 1.5-2.5mm. After cooling, the temperature is raised to 180 ° C. at 5 ° C./min, and the storage elastic modulus G ′ at 140 ° C. is obtained. Specifically, the measurement device is set as follows.

AutoTension Adjustment = On
Mode = Apply Constant Static Force
AutoTension Direction = Compression
Initial Static Force = 10.0 [g]
AutoTension Sensitivity = 10.0 [g]
When Sample Modulus <= 100.0 [Pa]
AutoTension Limits = Default
Max Autotension Displacement = 3.0 [mm]
Max Autotension Rate = 0.01 [mm / s]
AutoStrain = On
Max Applied Strain = 20.0 [%]
Max Allowed Torque = 300.0 [g-cm]
Min Allowed Torque = 1.0 [g-cm]
Strain Adjustment = 20.0 [% of Current Strain]
Strain Amplitude Control = Default Behavior
Limit Minimum Dynamic Force Used = No
Minimum Applied Dynamic Force = 1.0 [gmf]

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a 1.96 MPa load was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan and cool it from room temperature to 0 ° C at a rate of 10 ° C / min. Then, it was left still for 1 minute. Thereafter, the measurement was carried out at a heating rate of 50 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C of the softening point, the peak temperature is taken as the melting point.

[Glass transition point of amorphous resin]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and decrease the temperature from that temperature. Cooled to 0 ° C at 10 ° C / min. Next, the sample was measured at a heating rate of 10 ° C./min. The glass transition point is defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Glass transition point of crystalline resin (composite resin)]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and decrease the temperature from that temperature. Cooled to -80 ° C at 100 ° C / min. Next, the sample was measured in a modulated mode at a heating rate of 1 ° C./min. The glass transition point is defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Acid value of the resin]
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of release agent]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.

[Average particle diameter of external additive]
The average particle size refers to the average primary particle size, and the particle size (average value of major axis and minor axis) of 500 particles is measured from a scanning electron microscope (SEM) photograph, and the average value is referred to as the average particle size. To do.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by weight.
Dispersion conditions: 10 mg of a measurement sample was added to 5 ml of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 ml of the electrolyte was added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare sample dispersion.
Measurement conditions: The sample dispersion is added to 100 ml of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, and 30,000 particles are measured. Determine the median particle size (D ₅₀ ).

[Production Example 1 of crystalline resin (composite resin) (resins A to F)]
Put a specified amount of the raw material monomer of the polycondensation resin component other than acrylic acid, which is the amphoteric reaction monomer shown in Table 1, into a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. Heat to 160 ° C. to dissolve. A premixed solution of styrene, dicumyl peroxide and acrylic acid was added dropwise with a dropping funnel over 1 hour. Stirring was continued for 1 hour while maintaining at 170 ° C to polymerize styrene and acrylic acid, then 40 g of tin (II) 2-ethylhexanoate and 3 g of gallic acid were added, and the temperature was raised to 210 ° C and reacted for 8 hours It was. Further, the reaction was performed at 8.3 kPa for a predetermined time to obtain crystalline resins (resins A to F). Table 1 shows the resin physical properties of the obtained crystalline resin.

[Production Example 2 of crystalline resin (resins G to J)]
1,6-hexanediol 2407 g (20.4 mol), fumaric acid 2320 g (20 mol), hydroquinone 2.5 g, and dibutyltin oxide 10 g Put into a one-necked flask and react for 4 hours from 130 ° C to 160 ° C under a nitrogen atmosphere, then add 400 g of polypropylene wax (High Wax NP-105, Mitsui Chemicals) and take it to 200 ° C over 3 hours. Then, the mixture was reacted at 200 ° C. for 30 minutes, and further reacted at 8.3 kPa until a predetermined softening point was reached to obtain crystalline polyesters (resins G to J). Table 2 shows the resin physical properties of the obtained crystalline resin.

[Production Example 3 of Crystalline Resin (Resin K)]
1,6-hexanediol 2407 g (20.4 mol), fumaric acid 2320 g (20 mol), hydroquinone 2.5 g, and dibutyltin oxide 10 g After putting into a one-necked flask and reacting from 130 ° C to 160 ° C over 4 hours in a nitrogen atmosphere, the temperature was raised to 200 ° C over 3 hours and reacted at 200 ° C for 30 minutes, and then 8.3 kPa Was reacted until the softening point reached 114 ° C. to obtain a crystalline polyester (resin K). Table 2 shows the resin physical properties of the obtained crystalline resin.

