JP7174098B2 - Manufacturing method of toner binder - Google Patents

Description

The present invention relates to a method for manufacturing a toner binder.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copiers and laser printers has increased rapidly, and the performance requirements for toners have also increased. In addition, the requirements for toner binders, which are the main components in toners, are also becoming more sophisticated.

Conventionally, in full-color electrophotography, a latent image based on color image information is formed on a latent image carrier such as an electrophotographic photosensitive member, the latent image is developed with toner of a corresponding color, and then the toner image is formed. 2. Description of the Related Art A method and an apparatus for obtaining a multicolor image by heating and fixing a toner image on a transfer material after repeating an image forming process of transferring the image onto the transfer material are known. In order to pass through these processes without problems, the toner first needs to retain a stable amount of charge and then needs to have good fixability to paper.

Further, from the viewpoint of energy saving, i.e., reduction of energy consumption in the fixing process, there is a strong demand for improved low-temperature fixability of toner, along with promotion of miniaturization, high speed, and high image quality of electrophotographic apparatuses.
Recently, many kinds of paper such as recycled paper with a large uneven surface and coated paper with a smooth surface are used as transfer materials. In order to cope with these surface properties of the transfer material, a fixing device with a wide nip width such as a soft roller or belt roller is preferably used. However, if the nip width is widened, the contact area between the toner and the fixing roller increases, making it easier for melted toner to adhere to the fixing roller, the so-called high-temperature offset phenomenon. is.

Vinyl resins (polystyrene resins, styrene-acrylic resins, etc.), polyester resins, epoxy resins, polyurethane resins, polyamide resins, and the like are known as materials for toner binders capable of realizing the above-described toner characteristics. Recently, vinyl resins and polyester resins have attracted particular attention because of their ability to easily balance the charge retention rate and fixability.

As a method for further improving the balance between the charge retention rate and fixability, a toner binder is proposed that combines a vinyl resin obtained by polymerizing a long-chain alkyl acrylate and a polyester resin having an unsaturated carboxylic acid as a constituent (for example, See Patent Document 1). According to the technique described in Patent Document 1, it is possible to achieve both an improvement in low-temperature fixability due to the vinyl resin and a hot offset resistance due to the polyester resin. In the manufacturing process of the toner binder described in Patent Document 1, the vinyl resin and the polyester resin are mixed by methods such as powder mixing, melt mixing, and solvent mixing. Toner properties such as durability, image strength and durability are unsatisfactory.

A technique described in Patent Document 2 is known as a technique for solving these problems. According to the technique described in Patent Document 2, a toner having a sea-island structure is obtained by using a crystalline vinyl resin and an amorphous vinyl resin together, thereby maintaining fixability and resisting external forces such as rubbing and scratching. A strong toner can be realized. However, when a large amount (for example, 93% by weight or more) of long-chain alkyl acrylate is used as a constituent component of the crystalline vinyl resin, miscibility and durability are insufficient.

As described above, there has been no excellent toner binder that satisfies all of low-temperature fixability, heat-resistant storage stability, hot-offset resistance, fixation width, charge retention rate, image strength, and durability.

WO2019/073731 JP 2014-142632 A

An object of the present invention is to provide a toner binder which is excellent in hot offset resistance, fixation width, charge retention rate, image strength and durability while maintaining low-temperature fixability and heat-resistant storage stability.

The present inventor has arrived at the present invention as a result of intensive studies. That is, the present invention is a method for producing a toner binder containing an amorphous vinyl resin (A) and a crystalline vinyl resin (B), wherein the amorphous vinyl resin (A ), wherein the crystalline vinyl resin (B) comprises a monomer composition (B0) containing a monomer (a) and a monomer (b) It is a polymer, the monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group, and the monomer (b) is a monomer having 6 or less carbon atoms and having a vinyl group. and the viscosity of the crystalline vinyl resin (B) at 100° C. is 10 to 10,000 Pa·s.

According to the present invention, it is possible to provide a toner binder that is excellent in hot offset resistance, fixing width, charge retention rate, image strength and durability while maintaining low-temperature fixability and heat-resistant storage stability.

The toner binder of the present invention is a method for producing a toner binder containing an amorphous vinyl resin (A) and a crystalline vinyl resin (B), wherein the amorphous vinyl resin is prepared in the presence of the crystalline vinyl resin (B). A monomer composition ( B0), wherein the monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group, and the monomer (b) has 6 or less carbon atoms having a vinyl group. and the viscosity of the crystalline vinyl resin (B) at 100° C. is 10 to 10,000 Pa·s.
The method for producing the toner binder of the present invention will be sequentially described below.

In the method for producing a toner binder of the present invention, the monomer composition (A0) is polymerized to form the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B). Compared to the case where (A) and the crystalline vinyl resin (B) are separately prepared and mixed, the amorphous vinyl resin (A) is more easily dispersed in the toner binder, and the phase with the crystalline vinyl resin (B) is improved. Since the solubility is improved, it is possible to obtain a toner binder excellent in low-temperature fixability, fixation width, charge retention rate and durability.

The amorphous vinyl resin (A) in the present invention is a polymer of the monomer composition (A0), and the composition of the resin is not particularly limited as long as it is an amorphous vinyl resin. From the viewpoint of retention rate and durability, the polymer of the monomer composition (A0) containing styrene is preferred.
In the present invention, "amorphous" means that there is no endothermic peak top temperature when the transition temperature of the sample is measured using a differential scanning calorimeter (DSC).

In the monomer composition (A0), in addition to styrene, if necessary, other monomers may be used in combination. For example, styrene monomers other than styrene, (meth) acrylic monomers, vinyl ester monomers, aliphatic Hydrocarbon-based vinyl monomers, nitrile group-containing monomers, and the like are included. One of these monomers may be used, or two or more thereof may be used in combination.

Examples of styrenic monomers other than styrene include alkylstyrenes in which the alkyl group has 1 to 3 carbon atoms (eg, α-methylstyrene and p-methylstyrene). One of these monomers may be used, or two or more thereof may be used in combination.

(Meth)acrylic monomers include alkyl esters having 1 to 16 carbon atoms in the alkyl group [e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, , lauryl (meth)acrylate, stearyl (meth)acrylate, etc.], hydroxy group-containing (meth)acrylates [e.g., hydroxyethyl (meth)acrylate, etc.], amino group-containing (meth)acrylates having alkyl groups of 1 to 16 carbon atoms [For example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.], (meth)acrylic acid, and the like. In the present invention, "(meth)acrylate" means "acrylate" and/or "methacrylate".

Vinyl ester monomers include aliphatic vinyl esters (having 4 to 15 carbon atoms, such as vinyl acetate, vinyl propionate and isopropenyl acetate).

Aliphatic hydrocarbon-based vinyl monomers include olefins (having 2 to 10 carbon atoms, such as ethylene, propylene, butene and octene) and dienes (having 4 to 10 carbon atoms, such as butadiene, isoprene and 1,6-hexadiene). mentioned.

Nitrile group-containing monomers include acrylonitrile, methacrylonitrile, and nitrile group-containing monomers in which the methyl group of methacrylonitrile is replaced with an alkyl group having 2 to 16 carbon atoms.

Of the monomers other than styrene, preferably (meth)acrylic monomers and nitrile group-containing monomers, more preferably methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl ( meth)acrylates, (meth)acrylic acid, acrylonitrile and methacrylonitrile.

In the case where the monomer composition (A0) contains styrene, the weight ratio of styrene in the monomer composition (A0) is determined from the viewpoint of heat-resistant storage stability, charge retention rate, and durability. Based on the weight of the product (A0), preferably 50% by weight or more, more preferably 50 to 100% by weight, still more preferably 50 to 80% by weight, particularly preferably 57 to 72% by weight .

The crystalline vinyl resin (B) in the present invention is a polymer of a monomer composition (B0) containing monomers (a) and (b), and is a crystalline vinyl resin. Further, the monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group, and the monomer (b) is a monomer having 6 or less carbon atoms having a vinyl group. It is a monomer (b). In the present invention, "crystalline" means that the DSC curve has a peak top temperature of an endothermic peak in differential scanning calorimetry (also referred to as DSC measurement) described below.

