JP5084799B2 - Toner for electrostatic image development - Google Patents

Description

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

  In recent years, demand for on-demand printing has increased, and there has been a demand for a toner having higher image quality, higher speed, and higher reliability. Therefore, conventionally, from the viewpoint of durability and fixability, toners containing polyester as a main component of the binder resin have been widely used, but from the above viewpoint, further fixability, that is, low temperature fixability and offset resistance. Therefore, there is a demand for a toner that combines durability.

  Therefore, as a toner having both fixing properties and durability, a toner using two kinds of polyesters having different softening points and different molecular weights has been proposed (Patent Documents 1 and 2). However, these toners also require further improvement in low-temperature fixability and offset resistance from the viewpoint of satisfying performance required for speeding up and the like.

JP-A-4-338973 (Claim 1) JP-A-8-166688 (Claim 1)

  An object of the present invention is to provide a toner for developing an electrostatic image having excellent low-temperature fixability and offset resistance and excellent durability even in high-speed printing.

  The present invention relates to a toner containing a binder resin and a colorant, wherein the binder resin contains two types of resins having softening points different by 10 ° C. or more, and has a higher softening point. And the lower resin can be obtained by reacting polyethylene terephthalate or modified polyethylene terephthalate (hereinafter referred to as PET), an alcohol component containing a compound represented by formula (I), and a carboxylic acid component. The present invention relates to an electrostatic charge image developing toner which is polyester or a hybrid resin having the polyester as one of resin components.

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge image that has excellent low-temperature fixability and offset resistance and has excellent durability even in high-speed printing.

  The toner of the present invention contains two kinds of resins having different softening points as a binder resin, and a polyester obtained by reacting PET, an alcohol component, and a carboxylic acid component as a resin having a higher softening point. Or it has the characteristic in having excellent durability, without impairing fixing property by containing the hybrid resin which has this polyester as one of the resin components. Although the detailed reason is unknown, polyesters obtained from PET as a raw material are less likely to break molecular chains due to the shearing force during melt-kneading, thereby improving the durability of the toner without impairing fixing properties. It is estimated to be.

  In the present invention, polyethylene terephthalate or modified polyethylene terephthalate is used as PET, but polyethylene terephthalate is preferred. The modified polyethylene terephthalate in the present invention refers to a resin containing ethylene glycol and terephthalic acid as monomers as main components and 50 mol% or more, preferably 70 mol% or more in all monomers. For the purpose of modification, 1,6-hexanedimethanol, 1,4-butanediol, isophthalic acid, naphthalenedicarboxylic acid and the like are referred to as modified polyethylene terephthalate.

  The intrinsic viscosity number of PET is preferably from 0.7 to 1, more preferably from 0.75 to 0.95, from the viewpoint of offset resistance, durability and fixability. The intrinsic viscosity number is generally used as an indicator of the degree of polymerization of the polymer. The intrinsic viscosity number of PET is adjusted by the ratio of the alcohol component and the carboxylic acid component, the reaction temperature, the reaction time, the degree of pressure reduction, the type of catalyst, and the like.

  As PETs, those produced according to a conventional method by condensation polymerization of ethylene glycol with terephthalic acid, dimethyl terephthalate, or the like can be used. In the present invention, since PETs are widely used as products such as bottles and films, PETs that are collected as products and then discarded are preferably used from the viewpoint of environmental problems and prices. . The type of the recovered product is not particularly limited as long as it does not contain a compound that interferes with the performance of the toner and the polymerization reaction and has a certain degree of purity.

  When using the recovered product, flake-pulverized ones, pellets, and the like are preferably used for ease of handling, dispersion, and decomposition.

  In the present invention, as an alcohol component and a carboxylic acid component to be reacted with PETs, an alcohol component and a carboxylic acid component that are usually used as a raw material monomer for polyester are used.

  Divalent alcohol components include linear and hydrogenated ethylene glycol, 1,2-propanediol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, etc. Alicyclic diols such as bisphenol A and cyclohexanedimethanol; Formula (I):

(Wherein R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16, preferably 1.5 to 5.0). Compounds such as polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, bisphenols such as polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane Aromatic diols such as alkylene (C2-3) oxide adducts of A and the like.

