JP2019105834A - Toner binder and toner - Google Patents

Abstract

To provide a toner binder that is excellent in low-temperature fixability, image stability, and storage stability, and has a wide fixing temperature width.SOLUTION: A toner binder contains a copolymer (A), a copolymer (B), a hydrocarbon wax (C), and a hydrocarbon wax (D), wherein the copolymer (A) has a segment (a1) that is constituted of a polymer containing a styrene monomer as an essential constituent monomer and a segment (a2) that is derived from polyolefin having a melting point of 101 to 160°C; the peak molecular weight of the copolymer (A) is 3000 to 30000; the peak molecular weight of the copolymer (B) is 500000 to 1200000; the melting point of the hydrocarbon wax (C) is 65°C to 100°C; the melting point of the hydrocarbon wax (D) is 101°C to 160°C.SELECTED DRAWING: None

Description

  The present invention relates to a toner binder and toner used for electrophotography, electrostatic recording, electrostatic printing and the like.

In electrophotography, a system using a heat roller or a heat belt to fix an electrostatic latent image visualized with toner is widely adopted.
When this method is used, it is desirable that the low temperature fixing property of the toner (minimum temperature of the heat roller which can obtain a fixing rate of 70%) is low and the hot offset temperature (minimum temperature of the heat roller where hot offset occurs) is high. . In addition, it is desirable that clear images can be obtained even when used for a long time. In order to satisfy these demands, it has been proposed to set the molecular weight distribution of the toner binder to a wide range from low molecular weight to high molecular weight and to define the order of the glass transition point of the component (see Patent Document 1).

Unexamined-Japanese-Patent No. 9-297432

  However, if the molecular weight distribution is broadened in order to lower the low temperature fixability and raise the hot offset temperature, on the contrary, sufficient low temperature fixability, hot offset property, and image stability can not be obtained. Also, it is not sufficient to define the order of the glass transition points of the constituent components.

The present inventors arrived at the present invention as a result of earnestly examining in order to solve the above-mentioned subject.
That is, the present invention is a toner binder containing the copolymer (A), the copolymer (B), the hydrocarbon wax (C) and the hydrocarbon wax (D), and the copolymer (A) is styrene And gel segment of the copolymer (A), having a segment (a1) composed of a polymer containing a monomer as an essential constituent monomer and a segment (a2) derived from a polyolefin having a melting point of 101 to 160 ° C. The peak molecular weight in the molecular weight distribution curve obtained by the ation chromatography measurement is 3000 to 30,000, and the peak molecular weight in the molecular weight distribution curve obtained by the gel permeation chromatography measurement of the copolymer (B) is 500,000 to 1,200,000 And the melting point of the hydrocarbon wax (C) is 65 ° C. to 100 ° C., and the melting point of the hydrocarbon wax (D) is 101 to 1 Toner binder is a 0 ° C.; and a toner containing a and a colorant the toner binder.
The melting point in the present invention indicates the maximum melting peak temperature as measured by the method (DSC method) defined in ASTM D3418-82.

  According to the present invention, a toner binder having a wide fixing temperature range can be obtained because the low temperature fixing property, the image stability and the storage stability are excellent, and the occurrence of the low temperature offset and the high temperature offset is suppressed.

The copolymer (A) of the present invention has a segment (a1) composed of a polymer containing a styrene monomer as an essential component monomer and a segment (a2) derived from a polyolefin having a melting point of 101 to 160 ° C. .
The copolymer (A) of the present invention is a styrene monomer which becomes a segment (a1) in the presence of a polyolefin having a melting point of 101 to 160 ° C. which becomes a segment (a2) using a radical polymerization initiator (f) Obtained by polymerizing a monomer containing

  A segment (a1) composed of a polymer containing a styrene monomer as an essential component monomer has a styrene monomer as an essential component monomer, and further includes a (meth) acrylic acid ester monomer, a carboxyl group-containing vinyl monomer, a nitrile monomer, A vinyl ester monomer can be used in combination as a constituent monomer. It is preferable to include a carboxyl group-containing vinyl monomer as a constituent monomer among the constituent monomers. In the present invention, "(meth) acrylic" means "acrylic" and / or "methacrylic", and "(meth) acryl" means "acryl" and / or "methacryl".

