JP7018828B2 - Bound resin composition for toner - Google Patents

Description

The present invention relates to a binder resin composition for toner used for developing latent images formed in, for example, an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and an electrograph containing the binder resin composition. Regarding toner for printing.

Patent Document 1 describes an amorphous resin composition having a softening point of 120 ° C. or higher and 170 ° C. or lower as a binder resin composition for toner capable of obtaining an electrophotographic toner having excellent low-temperature fixability, durability, and glossiness of printed matter. A binder resin composition for toner containing a quality polyester (AH), an amorphous polyester (AL) having a softening point of 80 ° C. or higher and lower than 120 ° C., and a crystalline polyester (C). The polyester (AH) is a polyester obtained by polycondensing an alcohol component (AH-al) containing an alkylene oxide adduct (AH-bp) of bisphenol A and a carboxylic acid component (AH-ac). , The alcohol component (AH-al) contains 3 mol% or more and less than 20 mol% of the propylene oxide adduct of bisphenol A in which the number of added moles of propylene oxide is 3 mol or more and 6 mol or less, and the amorphous polyester ( AL) is a polyester obtained by polycondensing an alcohol component (AL-al) containing an alkylene oxide adduct (AL-bp) of bisphenol A and a carboxylic acid component (AL-ac). A binder resin composition for toner containing 20 mol% or more and 70 mol% or less of a propylene oxide adduct of bisphenol A having an alcohol component (AL-al) of 3 mol or more and 6 mol or less of propylene oxide. It has been disclosed.

Patent Document 2 describes heat treatment of toner particles containing a binder resin, a mold release agent, and a colorant as a toner capable of maintaining high transferability even in long-term image output while satisfying low-temperature fixability. The crystalline polyester obtained by subjecting the toner particles to a polycondensation reaction between an aliphatic diol having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms. A resin, crystalline with a moiety derived from one or more aliphatic compounds selected from the group consisting of an aliphatic monocarboxylic acid having 8 or more and 20 or less carbon atoms and an aliphatic monoalcohol having 8 or more and 20 carbon atoms or less. Toners containing polyester resins are disclosed.

Patent Document 3 describes amorphous resins, colorants, and crystals as toners that can satisfy high transferability even in long-term image output while achieving both low-temperature fixability and hot offset resistance. A toner having toner particles containing a sex resin, the amorphous resin contains a resin A containing polyester as a main component, a resin B containing polyester as a main component, and a resin C containing polyester as a main component. The crystalline resin is a resin containing polyester as a main component, and the resin A has a polyvalent alcohol unit and a polyvalent carboxylic acid unit, has a softening point of 130 ° C. or higher and 150 ° C. or lower, and has a Fedors formula. The compatibility parameter SP (A) required for the above is 12.55 ≦ SP (A) ≦ 13.00, and the resin B has a polyvalent alcohol unit and a polyvalent carboxylic acid unit, and has a softening point of 80. The temperature is equal to or higher than 95 ° C., and the compatibility parameter SP (B) required by the Polyester formula is 11.80 ≦ SP (B) ≦ 12.40, and the resin C has a polyvalent alcohol unit and a polyvalent value. It has a carboxylic acid unit, a softening point is 100 ° C. or higher and 120 ° C. or lower, and the compatibility parameter SP (C) required by the Polyester formula is 12.40 ≦ SP (C) ≦ 12.55. Characteristic toners are disclosed.

Japanese Unexamined Patent Publication No. 2016-45357 Japanese Unexamined Patent Publication No. 2017-15912 Japanese Unexamined Patent Publication No. 2017-146338

Printing using an electrophotographic toner has the advantage of being rich in variety of printing media, and it is possible to print on various media with one printing machine.
However, although printing is possible on smooth media such as coated paper and PET film, there is a problem that the scratch resistance of the image is easily impaired by rubbing with a sand eraser or the like. This is because in the case of paper, the adhesive area is large due to the unevenness of the surface, and there is no problem even if there is some insufficient melting on the adhesive surface, but with smooth media, the entire toner needs to be melted more evenly. Therefore, it is presumed that if there is even a slight lack of melting, the adhesive strength of the printed image will be weakened. Further, since the plastic film is sensitive to heat, it has a problem that it is easily curled by the heat at the time of fixing.

INDUSTRIAL APPLICABILITY The present invention provides a binder resin composition for toner, which has good heat-resistant storage stability, is excellent in scratch resistance of an image even when printed on a plastic film, and does not easily curl the film due to heat during fixing. The present invention relates to an electrophotographic toner containing the binder resin composition.

The present invention
[1] A binder resin for toner containing an amorphous polyester AH having a softening point of 130 ° C. or higher and 145 ° C. or lower, an amorphous polyester AL having a softening point of 90 ° C. or higher and 105 ° C. or lower, and a crystalline polyester C. It ’s a composition,
The glass transition temperature of the amorphous polyester AH is 1 ° C. or higher and 10 ° C. or lower lower than the glass transition temperature of the amorphous polyester AL.
The acid value of the amorphous polyester AH is 5 mgKOH / g or more and 25 mgKOH / g or less higher than the acid value of the amorphous polyester AL.
The crystalline polyester C is a polycondensate of an alcohol component containing 1,6-hexanediol and a carboxylic acid component containing dodecane diic acid and stearic acid, and the content of stearic acid is the carboxylic acid component. Medium, 1 mol% or more and 7 mol% or less,
The melting point of the crystalline polyester C is 70 ° C. or higher and 74 ° C. or lower.
Bound resin composition for toner,
[2] An image is printed on a plastic film using the electrophotographic toner containing the toner binding resin composition according to the above [1] and [3] the electrophotographic toner according to the above [2]. , Regarding the printing method.

