JP2010164837A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which has excellent filming resistance on a photoreceptor, prevents sticking to a developing blade and has excellent solid image follow-up ability and excellent fixability, with respect to a toner used in a nonmagnetic one-component developing device, particularly in an oilless nonmagnetic one-component developing device which needs to incorporate a release agent in large quantity into the toner, and to provide an image forming method using the toner. <P>SOLUTION: The toner comprises a binder resin, a colorant, a release agent and a negative charge type charge control agent. The binder resin comprises a crystalline polyester and an amorphous polyester, wherein the crystalline polyester is a polyester obtained by condensation polymerization of an alcohol component comprising 90-100 mol% of an α,ω-alkanediol and a carboxylic acid component comprising 70-100 mol% of an aromatic dicarboxylic acid compound. The negative charge type charge control agent is a condensation polymer obtained by condensation polymerization reaction between phenols and aldehydes, and the content of the condensation polymer is 0.3-5.0 pts.wt. based on 100 pts.wt. of the binder resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

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, and the like, and an image forming method using the toner.

  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 demand, a toner using a crystalline polyester and an amorphous polyester as a binder resin has been proposed. A toner using such a crystalline polyester and an amorphous polyester has improved low-temperature fixability but has a tendency to lower the resin strength. As a result, as the speed increases, when more mechanical or thermal stress is applied, adhesion to the transfer roll and the developing blade, filming to the photosensitive member, and the like are likely to occur. When used in a non-magnetic one-component developing device that is charged by friction with the developing blade, or when used in an oilless non-magnetic one-component developing device that requires the toner to contain a large amount of a release agent, it is particularly fixed to the developing blade. Filming on the photoconductor is also a big problem. In order to suppress these problems, for example, sticking to the developing blade, a method of weakening the frictional force by the developing blade can be considered, but as a result, the charge amount is reduced and the image quality such as solid followability is deteriorated. Happens.

  On the other hand, a crystalline polyester obtained by polycondensing an alcohol component containing 70 mol% or more of 1,6-hexanediol and a carboxylic acid component containing 70 mol% or more of an aromatic carboxylic acid compound is a binder resin 100. It has been shown that non-magnetic one-component toner containing 1 part by weight of a release agent with respect to parts by weight improves the chargeability, mechanical strength, and durability (see Patent Document 1). In addition, in a toner containing a polyester having an acid value of 10 mg / KOH and a hydroxyl value of 15 mg / KOH or a toner containing a styrene-acrylic copolymer, a specific negative charge control agent containing a polycondensate of phenols and aldehydes is charged. It is shown that it is excellent in stand-up property (refer patent document 2).

JP-A-2005-321747 Japanese Patent No. 3772910

  An object of the present invention is to improve the filming resistance of a toner to a photoreceptor in a toner used in 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. An object of the present invention is to provide a toner excellent in preventing sticking to a developing blade and having excellent solid followability and fixability, and an image forming method using the toner.

The present invention
[1] A toner comprising a binder resin, a colorant, a release agent, and a negative charge control agent, wherein the binder resin contains a crystalline polyester and an amorphous polyester, The polyester is a polyester obtained by condensation polymerization of an alcohol component containing 90 to 100 mol% of α, ω-alkanediol and a carboxylic acid component containing 70 to 100 mol% of an aromatic dicarboxylic acid compound, The negatively chargeable charge control agent is a condensation polymer obtained by a condensation polymerization reaction of phenols and aldehydes, and the content of the condensation polymer is 0.3 to 5.0 parts by weight with respect to 100 parts by weight of the binder resin. The present invention relates to an image forming method in which a toner and [2] the toner described in [1] are used in an image forming apparatus of an oilless non-magnetic one-component developing system.

  Even if the toner of the present invention is used in a non-magnetic one-component developing device, particularly an oil-less non-magnetic one-component developing device in which the toner needs to contain a large amount of a release agent, filming on the photoreceptor and fixing to the blade In addition, it has excellent effects in solid followability and low-temperature fixability.

  The toner of the present invention is a toner containing a binder resin containing a crystalline polyester and an amorphous polyester and a negatively chargeable charge control agent, and the crystalline polyester contains a specific amount of α, ω-alkanediol. Contains a polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing a specific amount of an aromatic dicarboxylic acid compound, and as a negatively chargeable charge control agent, by a condensation polymerization reaction of phenols and aldehydes. It has a great feature in that it contains the obtained condensation polymer.