  Examples of the styrene monomer include styrene and alkylstyrenes having 1 to 3 carbon atoms in the alkyl group (for example, α-methylstyrene, p-methylstyrene) and the like, each of which may be used alone or in combination of two or more You may Preferred is styrene from the viewpoint of cost.

As the (meth) acrylic acid ester monomer, an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms [eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate etc], C1-C18 hydroxyl alkyl (meth) acrylate of alkyl group [such as hydroxyl ethyl (meth) acrylate etc] and carbon number of alkyl group 1 to 18 alkylamino group-containing (meth) acrylates [for example, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate etc.] and the like can be mentioned.
Among these (meth) acrylic acid ester monomers, from the viewpoint of storage stability, preferred are alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group and a mixture of two or more thereof, more preferably the alkyl group Is a C 1-7 alkyl (meth) acrylate and a mixture of two or more thereof, more preferably a C 1-5 alkyl (meth) acrylate.

Examples of carboxyl group-containing vinyl monomers include monocarboxylic acids (including those having 3 to 15 carbon atoms, such as (meth) acrylic acid, crotonic acid and cinnamic acid), and dicarboxylic acids (including those having 4 to 15 carbon atoms). Such as (anhydride) maleic acid, fumaric acid, itaconic acid and citraconic acid etc.], and dicarboxylic acid monoesters [monoalkyl (carbon number 1 to 18) esters of the above dicarboxylic acids such as maleic acid monoalkyl esters, fumaric acid Monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid monoalkyl ester etc.] and the like.
Among these carboxyl group-containing vinyl monomers, from the viewpoint of charge stability, (meth) acrylic acid, dicarboxylic acid monoester, (anhydride) maleic acid, fumaric acid and a mixture of two or more thereof are preferable, and more preferable (Meth) acrylic acid, maleic acid monoester and mixtures of two or more thereof.

  The nitrile monomer includes those having 3 to 20 carbon atoms, and specific examples include (meth) acrylonitrile and cyanostyrene. Among these, preferred are acrylonitrile and methacrylonitrile.

  Vinyl ester monomers include aliphatic vinyl esters (including those having 4 to 15 carbon atoms, such as vinyl acetate, vinyl propionate and isopropenyl acetate), and aromatic vinyl esters (such as those having 9 to 15 carbon atoms) And, for example, methyl-4-vinylbenzoate etc.).

  The weight ratio of the styrene monomer which is an essential constituent monomer in the monomers constituting the segment (a1) is preferably 60 to 99% by weight based on the total weight of the monomers constituting the segment (a1) is there.

  In the segment (a1), a crosslinking agent may be used in the range of 0.0001 to 0.1% by weight with respect to the constituent monomers. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinyl ether, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, di 1,2-propylene glycol Di (meth) acrylate, poly 1,2-propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and tetramethylolmethane tetra (meth) acrylate etc It is below.

The polyolefin to be the segment (a2) is a homopolymer or copolymer of an olefin having 2 to 7 carbon atoms, and has a melting point of 101 to 160 ° C.
Examples of the olefin having 2 to 7 carbon atoms include ethylene, 1,2-propylene, 1-butene, isobutylene, 1-hexene and mixtures thereof.

  The melting point of the polyolefin to be the segment (a2) is 101 ° C. to 160 ° C. The image stability is insufficient at less than 101 ° C., and the hot offset property is insufficient at more than 160 ° C. Preferably it is 101-158 degreeC, More preferably, it is 102-156 degreeC.

  From the viewpoint of durability, the molecular weight of the polyolefin to be the segment (a2) is preferably a number average molecular weight of 1,000 to 10,000, and more preferably a number average molecular weight of 1,500 to 9,000.