  In the polyester obtained using PETs, the content of the aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% in the divalent alcohol component from the viewpoint of low-temperature fixability. More preferably (that is, the divalent alcohol component consists essentially of an aliphatic diol).

  Examples of the trihydric or higher polyhydric alcohol component include sorbitol, pentaerythritol, glycerin, trimethylolpropane and the like.

  Examples of the divalent carboxylic acid component include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and other aliphatic carboxylic acids; dodecenyl succinic acid, octyl succinic acid Succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as: aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; anhydrides of these acids and their Alkyl (C1-C3) ester of an acid etc. are mentioned.

  Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides thereof, and lower alkyl. (C1-C3) ester etc. are mentioned.

  Furthermore, a small amount of monovalent alcohol and carboxylic acid compound may be used for the purpose of adjusting the molecular weight and improving the offset resistance.

  Moreover, it is preferable that the polyester obtained using PET is a crosslinked polyester, and a polyester obtained using a trivalent or higher monomer is preferred. The content of at least one of a trivalent or higher monomer, that is, a trihydric or higher polyhydric alcohol component and a trivalent or higher polyvalent carboxylic acid component is preferably 0.05 to 40 mol in all monomers. %, More preferably 1 to 35 mol%, particularly preferably 3 to 30 mol%.

  The reaction of the PETs, the alcohol component and the carboxylic acid component can be carried out under the same conditions as in the case of mixing the PETs, the alcohol component and the carboxylic acid component, and usually polycondensing the polyester raw material monomer. For example, polycondensation can be progressed while depolymerizing PET by depolymerizing at a temperature of 180 to 250 ° C. using an esterification catalyst if necessary in an inert gas atmosphere. In addition, these reaction may add an alcohol component and a carboxylic acid component sequentially, and may advance reaction sequentially, or may add an alcohol component and a carboxylic acid component simultaneously, and may advance reaction simultaneously.

  In consideration of the reactivity of PETs, it is preferable to add the PETs divided into several times rather than adding them to the reaction system all at once.

  The content of the PETs in the total amount of the PETs, the alcohol component and the carboxylic acid component is preferably 10 to 70% by weight, preferably 15 to 65% by weight, from the viewpoint of using the PETs and adjusting the physical properties of the resin composition to be produced. More preferred is 20 to 60% by weight.

  In addition, the ratio of hydroxyl group to carboxyl group (hydroxyl group / carboxyl group) in the three components of PET, alcohol component and carboxylic acid component is preferably 0.9 to 1.1, preferably 0.95 to 1.05. More preferred. Since PET is a reaction product containing both an alcohol component and a carboxylic acid component, the valence is calculated by adding the valences of hydroxyl groups and carboxyl groups of each component contained in the PETs. To do.

  In the present invention, the hybrid resin is a resin composed of two polymerization resin components, and is a resin having polyester as one of the resin components. Here, the two polymerization resin components are partially chemically bonded to form a hybrid resin.

  As the raw material monomer for the polyester component, the same PETs, alcohol component and carboxylic acid component as described above can be used.

  The other resin component in the hybrid resin is preferably an addition polymerization resin component. Representative examples of addition polymerization resins include vinyl resins obtained by radical polymerization reaction.

  Examples of the raw material monomer for the vinyl resin include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate; Vinyl esters such as vinyl propionate; alkyl (1 to 18 carbon) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone and the like, and alkyl esters of styrene and / or (meth) acrylic acid from the viewpoint of reactivity, grindability and charge stability. Is 50% by weight or more, preferably 80-100 It is desirable that the contained amount%.

  In addition, when polymerizing the raw material monomer of the vinyl resin, a polymerization initiator, a crosslinking agent, or the like may be used as necessary.

  From the viewpoint of offset resistance, the weight ratio of the raw material monomer of the polyester used in the production of the hybrid resin to the raw material monomer of the addition polymerization resin is preferably a polyester, usually 50/50 to 95 / 5, preferably 60/40 to 95/5.

  As the hybrid resin in the present invention, in addition to the raw material monomers of the two polymerization resins, a monomer capable of reacting with both of the raw material monomers of the two polymerization resins (both reactive monomers) as one of the raw material monomers A resin obtained by mixing is preferred.