The electrophotographic toner containing the binder resin composition of the present invention has good heat-resistant storage properties, is excellent in scratch resistance of images even when printed on a plastic film, and is affected by heat during fixing. It has an excellent effect that the film is hard to curl.

The binder resin composition for toner of the present invention contains amorphous polyester AH and amorphous polyester AL having different softening points, and crystalline polyester C.

As a binder resin for toner, a technique of using a high softening point resin for ensuring a non-offset region and a low softening point resin for ensuring low temperature fixability in combination is widely used. In this case, the image is scratch resistant. In order to improve the properties, it is common to make the low softening point resin easier to melt by a method of lowering the thermophysical properties such as lowering the softening point and lowering the glass transition temperature. However, with a smooth medium such as a plastic film, the scratch resistance of the image deteriorates when the thermal characteristics are lowered. It is presumed that this is because the viscosity of the binder resin at the time of fixing is lowered, so that the adhesive area of the printed image becomes smaller due to being repelled by the base material (media).
On the other hand, in the present invention, for example, the glass transition temperature of the amorphous polyester AH at the high softening point is lowered and / or the glass transition temperature of the amorphous polyester AL at the low softening point is raised to be amorphous. By lowering the glass transition temperature of the amorphous polyester AH to the glass transition temperature of the amorphous polyester AL, the insufficient melting of the amorphous polyester AH is eliminated without impairing the heat storage stability, and the viscosity is partially extremely extreme. It is possible to suppress the decrease.
Further, by making the acid value of the amorphous polyester AH higher than the acid value of the amorphous polyester AL and using the crystalline polyester C obtained by using stearic acid in combination, the crystalline polyester C becomes an amorphous polyester. By interacting with AL, it is possible to prevent the amorphous polyester AH from being repelled by the plastic film at the time of fixing, and it is possible to further improve the adhesiveness of the printed image.
Further, by using the crystalline polyester C having a low melting point in combination, the low temperature fixability is improved and the curl of the plastic film at the time of fixing is suppressed.

The crystallinity of the resin is represented by the crystallinity index defined by the ratio of the softening point to the maximum endothermic temperature by the differential scanning calorimeter, that is, the value of [softening point / maximum endothermic temperature]. Crystalline resins have a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less, while amorphous resins have a crystallinity index of 0.6 or more. The resin is more than 1.4, preferably more than 1.5, more preferably 1.6 or more, or less than 0.6, preferably 0.5 or less. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, the production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In the crystalline resin, the melting point is the maximum peak temperature of endothermic process.

The amorphous polyester AH and the amorphous polyester AL are preferably a polycondensate of an alcohol component containing a propylene oxide adduct of bisphenol A and a carboxylic acid component from the viewpoint of heat storage stability.

In the propylene oxide adduct of bisphenol A, the average number of moles of propylene oxide added is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, still more preferably 6 or less. More preferably, it is 4 or less. The propylene oxide adduct of bisphenol A used in the amorphous polyester AH and the amorphous polyester AL may be the same or different.

The content of the propylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AH is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100. It is mol% or less, preferably 99.8 mol% or less, and more preferably 99.5 mol% or less. The same applies to the content of the propylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AL.

The alcohol component of the amorphous polyester AH and the amorphous polyester AL preferably further contains an ethylene oxide adduct of bisphenol A from the viewpoint of low temperature fixability. In the ethylene oxide adduct of bisphenol A, the average number of moles of ethylene oxide added is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, still more preferably 6 or less. More preferably, it is 4 or less.

The content of the ethylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AH is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, and preferably 10 mol% or less, more preferably. Is less than 5 mol%. The content of the ethylene oxide adduct of bisphenol A in the alcohol component of the amorphous polyester AL is also the same.

Other alcohol components include aromatic diols other than the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A, aliphatic diols, bisphenol A, hydrogenated bisphenol A, glycerin and other trihydric or higher polyhydric alcohols. And so on.

Examples of the carboxylic acid component of the amorphous polyester AH include aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and carboxylic acid compounds having a valence of 3 or more. From the viewpoint of compatibility, it is preferable to contain an aliphatic dicarboxylic acid compound having 4 or more and 14 or less carbon atoms. In the present invention, the carboxylic acid compound includes not only a free acid but also an anhydride which decomposes during a reaction to generate an acid, and an alkyl ester having 1 or more and 3 or less carbon atoms.

As aliphatic dicarboxylic acid compounds having 4 or more and 14 or less carbon atoms, adipic acid, succinic acid, sebacic acid, dodecanedioic acid, tetradecanoic acid, anhydrates of these acids and their acids have 1 or more and 3 or less carbon atoms. Of these, adipic acid is preferable.

The content of the aliphatic dicarboxylic acid compound having 4 or more and 14 or less carbon atoms, preferably adipic acid, is preferably 20 mol% or more, more preferably 25 mol% or more, in the carboxylic acid component of the amorphous polyester AH. It is more preferably 30 mol% or more, and from the viewpoint of heat storage stability, it is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less.

Further, the carboxylic acid component of the amorphous polyester AH preferably contains an aromatic dicarboxylic acid compound from the viewpoint of heat storage stability.

Examples of the aromatic dicarboxylic acid-based compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrates of these acids, and alkyl esters having 1 or more and 3 or less carbon atoms in these acids. Terephthalic acid is preferred.