  The reason for the crystalline polyester and the negatively chargeable charge control agent in the present invention is not clear, but it suppresses filming of the toner to the photoreceptor and sticking to the blade while maintaining low-temperature fixability of the toner. This improves the chargeability and improves the solid followability of the toner.

  In the present invention, the binder resin contains a crystalline polyester and an amorphous polyester from the viewpoint of achieving both low-temperature fixability and storage stability of the toner, and preferably contains polyester as a main component. Here, the crystallinity of the resin is represented by the ratio between the softening point and the highest endothermic peak temperature measured by a differential scanning calorimeter, that is, the crystallinity index defined by the softening point / the highest endothermic peak temperature. The crystalline polyester 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 polyester is more than 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 glass transition point if the difference from the softening point exceeds 20 ° C.

  In the present invention, the crystalline polyester is obtained by polycondensing an alcohol component containing an α, ω-alkanediol and a carboxylic acid component containing an aromatic dicarboxylic acid compound.

  α, ω-alkanediol is a compound having primary hydroxyl groups at both ends. As the α, ω-alkanediol, a diol having 2 to 8 carbon atoms is preferable, and a diol having 4 to 6 carbon atoms is more preferable from the viewpoint of preventing filming on the photoreceptor and adhesion to the developing blade. From the same viewpoint, linear alkanediol is preferable. Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, etc. Α, ω-straight chain alkanediols, and α, ω-branched alkanediols having 4 to 6 carbon atoms such as 2-methyl-1,3-propanediol and neopentyl glycol. -Butanediol and 1,6-hexanediol are preferred.

  The content of α, ω-alkanediol is 90 to 100 mol%, preferably 95 to 100 mol% in the alcohol component from the viewpoint of preventing filming of the toner on the photoreceptor.

  Examples of the polyhydric alcohol component other than α, ω-alkanediol that can be contained in the alcohol component include aliphatic unsaturated diols having 2 to 8 carbon atoms such as 1,4-butenediol; 1,2-propanediol, 1 Alkanediols having no hydroxyl groups at both ends having 2 to 8 carbon atoms, such as 1,3-butanediol and 2,3-butanediol; formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y represent 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, 1,4-sorbitan, and the like. Of these, aliphatic unsaturated diols and alkane diols having no hydroxyl groups at both ends are preferred from the viewpoint of preventing filming of the toner to the photoreceptor and prevention of adhesion to the developing blade.

  Examples of aromatic dicarboxylic acid compounds include compounds having a benzene ring such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and acid anhydrides thereof, and alkyl esters having 1 to 12 carbon atoms. Of these, terephthalic acid and isophthalic acid are more preferable, and terephthalic acid is more preferable from the viewpoint of improving the solid followability of the toner. As described above, the aromatic carboxylic acid compound refers to an aromatic carboxylic acid, an anhydride thereof, and an alkyl ester having 1 to 12 carbon atoms. Among these, an aromatic carboxylic acid is preferable.

  The content of the aromatic dicarboxylic acid compound is 70 to 100 mol%, preferably 80 to 90 mol% in the carboxylic acid component from the viewpoint of improving the solid followability of the toner and suppressing filming on the photoreceptor. %.

  Examples of polyvalent carboxylic acid compounds other than aromatic dicarboxylic acid compounds that can be contained in the carboxylic acid component include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, C2-C30 aliphatic dicarboxylic acid such as sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid; cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid; trivalent such as trimellitic acid and pyromellitic acid These polyhydric carboxylic acids; and their acid anhydrides, alkyl esters having 1 to 12 carbon atoms, and the like.

  Furthermore, from the viewpoint of adjusting the molecular weight of the resin, a monovalent alcohol or a monovalent carboxylic acid compound may be appropriately contained in the alcohol component and / or carboxylic acid component as long as the effects of the present invention are not impaired. .

  For example, a crystalline polyester is a polycondensation of an alcohol component and a carboxylic acid component 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 manufactured. Examples of esterification catalysts include esterification catalysts such as tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamate. The amount of esterification catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of alcohol components.