  Both reactive monomers have 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 in the molecule, an ethylenically unsaturated bond, It is preferable to use a monomer having such a property, and by using such a bireactive monomer, it is possible to improve the dispersibility of the resin to be a dispersed phase. Specific examples of the both reactive monomers include acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid and the like. Among these, acrylic acid, methacrylic acid and fumaric acid are preferable.

  The amount of both reactive monomers used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyester raw material monomer. In the present invention, the bi-reactive monomer is treated as a monomer different from the raw material monomer of the polyester and the raw material monomer of the addition polymerization resin because of the specificity of the performance.

  In the present invention, when the hybrid resin is obtained by performing the two polymerization reactions using the above raw material monomer mixture and both reactive monomers, the progress and completion of the polymerization reaction are simultaneous in time. It is not necessary, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to advance and complete the reaction.

  As a method for producing a hybrid resin using PET as one of raw materials, for example, a raw material monomer of polyester other than a trivalent or higher monomer acting as a cross-linking agent, PET, an esterification catalyst, and the like are added. After raising the temperature to ˜250 ° C., the polyester raw material monomer is reacted with the PET, and then the addition polymerization resin raw material monomer, the bireactive monomer, the polymerization initiator and the like are mixed, and the temperature is 150 ° C. to 180 ° C. There is a method in which an addition polymerization resin component is formed mainly by radical polymerization reaction, and then a trivalent or higher monomer is added to raise the temperature to 190 to 250 ° C., and then a polyester component is mainly formed by condensation polymerization reaction. preferable.

  In the present invention, the softening point of the polyester or hybrid resin contained as the resin having a higher softening point is preferably 120 to 170 ° C, more preferably 130 to 170 ° C, and particularly preferably 135 to 155 ° C.

  On the other hand, examples of resins having a lower softening point include polyesters, styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, and hybrid resins composed of two polymerization resin components. From the viewpoint of compatibility with the contained polyester or hybrid resin, a hybrid resin having polyester as one of the polyester and the resin component is preferable, and polyester is more preferable. As the raw material monomer for the polyester, the same alcohol component and carboxylic component as those of the polyester having a higher softening point can be used. Furthermore, from the viewpoint of improving fixability, the resin having a lower softening point can be obtained by reacting a polyester obtained by reacting PETs, an alcohol component, and a carboxylic acid component, or the polyester, in the same manner as the higher resin. A hybrid resin as one of the resin components is preferable.

  Therefore, in the present invention, both the resin having a higher softening point and the resin having a lower softening point are obtained by reacting PET, an alcohol component, and a carboxylic acid component with a polyester or the polyester. It is preferable that it is a hybrid resin as one of the resin components, and in any resin, it is preferable that the divalent alcohol component in the polyester consists essentially of an aliphatic diol.

  The softening point of the resin having the lower softening point is preferably 80 ° C. or higher and lower than 120 ° C., more preferably 90 to 115 ° C., and particularly preferably 95 to 110 ° C.

  The difference between the softening points of the resin having the higher softening point and the resin having the lower softening point is 10 ° C. or more, preferably 20 to 80 ° C., more preferably 30 to 60 ° C. The softening point of the resin can be adjusted by reaction conditions such as reaction temperature, reaction time, and reduced pressure during the production of the resin, and by using a trivalent or higher alcohol or carboxylic acid compound as the polyester raw material monomer.

  In the present invention, the resin having the higher softening point and the resin having the lower softening point are both preferably amorphous polyester, and the difference between the softening point and the glass transition point is preferably 20 ° C. or more, and 30 to 100 ° C. Is more preferable.

  The acid value of the resin is preferably 1 to 80 mgKOH / g regardless of the resin having the higher softening point and the resin having the lower softening point. In particular, in the case of a positively chargeable toner, 1 to 20 mgKOH / g is preferable, and 3 to 10 mgKOH / g is more preferable. In the case of a negatively chargeable toner, 10 to 80 mgKOH / g is preferable. The hydroxyl value is 5 to 60 mgKOH / g, preferably 10 to 50 mgKOH / g.

  The weight ratio of the resin having the higher softening point to the resin having the lower softening point (the resin having the higher softening point / the resin having the lower softening point) is preferably 50/50 to 95/5, more preferably 55/45. ~ 90/10.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Carbon black, metal composite oxide, aniline black, nigrosine dye, 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, Disazo Yellow, Benzidine Yellow, Monoazo Dye Pigment, Disazo Dye Pigment, etc. The toner of the present invention may be any of black toner, monocolor toner, and full color toner. The content of the colorant is preferably 1 to 30 parts by weight and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin.