The content of the aromatic dicarboxylic acid-based compound is preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more, and more preferably 40 mol% or more in the carboxylic acid component of the amorphous polyester AH. From the viewpoint of suppressing curl of the film, it is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 45 mol% or less.

The carboxylic acid component of the amorphous polyester AH preferably contains a carboxylic acid compound having a valence of 3 or more from the viewpoint of adjusting the softening point.

As the trivalent or higher carboxylic acid compound, a trivalent or higher aromatic carboxylic acid compound is preferable, for example, 1,2,4-benzenetricarboxylic acid (trimertic acid), 1,2,4,5-benzenetetra. Examples thereof include carboxylic acids (pyromellitic acids), anhydrides of these acids, and alkyl esters having 1 or more and 3 or less carbon atoms in these acids.

The content of the carboxylic acid compound having a valence of 3 or more is preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 30 mol% or less, in the carboxylic acid component of the amorphous polyester AH. More preferably, it is 25 mol% or less.

The molar ratio of the aliphatic dicarboxylic acid compound having 4 or more and 14 or less carbon atoms and the total amount of the aromatic dicarboxylic acid compound and the aromatic carboxylic acid compound having 3 or more valences (aliphatic dicarboxylic acid having 4 or more and 14 or less carbon atoms). The total amount of the acid compound / aromatic dicarboxylic acid compound and the aromatic carboxylic acid compound having a valence of 3 or more) is preferably 0.2 or more, more preferably 0.35, from the viewpoint of scratch resistance of the image and suppression of curl of the film. The above is more preferably 0.5 or more, and from the same viewpoint, it is preferably 0.9 or less, more preferably 0.75 or less, and even more preferably 0.6 or less.

Examples of the carboxylic acid component of the amorphous polyester AL include aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and carboxylic acid compounds having a valence of 3 or more. From the viewpoint of heat resistance, aromatic dicarboxylic acids are used. Acidic compounds are preferred. Examples of the aromatic dicarboxylic acid-based compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrates of these acids, and alkyl esters having 1 or more and 3 or less carbon atoms in these acids. Terephthalic acid is preferred.

The content of the aromatic dicarboxylic acid compound is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 100 mol% or more in the carboxylic acid component of the amorphous polyester AL.

Examples of other carboxylic acid components include aliphatic dicarboxylic acid compounds and carboxylic acid compounds having a valence of 3 or more, but the carboxylic acid component of amorphous polyester AL has a valence of 3 or more from the viewpoint of adjusting the softening point. It is preferable that the carboxylic acid-based compound is not contained, or even if it is contained, the amount is small.

The content of the carboxylic acid compound having a valence of 3 or more is preferably 3 mol% or less, more preferably 1 mol% or less, and further preferably 0 mol% in the carboxylic acid component of the amorphous polyester AL. The content of the aliphatic dicarboxylic acid compound is preferably 3 mol% or less, more preferably 1 mol% or less, still more preferably 0 mol% in the carboxylic acid component of the amorphous polyester AL.

Further, the alcohol component of the amorphous polyester AH and the amorphous polyester AL contains a monovalent alcohol, and the carboxylic acid component contains a monovalent carboxylic acid compound as appropriate from the viewpoint of molecular weight adjustment and the like. May be good.

The equivalent ratio (alcohol component / carboxylic acid component) of the alcohol component and the carboxylic acid component of the amorphous polyester AH is preferably 1.0 or more, more preferably 1.01 or more, and curls of the film from the viewpoint of heat storage stability. From the viewpoint of suppression, it is preferably 1.3 or less, more preferably 1.25 or less, and further preferably 1.18 or less.

The equivalent ratio (alcohol component / carboxylic acid component) of the alcohol component and the carboxylic acid component of the amorphous polyester AL is preferably 1.0 or more, more preferably 1.05 or more, and further preferably 1.11 or more from the viewpoint of heat storage stability. From the viewpoint of suppressing curl of the film, it is preferably 1.54 or less, more preferably 1.42 or less, and further preferably 1.33 or less.

The polycondensation reaction between the alcohol component and the carboxylic acid component of the amorphous polyester AH and the amorphous polyester AL is carried out, for example, in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, assists in esterification. In the presence of a catalyst, a polymerization inhibitor, etc., the reaction can be carried out at a temperature of preferably 130 ° C. or higher, more preferably 170 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.

In the present invention, the polyester may be a polyester modified to such an extent that its characteristics are not substantially impaired, regardless of whether it is amorphous or crystalline. The modified polyester may be grafted or blocked with phenol, urethane, epoxy or the like by the methods described in, for example, JP-A-11-133668, JP-A-10-239903, JP-A-8-20636 and the like. Among the modified polyesters, a urethane-modified polyester resin obtained by urethane-stretching a polyester resin with a polyisocyanate compound is preferable.

The softening point of the amorphous polyester AH is 130 ° C. or higher, preferably 132 ° C. or higher, and from the same viewpoint, 145 ° C. or lower, preferably 140 ° C. or lower, from the viewpoint of scratch resistance of the image. If the softening point of the amorphous polyester AH is too high, the melting resistance at the time of fixing is insufficient, and if it is too low, the melting viscosity of the entire binder resin is lowered, so that the scratch resistance of the image is lowered.