  As the polyolefin to be the segment (a2), the above-mentioned olefin having 2 to 7 carbon atoms may be polymerized and used according to a known method, and polyolefins available from the market [Sun wax series and Biscol series (both Sanyo Chemical Industries, Ltd. And the like, and polyolefins having a melting point of 101 to 160 ° C. may be used.

  The weight ratio of the content of (a1) to (a2) ((a1) / (a2)) is preferably 99.0 / 1.0 to 99.8 / 0.2 from the viewpoint of image stability. More preferably, it is 99.2 / 0.8 to 99.6 / 0.4.

  The peak molecular weight in the molecular weight distribution curve obtained by gel permeation chromatography measurement of the copolymer (A) is 3000 to 30,000. If it is less than 3,000, the image quality will be poor, and if it exceeds 30,000, the fixation will be poor. Preferably it is 3500-20000, More preferably, it is 4000-15000.

  The acid value of the copolymer (A) is preferably 0 to 35 mg KOH / g, more preferably 15 to 30 mg KOH / g from the viewpoint of image stability.

  The glass transition point (Tg) of the copolymer (A) is preferably 50 ° C. to 70 ° C., more preferably 55 ° C. to 65 ° C. from the viewpoint of storage stability and fixability.

  As a monomer which comprises the copolymer (B) of this invention, the monomer similar to a copolymer (A) can be used. It is preferable that it is a copolymer which contains a styrene monomer and a carboxyl group-containing vinyl monomer as a structural monomer among the said monomers, and what is preferable as a styrene monomer and a carboxyl group-containing vinyl monomer is the same as (A) . Moreover, it is preferable that a copolymer (B) does not have a segment (a2) derived from the polyolefin whose melting | fusing point is 101-160 degreeC.

  The peak molecular weight in the molecular weight distribution curve obtained by gel permeation chromatography measurement of the copolymer (B) is 500,000 to 1,200,000, preferably 550,000 to 1,150,000 from the viewpoint of hot offset property, more preferably It is 600,000 to 1,100,000.

  The acid value of the copolymer (B) is preferably 0 to 15 mg KOH / g, more preferably 1 to 10 mg KOH / g from the viewpoint of image stability.

  The glass transition point (Tg) of the copolymer (B) is preferably 50 to 80 ° C., more preferably 55 to 75 ° C., from the viewpoint of fixability and storage stability.

  The weight ratio of the content of the copolymer (A) to the copolymer (B) ((A) / (B)) is preferably 60/40 to 80/20 from the viewpoint of fixability and image stability. And more preferably 64/36 to 73/27.

  The toner binder of the present invention contains a hydrocarbon wax (C) having a melting point of 65 ° C. to 100 ° C. and a hydrocarbon wax (D) having a melting point of 101 to 160 ° C.

Examples of hydrocarbon wax (C) and hydrocarbon wax (D) include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, carnauba wax, montan wax, rice wax and low molecular weight polyolefin, etc. Wax may be used.
Among these, one having a melting point of 65 ° C. to 100 ° C. is used as the hydrocarbon wax (C), and one having a melting point of 101 to 160 ° C. is used as the hydrocarbon wax (D).

  Among them, the hydrocarbon wax (C) is preferably a paraffin wax having a melting point of 65 ° C. to 99 ° C., a microcrystalline wax having a melting point of 65 ° C. to 99 ° C., from the viewpoint of low temperature fixability and offset resistance. , A Fischer-Tropsch wax having a melting point of 65 ° C. to 99 ° C. and a low molecular weight polyolefin having a melting point of 65 ° C. to 99 ° C., more preferably a paraffin wax having a melting point of 65 ° C. to 98 ° C. C. Fischer Tropsch wax, which is available from the market.

  The hydrocarbon wax (C) has a melting point of 65 ° C. to 100 ° C., the storage stability of the toner is insufficient at 65 ° C. or less, and the low temperature fixability is insufficient at 101 ° C. or more. Preferably it is 65-99 degreeC, More preferably, it is 65-95 degreeC.