A method for measuring the peak top temperature of the endothermic peak of the crystalline vinyl resin (B) is described below.
It is measured using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments]}. The crystalline vinyl resin (B) is first heated from 20° C. to 150° C. at a rate of 10° C./min, then cooled from 150° C. to 0° C. at a rate of 10° C./min. The temperature indicating the top of the endothermic peak in the process of the second heating when the temperature was raised from 0°C to 150°C for the second time under the conditions of 10°C/min was taken as the endothermic peak temperature of the crystalline vinyl resin (B). Let it be the peak top temperature.

Monomer (a) is a (meth)acrylate having a chain hydrocarbon group and having 21 to 40 carbon atoms. The monomer (a) may be used alone or in combination of two or more.

Examples of the monomer (a) include (meth)acrylates having a linear alkyl group (alkyl group having 18 to 36 carbon atoms) [octadecyl (meth)acrylate (stearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, montanyl (meth)acrylate, triacontyl (meth)acrylate (myricyl (meth)acrylate) and dodriacon Chill (meth)acrylate, etc.] and (meth)acrylate having a branched alkyl group (alkyl group having 18 to 36 carbon atoms) [2-decyltetradecyl (meth)acrylate, etc.].

Among these, from the viewpoint of low-temperature fixability and heat-resistant storage stability, (meth)acrylates having a straight-chain alkyl group (alkyl group having 18 to 36 carbon atoms) are preferable, more preferably a straight-chain alkyl group (alkyl group (Meth)acrylates having 18 to 30 carbon atoms), more preferably octadecyl (meth)acrylate, arachidyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, and Triacontyl (meth)acrylates, particularly preferably octadecyl acrylate, arachidyl acrylate, behenyl acrylate and lignoceryl acrylate.

The monomer (b) is a vinyl group-containing monomer having 6 or less carbon atoms. Monomer (b) may be used alone or in combination of two or more.
Examples of the monomer (b) include (meth)acrylic monomers having 6 or less carbon atoms [(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl (meth) ) acrylate and ethyl-2-(hydroxymethyl)acrylate, etc.], vinyl ester monomers having 6 or less carbon atoms [vinyl acetate, vinyl propionate, isopropenyl acetate, etc.], aliphatic hydrocarbon-based vinyl monomers having 6 or less carbon atoms [ ethylene, propylene, butene, butadiene, isoprene, 1,5-hexadiene, etc.], and a monomer having 6 or less carbon atoms having a nitrile group [(meth)acrylonitrile, etc.].
Among these, from the viewpoint of hot offset resistance, image strength and durability, (meth)acrylic monomers having 6 or less carbon atoms, vinyl ester monomers having 6 or less carbon atoms, and monomers having 6 or less carbon atoms having a nitrile group are preferred, more preferably (meth)acrylic acid, methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, vinyl acetate, (meth)acrylonitrile and 2-hydroxypropyl acrylate, still more preferably (meth) acrylic acid, methyl (meth)acrylate and (meth)acrylonitrile. Moreover, in the present invention, "(meth)acrylonitrile" means "acrylonitrile" and/or "methacrylonitrile".

The monomer composition (B0) containing the monomer (a) and the monomer (b) may optionally be used in combination with other monomers, for example, the monomer (a) and the monomer A monomer (d) other than the body (b) can be mentioned. A monomer (d) may be used individually by 1 type, or may use 2 or more types together.
As the monomer (d), a styrene-based monomer (d1), a (meth)acrylic monomer having more than 6 carbon atoms (meth)acrylic monomer (d2) excluding (a), and a carbon number of 6 and a monomer (d4) other than the monomer (a), the monomer (b), and the monomers (d1) to (d3).

Examples of the styrenic monomer (d1) include styrene and alkylstyrenes having alkyl groups of 1 to 3 carbon atoms (eg α-methylstyrene and p-methylstyrene).
Of these, styrene is preferred.

(Meth)acrylic monomers (d2) include alkyl (meth)acrylates having 4 to 17 carbon atoms in the alkyl group [butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, etc.], Hydroxyalkyl (meth)acrylates in which the alkyl group has 4 to 17 carbon atoms, aminoalkyl group-containing (meth)acrylates in which the alkyl group has 4 to 17 carbon atoms [dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate etc.], esters of unsaturated carboxylic acids having 8 to 20 carbon atoms and polyhydric alcohols [ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri (meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc.] and the like.

Examples of the vinyl ester monomer (d3) include aliphatic vinyl esters having 7 to 15 carbon atoms and aromatic vinyl esters having 9 to 15 carbon atoms (eg, methyl-4-vinylbenzoate, etc.).

Examples of the monomer (d4) include alkoxypolyethyleneglycol (meth)acrylates (eg, methoxypolyethyleneglycol acrylate, etc.).

Among these monomers (d), styrene-based monomers (d1) and (a) among (meth)acrylic monomers having more than 6 carbon atoms are excluded from the viewpoint of charge retention rate and durability (meth) Acrylic monomer (d2) is preferred, more preferably styrene, an alkyl (meth)acrylate having an alkyl group having 4 to 17 carbon atoms and an ester of an unsaturated carboxylic acid having 8 to 20 carbon atoms and a polyhydric alcohol, More preferred are styrene, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and 1,6-hexanediol di(meth)acrylate.

The weight ratio of the monomer (a) in the monomer composition (B0) in the crystalline vinyl resin (B) is the weight of the monomer composition (B0) from the viewpoint of low-temperature fixability and heat-resistant storage stability. is preferably 30 to 93% by weight, more preferably 35 to 90% by weight, still more preferably 40 to 80% by weight, and particularly preferably 50 to 80% by weight.

The weight ratio of the monomer (b) in the monomer composition (B0) in the crystalline vinyl resin (B) is the monomer composition (B0 ), preferably 7 to 70% by weight, more preferably 7 to 50% by weight, still more preferably 8 to 30% by weight.

When the monomer composition (B0) in the crystalline vinyl resin (B) contains the monomer (d), the amount of the monomer in the monomer composition (B0) is The weight proportion of body (d) is preferably 9 to 32% by weight based on the weight of monomer composition (B0).

The crystalline vinyl resin (B) in the present invention can be obtained by polymerizing the monomer composition (B0) by a known method (e.g., radical polymerization, anionic polymerization, cationic polymerization, living radical polymerization, living anionic polymerization, living cationic polymerization, etc.). It can be produced by polymerization. In the case of radical polymerization, for example, it can be synthesized by a solution polymerization method (JP-A-5-117330, etc.) in which the monomer is reacted with a radical reaction initiator (c) in a solvent (toluene, etc.). The radical reaction initiator (c) in the case of radical polymerization includes those similar to those described later in the production of the toner binder.
The toner binder obtained by the method of the present invention may contain the compound used in the polymerization of the crystalline vinyl resin (B) and its residue, as long as the effect of the present invention is not impaired.

The amount of the radical reaction initiator (c) used is not particularly limited, but is preferably 0.01 to 2% by weight based on the total weight of the monomer composition (B0).

The viscosity at 100° C. of the crystalline vinyl resin (B) in the present invention is 10 to 10,000 Pa·s. When the viscosity is 10 Pa·s or more, the offset resistance and fixing width are good, and when it is 10,000 Pa·s or less, the low-temperature fixability and fixing width are good. Further, when the toner binder is produced, if the viscosity of the crystalline vinyl resin (B) at 100° C. is within the above range, the amorphous vinyl resin (A) and the monomer composition of the amorphous vinyl resin (A) The difference in viscosity with the product (A0) is suppressed, and the mixability is improved. The lower limit of the viscosity of the crystalline vinyl resin (B) at 100° C. is more preferably 20 Pa·s or more, still more preferably 40 Pa·s. The upper limit is more preferably 6500 Pa·s or less, still more preferably 3000 Pa·s.
The viscosity of the crystalline vinyl resin (B) at 100° C. varies depending on the type and composition ratio of the monomers constituting the crystalline vinyl resin (B) (for example, the monomer (a ), the weight ratio of the monomer (a) constituting the crystalline vinyl resin (B), etc.), the weight average molecular weight, and the like. For example, the viscosity of the crystalline vinyl resin (B) at 100° C. can be increased by reducing the weight ratio of the monomer (a) or increasing the weight average molecular weight of the crystalline vinyl resin (B).