The glass transition temperature of the amorphous polyester AH is preferably 48 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 52 ° C. or higher from the viewpoint of heat resistance storage, and from the viewpoint of suppressing curl of the film. It is preferably 63 ° C. or lower, more preferably 60 ° C. or lower, and even more preferably 57 ° C. or lower.

The glass transition temperature of the amorphous polyester AH is lower than the glass transition temperature of the amorphous polyester AL from the viewpoint of image abrasion resistance and curl suppression of the film, and the difference is 1 ° C. or higher, preferably 2 ° C. As described above, it is more preferably 3 ° C. or higher, and from the viewpoint of storage stability, it is 10 ° C. or lower, preferably 8 ° C. or lower, and more preferably 6 ° C. or lower.

The acid value of the amorphous polyester AH is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and suppresses curl of the film, from the viewpoint of scratch resistance of the image. From the viewpoint of the above, it is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and further preferably 20 mgKOH / g or less.

The acid value of the amorphous polyester AH is higher than the acid value of the amorphous polyester AL from the viewpoint of scratch resistance of the image, and the difference is 5 mgKOH / g or more, preferably 8 mgKOH / g or more, more preferably. It is 10 mgKOH / g or more, and from the same viewpoint, it is 25 mgKOH / g or less, preferably 20 mgKOH / g or less, and more preferably 16 mgKOH / g or less.

The softening point of the amorphous polyester AL is 90 ° C. or higher, preferably 95 ° C. or higher, and 105 ° C. or lower, preferably 102 ° C. or lower, from the viewpoint of curl suppression of the film. ..

The glass transition temperature of the amorphous polyester AL is preferably 50 ° C. or higher, more preferably 54 ° C. or higher, still more preferably 58 ° C. or higher from the viewpoint of heat resistance storage, and from the viewpoint of suppressing curl of the film. It is preferably 70 ° C. or lower, more preferably 65 ° C. or lower, and even more preferably 60 ° C. or lower.

The acid value of the amorphous polyester AL is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 3 mgKOH / g or more, and the scratch resistance of the image, from the viewpoint of suppressing curl of the film. From the viewpoint of the above, it is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, and further preferably 5 mgKOH / g or less.

The number average molecular weight of the amorphous polyester AL is preferably 1000 or more, more preferably 1300 or more, still more preferably 1500 or more from the viewpoint of scratch resistance of the image, and preferably from the viewpoint of suppressing curl of the film. Is below, more preferably 3000 or less, still more preferably 2600 or less.

From the same viewpoint, the weight average molecular weight of the amorphous polyester AL is preferably 3000 or more, more preferably 3500 or more, still more preferably 3600 or more, and preferably 6500 or less, more preferably 6100 or less. More preferably, it is 5900 or less.

The solution viscosity of the amorphous polyester AL at 20 ° C. is preferably 2.4 mPa · s or more, more preferably 2.5 mPa · s or more, still more preferably 2.6 mPa · s or more, from the viewpoint of scratch resistance of the image. From the viewpoint of suppressing curl of the film, it is preferably 4.0 mPa · s or less, more preferably 3.9 mPa · s or less, and further preferably 3.7 mPa · s or less.

The mass ratio of the amorphous polyester AH and the amorphous polyester AL (amorphous polyester AH / amorphous polyester AL) is preferably 0.1 or more, more preferably 0.15 or more, and more preferably from the viewpoint of suppressing curl of the film. Is 0.2 or more, and from the viewpoint of scratch resistance of the image, it is preferably 0.8 or less, more preferably 0.6 or less, and more preferably 0.4 or less.

The content of the amorphous polyester AH in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less. Is.

The content of the amorphous polyester AL in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less. , More preferably 75% by mass or less.

The crystalline polyester C is a polycondensate of an alcohol component containing 1,6-hexanediol and a carboxylic acid component containing dodecane diic acid and stearic acid.

The combination of 1,6-hexanediol and dodecane diacid is effective as a raw material monomer that easily forms a regular crystal structure and enhances the crystallinity of polyester. In the present invention, in addition to these, as described above. Therefore, it has one feature in using stearic acid. Stearic acid improves sharp meltability and makes it possible to suppress curl of the plastic film during fixing.

The content of 1,6-hexanediol in the alcohol component of crystalline polyester C is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more. , More preferably 100 mol%.

Other alcohol components include aliphatic diols other than 1,6-hexanediol, aromatic diols such as alkylene oxide adducts of bisphenol A, and trihydric or higher polyhydric alcohols such as bisphenol A, hydrogenated bisphenol A, and glycerin. And so on.

The content of dodecane diic acid in the carboxylic acid component of the crystalline polyester C is preferably 95 mol% or more, more preferably 96 mol% or more, and 100 mol% or less from the viewpoint of crystallinity. , Preferably 99 mol% or less.

The content of stearic acid in the carboxylic acid component of the crystalline polyester C is 1 mol% or more, preferably 2 mol% or more, from the viewpoint of scratch resistance of the image, and from the viewpoint of heat storage stability. , 7 mol% or less, preferably 5 mol% or less.

Other carboxylic acid components include aliphatic dicarboxylic acids other than dodecanedioic acid, aromatic dicarboxylic acids, trivalent or higher carboxylic acids, anhydrides of these acids, and alkyls having 1 or more and 3 or less carbon atoms in these acids. Examples include esters.