  Furthermore, the toner of the present invention preferably contains a low-melting-point wax from the viewpoint of low-temperature fixability and offset resistance. The melting point of the low melting point wax is preferably 50 to 120 ° C, more preferably 60 to 120 ° C. The low melting point wax is preferably at least one selected from the group consisting of carnauba wax, montan ester wax, rice wax and candelilla wax from the viewpoint of dispersibility in the binder resin and low temperature fixability. Wax is more preferred.

  The content of the low melting point wax is preferably from 0.1 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin, from the viewpoint of low-temperature fixability and offset resistance. 1-3 parts by weight are particularly preferred.

  The toner of the present invention further includes a charge control agent, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a fluidity improver, and a cleaning improver. An agent may be appropriately contained.

  The toner production method of the present invention may be any conventionally known method such as a kneading and pulverizing method. For example, in the case of a pulverized toner by the kneading and pulverizing method, a binder resin, a colorant, a low melting point wax, etc. Can be uniformly mixed with a mixer such as a Henschel mixer or a ball mill, then melt-kneaded with a closed kneader or a single-screw or twin-screw extruder, etc., cooled, ground, and classified. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  When the toner of the present invention contains a magnetic fine powder, it is used alone as a developer, and when it does not contain a magnetic fine powder, it is used as a non-magnetic one-component developer or mixed with a carrier to develop a two-component developer. The toner of the present invention is preferably used as a two-component developer because it is excellent in durability.

When the toner of the present invention is used as a two-component developer, it is preferable to use a carrier with low saturation magnetization that weakens the contact with the magnetic brush from the viewpoint of image characteristics.
Saturation magnetization of the carrier is preferably ^{40~100Am 2 / kg, 50~90Am 2 /} kg is more preferable. The saturation magnetization is preferably 100 Am ² / kg or less from the viewpoint of adjusting the hardness of the magnetic brush and maintaining gradation reproducibility, and preferably 40 Am ² / kg or more from the viewpoint of preventing carrier adhesion and toner scattering.

  As the core material of the carrier, those made of known materials can be used without particular limitation, for example, ferromagnetic metals such as iron, cobalt, nickel, magnetite, hemite, ferrite, copper-zinc-magnesium ferrite, Examples thereof include alloys and compounds such as magnesium ferrite and manganese ferrite, and glass beads. Among these, iron powder, magnetite, ferrite, copper-zinc-magnesium ferrite, magnesium ferrite and manganese ferrite are preferable.

  The surface of the carrier is preferably coated with a resin from the viewpoint of reducing carrier contamination. The resin that coats the carrier surface varies depending on the toner material. For example, fluororesin such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin such as dimethylsilicone, polyester resin, styrenic resin, Acrylic resins, polyamides, polyvinyl butyral, amino acrylate resins, and the like can be used. These can be used alone or in combination of two or more. When the toner is positively charged, the chargeability and surface From the viewpoint of energy, fluorine resin and silicone resin are preferable.

  The method for coating the core material with the resin is not particularly limited, for example, a method in which a coating material such as a resin is dissolved or suspended in a solvent and applied to the core material, or a method of simply mixing with a powder.

  In the two-component developer obtained by mixing the toner and the carrier, the toner / carrier weight ratio (toner / carrier) is preferably 0.5 / 100 to 8/100, more preferably 1/100 to 6/100. preferable.

  The toner of the present invention can maintain good durability even in a printing machine having a linear velocity of 370 mm / sec or more, preferably 500 mm / sec or more, more preferably 1000 mm / sec or more. Here, the linear speed refers to the process speed of the printing press and is determined by the paper feed speed of the fixing unit.

[Softening point]
It is measured by the method of ASTM D36-86.

[Glass transition point and melting point]
A differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., DSC210) is used to measure at a heating rate of 10 ° C./min.

[Acid value]
Measured according to JIS K0070.

[Inherent viscosity number]
Measure according to ASTM D2857.