The viscosity at 100° C. of the crystalline vinyl resin (B) in the present invention is the complex viscosity at 100° C. obtained by the following viscoelasticity measuring device, and can be measured using the following conditions.
Apparatus: ARES-24A (manufactured by Rheometric Co.)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Heating rate: 5°C/min

The peak top temperature of the endothermic peak of the crystalline vinyl resin (B) in the present invention is preferably 40 to 100° C. from the viewpoint of low temperature fixability, heat resistant storage stability, durability and image strength. When the peak top temperature of the endothermic peak of the crystalline vinyl resin (B) is 40°C or higher, heat-resistant storage stability, durability and image strength are good, and when it is 100°C or lower, low-temperature fixability is good.
The endothermic peak top temperature of the crystalline vinyl resin (B) is more preferably 45 to 95°C, still more preferably 50 to 90°C, and particularly preferably 53 to 75°C.

The half width of the endothermic peak indicating the peak top temperature of the crystalline vinyl resin (B) in the present invention is preferably 6° C. or less from the viewpoint of low-temperature fixability and heat-resistant storage stability.
The half-value width of the endothermic peak indicating the peak top temperature of the crystalline vinyl resin (B) is based on the DSC curve obtained by measuring the peak top temperature of the endothermic peak, from the baseline of the endothermic peak to the peak maximum height. It refers to the temperature width of the peak at half height.

The acid value of the crystalline vinyl resin (B) in the present invention is preferably 60 mgKOH/g or less. When the acid value is 60 mgKOH/g or less, the endothermic peak top temperature Tm increases and the hygroscopicity decreases, resulting in good heat-resistant storage stability. The acid value of the crystalline vinyl resin (B) is more preferably 50 mgKOH/g or less, still more preferably 40 mgKOH/g or less, and particularly preferably 0 to 30 mgKOH/g.
The acid value of the crystalline vinyl resin (B) can be adjusted by adjusting the acid value of the monomer and the content of the monomer having the acid value. The acid value of (B) is measured, for example, by a method such as JISK0070.

The weight average molecular weight of the crystalline vinyl resin (B) in the present invention as measured by gel permeation chromatography (GPC) is 2,000 to 200,000 from the viewpoint of low temperature fixability, hot offset resistance and fixation width. It is preferably 5,000 to 100,000, still more preferably 15,000 to 80,000, and particularly preferably 25,000 to 80,000.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) and the weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the crystalline vinyl resin (B) in the present invention are determined by GPC as follows. conditions can be measured.
Apparatus (example): HLC-8120 [manufactured by Tosoh Corporation]
Column (one example): TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40°C
Sample solution: 0.25% by weight THF solution Mobile phase: Tetrahydrofuran (without polymerization inhibitor)
Solution injection volume: 100 μL
Detection device: refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1, 090,000 2,890,000)
For molecular weight measurement, a sample is dissolved in THF to a concentration of 0.25% by weight, and the undissolved portion is filtered through a PTFE filter with a diameter of 1 μm to obtain a sample solution.

The toner binder in the present invention includes other resins (C) known as resins for toner binders other than the amorphous vinyl resin (A) and the crystalline vinyl resin (B) (Japanese Patent No. 4493080 and JP-A-06- 194876) may be used for production. (C) may be one kind of resin or a mixture of two or more kinds of resins.

As described above, the method for producing a toner binder of the present invention has a step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B).

The method for polymerizing the monomer composition (A0) in the present invention is not particularly limited as long as it is present in the presence of the crystalline vinyl resin (B). radical polymerization, living anionic polymerization, living cationic polymerization, etc.). In the case of radical polymerization, it can be reacted together with a radical reaction initiator (c), and the radical reaction initiator (c) is not particularly limited, and inorganic peroxide (c1) and organic peroxide (c2). and an azo compound (c3). Moreover, these radical reaction initiators may be used alone, or two or more of them may be used in combination.

Examples of the inorganic peroxide (c1) include, but are not particularly limited to, hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate.

Examples of the organic peroxide (c2) include, but are not limited to, benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butyl peroxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butylperoxyhexyne-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5 -trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylmonocarbonate and t-butylperoxyacetate.

Examples of the azo compound (c3) include, but are not limited to, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis(2-methylbutyronitrile) and azobisisobutyronitrile, etc. is mentioned.

The amount of the radical reaction initiator (c) used is not particularly limited, but is preferably 0.01 to 1% by weight based on the total weight of the monomer composition (A0).

The method of polymerizing the monomer composition (A0) in the present invention may be batch polymerization or divisional polymerization (dropping polymerization), but divisional polymerization (dropping polymerization) is preferable from the viewpoint of uniformity.

The method of mixing the monomer composition (A0) and the crystalline vinyl resin (B) in the polymerization step may be a commonly used known method or the like, and if necessary solvents (toluene, xylene, ethyl acetate, tetrahydrofuran and methyl ethyl ketone etc.) may be used.
Mixing devices include batch mixing devices such as reaction tanks and continuous mixing devices. A batch-type mixing apparatus is preferable because pressure adjustment such as pressurization and decompression is easy.

In the method for producing a toner binder of the present invention, when the monomer composition (AO) of the amorphous vinyl resin (A) is polymerized in the presence of the crystalline vinyl resin (B), ) while pressurizing the monomer composition (A0) of the amorphous vinyl resin (A) from the viewpoint of uniformity and productivity. The pressure for polymerizing the monomer composition (A0) is preferably 0.01-0.5 MPa, more preferably 0.03-0.4 MPa.

The polymerization temperature in the step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B) is 110° C. to 190° C. for uniformity and productivity. is preferable from the viewpoint of The polymerization temperature is more preferably 120 to 190°C, still more preferably 130 to 190°C, particularly preferably 140 to 170°C, most preferably 140 to 155°C. When the polymerization temperature is 190° C. or lower, decomposition of the crystalline vinyl resin (B) is unlikely to occur, and good heat-resistant storage stability can be obtained. When the polymerization temperature is 110° C. or higher, the viscosity of the crystalline vinyl resin (B) is lowered, and the uniformity between the crystalline vinyl resin (B) and the monomer composition (A0) can be improved. It is possible to obtain a toner binder having excellent uniformity.

In the step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B) of the present invention, the monomer composition of the amorphous vinyl resin (A) before the reaction is The weight ratio [(A0):(B)] of the polymer composition (A0) and the crystalline vinyl resin (B) is [20:80] to [65:35], which improves low-temperature fixability and heat resistance. Preferred from the viewpoint of storage stability, hot offset resistance, charge retention rate, durability and image strength, more preferably [30:70] to [65:35], still more preferably [40:60] to [60] : 40].

In the present invention, the step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B) may include steps other than the polymerization step. good. The other process is not particularly limited, and a process performed in a general toner binder manufacturing process can be employed.
Other steps include, for example, a step of reducing the pressure in the reaction system after the polymerization step in order to remove the organic solvent, initiator decomposition residue, etc. (decompression step), and a step of taking out and pulverizing the toner binder obtained in the polymerization step ( pulverization step) and the like.

The temperature of the pressure reducing step is preferably 110 to 190°C, more preferably 130 to 190°C, still more preferably 140 to 170°C.

The degree of pressure reduction in the pressure reduction step is preferably 0.01 to 30 kPa, more preferably 0.05 to 20 kPa, still more preferably 0.08 to 10 kPa, particularly from the viewpoint of heat resistant storage stability, hot offset resistance and productivity. It is preferably 0.1 to 5 kPa.