The equivalent ratio (alcohol component / carboxylic acid component) of the alcohol component and the carboxylic acid component of the crystalline polyester C is preferably 1.00 or more, more preferably 1.01 or more, and is resistant to the surface smoothness of the printed image. From the viewpoint of document offset, it is preferably 1.05 or less, more preferably 1.04 or less. The equivalent ratio of the alcohol component and the carboxylic acid component is the ratio of the OH group contained in the alcohol component to the COOH group contained in the carboxylic acid component, and is the valence of the raw material monomer constituting each of the alcohol component and the carboxylic acid component. Calculate the ratio of the sum of the products of the number of moles and the number of moles.

The polycondensation reaction between the alcohol component and the carboxylic acid component of the crystalline polyester C is carried out, for example, in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification co-catalyst or the like. , Can be carried out at a temperature of 135 ° C or higher and 250 ° C or lower.

The melting point of the crystalline polyester C is 70 ° C. or higher, preferably 71 ° C. or higher, and 74 ° C. or lower, preferably 73 ° C. or lower, from the viewpoint of curl suppression of the film. , More preferably 72 ° C. or lower.

From the viewpoint of sharp meltability, the acid value of the crystalline polyester C is preferably 1 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, still more preferably 2 mgKOH / g or more, and the scratch resistance of the image. From the viewpoint, it is preferably 10 mgKOH / g or less, more preferably 8 mgKOH / g or less, still more preferably 6 mgKOH / g or less, still more preferably 4 mgKOH / g or less.

The total acid value and hydroxyl value of the crystalline polyester C is preferably 8 mgKOH / g or more, more preferably 9 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and more preferably 10 mgKOH / g or more, from the viewpoint of scratch resistance of the image. From the viewpoint of heat-resistant storage, it is preferably 20 mgKOH / g or less, more preferably 18 mgKOH / g or less, and further preferably 17 mgKOH / g or less.

The number average molecular weight of the crystalline polyester C is preferably 4,000 or more, more preferably 4,500 or more, still more preferably 4,800 or more from the viewpoint of scratch resistance of the image, and preferably from the viewpoint of suppressing curl of the film. It is 10,000 or less, more preferably 9,500 or less, still more preferably 9,000 or less.

From the same viewpoint, the weight average molecular weight of the crystalline polyester C is preferably 17,000 or more, more preferably 19,000 or more, still more preferably 21,000 or more, and preferably 35,000 or less, more preferably 33,000 or less, and further. It is preferably 31,000 or less.

The solution viscosity of the crystalline polyester C at 20 ° C. is preferably 3 mPa · s or more, more preferably 3.5 mPa · s or more, still more preferably 3.6 mPa · s or more, and more preferably 3.6 mPa · s or more, from the viewpoint of scratch resistance of the image. From the same viewpoint, it is preferably 6 mPa · s or less, more preferably 5.5 mPa · s or less.

The content of the crystalline polyester C in the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more from the viewpoint of curl suppression of the film, and preferably from the viewpoint of heat storage stability. It is 15% by mass or less, more preferably 12% by mass or less.

Further, the mass ratio of the total amount of the crystalline polyester C, the amorphous polyester AH and the amorphous polyester AL (the total amount of the crystalline polyester C / amorphous polyester AH and the amorphous polyester AL) is the curl of the film. From the viewpoint of suppression, it is preferably 5/95 or more, more preferably 8/92 or more, and from the viewpoint of heat-resistant storage, it is preferably 15/85 or less, more preferably 12/88 or less.

The binder resin composition of the present invention may contain a resin other than the above-mentioned amorphous polyester AH, amorphous polyester AL, and crystalline polyester C, but amorphous polyester AH and amorphous polyester AH. The total content of the quality polyester AL and the crystalline polyester C is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass in the binder resin composition. % Or more, more preferably 100% by mass.

Using the binder resin composition of the present invention as a binder resin, the toner for electrophotographic of the present invention can be obtained. In the binder resin composition of the present invention, a mixture of amorphous polyester AH, amorphous polyester AL, and crystalline polyester C may be used as the binder resin, and these may be used when producing toner. The resin may be directly used for mixing the raw materials.

In addition to the binder resin, the toner of the present invention includes colorants, mold release agents, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, and the like. Additives such as a cleaning property improving agent may be contained.

As the colorant, dyes, pigments and the like used as colorants for toner can be used. For example, Carbon Black, Phthalocyanine Blue, Permanent Brown FG, Brilliant First Scarlet, Pigment Red 122, Pigment Green B, Rhodamine-B Base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmin 6B, Isoindoline, Disazoero And so on. In the present invention, the toner particles may be either black toner or color toner.

The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image concentration and low temperature fixability of the toner. It is preferably 40 parts by mass or less, more preferably 10 parts by mass or less.

As the release agent, hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax and their oxides; carnauba wax, montane. Waxes and ester waxes such as deoxidized waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like can be mentioned, and these can be used alone or in combination of two or more.

The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher from the viewpoint of toner transferability, and preferably 160 ° C. or lower, more preferably 150 ° C. or higher from the viewpoint of low temperature fixability. It is as follows.

The content of the release agent is preferably 0.5 part by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of low temperature fixing property and offset resistance of the toner and dispersibility in the binder resin. It is preferably 1.0 part by mass or more, more preferably 1.5 part by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 7 parts by mass or less.

The charge control agent is not particularly limited and may contain either a positive charge control agent or a negative charge control agent.

Positive charge control agents include niglosin dyes such as "niglocin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industry Co., Ltd.), etc .; Triphenylmethane dyes containing a tertiary amine as a side chain, for example, a quaternary ammonium salt compound. "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant), etc .; (Manufactured), etc .; imidazole derivatives such as "PLZ-2001", "PLZ-8001" (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc .; styrene-acrylic resin, for example "FCA-701PT" (Fujikura Kasei Co., Ltd.) Made) and the like.