  The softening point of the crystalline polyester is preferably 160 ° C. or lower, more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, and still more preferably 120 ° C. or lower, from the viewpoint of low-temperature fixability of the toner. Further, from the viewpoint of preventing filming of the toner on the photoreceptor and adhesion to the developing blade, the temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and further preferably 100 ° C. or higher. That is, when these viewpoints are put together, 80-160 degreeC is preferable, 80-140 degreeC is more preferable, 90-130 degreeC is further more preferable, 100-120 degreeC is still more preferable.

  The content of the crystalline polyester is preferably 5 to 40% by weight in the binder resin from the viewpoint of low-temperature fixability of the toner, filming of the toner on the photoreceptor, and prevention of sticking to the developing blade. Weight percent is more preferred.

As with the crystalline polyester, the amorphous polyester also has 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. at 180 to 250 ° C. It can be produced by polycondensation at a moderate temperature. However, in order to make amorphous polyester,
(1) When using 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, two or more of these monomers may be used in combination. Inhibiting crystallization, that is, in any of the alcohol component and the carboxylic acid component, one of these monomers accounts for 10 to 70 mol%, preferably 20 to 60 mol% in each component, and these monomers 2 or more, preferably 2 to 4 are used, or
(2) A monomer that promotes amorphization of the resin, preferably an alkylene oxide adduct of bisphenol A in the alcohol component, or a succinic acid substituted with an alkyl group or alkenyl group in the alcohol component, respectively in the alcohol component. Alternatively, in at least one component in the carboxylic acid component, preferably 30 to 100 mol%, preferably 50 to 100 mol% is preferably used in each of both components.

  The acid value of the amorphous polyester is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and even more preferably 10 mgKOH / g or less from the viewpoint of preventing filming on the photoreceptor and adhesion to the developing blade.

  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 polyester is preferably 180 ° C. or less and more preferably 160 ° C. or less from the viewpoint of low-temperature fixability of the toner. Further, from the viewpoint of preventing filming of the toner on the photoreceptor and fixing to the developing blade, the temperature is preferably 70 ° C. or higher, more preferably 100 ° C. or higher. That is, when these viewpoints are put together, 70-180 degreeC is preferable and 100-160 degreeC is more preferable. The glass transition point is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, from the viewpoint of low-temperature fixability of the toner. Further, from the viewpoint of preventing filming of the toner on the photoreceptor and fixing to the developing blade, 45 ° C. or higher is preferable, and 55 ° C. or higher is more preferable. That is, when these viewpoints are put together, it is preferably 45 to 80 ° C, more preferably 55 to 75 ° C. The glass transition point is a physical property peculiar to an amorphous resin, and is distinguished from the maximum peak temperature of endotherm.

  The amorphous polyester preferably has a softening point of 5 ° C. or more, more preferably 10 to 50 from the viewpoint of improving the low-temperature fixability and preventing the filming of the toner to the photoreceptor and the fixing to the developing blade. It is preferably made of two kinds of polyesters having different temperatures. From the viewpoint of low-temperature fixability, the softening point of the polyester having a low softening point is preferably 80 to 125 ° C, more preferably 85 to 120 ° C. The softening point of the polyester having a high softening point is that of the toner on the photoreceptor. From the viewpoint of preventing filming and sticking to the developing blade, the temperature is preferably 110 to 150 ° C, more preferably 120 to 145 ° C. 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 10/90 to 90/10, and more preferably 20/80 to 80/20.

  The weight ratio of crystalline polyester to amorphous polyester (crystalline polyester / amorphous polyester) is suitable for improving low-temperature fixability and solid followability of the toner, filming of the toner on the photoreceptor and developing blade. 5/95 to 50/50 is preferable, 5/95 to 40/60 is more preferable, and 5/95 to 20/80 is more preferable.

  The binder resin may contain a binder resin other than the crystalline polyester and the amorphous polyester as long as the effects of the present invention are not impaired. Examples of binder resins other than crystalline polyester and amorphous polyester include vinyl resins, epoxy resins, polycarbonates, polyurethanes, and the like.

  The negatively chargeable charge control agent in the present invention contains a condensation polymer obtained by condensation polymerization of phenols and aldehydes.