[Production Example 1 of Amorphous Resin (Resin a and b)]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1225g, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2113g, terephthalic acid 1528g and 2-ethylhexane 10 g of tin (II) oxide and 2 g of gallic acid were placed in a 10 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, and the reaction rate was 90% at 230 ° C. in a nitrogen atmosphere. Then, the reaction was continued until a predetermined softening point was reached at 8.3 kPa to obtain amorphous polyesters (resins a and b). Table 3 shows the physical properties of the obtained amorphous resin.

[Amorphous resin production example 2 (resins cf)]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, terephthalic acid, dodecenyl succinic anhydride, trianhydride Mellitic acid and 10 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were placed in a 10 liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple. After reacting at 90 ° C. until the reaction rate reached 90%, the reaction was continued at 8.3 kPa until a predetermined softening point was reached, thereby obtaining amorphous polyesters (resins cf). Table 3 shows the physical properties of the obtained amorphous resin.

[Examples 1 to 17 and Comparative Examples 1 to 24]
Predetermined amounts of amorphous resin, crystalline resin, and negative charge control agent “Bontron E-304” (manufactured by Orient Chemical Co., Ltd.) 0.2 parts by weight shown in Tables 4 and 5, Carnauba Wax C1 (manufactured by Hiroyuki Kato) 3 parts by weight, melting point: 88 ° C.), 3 parts by weight of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point: 75 ° C.), and colorant “ECB-301” (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue) (PB15: 3)) 5.0 parts by weight were mixed for 1 minute using a Henschel mixer, and then melt-kneaded under the conditions shown below.

  A continuous two-open roll kneader “NIDEX” (manufactured by Mitsui Mining Co., Ltd., roll outer diameter: 14 cm, effective roll length: 80 cm) was used. The operating conditions of the continuous two open roll type kneader are: high rotation side roll (front roll) peripheral speed 75r / min (32.97m / min), low rotation side roll (back roll) peripheral speed 50r / min (21.98m) / min), the roll gap at the end of the kneaded product supply port was 0.1 mm. The heating medium temperature and cooling medium temperature in the roll are 135 ° C. on the raw material input side of the high rotation side roll and 90 ° C. on the kneaded material discharge side, 35 ° C. on the raw material input side of the low rotation side roll and 35 ° C. on the kneaded material discharge side. there were. The feed rate of the raw material mixture was 10 kg / hour, and the average residence time was about 6 minutes.

The obtained kneaded product is cooled to 20 ° C. or lower while being rolled with a cooling roll, and the cooled melt-kneaded product is coarsely pulverized to 3 mm with a Rotoplex (manufactured by Toa Machinery Co., Ltd.). -400 "was triturated with (Alpine Co.), and classified by a rotor type classifier" TTSP "(Alpine Co.), the volume-median particle size (D ₅₀₎ to obtain toner particles of 8.0 .mu.m. 100 parts by weight of the toner particles are 1.5 parts by weight of hydrophobic silica “RY50” (Nippon Aerosil, average particle size: 40 nm) and 1.5 parts by weight of hydrophobic silica “R972” (Nippon Aerosil, average particle size: 16 nm). Was mixed with a Henschel mixer (Mitsui Mining Co., Ltd.) at 1500 r / min for 1 minute to obtain a toner.

Test Example 1 [low temperature fixability]
Mount toner on the non-magnetic one-component developing device “OKI MICROLINE 5400” (Oki Data Co., Ltd.), adjust the toner adhesion amount to 0.40 ± 0.03mg / cm ^2, and print a solid image of 4.1cm x 4.1cm at Fuji Xerox Printed on J paper manufactured by Office Supply. A solid image was taken out before passing through the fixing machine to obtain an unfixed image. Load the resulting paper with unfixed images into the non-magnetic one-component developer “OKI MICROLINE 5400” (Oki Data), print a 4.1cm x 4.1cm solid image again, and pass through the fixing machine. A solid image was taken out to obtain 0.80 ± 0.06 mg / cm ² unfixed image (two layers). The same operation was repeated to obtain 1.20 ± 0.09 mg / cm ² unfixed image (3 layers).