Examples of the negative charge control agent include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36". (The above is manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-" 147 ”,“ LR-297 ”(above, manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example,“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ Bontron E-304 "(above, manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 "(manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt, for example," COPY CHARGE NX VP434 " (Manufactured by Clariant), nitroimidazole derivatives, etc .; organic metal compounds and the like can be mentioned.

The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.2 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of charge stability of the toner. Parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, etc., but from the viewpoint of productivity and dispersibility of the colorant, the toner may be obtained. Crushed toner by the melt-kneading method is preferable. In the case of crushed toner by the melt-kneading method, for example, raw materials such as a binder resin, a colorant, a mold release agent, and a charge control agent are uniformly mixed with a mixer such as a Henshell mixer, and then a closed kneader, 1 shaft or 2 It can be manufactured by melt-kneading with a shaft extruder, an open roll type kneader, etc., cooling, crushing, and classifying.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

It is preferable to use an external additive for the toner of the present invention in order to improve the transferability. 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 particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles. The above may be used together. Among these, silica is preferable, and from the viewpoint of toner transferability, hydrophobicized silica is more preferable.

Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Will be.

The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and further, from the viewpoint of the chargeability, fluidity, and transferability of the toner. It is preferably 90 nm or less.

From the viewpoint of the chargeability, fluidity, and transferability of the toner, the content of the external additive is preferably 0.05 part by mass or more, more preferably 0.1 mass by mass, based on 100 parts by mass of the toner before being treated with the external additive. More than parts, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The toner of the present invention can be used as it is as a toner for one-component development or as a toner for two-component development used by mixing with a carrier, respectively, in a one-component development method or a two-component development method image forming apparatus.

Images can be printed on a plastic film using the toner of the present invention. Examples of the plastic film film include films such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, ethylene / vinyl acetate copolymer, polypropylene, cellulose acetate, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), and polycarbonate. However, polyethylene terephthalate (PET) film is preferable.

Printing on a plastic film using the toner of the present invention can be performed by an electrophotographic method or the like. Specifically, for example, a charging step of charging the photoconductor, an exposure step of exposing the photoconductor, and photosensitization. A developing step of adhering toner particles in a liquid developer to form a toner image on an electrostatic latent image formed on the body, a transfer step of transferring the formed toner image to a resin film, and a transfer step. Examples thereof include a fixing step of heating a toner image and fixing it to a plastic film.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical properties of the resin and the like were measured by the following methods.

[Plastic softening point]
Using the flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C / min, a load of 1.96 MPa was applied by a plunger to a diameter of 1 mm and a length of 1 mm. Extrude from the nozzle of. 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 used as the softening point.

[Maximum endothermic temperature of resin]
Using the differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, and cool down from room temperature (25 ° C) to 10 ° C. Cool to 0 ° C at / min and maintain at 0 ° C for 1 minute. Then, the temperature is measured at a heating rate of 10 ° C./min. Of the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the maximum endothermic temperature.

[Resin glass transition temperature]
Using the differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan), weigh 0.01 to 0.02 g of the sample in an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from that temperature to 10. Cool to 0 ° C at ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum peak temperature of heat absorption and the tangent line indicating the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition temperature.

[Acid value of resin]
Measure based on the method of JIS K 0070: 1992. However, only the measurement solvent is from the mixed solvent of ethanol and ether specified in JIS K 0070, the amorphous resin is the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)), and the crystalline resin is chloroform. : Change to a mixed solvent of dimethylformamide (chloroform: dimethylformamide = 7: 3 (volume ratio)).

[Hydroxyl group value of resin]
Measure based on the method of JIS K 0070: 1992. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to tetrahydrofuran.

[Number average molecular weight (Mn) and weight average molecular weight (Mw) of resin]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by the gel permeation chromatography (GPC) method by the following method.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) at 40 ° C so that the concentration becomes 0.5 g / 100 mL. Next, this solution is filtered using a PTFE type membrane filter "DISMIC-25JP" (manufactured by Toyo Filter Paper Co., Ltd.) having a pore size of 0.20 μm to remove insoluble components, and the sample solution is used.
(2) Molecular weight measurement Using the following measuring device and analysis column, tetrahydrofuran (amorphous resin) or chloroform (crystalline resin) was flowed as an eluent at a flow rate of 1 mL per minute, and the column was placed in a constant temperature bath at 40 ° C. To stabilize. Inject 100 μL of the sample solution into it and measure. The molecular weight of the sample is calculated based on the calibration curve prepared in advance. At this time, the calibration curve includes several types of monodisperse polystyrene (A-500 (5.0 x 10 ² ), A-1000 (1.01 x 10 ³ ), A-2500 (2.63 x 10 ³ ) manufactured by Tosoh Corporation). A-5000 (5.97 x 10 ³ ), F-1 (1.02 x 10 ⁴ ), F-2 (1.81 x 10 ⁴ ), F-4 (3.97 x 10 ⁴ ), F-10 (9.64 x 10 ⁴ ), F-20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) are used as standard samples. The numbers in parentheses indicate the molecular weight.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: TSKgel GMH _XL + TSKgel G3000H _XL (manufactured by Tosoh Corporation)

[Solution viscosity of crystalline resin]
Accurately weigh 0.50 g of resin and 9.50 g of chloroform in a screw bottle. Then, the screw bottle is stirred with a ball mill for 30 minutes or more, and the solution is uniformly dissolved as a sample solution. Set the temperature of the constant temperature water tank to 20 ° C, and attach the rotor to the E-type viscometer (TVE-25L (manufactured by Toki Sangyo Co., Ltd.)). Using Pipetman, inject 1.1 mL of the sample solution into the sample cup of the E-type viscometer so that bubbles do not enter. A sample cup is attached to the main body of the E-type viscometer, and measurement is performed under the conditions of a rotation speed of 50 r / min, a measurement range of M, and a measurement time of 1 minute. The value after the equipment is stopped is taken as the value of the solution viscosity.