  Phenols include p-alkylphenol (a) having one phenolic hydroxyl group and no substituent at the ortho position of the hydroxyl group, and bisphenol having two phenolic hydroxyl groups and no substituent at the ortho position of each hydroxyl group. It is preferable to use a raw material containing the compound (b). “No substituent” means that a carbon atom adjacent to a carbon atom to which a hydroxyl group is bonded is a hydrogen atom except that it is bonded to another carbon that forms an aromatic ring together with the carbon atom to which the hydroxyl group is bonded. Indicates that it is bound only with. It is considered that an aldehyde is added to carbon adjacent to the phenolic hydroxyl group of the phenol by a condensation polymerization reaction of the phenol and the aldehyde to form a condensation polymer in which the phenol and the aldehyde are alternately linked. Since this polycondensate has a structure in which phenols excellent in charge retention are linked, it is presumed that excellent chargeability can be obtained.

  As p-alkylphenol (a), the formula (i):

(In the formula, X ¹ and X ³ each independently represent a hydrogen atom, halogen, or an alkyl group having 1 to 3 carbon atoms, and X ² represents an alkyl group having 1 to 12 carbon atoms, preferably 4 to 8 carbon atoms. (Show)
It is preferable that the p-alkylphenol represented by these is contained.

  Examples of the p-alkylphenol represented by the formula (i) include pt-butylphenol, pt-octylphenol, pt-dodecylphenol, and the like.

  The content of p-alkylphenol (a) is preferably from 70 to 99 mol%, more preferably from 80 to 98 mol%, in the phenols, from the viewpoint of chargeability of the toner.

  As the bisphenol compound (b), the formula (ii):

(In the formula, X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent a hydrogen atom, a halogen, or an alkyl group having 1 to 3 carbon atoms, and X ⁸ has 1 to 5 carbon atoms, preferably carbon. (Indicates an alkylene group of formula 3)
It is preferable that the bisphenol compound represented by these is contained.

  Examples of the bisphenol compound represented by the formula (ii) include bisphenol A such as 2,2-bis (4-hydroxyphenyl) propane.

  The content of the bisphenol compound (b) is preferably 1 to 30 mol% and more preferably 2 to 20 mol% in the phenols from the viewpoint of dispersibility in the polyester.

  The molar ratio (a / b) between the p-alkylphenol (a) and the bisphenol compound (b) is preferably 99/1 to 70/30, more preferably 98/2 to 80/20.

  The aldehyde is preferably at least one selected from paraformaldehyde and formaldehyde.

  The raw material molar ratio of phenols to aldehydes (phenols / aldehydes) in the condensation polymer is preferably 2 to 0.2, more preferably 1 to 0.5.

  As a polycondensation reaction method of phenols and aldehydes, for example, phenols and aldehydes are added to an organic solvent having a boiling point of 80 ° C. or higher, such as xylene, and alkali metal or alkaline earth metal hydroxides are added. In the presence of a strong base compound such as 80 ° C. or higher at the boiling point of the solvent while distilling off the water for 3 to 20 hours, and then recrystallization using a poor solvent such as alcohol, Examples include a method of drying the solvent under reduced pressure and then washing with an alcohol such as methanol, ethanol, or isopropanol. In addition, as a strong base compound, sodium hydroxide, rubidium hydroxide, potassium hydroxide, etc. can be used preferably.

  The content of the condensation polymer obtained by the condensation polymerization reaction of phenols and aldehydes is the binder resin 100 from the viewpoint of improving the toner charge amount and solid followability and preventing filming on the photoreceptor. It is 0.3 parts by weight or more, preferably 0.5 parts by weight or more, and more preferably 1.0 parts by weight or more with respect to parts by weight. Further, from the viewpoint of improving toner fixability, it is 5.0 parts by weight or less, preferably 4.0 parts by weight or less, and more preferably 3.0 parts by weight or less with respect to 100 parts by weight of the binder resin. That is, taking these viewpoints together, it is 0.3 to 5.0 parts by weight, preferably 0.5 to 4.0 parts by weight, and more preferably 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the binder resin.

  In the toner of the present invention, in addition to the polycondensation obtained by the polycondensation reaction of phenols and aldehydes, other negatively chargeable charge control agents are appropriately contained as long as the effects of the present invention are not impaired. Also good. Other negatively chargeable charge control agents include metal-containing azo dyes, copper phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, boron complexes of benzyl acid, and the like. The content of the condensation polymer obtained by the condensation polymerization reaction of phenols and aldehydes is not particularly limited, but is preferably 50% by weight or more, more preferably 80% by weight or more in the negatively chargeable charge control agent.

  The toner of the present invention contains at least a colorant and a release agent in addition to the binder resin and the negatively chargeable charge control agent.