The glass transition temperature (Tg) of the toner binder obtained by the present invention is preferably 25 to 80° C., more preferably 40 to 65° C., particularly preferably 40 to 65° C., from the viewpoint of low-temperature fixability and heat-resistant storage stability. 44-54°C.
When the Tg is 80° C. or less, the low-temperature fixability is good, and when it is 25° C. or more, the heat-resistant storage stability is good.
The glass transition temperature (Tg) can be measured by a method (DSC method) defined in ASTM D3418-82 using, for example, DSCQ20 manufactured by TA Instruments.

The toner binder obtained by the present invention preferably has at least one endothermic peak top temperature (Tm) in the range of 40 to 100.degree. When the Tm is within this range, the toner binder has a good balance between low-temperature fixability and heat-resistant storage properties. Tm is preferably 43 to 95°C, more preferably 45 to 90°C, still more preferably 50 to 90°C, and particularly preferably 51 to 88°C. The peak top temperature (Tm) of the endothermic peak is measured using a differential scanning calorimeter {for example, "DSCQ20" [manufactured by TA Instruments]}, and the toner binder is heated from 20°C to 150°C under conditions of 10°C/min. A first temperature increase was performed, followed by cooling from 150°C to 0°C at 10°C/min, followed by a second temperature increase from 0°C to 150°C at 10°C/min. It is the temperature indicating the top of the endothermic peak in the second temperature rising process.
In the present invention, the peak top temperature (Tm) of the endothermic peak is preferably the peak top temperature of the endothermic peak derived from the crystalline vinyl resin (B).

In the toner binder obtained by the present invention, the half width of the endothermic peak indicating the peak top temperature (Tm) of the toner binder is preferably 6° C. or less from the viewpoint of low-temperature fixability, fixation width, and heat-resistant and heat-retaining properties. The temperature is preferably 5°C or less, and particularly preferably 2 to 5°C.
The half-value width of the endothermic peak indicating the peak top temperature (Tm) of the toner binder is 2 at the peak maximum height from the baseline of the endothermic peak based on the DSC curve obtained by measuring the peak top temperature (Tm) of the endothermic peak. The temperature width of the peak at one minute height.

The acid value of the toner binder obtained by the present invention is preferably 60 mgKOH/g or less from the viewpoint of heat-resistant storage stability and charge retention rate. When the acid value is 60 mgKOH/g or less, the peak top temperature (Tm) of the endothermic peak increases and the hygroscopicity decreases, resulting in good heat-resistant storage stability. The acid value of the toner binder is more preferably 30 mgKOH/g or less, more preferably 0 to 22 mgKOH/g.
The acid value of the toner binder can be adjusted by adjusting the acid value of the monomer constituting the amorphous vinyl resin (A) and the crystalline vinyl resin (B) or the content of the monomer having an acid value. The acid value of the toner binder is measured by a method such as JISK0070.

The weight average molecular weight (Mw) of the toner binder obtained by the present invention is preferably from 5,000 to 200,000, more preferably from 10,000 to 10,000, from the viewpoint of achieving both hot offset resistance and low-temperature fixability of the toner. 200,000, more preferably 50,000 to 200,000, and particularly preferably 75,000 to 190,000.
The weight average molecular weight of the toner binder can be measured under the same conditions as for the amorphous vinyl resin (A).

When producing a toner using the toner binder obtained by the present invention, in addition to the toner binder of the present invention, if necessary, one or more known additives selected from colorants, release agents, charge control agents, fluidizing agents, etc. can be used.

As the colorant, all dyes and pigments used as colorants for toners can be used. For example, carbon black, iron black, Sudan black SM, fast yellow G, benzidine yellow, pigment yellow, India first orange, irgasin red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red 2G, rhodamine. FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B, Oil Pink OP, etc., and the coloring agents are or a mixture of two or more. If necessary, magnetic powder (powder of ferromagnetic metal such as iron, cobalt, nickel, etc., or compounds such as magnetite, hematite, ferrite, etc.) can be incorporated so as to function also as a coloring agent.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder. When magnetic powder is used as the coloring agent, the amount is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

The release agent preferably has a flow softening point [T _1/2 ] of 50 to 170° C. in a constant test force extrusion capillary rheometer flow tester, such as polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax. and their oxides, carnauba wax, montan wax and their deacidified waxes, ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and mixtures thereof. .

A method for measuring the flow softening point [T _1/2 ] is described.
Using a constant test force extrusion type capillary rheometer flow tester {eg, CFT-500D manufactured by Shimadzu Corporation}, while heating 1 g of a measurement sample at a temperature elevation rate of 6 ° C./min, a plunger was used to perform 1. Apply a load of 96 MPa, extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger descent amount (flow value)" and "temperature", and measure 1/2 of the maximum plunger descent amount. is the flow softening point [T _1/2 ].

Polyolefin waxes include (co)polymers of olefins (e.g., ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof) [those obtained by (co)polymerization and those obtained by further thermal degradation thereof], (e.g. low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer), oxidation of olefin (co)polymers with oxygen and / or ozone olefins, maleic acid-modified olefin (co)polymers [e.g., maleic acid and its derivatives (maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [ (Meth)acrylic acid, itaconic acid, maleic anhydride, etc.] and/or unsaturated carboxylic acid alkyl esters [(meth)acrylic acid alkyl (alkyl having 1 to 18 carbon atoms) and maleic acid alkyl (alkyl having 1 carbon 18) Esters, etc.] and the like.

As the microcrystalline wax, for example, Hi-Mic-2095, Hi-Mic-1090, Hi-Mic-1080, Hi-Mic-1070, Hi-Mic-2065, Hi-Mic- 1045, Hi-Mic-2045 and the like.

As the paraffin wax, for example, Paraffin WAX-155, Paraffin WAX-150, Paraffin WAX-145, Paraffin WAX-140, Paraffin WAX-135, HNP-3, HNP-5, HNP- manufactured by Nippon Seiro Co., Ltd. 9, HNP-10, HNP-11, HNP-12, HNP-51 and the like.

Examples of Fischer-Tropsch wax include Sasolwax C80 manufactured by Sasol Co., Ltd., FT-0070 manufactured by Nippon Seiro Co., Ltd., and the like.

Examples of carnauba wax include Refined Carnauba Wax Tokusei No. 1 manufactured by Kato Yoko Co., Ltd., and the like.

Ester waxes include fatty acid ester waxes (eg Nissan Elector WEP-2, WEP-3, WEP-4, WEP-5 and WEP-8 manufactured by NOF Corporation) and the like.

Higher alcohols include aliphatic alcohols having 30 to 50 carbon atoms, such as triacontanol. Examples of fatty acids include fatty acids having 30 to 50 carbon atoms, such as triacontanecarboxylic acid.

Examples of fatty acid amides include Diamid Y and Diamid 200 manufactured by Mitsubishi Chemical Corporation.

The charge control agent may contain either a positive charge control agent or a negative charge control agent, and includes a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, and a quaternary ammonium salt. , polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, benzylic acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers and halogen-substituted aromatic ring-containing polymers, etc. is mentioned.

Examples of fluidizing agents include silica, titania, alumina, calcium carbonate, fatty acid metal salts, silicone resin particles and fluororesin particles, and two or more of them may be used in combination. Silica is preferable from the viewpoint of charging property of the toner. Silica is preferably hydrophobic silica from the viewpoint of toner transferability. Silica is preferably hydrophobic silica from the viewpoint of toner transferability.

The content of the toner binder in the toner is preferably 30-97% by weight, more preferably 40-95% by weight, still more preferably 45-92% by weight, based on the weight of the toner.
The content of the colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, still more preferably 0.5 to 50% by weight, based on the weight of the toner.
The content of the releasing agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 10% by weight, based on the weight of the toner.
The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7.5% by weight, based on the weight of the toner.
The fluidizing agent content is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and even more preferably 0.1 to 4% by weight, based on the weight of the toner.
The total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, still more preferably 5 to 50% by weight, based on the weight of the toner.