[Carrier saturation magnetization]
(1) Fill a plastic case with a lid with an outer diameter of 7 mm (inner diameter of 6 mm) and a height of 5 mm while tapping the carrier, and calculate the mass of the carrier from the difference between the weight of the plastic case and the weight of the plastic case filled with the carrier. .
(2) Set a plastic case filled with a carrier in the sample holder of the magnetic property measuring device “BHV-50H” (VS Magnetometer) of RIKEN ELECTRONICS CO., LTD. And add the plastic case using the vibration function. While shaking, a saturation magnetic field is measured by applying a magnetic field of 79.6 kA / m. The obtained value is converted into saturation magnetization per unit mass in consideration of the mass of the filled carrier.

Resin production example 1 (resins A to D, resin e)
Alcohol components and dibutyl oxide shown in Tables 1 and 3 were added to a 5-liter four-necked flask equipped with a dehydrating tube equipped with a rectifying column through which hot water of 95 ° C was passed, a nitrogen introducing tube, a stirrer and a thermocouple. After adding tin, the temperature was raised to 180 ° C., and half the amount of PET shown in Tables 1 and 3 was added. Thereafter, the temperature was raised to 200 ° C. and the remaining PET was added, and then carboxylic acid components other than trimellitic anhydride shown in Tables 1 and 3 were added. The reaction mixture was further heated, and finally reacted at 230 ° C. for 7 hours, and further reacted under reduced pressure at 50 kPa for 1 hour to obtain an intermediate.
Trimellitic anhydride was added to the obtained intermediate and reacted at 215 ° C. under the condition of 40 kPa until a desired softening point was reached to obtain Resins A to D and Resin e.

Resin Production Example 2 (Resin E)
The alcohol component and dibutyltin oxide shown in Table 2 were added to a 5-liter four-necked flask equipped with a dehydration tube equipped with a rectifying column through which hot water was passed at 95 ° C., a nitrogen introduction tube, a stirrer and a thermocouple. After the charging, the temperature was raised to 180 ° C., and half of the PET shown in Table 2 was charged. Thereafter, the temperature was raised to 200 ° C. and the remaining PET was added, then carboxylic acid components other than trimellitic anhydride shown in Table 2 were added, the temperature was raised, and the reaction was finally carried out at 230 ° C. for 8 hours. . Furthermore, after reacting under reduced pressure at 50 kPa for 1 hour, the mixture was cooled to 160 ° C., and a mixture of the raw material monomer of the addition polymerization resin shown in Table 2, the both reactive compounds and dibutyl peroxide was added dropwise over 1 hour. And polymerized. Furthermore, after aging the polymerization reaction for 1 hour, the temperature was raised to 210 ° C., trimellitic anhydride was added, and the reaction was carried out under the conditions of 215 ° C. and 40 kPa until a desired softening point was reached, thereby obtaining Resin E. .

Resin production example 3 (resins F, b)
The alcohol component, carboxylic acid component and dibutyltin oxide shown in Tables 2 and 3 were placed in a 5-liter four-necked flask equipped with a dehydrating tube, a nitrogen introducing tube, a stirrer and a thermocouple, and the temperature was raised to 235 ° C. The reaction was performed for 4 hours. Furthermore, it was made to react until it reached a desired softening point under reduced pressure at 8 kPa, and resin F and b were obtained.

Resin Production Example 4 (Resin G, c)
Dehydration tube, nitrogen introduction tube, stirrer, and thermocouple equipped with a rectifying column in which hot water at 95 ° C. was passed through the alcohol component, carboxylic acid component other than trimellitic anhydride and dibutyltin oxide shown in Tables 2 and 3 Was put in a 5 liter four-necked flask equipped with a temperature reaction from 185 ° C. to 230 ° C. over 8 hours, reacted at 50 kPa under reduced pressure for 1 hour, and trimellitic anhydride was added. Furthermore, it was made to react until it reached a desired softening point at 215 degreeC and 40 kPa, and resin G and c were obtained.

Resin Production Example 5 (Resin a)
Put the alcohol component, carboxylic acid component other than fumaric acid and dibutyltin oxide shown in Table 3 into a 5 liter four-necked flask equipped with a dehydration tube, a nitrogen introduction tube, a stirrer and a thermocouple, and raise the temperature to 230 ° C. And reacted for 7 hours. Next, the mixture was cooled to 180 ° C., fumaric acid and hydroquinone were added, the temperature was raised to 210 ° C. over 4 hours, and the reaction was further carried out under reduced pressure at 8 kPa until the desired softening point was reached to obtain a resin a. .