  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 waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax and their oxides, 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, and fatty acid metal salts. 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 viewpoints of low-temperature fixability and 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, from the viewpoint of preventing filming on the photoreceptor and fixing to the developing blade with respect to 100 parts by weight of the binder resin. 7 parts by weight or less is more preferable. From the viewpoint of oilless fixing, the amount is preferably 3 parts by weight or more, more preferably 3.5 parts by weight or more, and further preferably 4 parts by weight or more. 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 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.

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by a melt kneading method is preferred. Specifically, raw materials such as a binder resin, a colorant, a charge control agent, and a release agent are uniformly mixed with a mixer such as a Henschel mixer, and then a sealed kneader, a single or twin screw extruder, and an open The toner can be produced by melt-kneading with a roll-type kneader or the like, cooling, pulverizing, and classifying. From the viewpoint of suppressing adhesion of the toner to the blade, a heating and holding step may be performed after the melt kneading. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.

The volume median particle size (D ₅₀ ) of the toner is preferably from 3.0 to 11 μm, more preferably from 3.5 to 9 μm, and even more preferably from 4 to 8 μm, from the viewpoint of improving the image quality.

  The toner of the present invention may be obtained by a method including a step of mixing with external additives such as inorganic fine particles and resin fine particles such as polytetrafluoroethylene after the pulverization and classification steps.

  For mixing the pulverized material and the toner particles obtained after the classification step and the external additive, it is preferable to use a stirrer having a stirrer such as a rotary blade, and a more preferable stirrer is a Henschel mixer.

  The toner of the present invention can be used in an image forming apparatus of a one-component development system or a two-component development system as a one-component development toner as it is or as a two-component development toner mixed with a carrier.

  The toner of the present invention can be suitably used in non-magnetic one-component development type image forming apparatuses and oilless non-magnetic one-component development type image forming apparatuses. Accordingly, the present invention provides an image forming method in which the toner of the present invention is used in an image forming apparatus of an oilless non-magnetic one-component developing system. 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.

[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.

[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample cooled from that temperature to -10 ° C at a temperature reduction rate of 10 ° C / min was increased at a temperature increase rate of 10 ° C / min. The temperature is the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent that indicates the maximum slope from the peak rise to the peak apex.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., Q-100), the sample cooled from room temperature to 0 ° C at a temperature lowering rate of 10 ° C / min is left still for 1 minute, and then the temperature is raised Measure at a rate of 50 ° C / min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point is set, and the peak having a difference from the softening point exceeding 20 ° C. is a peak due to glass transition.

[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.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
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 dispersion is added to 100 ml of the electrolyte so that the particle size of 30,000 particles can be measured in 20 seconds, and 30,000 particles are measured. Kuraitsubu径Request (D _50).

[Production Example 1 of Crystalline Polyester]
30 g of 1,6-hexanediol, terephthalic acid, and tin (II) 2-ethylhexanoate in the amounts shown in Table 1 are provided in four 10-liter volumes equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple. The mixture was placed in a neck flask, reacted at 180 ° C. for 4 hours under a nitrogen atmosphere, further heated to 210 ° C. for 3 hours, and then reacted at 8.3 kPa for 1 hour. Then, it cooled to 180 degreeC, the amount of adipic acid shown in Table 1 was added, and it was made to react at 180 degreeC for 2 hours, Then, it heated up at 200 degreeC and was made to react for 2 hours. Finally, the reaction was carried out at 8.3 kPa until a resin having a desired softening point was obtained to obtain crystalline polyesters (resins A to C). Table 1 shows the resin physical properties of the softening points of resins A to C, the highest endothermic peak temperature, and the softening point / endothermic maximum peak temperature ratio.

[Production Example 2 of crystalline polyester]
In the same manner as in Production Example 1 of crystalline polyester, except that stearic acid was used instead of adipic acid and 1,6-hexanediol, terephthalic acid and stearic acid were used in the amounts shown in Table 1, Polyester (resin D) was obtained. Table 1 shows the resin physical properties of Resin D.

[Production Example 3 of crystalline polyester]
Equipped with 30 g of 1,6-hexanediol, 1,4-butanediol, terephthalic acid and tin (II) 2-ethylhexanoate in the amounts shown in Table 1, equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple In a 10 liter four-necked flask, reacted at 180 ° C. for 4 hours under a nitrogen atmosphere, further heated to 210 ° C. and reacted for 3 hours, and then at 8.3 kPa for the desired softening point. It was made to react until resin was obtained, and crystalline polyester (resin E) was obtained. Table 1 shows the resin physical properties of Resin E.