The toner containing the toner binder obtained by the present invention can be obtained by any known method such as kneading pulverization method, emulsion phase inversion method, emulsion polymerization method, suspension polymerization method, dissolution suspension method and emulsion aggregation method. It may have been
For example, when a toner is obtained by a kneading pulverization method, the components constituting the toner except the fluidizing agent are dry-blended with a Henschel mixer, a Nauta mixer, a Banbury mixer, or the like, followed by a twin-screw kneader, an extruder, a continuous kneader and Melt and knead with a continuous mixing device such as three rolls, then coarsely pulverize with a mill, finally pulverize with an air flow pulverizer, etc., and adjust the particle size distribution with a classifier such as an elbow jet. As a result, toner particles [preferably particles having a volume average particle diameter (D50) of 5 to 20 μm] can be prepared by mixing with a fluidizing agent.

The volume average particle diameter (D50) of toner particles (toner) can be measured using a Coulter counter [eg, trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].
Specifically, 0.1 to 5 mL of a surfactant (alkylbenzenesulfonate) as a dispersant is added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter, Inc.), which is an electrolytic aqueous solution. Further, 2 to 20 mg of a sample to be measured is added, and the electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser. , the number is measured, and the volume distribution and the number distribution are calculated. From the obtained distribution, the volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter/number average particle diameter) of the toner particles are determined.

When the toner is obtained by the emulsification phase inversion method, it is possible to dissolve or disperse the components constituting the toner, excluding the fluidizing agent, in an organic solvent, emulsify the emulsion by adding water or the like, and then separate and classify the emulsion. can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

The toner containing the toner binder obtained by the present invention includes carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. It is mixed and used as a developer for latent electrical images. When carrier particles are used, the weight ratio of toner to carrier particles is preferably 1/99 to 99/1. It is also possible to form an electric latent image by friction with a member such as a charging blade instead of carrier particles.
The toner containing the toner binder obtained by the present invention may not contain carrier particles.

A toner containing a toner binder obtained by the present invention is fixed on a support (paper, polyester film, etc.) by a copier, printer, or the like to form a recording material. As a method for fixing onto the support, a known hot roll fixing method, flash fixing method, and the like can be applied.

The toner produced using the toner binder obtained by the present invention is used for developing electrostatic charge images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, it is used for developing electrostatic charge images or magnetic latent images particularly suitable for full-color applications.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these. Hereinafter, "parts" means parts by weight unless otherwise specified.

Physical properties of the crystalline vinyl resin (B) and the toner binder were measured by the following methods.

[Acid value]
The acid value was measured by the method specified in JIS K0070. However, the measurement solvent was a mixed solvent of acetone, methanol and toluene (acetone:methanol:toluene=12.5:12.5:75).

[Weight average molecular weight]
The weight average molecular weight was measured using GPC under the following conditions.
Apparatus: HLC-8120 [manufactured by Tosoh Corporation]
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40°C
Sample solution: 0.25% by weight THF solution Mobile phase: Tetrahydrofuran (without polymerization inhibitor)
Sample solution injection volume: 100 μL
Detection device: refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) (molecular weight 500 1,050 2,800 5,970 9,100 18,100 37,900 96,400 190,000 355,000 1, 090,000 2,890,000) [manufactured by Tosoh Corporation]
In the measurement of the weight average molecular weight, the sample was dissolved in THF so as to have a concentration of 0.25% by weight, and the undissolved portion was filtered through a PTFE filter having an aperture of 1 μm to obtain a sample solution.

[Glass-transition temperature]
The glass transition temperature (Tg) was measured by the method (DSC method) specified in ASTM D3418-82 using DSC Q20 manufactured by TA Instruments. The measurement conditions for the glass transition temperature are described.
<Measurement conditions>
(1) Heating from 30°C to 150°C at 20°C/min (2) Holding at 150°C for 10 minutes (3) Cooling at 20°C/min to -35°C (4) Holding at -35°C for 10 minutes (5) ) Heating up to 150°C at 20°C/min (6) The differential scanning calorimetric curve measured in the process of (5) was analyzed.

[Peak top temperature and half width of endothermic peak]
The peak top temperature (Tm) of the endothermic peak and the half width of the endothermic peak indicating Tm were measured using a differential scanning calorimeter {“DSCQ20” [manufactured by TA Instruments]} under the following conditions.
<Measurement conditions>
(1) Raise temperature from 20°C to 150°C at 10°C/min (2) Cool from 150°C to 0°C at 10°C/min (3) Raise temperature from 0°C to 150°C at 10°C/min (4) A differential scanning calorimetry curve measured in the process of (3) was analyzed.
The half-value width of the endothermic peak indicating the peak top temperature of the crystalline vinyl resin (B) is 2 minutes from the baseline of the endothermic peak to the peak maximum height based on the DSC curve obtained by measuring the endothermic peak temperature. is the temperature width of the peak at one height of

[Viscosity at 100°C]
The viscosity at 100°C was measured using the following viscoelasticity measuring device and conditions.
Apparatus: ARES-24A (manufactured by Rheometric Co.)
Jig: 25mm parallel plate Frequency: 1Hz
Distortion rate: 5%
Heating rate: 5°C/min

[Method for calculating reaction rate of monomer (a)]
The reaction rate (%) of the monomer (a) in Production Examples 1-8 and Comparative Production Examples 1-3 was calculated by a method of identifying the amount of the remaining monomer using NMR. Measurement conditions, sample preparation methods, analysis and calculation methods are as follows.
<Measurement conditions>
Apparatus: "AVANCE III HD400" manufactured by Bruker Biospin
Accumulation times: 4 Relaxation time: 1 second <Sample preparation>
100 mg of the sample and 0.8 mL of a deuterated solvent (eg, deuterated chloroform) were added to the NMR tube to dissolve the resin.
<Analysis and calculation>
Area of protons of monomer (a) before reaction, area of protons of remaining monomer (a), and terminal methyl of chain hydrocarbon groups of monomer (a) and crystalline vinyl resin (B) Based on the proton area of the group, the reaction rate was calculated by the following formula.
Reaction rate: 100 × [{area of protons bonded to double bond carbons of monomer (a) before reaction/chain hydrocarbon groups of monomer (a) and crystalline vinyl resin (B) area of the proton of the terminal methyl group}-{area of the proton bonded to the double bond carbon of the remaining monomer (a)/chain shape of the monomer (a) and the crystalline vinyl resin (B) Area of proton of terminal methyl group of hydrocarbon group}]/{Area of proton bonded to double bond carbon of monomer (a) before reaction/monomer (a) and crystalline vinyl resin ( Area of proton of terminal methyl group of chain hydrocarbon group in B)}
For example, if the monomer (a) is behenyl acrylate, the protons (about 6.4 ppm) bonded to the double bond carbon and the protons (about 0.9 ppm) of the terminal methyl group of the chain hydrocarbon group are used.

[Method for calculating reaction rate of styrene]
The styrene reaction rate (%) in the examples and comparative examples was calculated by the following method. Measurement conditions, sample preparation methods, analysis and calculation methods are as follows.
<Measurement conditions>
Apparatus: GC-14A manufactured by Shimadzu Corporation
Column: PEG20M20% Chromosolve W-supported 2 m glass column (manufactured by Phenomenex)
Internal standard: Amyl alcohol Detector: FID detector Column temperature: 100°C
Sample concentration: 5% DMF solution <Sample preparation method, analysis and calculation method>
A calibration curve for styrene and amyl alcohol was prepared in advance, the content of styrene monomer in the sample was determined based on this calibration curve, and the polymerization rate was calculated from the residual amount of styrene monomer with respect to the charged amount. Also, the sample was dissolved in dimethylformamide (DMF) so as to have a concentration of 5% by weight, and the supernatant obtained by standing still for 10 minutes was used as a sample solution.