Resin Production Example 6 (Resin d)
The alcohol component shown in Table 3, carboxylic acid components other than fumaric acid, PET, and dibutyltin oxide were put into a 5-liter four-necked flask equipped with a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermocouple. The temperature was raised to 230 ° C. and reacted for 7 hours. Next, the mixture was cooled to 180 ° C., fumaric acid and hydroquinone were added, the temperature was raised to 210 ° C. over 4 hours, and the reaction was further performed under reduced pressure at 8 kPa until the desired softening point was reached, to obtain a resin d. .

Example of Carrier Production Magnesium oxide was blended with hematite so that the magnesium content was 3.0% by weight, and 100 parts by weight of the resulting mixture was mixed with 1.5 parts by weight of binder (polyvinyl alcohol) and 0. 5 parts by weight were added, and water was added so that the slurry concentration was 50%.
This was wet pulverized and mixed with an attritor manufactured by Mitsui Mining Co., Ltd. for 1 hour to prepare a slurry.

The slurry is granulated and dried with a spray dryer, then fired at about 1500 ° C. in a nitrogen atmosphere in an electric furnace, classified with a vibrating sieve, and expressed as MgO.Fe ₂ O ₃ .Fe ₃ O ₄ A magnesium ferrite carrier was obtained as the carrier core material.

With respect to 1000 parts by weight of the obtained core material, 6.5 parts by weight of the fluororesin “HYLAR301F” (Audimont) and 3.5 parts by weight of the acrylic resin “Dianar BR-80” (Mitsubishi Rayon Co., Ltd.) Methyl ethyl ketone was added to prepare a coating resin solution. This resin solution was spray coated on the core material using a fluid coating apparatus. Thereafter, a heat treatment was performed at 100 ° C. for 60 minutes in a fluidized bed to obtain a carrier A having an average particle size of 110 μm. The saturation magnetization of carrier A was 52.5 Am ² / kg.

Examples 1-6, 8-11, Comparative Examples 1-4 ( Examples 1-6, 8, 9, 11 are reference examples)
Binder resin shown in Table 4, carbon black “R330R” (Cabot) 8 parts by weight, charge control agent “Bontron N-01” (Orient Chemical Co., Ltd.) 2 parts and “Carnauba Wax C1” (Kato Yoko) 1 part by weight using a Henschel mixer was melted and kneaded with a twin screw extruder, cooled, and then subjected to normal pulverization and classification steps to obtain a powder. On the surface of 100 parts by weight of the obtained powder, 0.2 part by weight of hydrophobic silica “HVK2150” (manufactured by Clariant) was mixed and adhered using a Henschel mixer to obtain a toner having a volume average particle diameter of 10.2 μm. It was.

Example 7 (Reference Example)
A toner was obtained in the same manner as in Example 6 except that 8 parts by weight of a metal composite oxide “K-002” (manufactured by Toda Kogyo Co., Ltd.) containing iron and titanium as main components was used instead of carbon black. It was.

Test example 1
39 parts by weight of toner and 1261 parts by weight of carrier A were mixed with a Nauta mixer to obtain a two-component developer.

  Copying machine with modified two-component developer “LS-1550” (manufactured by Kyocera Corporation) (photosensitive material is amorphous silicon, rotation speed of fixing roller is set to 400 mm / sec, fixing roller in fixing device) The image is taken out while the fixing roller temperature in the fixing device is gradually increased from 90 ° C. to 240 ° C., and the minimum fixing temperature and hot offset are as follows. The generated temperature was measured. The results are shown in Table 4. Although the lowest fixing temperature is preferably low, the hot offset generation temperature needs to be 240 ° C. or higher in consideration of heat accumulation in the fixing roller.

[Minimum fixing temperature]
A sand eraser with a bottom of 15 mm x 7.5 mm under a load of 600 g. The image fixed through the fixing machine is rubbed 10 times, and the optical reflection density before and after rubbing is measured by a reflection densitometer “RD-915” (Macbeth) The fixing roller temperature at which the ratio of the two (image density after rubbing / image density before rubbing) first exceeds 70% is defined as the minimum fixing temperature.