[Production Example 4 of Crystalline Polyester]
Similar to Production Example 3 of crystalline polyester except that neopentyl glycol was used in place of 1,4-butanediol and 1,6-hexanediol, neopentyl glycol and terephthalic acid were used in the amounts shown in Table 1. By this method, crystalline polyester (resin F) was obtained. Table 1 shows the softening point of the resin F, the highest endothermic peak temperature, and the softening point / endothermic highest peak temperature ratio.

[Production Example 5 of crystalline polyester]
1,6-hexanediol, fumaric acid, tin (II) 2-ethylhexanoate, and 5.5 g of tertiary butylcatechol in the amounts shown in Table 1 were equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple. Place in a 10-liter four-necked flask, react for 5 hours at 180 ° C in a nitrogen atmosphere, further raise the temperature to 200 ° C and react for 5 hours, then at 8.3 kPa for the desired softening point resin To obtain a crystalline polyester (resin G). Table 1 shows the resin physical properties of Resin G.

[Production Example 6 of crystalline polyester]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane was used instead of 1,4-butanediol, and 1,6-hexanediyl, polyoxypropylene (2.2) -2,2- A crystalline polyester (resins H and I) was obtained in the same manner as in Production Example 3 for a crystalline polyester except that bis (4-hydroxyphenyl) propane and terephthalic acid were used in the amounts shown in Table 1. Table 1 shows the resin physical properties of the resins H and I.

[Production Example 1 of Amorphous Polyester]
1286 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 2218 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1603 g of terephthalic acid, and 2-ethyl Put 10 g of tin (II) hexanoate into a 10 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple until the reaction rate reaches 90% at 230 ° C in a nitrogen atmosphere After the reaction, the reaction was carried out at 8.3 kPa until the desired softening point was reached to obtain an amorphous polyester (resin a). Resin a had a softening point of 111.4 ° C., a maximum endothermic peak temperature of 71.0 ° C., a maximum softening point / endothermic peak temperature of 1.6, a glass transition point of 68.5 ° C., and an acid value of 3.2 mgKOH / g. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

[Production Example 2 of Amorphous Polyester]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3486g, Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3240g, Terephthalic acid 1881g, Tetrapropenyl anhydride 269 g of acid and 30 g of tin (II) 2-ethylhexanoate were placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, and reacted at 230 ° C. in a nitrogen atmosphere. After reacting until the rate reached 90%, it was reacted at 8.3 kPa for 1 hour. Next, 789 g of trimellitic anhydride was added, and a reaction was performed at 220 ° C. until a desired softening point was reached, thereby obtaining an amorphous polyester (resin b). Resin b had a softening point of 122.2 ° C., a maximum endothermic peak temperature of 65.22 ° C., a maximum softening point / endothermic peak temperature of 1.9, a glass transition point of 63.7 ° C., and an acid value of 18.9 mgKOH / g.

[Production Example 1 of Negatively Charged Charge Control Agent]
300 mL of xylene using 0.225 mol of pt-butylphenol, 0.225 mol of pt-octylphenol, 0.032 mol of 2,2-bis (4-hydroxyphenyl) propane, 18.5 g of paraformaldehyde (0.6 mol of formaldehyde) and 3 g of 5N aqueous potassium hydroxide solution The refluxing reaction was carried out for 8 hours while distilling off water at 120 ° C. The reaction solution was recrystallized using methanol, filtered, and the filtrate was further washed with methanol, and the resulting solid was dried to obtain a negatively chargeable charge control agent α. The contents of p-alkylphenol (a) [pt-butylphenol and pt-octylphenol] and bisphenol compound (b) [2,2-bis (4-hydroxyphenyl) propane] in phenols were 93 mol% and 7 mol, respectively. The mol% (molar ratio 93/7), and the raw material molar ratio (phenols and aldehydes) in the condensation polymer is 1 / 1.2.