[Method for Confirming Dispersed State of Amorphous Vinyl Resin]
The toner binders obtained in Examples and Comparative Examples were cut into ultra-thin slices having a thickness of about 100 μm, and the dispersed state of the amorphous vinyl resin (A) was subjected to a vacuum electron dyeing apparatus (VSC1R1H manufactured by Filgen Co., Ltd.) using ruthenium tetroxide. After staining for 3 minutes at a concentration of 1, the dispersed state of the amorphous vinyl resin (A) displayed in gray or black by ruthenium tetroxide staining was observed with a transmission electron microscope (TEM) at a magnification of 10,000. was confirmed by observing the cross section of the toner binder.

<Production Example 1> [Production of crystalline vinyl resin (B-1)]
An autoclave was charged with 260 parts of behenyl acrylate [manufactured by Nisshoku Techno Fine Chemical Co., Ltd., the same applies hereinafter] and 140 parts of xylene, and the autoclave was purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. A mixed solution of 234 parts of styrene, 130 parts of methyl acrylate, 26 parts of acrylic acid, 1.5 parts of di-t-butyl peroxide [manufactured by NOF Corporation, the same shall apply hereinafter], and 203 parts of xylene was added to the autoclave. While controlling the temperature at 170° C., polymerization was carried out by dropwise addition over 1.5 hours. After dropping, the dropping line was washed with 7 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-1).

<Production Example 2> [Production of crystalline vinyl resin (B-2)]
An autoclave was charged with 600 parts of behenyl acrylate and 138 parts of xylene and purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. A mixed solution of 50 parts of styrene, 50 parts of methyl methacrylate, 50 parts of acrylonitrile [manufactured by Nacalai Tesque Co., Ltd.; While controlling the temperature, the mixture was added dropwise over 2 hours to carry out polymerization. After dropping, the dropping line was washed with 12 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-2).

<Production Example 3> [Production of crystalline vinyl resin (B-3)]
An autoclave was charged with 138 parts of xylene and purged with nitrogen. A mixed solution of 450 parts of behenyl acrylate, 75 parts of styrene, 225 parts of acrylonitrile, 3.5 parts of di-t-butyl peroxide, and 100 parts of xylene was adjusted to 60°C, and the temperature inside the autoclave was controlled at 165°C. was added dropwise over 3 hours to carry out polymerization. After dropping, the dropping line was washed with 12 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70°C. Since the reaction rate of the monomer (a) was less than 95%, 1.8 parts of di-t-butyl peroxide was further added and reacted until the reaction rate was 95% or higher. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-3).

<Production Example 4> [Production of crystalline vinyl resin (B-4)]
An autoclave was charged with 450 parts of behenyl acrylate and 150 parts of xylene and purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. 240 parts of styrene, 38 parts of methyl acrylate, 3.8 parts of 1,6-hexanediol diacrylate [manufactured by Kyoeisha Chemical Co., Ltd.; and 93 parts of xylene was added dropwise over 2 hours while controlling the temperature inside the autoclave at 170° C. to carry out polymerization. After dropping, the dropping line was washed with 7 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-4).

<Production Example 5> [Production of crystalline vinyl resin (B-5)]
An autoclave was charged with 375 parts of stearyl acrylate [manufactured by Kyoeisha Chemical Co., Ltd.; After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. A mixed solution of 290 parts of styrene, 75 parts of methyl methacrylate, 10 parts of acrylic acid, 0.7 parts of di-t-butyl peroxide, and 93 parts of xylene was added over 2 hours while controlling the temperature inside the autoclave at 170 ° C. Polymerization was carried out by dropping. After dropping, the dropping line was washed with 7 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-5).

<Production Example 6> [Production of crystalline vinyl resin (B-6)]
An autoclave was charged with 335 parts of behenyl acrylate and 363 parts of ethyl acetate [manufactured by Sankyo Kagaku Co., Ltd., the same shall apply hereinafter], and after purging with nitrogen, the temperature was raised to 78° C. in a sealed state while stirring. 50 parts of acrylonitrile, 79 parts of styrene, 15 parts of methyl acrylate, 21 parts of methacrylic acid, 2,2′-azobis(2-methylbutyronitrile) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., the same shall apply hereinafter] 9 parts, acetic acid A mixed solution of 112 parts of ethyl was added dropwise over 2 hours while controlling the internal temperature of the autoclave at 78° C. to carry out polymerization. After dropping, the dropping line was washed with 25 parts of ethyl acetate. After maintaining the same temperature for 5 hours, the internal temperature of the autoclave was raised to 92° C. over 1 hour. After maintaining the same temperature for 2 hours, the reaction rate of the monomer (a) was confirmed after cooling to 60°C. Since the reaction rate of the monomer (a) was less than 95%, the temperature was raised to 80° C. and 2,2′-azobis(2,4-dimethylvaleronitrile) [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., Same below] A mixed solution of 2.0 parts and 38 parts of ethyl acetate was added dropwise over 1 hour. After the dropwise addition, the temperature was kept at 80° C. for 2 hours to allow the reaction to reach a reaction rate of 95% or higher. The solvent was removed at 110° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-6).

<Production Example 7> [Synthesis of triacontyl acrylate]
50 parts of 1-triacontanol, 50 parts of toluene, 12 parts of acrylic acid, and 0.05 parts of hydroquinone are added to a reaction vessel equipped with a stirring device, a heating/cooling device, a thermometer, an air inlet tube, a pressure reducing device, and a water reducing device. and stirred to homogenize. After that, 2 parts of p-toluenesulfonic acid was added, and after stirring for 30 minutes, reaction was carried out for 5 hours while blowing air at a flow rate of 30 mL/min at 100° C. while removing generated water. After that, the pressure inside the reactor was adjusted to 300 mmHg, and the reaction was continued for another 3 hours while removing the generated water. After cooling the reaction solution to room temperature, 30 parts of a 10% by weight sodium hydroxide aqueous solution was added, and the mixture was stirred for 1 hour and allowed to stand to separate an organic phase and an aqueous phase. The organic phase was collected by liquid separation and centrifugal separation, 0.01 part of hydroquinone was added, and the solvent was removed under reduced pressure while blowing air to obtain triacontyl acrylate.

<Production Example 8> [Production of crystalline vinyl resin (B-7)]
An autoclave was charged with 375 parts of triacontyl acrylate obtained in Production Example 7 and 125 parts of xylene, and the autoclave was purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. A mixed solution of 163 parts of styrene, 97 parts of butyl acrylate, 100 parts of methyl methacrylate, 15 parts of acrylic acid, 2.9 parts of di-t-butyl peroxide, and 118 parts of xylene was added while controlling the temperature inside the autoclave to 170°C. was added dropwise over 2 hours to carry out polymerization. After dropping, the dropping line was washed with 7 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B-7).

<Comparative Production Example 1> [Production of crystalline vinyl resin (B'-1)]
An autoclave was charged with 750 parts of behenyl acrylate and 175 parts of xylene and purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state while stirring, and the temperature was controlled at 170°C for 2 hours. A mixed solution of 1.1 parts of di-t-butyl peroxide and 65 parts of xylene was added dropwise over 2 hours while controlling the internal temperature of the autoclave at 170° C. to carry out polymerization. After dropping, the dropping line was washed with 10 parts of xylene. After maintaining the same temperature for 0.5 hour, the reaction rate of the monomer (a) was confirmed after cooling to 70° C. and found to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a crystalline vinyl resin (B'-1).

<Comparative Production Example 2> [Production of amorphous vinyl resin (B'-2)]
An autoclave was charged with 175 parts of xylene and purged with nitrogen. After the temperature was raised to 140° C. in an open state with stirring, it was sealed. A mixed solution of 538 parts of styrene, 202 parts of butyl acrylate, 10 parts of acrylic acid, 1.0 parts of di-t-butyl peroxide, and 65 parts of xylene was added over 3 hours while controlling the temperature inside the autoclave at 140 ° C. Polymerization was carried out by dropping. After dropping, the dropping line was washed with 10 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain an amorphous vinyl resin (B'-2).