The hydrocarbon wax (D) is preferably a homopolymer or copolymer of an olefin having 2 to 7 carbon atoms and having a melting point of 101 to 160 ° C. from the viewpoint of hot offset property, and the segment ((2) The same ones as exemplified for the polyolefin constituting a2) can be used.
In the toner binder of the present invention, the hydrocarbon wax (D) may be the same as or different from the above-mentioned polyolefin which becomes the segment (a2) of the copolymer (A). Also, plural types of waxes may be used.

  The melting point of the hydrocarbon wax (D) is 101 ° C. to 160 ° C. When the temperature is less than 101 ° C., the image stability is insufficient, and when it exceeds 160 ° C., the hot offset property is insufficient. Preferably it is 102-158 degreeC, More preferably, it is 130-156 degreeC.

The total proportion of the segment (a2) contained in the copolymer (A), the hydrocarbon wax (C) and the hydrocarbon wax (D) is preferably 3 to 8% by weight based on the weight of the toner binder, and more preferably It is 4 to 8% by weight, more preferably 4 to 7% by weight. When the amount is less than 3% by weight, the low temperature fixability is deteriorated, and when the amount is more than 8% by weight, the image stability is deteriorated.
The weight of the segment (a2) contained in the copolymer (A) is the weight of the polyolefin present when polymerizing the copolymer (A).

The copolymer (A) can be obtained by polymerizing a monomer composition containing a styrene monomer in the presence of a polyolefin having a melting point of 101 to 160 ° C. to be the segment (a2). The copolymer (A) dissolves, for example, a polyolefin having a melting point of 101 to 160 ° C. in toluene or xylene heated to 100 ° C. to 200 ° C., and a constituent monomer of the segment (a1) and a radical polymerization initiator It is obtained by distilling off the solvent after the polymerization of (f) simultaneously or separately by dropwise addition.
The polymerization temperature is preferably 60 to 230 ° C, more preferably 110 to 200 ° C.
The polymerization time is preferably 1 to 30 hours, more preferably 2 to 10 hours.
The copolymer (A) obtained by the above polymerization method has a styrene monomer as an essential component because the monomer composition containing the styrene monomer is polymerized starting from the radical generated in the polyolefin having a melting point of 101 to 160 ° C. The copolymer (A) which has a segment (a1) comprised from the polymer contained as a monomer, and a segment (a2) derived from the polyolefin whose melting | fusing point is 101-160 degreeC is obtained.

A copolymer (B) can synthesize | combine the said monomer by well-known polymerization methods, such as solution polymerization, block polymerization, suspension polymerization, and emulsion polymerization, using a radical polymerization initiator (f). Preferred is solution polymerization, suspension polymerization, bulk polymerization and combinations thereof.
The polymerization temperature is preferably 60 to 230 ° C, more preferably 80 to 200 ° C.
The polymerization time is preferably 1 to 30 hours, more preferably 2 to 20 hours.

Examples of the radical polymerization initiator (f) include azo polymerization initiators (eg, azobisisobutyronitrile, azobisvaleronitrile and azobiscyanovaleric acid) and organic peroxide polymerization initiators [eg, benzoyl peroxide, di- t-Butyl peroxide, t-butyl peroxybenzoate, 1,1-di- (t-butyl peroxy) cyclohexane, di-t-butyl peroxyhexahydrophthalate and 2,2-bis (4,4-di -T-butylperoxycyclohexyl) propane] and the like.
Among these, di-tert-butyl peroxide, 1,1-di- (tert-butylperoxy) cyclohexane, di-tert-butylperoxyhexahydrophthalate and 2,2-bis (4,4 Di-t-butylperoxycyclohexyl) propane.
The amount of the polymerization initiator used is preferably 0.01 to 5% by weight, more preferably 0.05 to 4% by weight, based on the total amount of monomers.