[Examples 1 to 9 and Comparative Examples 1 to 7]
Resin a 60 parts by weight, resin b 30 parts by weight, crystalline polyester 10 parts by weight shown in Table 2, negatively chargeable charge control agent, paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point: 75 ° C.) 4 Part by weight and 4.5 parts by weight of colorant “ECB-301” (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue (PB15: 3)) 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 as follows: high rotation side roll (front roll) peripheral speed 9m / min, low rotation side roll (back roll) peripheral speed 6m / min, kneaded product supply port side end The roll gap 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 4 kg / hour, and the average residence time was about 10 minutes.

The obtained melt-kneaded product was cooled to 20 ° C. or lower while being rolled with a cooling roll, and the obtained melt-kneaded product was left in a constant temperature bath set at 65 ° C. for 6 hours for heat treatment. The heat-kneaded melt-kneaded product is roughly pulverized to 3 mm with Rotoplex (manufactured by Toa Machinery Co., Ltd.), and then 100 parts by weight of the coarsely crushed product and three types of hydrophobic silica `` R972 '' (manufactured by Nippon Aerosil Co., Ltd.) Mix 0.3 parts by weight of HVK2150 (Wacker Chemicals) and 1.2 parts by weight of HDK H13TX (Wacker Chemicals) with a Henschel mixer (Mitsui Mining Co., Ltd.) for 1 minute at 1500 r / min. Grind with a mill “AFG-400” (manufactured by Alpine) and classify with a rotor classifier “TTSP” (manufactured by Alpine) to obtain toner base particles having a volume median particle size (D <sub>50</sub> ) of 5.5 μm. It was. Hydrophobic silica RY50 (made by Nippon Aerosil Co., Ltd.) 0.9 parts by weight, toner silica particles 100 parts by weight, hydrophobic silica `` RX50 '' (made by Nippon Aerosil Co., Ltd.) 0.8 parts by weight, melamine formaldehyde resin fine particles `` Eposter S '' (Japan) A toner was obtained by mixing 0.3 parts by weight of a catalyst company) at 1500 r / min with a Henschel mixer (manufactured by Mitsui Mining) for 1 minute.

Test Example 1 [Photoreceptor Filming Resistance]
The non-magnetic one-component developing device `` MicroLine 710 '' (Oki Data Co., Ltd.) was remodeled to a linear speed of 240 mm / sec (equivalent to A4 vertical 40 sheets / min), and the toner of each example and each comparative example was mounted and the printing rate After printing 120,000 sheets with a pattern of 0.3%, the photoreceptor unit is removed from the printer, the presence or absence of photoreceptor filming is visually confirmed, and the filming resistance of the photoreceptor is evaluated according to the following evaluation criteria. . The results are shown in Table 2.

〔Evaluation criteria〕
A: Filming does not occur in the image area and the non-image area of the photoreceptor.
B: Filming slightly occurs in the non-image area of the photoconductor, but filming does not occur in the image area.
C: Filming occurs in the image area and the non-image area of the photoconductor.

Test Example 2 [Fixing to developing blade]
The non-magnetic one-component developing device `` MicroLine 710 '' (Oki Data Co., Ltd.) was remodeled to a linear speed of 240 mm / sec (equivalent to A4 vertical 40 sheets / min), and the toner of each example and each comparative example was mounted and the printing rate After printing 120,000 sheets with a pattern of 0.3%, two sheets of black solid were printed on the entire surface. The streaks of the print sample were visually confirmed, and toner adhesion to the developing blade was evaluated according to the following evaluation criteria. The results are shown in Table 2.

〔Evaluation criteria〕
A: No streaks B: Streaks

Test Example 3 [Solid Follow-up]
Non-magnetic one-component developing device “MicroLine 710” (Oki Data Co., Ltd.) was remodeled to a linear speed of 240 mm / sec (equivalent to A4 vertical 40 sheets / min), and the toner of each example and each comparative example was mounted, and the printing rate After printing 120,000 sheets with a pattern of 0.3%, two sheets of black solid were printed on the entire surface. Reflection densitometer “RD-915” (manufactured by Macbeth Co., Ltd.) displays the image density (ID ₁ ) of the center part 10 cm from the top of the first printed sheet and the image density (ID ₂ ) of the center part 10 cm from the bottom of the second sheet. The solid followability was evaluated according to the following evaluation criteria based on the difference in image density between the two. The results are shown in Table 2.