<Comparative Production Example 3> [Production of crystalline vinyl resin (B'-3)]
An autoclave was charged with 390 parts of methyl ethyl ketone, 420 parts of behenyl acrylate, 180 parts of butyl acrylate, and 6 parts of t-butyl peroxy 2-ethylhexanoate [manufactured by Arkema Yoshitomi Co., Ltd.; Polymerization was carried out for 4 hours in a closed state with stirring. After that, 6 parts of t-butyl peroxy 2-ethylhexanoate was further added, and after stirring for 4 hours, the solvent was removed under a reduced pressure of 0.5 to 2.5 kPa at 120 ° C. for 5 hours to obtain a crystalline vinyl resin ( B'-3) was obtained.

Table 1 shows the compositions and physical properties of the crystalline vinyl resins (B-1) to (B-7) and (B'-1) to (B'-3).

<Example 1> [Production of toner binder (C-1)]
An autoclave was charged with 60.0 parts of the crystalline vinyl resin (B-1) obtained in Production Example 1 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 28.6 parts of styrene, 10.8 parts of butyl acrylate, 0.6 parts of acrylic acid, 0.06 parts of di-t-butyl peroxide, and 9.4 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.6 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-1) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 2> [Production of toner binder (C-2)]
An autoclave was charged with 50.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 35.8 parts of styrene, 13.5 parts of butyl acrylate, 0.8 parts of acrylic acid, 0.08 parts of di-t-butyl peroxide, and 10.4 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.7 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-2) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 3> [Production of toner binder (C-3)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-3) obtained in Production Example 3 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 42.9 parts of styrene, 16.2 parts of butyl acrylate, 0.9 parts of acrylic acid, 0.09 parts of di-t-butyl peroxide, and 9.9 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.6 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-3) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 4> [Production of toner binder (C-4)]
An autoclave was charged with 35.0 parts of the crystalline vinyl resin (B-4) obtained in Production Example 4 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 46.5 parts of styrene, 17.6 parts of butyl acrylate, 1.0 parts of acrylic acid, 0.1 parts of di-t-butyl peroxide, and 6.5 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.4 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-4) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 5> [Production of toner binder (C-5)]
An autoclave was charged with 45.0 parts of the crystalline vinyl resin (B-5) obtained in Production Example 5 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.3 parts of styrene, 14.9 parts of butyl acrylate, 0.8 parts of acrylic acid, 0.11 parts of di-t-butyl peroxide, and 5.5 parts of xylene was heated to 140°C in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.3 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-5) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 6> [Production of toner binder (C-6)]
An autoclave was charged with 70.0 parts of the crystalline vinyl resin (B-6) obtained in Production Example 6 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 21.5 parts of styrene, 8.1 parts of butyl acrylate, 0.5 parts of acrylic acid, 0.06 parts of di-t-butyl peroxide, and 10.4 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.7 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-6) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 7> [Production of toner binder (C-7)]
An autoclave was charged with 80.0 parts of the crystalline vinyl resin (B-7) obtained in Production Example 8 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 14.3 parts of styrene, 5.4 parts of butyl acrylate, 0.3 parts of acrylic acid, 0.04 parts of di-t-butyl peroxide, and 4.7 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.3 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-7) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 8> [Production of toner binder (C-8)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-8) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 9> [Production of toner binder (C-9)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-3) obtained in Production Example 3 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-9) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 10> [Production of toner binder (C-10)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-4) obtained in Production Example 4 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-10) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 11> [Production of toner binder (C-11)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-5) obtained in Production Example 5 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-11) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 12> [Production of toner binder (C-12)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-6) obtained in Production Example 6 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-12) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 13> [Production of toner binder (C-13)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-7) obtained in Production Example 8 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-13) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 14> [Production of toner binder (C-14)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 170°C in a closed state with stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.3 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 170° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After the dropping, the dropping line was washed with 0.9 part of xylene and held for 30 minutes to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-14) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 15> [Production of toner binder (C-15)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 140°C in an open state with stirring, the temperature was raised to 190°C in a closed state with stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.5 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 190° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 parts of xylene. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-15) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 16> [Production of toner binder (C-16)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 110° C. in an open state while stirring, the state was closed while stirring. 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.2 parts of t-butyl peroxy-2-ethylhexanoate [manufactured by NOF Corporation, the same shall apply hereinafter], and xylene While controlling the internal temperature of the autoclave at 170° C., 14.1 parts of the mixed solution was added dropwise over 3 hours to carry out polymerization. After the dropping, the dropping line was washed with 0.9 part of xylene and held for 30 minutes to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-16) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 17> [Production of toner binder (C-17)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 34.0 parts of styrene, 20.0 parts of butyl acrylate, 6.0 parts of acrylonitrile, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was prepared so that the temperature inside the autoclave was controlled at 140°C. Polymerization was carried out by adding dropwise over 3 hours. After dropping, the dropping line was washed with 0.9 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-17) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 18> [Production of toner binder (C-18)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-3) obtained in Production Example 3 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 34.0 parts of styrene, 20.0 parts of butyl acrylate, 6.0 parts of acrylonitrile, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was prepared so that the temperature inside the autoclave was controlled at 140°C. Polymerization was carried out by adding dropwise over 3 hours. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-18) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 19> [Production of toner binder (C-19)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-4) obtained in Production Example 4 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 34.0 parts of styrene, 20.0 parts of butyl acrylate, 6.0 parts of acrylonitrile, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was prepared so that the temperature inside the autoclave was controlled at 140°C. Polymerization was carried out by adding dropwise over 3 hours. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-19) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Example 20> [Production of toner binder (C-20)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B-3) obtained in Production Example 3 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 30.0 parts of styrene, 24.0 parts of butyl acrylate, 6.0 parts of acrylonitrile, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was controlled at an autoclave temperature of 140 ° C. Polymerization was carried out by adding dropwise over 3 hours. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C-20) was obtained. Further, when the dispersed state of the amorphous vinyl resin was confirmed, it was found that the amorphous vinyl resin was dispersed in the toner binder.

<Comparative Example 1> [Production of toner binder (C'-1)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B'-1) obtained in Comparative Production Example 1 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C'-1) was obtained.

<Comparative Example 2> [Production of toner binder (C'-2)]
An autoclave was charged with 40.0 parts of the crystalline vinyl resin (B'-2) obtained in Comparative Production Example 2 and purged with nitrogen. After the temperature was raised to 140° C. in an open state while stirring, the state was closed while stirring. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 14.1 parts of xylene was heated to 140° C. in the autoclave. Polymerization was carried out by dropwise addition over 3 hours while controlling. After dropping, the dropping line was washed with 0.9 parts of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under reduced pressure of 0.5 to 2.5 kPa. By cooling the resulting product, a toner binder (C'-2) was obtained.

<Comparative Example 3> [Production of toner binder (C'-3)]
An autoclave was charged with 10 parts of xylene and purged with nitrogen. After the temperature was raised to 140° C. in an open state with stirring, it was sealed. A mixed solution of 39.0 parts of styrene, 20.3 parts of butyl acrylate, 0.7 parts of acrylic acid, 0.12 parts of di-t-butyl peroxide, and 4 parts of xylene was prepared while controlling the temperature inside the autoclave to 140°C. Polymerization was carried out by adding dropwise over 3 hours. After dropping, the dropping line was washed with 1 part of xylene. After further holding at 140° C. for 1 hour, the temperature was raised to 170° C. over 1 hour to decompose the initiator. After cooling to 120° C., the reaction rate of styrene was confirmed to be 95% or more. The solvent was removed at 170° C. for 5 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain an amorphous vinyl resin (A). 60.0 parts of this amorphous vinyl resin (A) and 40.0 parts of the crystalline vinyl resin (B-2) obtained in Production Example 2 were mixed in powder form, supplied to a twin-screw kneader, and C. for 2 minutes. By cooling the resulting product, a toner binder (C'-3) was obtained.

<Comparative Example 4> [Production of toner binder (C'-4)]
As an amorphous vinyl resin (A), 98 parts of FSR-055 [manufactured by Fujikura Kasei Co., Ltd.] and 2 parts of the crystalline vinyl resin (B'-3) obtained in Comparative Production Example 3 were mixed in powder form, It was supplied to a twin-screw kneader and kneaded at 140° C. for 2 minutes. By cooling the resulting product, a toner binder (C'-4) was obtained.