Solvents for solution polymerization include cycloalkane solvents having 5 to 12 carbon atoms (eg cyclohexane and methylcyclohexane), aromatic solvents having 6 to 12 carbon atoms (eg benzene, toluene, xylene, ethylbenzene and cumene), ester solvents (Ethyl acetate and butyl acetate etc.) and ether solvents (methyl cellosolve, ethyl cellosolve and butyl cellosolve etc.) etc. are used.
Among these, preferred are C6-C12 aromatic solvents, and more preferred are toluene, xylene and ethylbenzene.

  Moreover, when performing suspension polymerization, it can superpose | polymerize in water using an inorganic acid salt dispersing agent (a calcium carbonate, a calcium phosphate, etc.), an organic dispersing agent (a polyvinyl alcohol, a methylcellulose, etc.), etc.

The toner binder of the present invention contains a copolymer (A), a copolymer (B), a hydrocarbon wax (C) and a hydrocarbon wax (D).
The method of mixing the copolymer (A), the copolymer (B), the hydrocarbon wax (C) and the hydrocarbon wax (D) is not limited, but a method of separately polymerizing each polymer and mixing in a solution state, Examples thereof include a method of melt mixing in a twin-screw extruder, a mixing tank capable of heating and stirring, and a method of polymerizing other polymers in the presence of each polymer.

  The acid value of the toner binder of the present invention is preferably 13 to 25 mg KOH / g, more preferably 13 to 24 mg KOH / g from the viewpoint of image stability.

  The weight average molecular weight of the toner binder of the present invention is preferably 200,000 to 300,000, and more preferably 210,000 to 270,000, from the viewpoint of fixability.

  The glass transition point (Tg) of the toner binder of the present invention is preferably 50 to 80 ° C., more preferably 55 to 75 ° C. from the viewpoint of fixability and storage stability.

The number average molecular weight, weight average molecular weight and peak molecular weight of each of the copolymer (A), copolymer (B) and toner binder of the present invention are measured under the following conditions using gel permeation chromatography (GPC) be able to.
Device (example): "HLC-8120" (manufactured by Tosoh Corporation)
Column (one example): "TSK GEL GMH6" (manufactured by Tosoh Corporation) Measurement temperature: 40 ° C
Sample solution: 0.25% by weight solution in tetrahydrofuran (Insoluble content filtered off with a glass filter)
Solution injection volume: 100 μl
Detection device: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (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 Corp.)

The number average molecular weight, weight average molecular weight and peak molecular weight of each of the hydrocarbon wax (C) and the hydrocarbon wax (D) of the present invention are measured, for example, by the following apparatus.
Device (example): High temperature GPC
Solvent: ortho-dichlorobenzene standard substance: polystyrene sample concentration: 3 mg / ml
Column (Example: PLgel 10 μm, MIXED-B [manufactured by Polymer Laboratories, Inc.])
Column temperature: 135 ° C

  The acid value of the present invention is measured by the method defined in JIS K 0070.

  The glass transition point (Tg) of the present invention is measured by a method (DSC method) defined in ASTM D3418-82 using a differential scanning calorimeter (DSC Q20, manufactured by TA Instruments).

  The melting point of the present invention can be measured by a method (DSC method) defined in ASTM D3418-82 using a differential scanning calorimeter (manufactured by TA Instruments, Inc., DSC Q20).

  The toner of the present invention contains the toner binder of the present invention and a colorant, and if necessary, various additives such as a charge control agent and a fluidizing agent can be mixed.

As the colorant, known pigments, dyes and magnetic powders can be used.
Specifically, carbon black, Sudan black SM, fast yellow-G, benzidine yellow, pigment yellow, indofirst orange, irgasine 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, Kayset YG, Orazol Brown B, Oil Pink OP and Magnetic Powder [eg ferromagnetic metal powder ( Iron, cobalt and nickel etc.), magnetite, hematite and ferrite] and the like.

  The content of the colorant in the toner is preferably 1 to 15% by weight, more preferably 2 to 10% by weight based on the weight of the toner when using a dye or pigment, and when using a magnetic powder Is preferably 15 to 70% by weight, more preferably 30 to 60% by weight.