[Hot offset generation temperature]
After the image is printed at each fixing temperature, the white transfer paper is continuously sent to the fixing roller under the same conditions, and the temperature of the fixing roller at which the toner is first smeared on the white paper is defined as the hot offset occurrence temperature.

Test example 2
The same two-component developer as that prepared in Test Example 1 was applied to a reversal development type printing machine “Infoprint4000ISl” (manufactured by IBM Japan, line speed: 1066 mm / sec, resolution: 240 dpi, developing machine magnet). The developer is mounted on 3 rolls (selenium photoconductor, contact development system), and a print pattern with a printing rate of 30% is printed on a 11 × 18 inch continuous paper sheet of 1 million sheets according to the following method. The charge amount of the toner after initial printing (10,000 sheets) and after printing (1 million sheets) was measured. The results are shown in Table 4. However, when it is confirmed that the image stain (solid non-uniformity or fogging) due to the deterioration of the toner is below the actual use level, it is determined that the toner has reached the end of its life, continuous printing is stopped, and the charge amount is measured. did.

[Charge amount]
It is measured using a q / m meter (manufactured by Epping). A specified amount of developer is introduced into a cell attached to the q / m meter, and only the toner is sucked through a sieve having a mesh size of 32 μm (made of stainless steel, twill, wire diameter: 0.0035 mm) for 90 seconds. The change in the voltage on the carrier generated at that time is monitored, and the value of [total amount of electricity after 90 seconds (μC) / amount of attracted toner (g)] is defined as the charge amount (μC / g).

  From the above results, the toner of the example has a low minimum fixing temperature and a high hot offset generation temperature, so that the fixing temperature range is wide, the life is long, and a good charge amount is maintained even after printing. can do. On the other hand, the toners of Comparative Examples 1, 2, and 4 containing polyester that does not use PET as a raw material have a low hot-fixing temperature and a short life although the minimum fixing temperature is low. Further, the toner of Comparative Example 3 containing only polyester using PET as a raw material as a binder resin has a high hot offset occurrence temperature but a high minimum fixing temperature.

In addition, the following are mentioned as an aspect of this invention.
[1] A toner containing a binder resin and a colorant, wherein the binder resin contains two kinds of resins having softening points different by 10 ° C. or more, and a resin having a higher softening point is A toner for developing an electrostatic charge image, which is a polyester obtained by reacting polyethylene terephthalate or modified polyethylene terephthalate, an alcohol component and a carboxylic acid component, or a hybrid resin having the polyester as one of resin components.
[2] The electrostatic image developing toner according to [1], wherein the polyethylene terephthalate or modified polyethylene terephthalate has an intrinsic viscosity of 0.7 to 1.
[3] The weight ratio of the resin having the higher softening point and the resin having the lower softening point (the resin having the higher softening point / the resin having the lower softening point) is 50/50 to 95/5. The toner for developing an electrostatic charge image according to 1 or 2.
[4] The toner for developing an electrostatic charge image according to any one of [1] to [3], further comprising a low melting point wax having a melting point of 50 to 120 ° C.
[5] The electrostatic image developing toner according to claim 4, wherein the low melting point wax is at least one selected from the group consisting of carnauba wax, montan ester wax, rice wax and candelilla wax.

Claims (4)

A toner comprising a binder resin and a colorant, wherein the binder resin contains two types of resins having different softening points of 10 ° C. or more, and the softening point of the resin having the higher softening point is The softening point of the resin having a lower softening point of 120 to 170 ° C. is 80 ° C. or higher and lower than 120 ° C., and either the resin having the higher softening point or the resin having the lower softening point is either polyethylene terephthalate or modified polyethylene terephthalate. And formula (I):

(Wherein R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16) Ri polyester der obtained by reacting a component, the weight ratio of the resin of the lower softening point resin having a higher softening point (resin lower of higher resin / softening point softening point) 50 / 50-95 / 5 der Ru toner for electrostatic image development.   2. The electrostatic image developing toner according to claim 1, wherein the polyethylene terephthalate or the modified polyethylene terephthalate has an intrinsic viscosity of 0.7 to 1. Further, according to claim 1 or 2 toner according comprising a low melting wax having a melting point of 50 to 120 ° C.. 4. The electrostatic image developing toner according to claim 3 , wherein the low melting point wax is at least one selected from the group consisting of carnauba wax, montan ester wax, rice wax and candelilla wax.