Tables 2 and 3 show the compositions and physical properties of the toner binders (C-1) to (C-20) and (C'-1) to (C'-4).

<Example 21> [Production of Toner (T-1)]
To 86 parts of the toner binder (C-1) according to Example 1, 7 parts of carbon black [manufactured by Mitsubishi Chemical Corporation, MA-100] as a pigment, Fischer-Tropsch wax [Nippon Seiro FT-0070 manufactured by Co., Ltd.] and 1 part of a charge control agent [T-77 manufactured by Hodogaya Chemical Industry Co., Ltd.] were added to prepare a toner by the following method.
First, the mixture was premixed using a Henschel mixer [FM10B, manufactured by Nippon Coke Kogyo Co., Ltd.], and then kneaded using a twin-screw kneader [PCM-30, manufactured by Ikegai Co., Ltd.]. Then, after fine pulverization using a supersonic jet grinder Labjet [Kurimoto Co., Ltd., KJ-25], an elbow jet classifier [Matsubo Co., Ltd., EJ-L-3 (LABO) type ] to obtain toner particles having a volume average particle diameter D50 of 7 μm.
Then, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 100 parts of the toner particles using a sample mill to obtain toner (T-1) according to Example 21. .

<Examples 22 to 40> [Production of Toners (T-2) to (T-20)]
Toners were produced in the same manner as in Example 21 using the blending parts of the raw materials shown in Tables 4 and 5, and toners (T-2) to (T-20) according to Examples 22 to 40 were obtained.

<Comparative Examples 5 to 8> [Production of Toners (T'-1) to (T'-4)]
Toners were produced in the same manner as in Example 21 using the blending parts of the raw materials shown in Table 5, and toners (T'-1) to (T'-4) according to Comparative Examples 5 to 8 were obtained.

Tables 4 and 5 show the compositions and evaluation results of the toners using the toner binders obtained in Examples and Comparative Examples.

[Evaluation method]
Below, the obtained toners (T-1) to (T-20) and (T'-1) to (T'-4) have low-temperature fixability, hot offset resistance, fixation width, heat-resistant storage stability, and chargeability. Methods for measuring and evaluating the retention rate, image strength, and durability will be described, including criteria for determination.

<Low temperature fixability>
The toner was evenly placed on the paper so as to be 1.00 mg/cm ² . At this time, a printer without a heat fixing device was used as the method of placing the powder on the paper surface. This paper was passed through a soft roller at a fixing speed (peripheral speed of the heating roller) of 213 mm/sec and a heating roller temperature of 90 to 230°C in increments of 5°C. Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which cold offset occurred (MFT) was measured.
The lower the temperature at which cold offset occurs, the better the low-temperature fixability. Under these evaluation conditions, the MFT is generally preferably 125° C. or less.

<Hot offset resistance>
In the same manner as described for low-temperature fixability, toner is placed on paper, and this paper is applied to a soft roller at a fixing speed (peripheral speed of heating roller) of 213 mm/sec and a temperature of the heating roller in the range of 90 to 230°C. It was passed in increments of 5°C. Next, the presence or absence of hot offset on the fixed image was visually observed, and the temperature at which hot offset occurred was measured.
It means that the higher the temperature at which hot offset occurs, the better the hot offset resistance. Under this evaluation condition, the temperature is preferably 180° C. or higher.

<Fixing width>
The difference between the low temperature fixing temperature and the hot offset resistance temperature was taken as the fixing width.
It means that the wider the fixing width, the better. Under this evaluation condition, the temperature is preferably 70° C. or higher.

<Heat-resistant storage stability>
1 g of toner and 0.01 g of Aerosil R8200 (manufactured by Evonik Japan Co., Ltd.) are mixed with a shaker for 1 hour. The mixture was placed in an airtight container and allowed to stand in an atmosphere of 40° C. and 80% humidity for 48 hours.

[criterion]
⊚: No blocking at all, excellent heat-resistant storage stability.
◯: Blocking occurs in part, but it easily crumbles when touched.
Δ: Blocking occurs in part and does not collapse easily even when touched.
x: Blocking occurs in the whole, and the heat-resistant storage stability is greatly inferior.

<Charge retention rate>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) were placed in a 50 mL glass bottle and conditioned at 23° C. and a relative humidity of 50% for 8 hours or more.
(2) The mixture was friction-stirred at 50 rpm for 10 minutes and 60 minutes with a Turbula shaker mixer, and the charge amount at each time was measured using a blow-off charge amount measuring device (manufactured by Kyocera Chemical Co., Ltd.).
Using the obtained values, "the amount of charge after 60 minutes of friction/the amount of charge after 10 minutes of friction" was calculated and used as the charge stability index.
It means that the higher the charging stability index, the better the charging stability. In this evaluation condition, it is preferably 0.8 or more.

<Image intensity>
The image fixed by the evaluation of low-temperature fixability was applied by a hand scraping method in accordance with JIS K5600-5-4 (1999) so that a load of 10 g was applied from directly above a pencil fixed at an angle of 45 degrees. A scratch hardness test was performed and image strength was evaluated from scratch free pencil hardness.
Higher pencil hardness means better image strength. In general, it is preferably HB or more.

<Durability>
Using toner as a two-component developer, continuous copying was performed using a commercially available monochrome copier [AR5030, manufactured by Sharp Corporation], and durability was evaluated according to the following criteria.

[criterion]
⊚: No change in image quality and no occurrence of fogging at the 10,000th copy.
A: Fogging occurs at the 10,000th copy.
Δ: Fog occurs on the 6,000th copy.
x: Fog occurs on the 2,000th copy.

As is clear from the evaluation results in Tables 4 and 5, the toners (T-1) to (T-20) according to Examples 21 to 40 all gave excellent results in all performance evaluations. On the other hand, the toners (T'-1) to (T'-4) according to Comparative Examples 5 to 8 were unsatisfactory in some performance items.

The toner binder obtained by the present invention is excellent in heat-resistant storage stability, fixing width, charge retention rate, image strength and durability while maintaining low-temperature fixability and hot-offset resistance. It can be suitably used as a toner binder for electrostatic charge image development used in printing and the like.
Furthermore, it is suitable for applications such as additives for paints, additives for adhesives, and particles for electronic paper.

Claims (6)

A method for producing a toner binder containing an amorphous vinyl resin (A) and a crystalline vinyl resin (B),
a step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B);
The crystalline vinyl resin (B) is a polymer of a monomer composition (B0) containing a monomer (a) and a monomer (b),
The monomer (a) is a (meth)acrylate having 21 to 40 carbon atoms having a chain hydrocarbon group, and the monomer (b) is a vinyl group-containing monomer having 6 or less carbon atoms,
A method for producing a toner binder in which the crystalline vinyl resin (B) has a viscosity of 10 to 10,000 Pa·s at 100°C. 2. The toner according to claim 1, wherein the weight ratio of the monomer (a) in the monomer composition (B0) is 30 to 93% by weight based on the weight of the monomer composition (B0). A method for manufacturing a binder. 3. The weight ratio of the monomer (b) in the monomer composition (B0) is 7 to 70% by weight based on the weight of the monomer composition (B0). method of manufacturing a toner binder. The amorphous vinyl resin (A) is a polymer of a monomer composition (A0) containing styrene, and the weight ratio of styrene in the monomer composition (A0) is The method for producing a toner binder according to any one of claims 1 to 3, wherein (A0) is 50% by weight or more based on the weight of (A0). Monomer composition of the amorphous vinyl resin (A) before reaction in the step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B) The weight ratio [(A0):(B)] of the substance (A0) and the crystalline vinyl resin (B) is [20:80] to [65:35]. A method of making the described toner binder. Any one of claims 1 to 5, wherein the polymerization temperature in the step of polymerizing the monomer composition (A0) of the amorphous vinyl resin (A) in the presence of the crystalline vinyl resin (B) is 110°C to 190°C. 2. A method for producing a toner binder according to item 1 or 2.