  Fix the obtained unfixed three-layer image to a fixing roller of 120 mm / sec by setting the temperature of the fixing roll to 100 ° C with an external fixing device that took out the fixing device of “OKI MICROLINE 3010” (manufactured by Oki Data). Fixed at speed. Thereafter, the fixing roll temperature was set to 105 ° C., and the same operation was performed. This was performed while increasing the temperature up to 190 ° C by 5 ° C.

  A mending tape (manufactured by Sumitomo 3M Co., Ltd.) was attached to the image fixed at each temperature, and then a weight of 500 g of cylinder was placed on the image to sufficiently attach the tape to the fixed image. Thereafter, the mending tape was slowly peeled off from the fixed image, and the optical reflection density of the image after tape peeling was measured using a reflection densitometer “RD-915” (manufactured by Macbeth). The optical reflection density is also measured for the image before applying the tape in advance, and the temperature of the fixing roll whose ratio to the value (after tape peeling / before tape application) first exceeds 90% is set as the minimum fixing temperature. Fixability was evaluated. The results are shown in Tables 4 and 5.

Test Example 2 [High temperature offset resistance]
The fixing image of 105 ° C. to 190 ° C. obtained in Test Example 1 was visually confirmed, and the maximum fixing roll temperature at which no hot offset was observed was taken as the maximum fixing temperature. The results are shown in Tables 4 and 5.

Test Example 3 [Fixable temperature range]
The fixed image of 105 ° C. to 190 ° C. obtained in Test Example 1 was visually confirmed, and the difference between the maximum fixing temperature and the minimum fixing temperature (maximum fixing temperature−minimum fixing temperature) + 5 ° C. was defined as the fixable temperature range. The results are shown in Tables 4 and 5.

Test Example 4 [Gloss of image]
The glossiness at each fixing temperature of the three-layer fixed image obtained in Test Example 1 was measured, and the maximum value was defined as the gloss of the sample. Glossiness was measured using a gloss meter “PG-1” (Nippon Denshoku Industries Co., Ltd.) with the light source set at 60 °. The higher the glossiness, the better the gloss. The results are shown in Tables 4 and 5.

  From the above results, in the toners of Examples 1 to 17, the toners of Comparative Examples 1 to 9 in which the crystalline resin is not a composite resin, and the storage elastic modulus G ′ (140) at 140 ° C. of the composite resin is less than 100 Pa or 8000 Pa. Compared to the toners of Comparative Examples 10-18, 22, and 23 exceeding 140, the storage elastic modulus G ′ (140) at 140 ° C. of the amorphous resin is less than 360 Pa, and compared with the toners of Comparative Examples 19 to 21 and 24 exceeding 1300 Pa. It can be seen that the fixing property and the high temperature offset resistance are excellent, the fixing range is wide, and the gloss is excellent.

  The toner of the present invention is suitably used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.

Claims (5)

  A toner comprising a binder resin, wherein the binder resin comprises a crystalline resin and an amorphous resin, and the crystalline resin comprises an alcohol component and an aromatic component containing an aliphatic diol having 2 to 10 carbon atoms. A composite resin containing a polycondensation resin component obtained by polycondensation of a carboxylic acid component containing an aromatic dicarboxylic acid compound and a styrene resin component, and the storage modulus of the composite resin at 140 ° C. Is a toner having a storage elastic modulus at 140 ° C. of 360 to 1300 Pa.   A raw material monomer of a polycondensation resin component, wherein the composite resin comprises (a) an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms and a carboxylic acid component containing an aromatic dicarboxylic acid compound, (b) styrene A resin obtained by polymerizing a bifunctional monomer capable of reacting with either a raw material monomer of a resin-based resin component, and (c) a raw material monomer of a polycondensation-based resin component and a raw material monomer of a styrene-based resin component. 1. The toner according to 1.   The toner according to claim 1, wherein the absolute value of the difference between the glass transition point of the composite resin and the glass transition point calculated by the Fox formula of the styrene resin component in the composite resin is 10 ° C. or more.   The toner according to claim 1, wherein the content of the composite resin is 7 to 50% by weight in the binder resin. Ratio of storage elastic modulus at 140 ° C. of composite resin to storage elastic modulus at 140 ° C. of amorphous resin [storage elastic modulus of composite resin at 140 ° C./storage elastic modulus of amorphous resin at 140 ° C.] is 0.16 to 4.5 The toner according to claim 1.