Examples of charge control agents include metal-containing azo dyes, nigrosine dyes and quaternary ammonium salt compounds.
When a charge control agent is used, the content of the charge control agent in the toner is preferably 0.001 to 5% by weight, more preferably 1 to 5% by weight based on the weight of the toner.

Examples of the fluidizing agent include known materials such as colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like.
When a fluidizing agent is used, the content of the fluidizing agent in the toner is preferably 0.001 to 5% by weight based on the weight of the toner.

Examples of the method for producing the toner include known kneading and pulverizing methods. For example, the toner components are dry-blended using a Henschel mixer or the like, then melt-kneaded at 70 ° C. to 190 ° C. using a twin-screw extruder or the like, and then coarsely crushed, and finally a jet crusher etc. The particles are made into fine particles using the above, and the particle size distribution is adjusted with a classifier such as an elbow jet to obtain fine particles having a volume average particle diameter (D50) of 5 to 15 microns.
In addition, volume average particle diameter (D50) is measured using a Coulter counter [For example, brand name: Multisizer 3 (made by Beckman Coulter Co., Ltd.)].
In the above method, the fluidizing agent can be used by mixing (externally adding) after micronizing the toner.

The toner is mixed with carrier particles such as ferrite coated on the surface with glass bead particles and / or resin (acrylic resin, silicone resin, etc.) as needed, and used as a developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. Also, instead of the carrier particles, they can be charged by friction with a member such as a charging blade.
The toner is then transferred to the electrostatic latent image on the photoreceptor and further transferred onto a support (paper, polyester film, etc.).
Further, the toner is fixed on the support by a known heat roll fixing method or the like to make a recording material.

The present invention will be further described by the following examples, but the present invention is not limited thereby. Hereinafter, parts indicate parts by weight.
The toner test method is as follows.

(1) Low-Temperature Fixing Property A two-component developer was obtained by uniformly mixing 30 parts of an evaluation sample (toner) and 800 parts of a ferrite carrier (F-150 manufactured by Powder Tech Co., Ltd.), and subjected to the following test.
The unfixed image developed using a commercial monochrome copier [AR 5030, manufactured by Sharp Corp.] was modified from the fixing unit of a commercial monochrome copier [SF 8400 A, manufactured by Sharp Corp.] to make the heat roller temperature variable. Fixing was performed at a process speed of 145 mm / sec with a fixing device. The image density (I.D.) = 0.6 measured with RD-19 manufactured by GretagMacbeth is rubbed by reciprocation friction fastness test (friction with paper) in 5 reciprocation times, and the fixing rate ( The heat roller temperature at which I.D. × 100 after friction / I.D. Before friction became 70% or more was taken as the low temperature fixability.

(2) Hot Offset Occurrence Temperature Fixing was performed in the same manner as in the above (1), and the presence or absence of a hot offset on a fixed image was visually determined.
The temperature at which the hot offset began to occur was taken as the hot offset occurrence temperature.

(3) Image Stability Similar to the above (1), continuous copying was performed using a commercial monochrome copying machine [AR 5030, manufactured by Sharp Corp.] as a two-component developer, and the image quality change was evaluated based on the following criteria.
: 1: There is no change in image quality even after copying of 10,000 sheets, and no fogging.
○: A fog has occurred after copying of 10,000 sheets.
Fair: fogging occurred after copying of 6,000 sheets.
X: Fog has occurred after copying of 2,000 sheets.

(4) Storage stability (blocking resistance)
The toner is put in a polyethylene bottle, kept in a 45 ° C. constant temperature water bath for 8 hours, transferred to a 42 mesh sieve, and shaken for 10 seconds at a vibration strength of 5 using a powder tester manufactured by Hosokawa Micron Corporation The percent by weight of the toner remaining on the sieve was measured, and judged based on the following criteria to evaluate storage stability.
Weight of residual toner on sieve
:: less than 15% ○: 15% or more and less than 25% △: 25% or more and less than 30% ×: 30% or more