[Solution viscosity of amorphous resin]
Accurately weigh 2.0 g of resin and 8.0 g of tetrahydrofuran in a screw bottle. After that, it is measured in the same manner as the melt viscosity of the crystalline resin.

[Melting point of mold release agent]
Using the differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan and heat up to 200 ° C at a temperature rise rate of 10 ° C / min. Raise the temperature and cool from that temperature to -10 ° C at a lowering rate of 5 ° C / min. Next, the sample is heated to 180 ° C at a heating rate of 10 ° C / min and measured. The maximum peak temperature of endothermic observed from the melted endothermic curve obtained there is taken as the melting point of the mold release agent.

[Average particle size of external additive]
The average particle size refers to the number average particle size, and the particle size (the average value of the major axis and the minor axis) of 500 particles is measured from a scanning electron microscope (SEM) photograph, and the number average value thereof is used.

[Medium particle size of toner]
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter Co., Ltd.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter Co., Ltd.)
Electrolyte: Isoton II (manufactured by Beckman Coulter Co., Ltd.)
Dispersion solution: Emulgen 109P (manufactured by Kao Co., Ltd., polyoxyethylene lauryl ether, HLB (griffin): 13.6) was dissolved in an electrolytic solution to adjust the content to 5% by mass. Was added and dispersed with an ultrasonic disperser (machine name: US-1, manufactured by SND Co., Ltd., output: 80 W) for 1 minute, then 25 mL of the electrolytic solution was added, and further to the ultrasonic disperser. Disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: To 100 mL of the electrolytic solution, add the sample dispersion so that the particle size of 30,000 particles can be measured in 20 seconds, measure 30,000 particles, and measure the volume from the particle size distribution. Determine the medium particle size (D ₅₀ ).

Resin production example 1
BPA-PO, BPA-EO, terephthalic acid shown in Table 1, 40 g of polonium dihydroxybis (triethanolaminate) as an esterification catalyst and 1 g of gallic acid as an esterification co-catalyst were added, and the reaction was carried out at 230 ° C. for 10 hours. went. After the reaction, the temperature was lowered to 190 ° C., adipic acid was added, and the reaction was carried out at normal pressure for 2 hours. Further, trimellitic anhydride was added, and after the reaction for 11 hours, the reaction was carried out at 8 KPa until the softening point shown in Table 1 was reached to obtain an amorphous polyester (resins AH1 to AH5).

Resin production example 2
BPA-PO, BPA-EO, terephthalic acid shown in Table 2, 40 g of titanium dihydroxybis (triethanolaminate) as an esterification catalyst and 1 g of gallic acid as an esterification co-catalyst were added, and the reaction was carried out at 230 ° C. for 10 hours. went. Further, the reaction was carried out at 8 KPa until the softening point shown in Table 2 was reached to obtain amorphous polyesters (resins AL1 to AL5).

Resin production example 3
The alcohol component and carboxylic acid component shown in Table 3 were placed in a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, heated to 140 ° C, and reacted for 6 hours. (Reaction rate 65%), the reaction was carried out while raising the temperature to 200 ° C. at 10 ° C./h. After reacting to a reaction rate of 80% at 200 ° C., 20 g of titanium dihydroxybis (triethanolamineate) was added as an esterification catalyst, and the reaction was further carried out at 200 ° C. for 2 hours. Further, the reaction was carried out at 8 kPa for 2 hours to obtain crystalline polyesters (resins C1 to C7).

Examples 1 to 12 and Comparative Examples 1 to 5
100 parts by mass of binder resin shown in Table 4, colorant "Fastgen Super Magenta R" (CI Pigment Red 122, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 6 parts by mass, charge control agent "LR-147" (Japan) 1 part by mass of Carlit) and 4 parts by mass of mold release agent "Carnauba Wax C1" (Made by Hiroyuki Kato, melting point: 80 ° C) are thoroughly stirred with a Henshell mixer, and then the total length of the kneaded part is 1560 mm and the screw diameter. It was melt-kneaded using a co-rotating twin-screw extruder with a barrel inner diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the set heating temperature in the roll was 100 ° C., the temperature of the kneaded product was 160 ° C., the supply speed of the kneaded product was 10 kg / hour, and the average residence time was about 18 seconds. After cooling, toner particles having a volume medium particle size (D ₅₀ ) of 6.5 μm were obtained by a jet mill.

To 100 parts by mass of the obtained toner particles, 2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) was added. , The mixture was mixed with a Henshell mixer at 3600 r / min for 5 minutes to treat with an external additive to obtain toner.
To 100 parts by mass of the obtained toner particles, 2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) was added. , The mixture was mixed at 3600 r / min for 5 minutes using a Henshell mixer to treat with an external additive, and toner was obtained.