〔Evaluation criteria〕
A: Difference between ID ₁ and ID ₂ is less than 0.1 B: Difference between ID ₁ and ID ₂ is 0.1 or more and less than 0.3 C: Difference between ID ₁ and ID ₂ is 0.3 or more and less than 0.5 D: ID ₁ and ID ₂ are 0.5 or more

Test Example 4 [low temperature fixability]
The toner of each Example and each Comparative Example is mounted on the non-magnetic one-component developing device “MicroLine 710” (Oki Data Co., Ltd.) with the fixing machine removed, and the toner adhesion amount is adjusted to 0.50 mg / cm ² to 3 cm. A solid image of × 8 cm was printed on Xerox L paper (A4) to obtain an unfixed image. The obtained unfixed image was fixed at a fixing roll temperature of 130 mm and fixed at a fixing speed of 240 mm / sec using an external fixing machine modified from the fixing machine of "MicroLine 3050" (manufactured by Oki Data). . Thereafter, the fixing roll temperature was set to 135 ° C., and the same operation was performed. This was performed while increasing the temperature up to 195 ° C by 5 ° C. "UNICEF Cellophane" (Mitsubishi Pencil Co., Ltd., width: 18mm, JISZ-1522) is pasted on the image fixed at each temperature, passed through the fixing roll of the fixing machine set at 30 ° C, and then the tape is peeled off. The optical reflection density of the image after tape peeling was measured using a reflection densitometer “RD-915” (manufactured by Macbeth). Measure the optical reflection density of the image before applying the tape in advance, and the ratio of the value (after tape peeling / before tape application) first exceeds 90%. The low-temperature fixability was evaluated according to the evaluation criteria. The results are shown in Table 2.

〔Evaluation criteria〕
A: The minimum fixing temperature is less than 160 ° C.
B: The minimum fixing temperature is 160 ° C. or higher and lower than 180 ° C.
C: The minimum fixing temperature is 180 ° C. or higher.

  From the above results, it can be seen that the toners of Examples 1 to 9 are excellent in solid followability and low-temperature fixability, and also have a good effect of preventing photoconductor filming and fixing to the developing blade. On the other hand, the toners of Comparative Examples 1 and 2 that do not use a predetermined negatively chargeable charge control agent have a significant occurrence of photoconductor filming, and the toner of Comparative Example 2 has poor solid followability. Further, in the toner of Comparative Example 3 using the crystalline polyester in which the content of the aromatic dicarboxylic acid compound in the carboxylic acid component is outside the desired range, the decrease in solid followability and the occurrence of photoconductor filming are remarkable. is there. On the other hand, in the toner of Comparative Example 4 which does not use an aromatic dicarboxylic acid compound as the carboxylic acid component, the solid followability is lowered, and the photosensitive filming and the fixing to the developing blade also occur. Further, even when a predetermined negatively chargeable charge control agent is used, in the toner of Comparative Example 5 whose content is too small, the decrease in solid followability and the occurrence of photoconductor filming are significant, and the content is too high. With too much toner of Comparative Example 6, the low-temperature fixability is deteriorated. In the toner of Comparative Example 7 in which the α, ω-alkanediol content is less than the predetermined amount, the photoreceptor filming is remarkable.

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

Claims (4)

  A toner comprising a binder resin, a colorant, a release agent, and a negatively chargeable charge control agent, wherein the binder resin contains a crystalline polyester and an amorphous polyester, A polyester obtained by polycondensation of an alcohol component containing 90 to 100 mol% of an α, ω-alkanediol and a carboxylic acid component containing 70 to 100 mol% of an aromatic dicarboxylic acid compound, the negative chargeability A toner in which the charge control agent is a condensation polymer obtained by a condensation polymerization reaction of phenols and aldehydes, and the content of the condensation polymer is 0.3 to 5.0 parts by weight with respect to 100 parts by weight of the binder resin. .   In a polycondensation product obtained by a polycondensation reaction between a phenol and an aldehyde, the phenol has one phenolic hydroxyl group, and there is no substituent at the ortho position of the hydroxyl group. And a bisphenol compound (b) having two phenolic hydroxyl groups and having no substituent at the ortho position of each hydroxyl group, and the content of the bisphenol compound (b) in the phenols is 1 to 30 mol% The toner according to claim 1, wherein the aldehyde is at least one selected from paraformaldehyde and formaldehyde.   The toner according to claim 1, wherein the content of the release agent is 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.   An image forming method using the toner according to claim 1 for an image forming apparatus of an oilless non-magnetic one-component developing system.