<Production Example 1>
In an autoclave, 5 parts of polypropylene wax (manufactured by Sanyo Chemical Industries, Ltd., Biscor 550-P, melting point 142 ° C.) and 330 parts of xylene were charged, and after replacing with nitrogen, the temperature was raised to 170 ° C. in a closed state under stirring. A mixed solution of 450 parts of styrene, 160 parts of n-butyl acrylate, 27 parts of methacrylic acid, 3 parts of di-t-butyl peroxide and 100 parts of xylene is controlled for 2.5 hours while controlling the temperature inside the autoclave at 170 ° C. It was dropped and polymerized. The polymerization was further completed by maintaining the temperature at the same temperature for 1 hour to obtain a xylene solution (a-1) containing the copolymer (A-1). The peak molecular weight of the copolymer (A-1) was 11000, the acid value was 27 mg KOH / g, and the glass transition point was 57 ° C.

<Production Example 2>
In a four-necked flask, 1900 parts of water and 100 parts of a 2% by weight aqueous solution of polyvinyl alcohol [PVA 235 manufactured by Kuraray Co., Ltd.] are added, and 760 parts of styrene, 220 parts of n-butyl acrylate, 20 parts of methacrylic acid, 2.2- A mixture of 3 parts of bis (4,4-di-t-butylperoxycyclohexyl) propane was added and stirred to form a suspension. After the flask was sufficiently purged with nitrogen, the temperature was raised to 88 ° C. to initiate polymerization. The polymerization was continued at the same temperature, and when the conversion reached 80%, 0.4 part of di-t-butylperoxyhexahydrophthalate was added and the temperature was raised to 98 ° C. The polymerization was continued at 98 ° C., and it was confirmed that the conversion had reached 99% to complete the polymerization. As post-treatment, the resultant was separated by filtration, washed with water and dried to obtain a copolymer (B-1).
The peak molecular weight of the copolymer (B-1) was 750,000, the acid value was 11 mg KOH / g, and the glass transition point was 73 ° C.

<Production Example 3>
Polyolefin, 2 parts of polyethylene wax (San Wax 151-P manufactured by Sanyo Chemical Industries, Ltd., melting point 103 ° C.), 499 parts of styrene, 1 part of acrylic acid, di-t- radical polymerization initiator (f) A xylene solution (a-2) containing a copolymer (A-2) was obtained in the same manner as in Production Example 1 except that 11 parts of butyl peroxide and the polymerization temperature were changed to 190 ° C. The peak molecular weight of the copolymer (A-2) was 4,000, the acid value was 1.5 mg KOH / g, and the glass transition point was 64 ° C.

Production Example 4
Polyolefin, 5 parts of polypropylene wax (Biscol 440-P manufactured by Sanyo Chemical Industries, Ltd., melting point 146 ° C.), 379 parts of styrene, 11 parts of methacrylic acid, 110 parts of n-butyl acrylate, radical polymerization initiator (f In the same manner as in Production Example 1 except that 1.2 parts of di-t-butyl peroxide was used, a xylene solution (a-3) containing the copolymer (A-3) was obtained. The peak molecular weight of the copolymer (A-3) was 16000, the acid value was 14 mg KOH / g, and the glass transition point was 56 ° C.

<Production Example 5>
Production except that 720 parts of styrene, 280 parts of n-butyl acrylate, 3 parts of 1,1-di- (t-butylperoxy) cyclohexane as radical polymerization initiator (f), and polymerization temperature of 95 ° C. Polymerization was carried out in the same manner as in Example 2 to obtain a copolymer (B-2). The peak molecular weight of the copolymer (B-2) was 600,000, the acid value was 0 mg KOH / g, and the glass transition point was 55 ° C.

<Production Example 6>
In an autoclave, 10 parts of polypropylene wax (manufactured by Sanyo Chemical Industries, Ltd., Biscoll 550-P, melting point 142 ° C.) and 700 parts of xylene were charged and purged with nitrogen, and then heated to 190 ° C. in a closed state under stirring. A mixed solution of 965 parts of styrene, 35 parts of acrylic acid, 45 parts of di-t-butyl peroxide, and 180 parts of xylene was added dropwise over 4.5 hours while controlling the temperature inside the autoclave at 190 ° C. . The polymerization was further completed by maintaining the temperature for 0.5 hours at the same temperature to obtain a xylene solution (a-4) containing the copolymer (A-4). The peak molecular weight of the copolymer (A-4) was 3000, the acid value was 27 mg KOH / g, and the glass transition point was 56 ° C.