Test Example 1 [Heat-resistant storage]
4 g of toner was placed in a 19 mL polypropylene container (Maruem container) and left in an environment with a temperature of 50 ° C for 48 hours. After being left to stand, the degree of cohesion was measured with a powder tester (manufactured by Hosokawa Micron Co., Ltd.) by the following method, and the heat-resistant storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

[Measurement of cohesion]
On the shaking table of the powder tester, set three different open-opening fluids in the order of upper 250 μm, middle 149 μm, and lower 74 μm, place 4 g of toner on them, give vibration, and measure the mass of toner remaining on each fluid. do. Calculate by applying the measured toner mass to the following equation to obtain the degree of cohesion (%).
Cohesion [%] = a + b + c
a = (mass of toner remaining in the upper flue) / 4 (g) x 100
b = (mass of toner remaining in the middle flue) / 4 (g) x 100 x (3/5)
c = (mass of toner remaining in the lower flue) / 4 (g) x 100 x (1/5)

〔Evaluation criteria〕
A: The degree of cohesion is less than 10% and the heat-resistant storage property is good.
B: The degree of cohesion is 10% or more and less than 60%, and the heat-resistant storage property is good.
C: The degree of cohesion is 60% or more and the heat-resistant storage property is poor.

Test Example 2 [Abrasion resistance of images]
Toner was mounted on the K cartridge position of the color printer "C612dnw" (trade name, manufactured by Oki Data Corporation), printed in monochrome mode, and the image was output without fixing (printing area: 2 cm x 12 cm, Adhesion amount: 0.5 mg / cm ² ).
The fixing machine of the printer is heated offline at 100 mm / sec from 100 ° C to 10 ° C to fix it on PET film (Lumirror T60 (manufactured by Toray Industries, Inc., length 210 mm x width 297 mm, thickness: 75 μm)). went.
The fixed image in the temperature range where hot offset did not occur was rubbed 5 times with a sand eraser with a bottom surface of 15 mm x 7.5 mm under a load of 500 g. The optical reflection density before and after rubbing is measured using a reflection densitometer "RD-915" (manufactured by Macbeth), and the value at which the ratio of the two (after rubbing / before rubbing x 100,%) is maximized is the rubbing strength. The temperature at that time is defined as the fixing temperature. The rubbing strength (%) is shown in Table 4.

Test Example 3 [Film curl suppression]
At the temperature defined as the fixing temperature in Test Example 2, a rod-shaped sentence holder (bottom surface: 12 mm × 227 mm, weight 250 g, made of Kuretake) was placed on the fixed image of the printed PET film on the center line in the longitudinal (horizontal) direction of the film. After arranging the film, the extent to which the edges of the PET film were lifted from the horizontal plane on each of the left and right sides was measured, and the average value on the left and right was used as the curl value. The results are shown in Table 4. The smaller the curl value, the more the curl is suppressed.

From the above results, it can be seen that the toners of Examples 1 to 12 have better heat-resistant storage stability and image scratch resistance than the toners of Comparative Examples 1 to 5, and curl of the film is suppressed. ..

The toner binding resin composition of the present invention is, for example, a binder resin for an electrophotographic toner used for developing a latent image formed in an electrostatic charge image developing method, an electrostatic recording method, an electrostatic printing method, or the like. It is preferably used as a toner.

Claims (9)

A binder resin composition for toner containing an amorphous polyester AH having a softening point of 130 ° C. or higher and 145 ° C. or lower, an amorphous polyester AL having a softening point of 95 ° C. or higher and 105 ° C. or lower, and a crystalline polyester C. There,
The glass transition temperature of the amorphous polyester AH is 2.9 ° C. or higher and 10 ° C. or lower lower than the glass transition temperature of the amorphous polyester AL.
The acid value of the amorphous polyester AH is 5 mgKOH / g or more and 25 mgKOH / g or less higher than the acid value of the amorphous polyester AL.
The crystalline polyester C is a polycondensate of an alcohol component containing 1,6-hexanediol and a carboxylic acid component containing dodecane diic acid and stearic acid, and the content of stearic acid is the carboxylic acid component. Medium, 2 mol% or more and 5 mol% or less,
The melting point of the crystalline polyester C is 70 ° C. or higher and 74 ° C. or lower.
Bending resin composition for toner. The binder resin composition for toner according to claim 1, wherein the crystalline polyester C has an acid value of 10 mgKOH / g or less. The binder resin composition for toner according to claim 1 or 2, wherein the solution viscosity of the crystalline polyester C at 20 ° C. is 3 mPa · s or more and 6 mPa · s or less. Claims 1 to 30%, which contain 10% by mass or more and 30% by mass or less of amorphous polyester AH, 60% by mass or more and 85% by mass or less of amorphous polyester AL, and 5% by mass or more and 15% by mass or less of crystalline polyester C. 3. The binder resin composition for toner according to any one of the above. The binder resin composition for toner according to any one of claims 1 to 4, wherein the equivalent ratio (alcohol component / carboxylic acid component) of the alcohol component and the carboxylic acid component of the crystalline polyester C is 1.01 or more and 1.05 or less. The binder resin composition for toner according to any one of claims 1 to 5, wherein the amorphous polyester AH is a polycondensate of an alcohol component and a carboxylic acid component containing 20 mol% or more and 50 mol% or less of adipic acid. .. An electrophotographic toner containing the binder resin composition for toner according to any one of claims 1 to 6. A printing method for printing an image on a plastic film using the electrophotographic toner according to claim 7. The printing method according to claim 8, wherein the plastic film is a polyethylene terephthalate film.