Production Example 7
In an autoclave, 10 parts of polypropylene wax (manufactured by Sanyo Chemical Industries, Ltd., Biscoll 550-P, melting point 142 ° C.) and 250 parts of xylene were charged and purged with nitrogen, and then heated to 150 ° C. in a closed state under stirring. A mixed solution of 705 parts of styrene, 221 parts of n-butyl acrylate, 74 parts of monobutyl maleate, 4.5 parts of di-t-butyl peroxide, and 100 parts of xylene while controlling the temperature inside the autoclave at 150 ° C. Over time, it was added dropwise and polymerized. The temperature was further raised to 180 ° C. to complete the polymerization to obtain a xylene solution (a-5) containing the copolymer (A-5). The peak molecular weight of the copolymer (A-5) was 28,000, the acid value was 24 mg KOH / g, and the glass transition point was 55 ° C.

<Production Example 8>
1900 parts of water and 100 parts of a 2% by weight aqueous solution of polyvinyl alcohol [PVA 235 manufactured by Kuraray Co., Ltd.] are added to a four-necked flask, and 730 parts of styrene, 250 parts of n-butyl acrylate, 20 parts of methacrylic acid, 2.2- A mixture of 3 parts of bis (4,4-di-t-butylperoxycyclohexyl) propane was added and stirred to form a suspension. After the flask was sufficiently purged with nitrogen, the temperature was raised to 80 ° C. to initiate polymerization. The polymerization was continued at the same temperature, polymerized to a conversion of 60%, and then heated to 85 ° C. to continue the polymerization. After confirming that the conversion was 98%, the temperature was raised to 100 ° C., and the temperature was maintained for 2 hours to complete the polymerization. As post-treatment, the resultant was separated by filtration, washed with water and dried to obtain a copolymer (B-3).
The peak molecular weight of the copolymer (B-3) was 1,160,000, the acid value was 11 mg KOH / g, and the glass transition point was 62 ° C.

<Production Example 9>
After the autoclave was purged with nitrogen, 709 parts of styrene, 260 parts of n-butyl acrylate, 31 parts of acrylic acid and 0.19 parts of 1,6-hexanediol diacrylate were charged, and the temperature was raised to 95 ° C. in one hour. Then, 8 parts of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was charged, and bulk polymerization was performed at 95 ° C. for 3 hours. Subsequently, 240 parts of xylene was dropped over 1 hour, and the temperature was raised to 110 ° C. in 1 hour, and polymerization was performed at the same temperature for 2 hours. Further, 3.2 parts of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was charged and polymerized for 4 hours. Thereafter, the temperature is raised to 150 ° C. for 1 hour, and polymerization is carried out at the same temperature for 1 hour, and then 1400 parts of xylene is added and diluted to obtain a xylene solution (b-4) containing a (co) polymer (B-4). The The peak molecular weight of the (co) polymer (B-4) was 500,000, the acid value was 24 mg KOH / g, and the glass transition point was 55 ° C.

<Comparative Production Example 1>
It is polymerized in the same manner as in Production Example 1 except that polypropylene wax is not used in Production Example 1 to obtain a xylene solution (Ra-1) of a comparative copolymer composition (RA-1) containing a polymer (RA-1). The The peak molecular weight of the copolymer (RA-1) was 10600, the acid value was 28 mg KOH / g, and the glass transition point was 57 ° C.

<Comparative Production Example 2>
Polyolefin, 2 parts of polypropylene wax (Biscol 550-P, Sanyo Chemical Industries, Ltd., melting point 142 ° C.), monomer: 499 parts of styrene, acrylic acid 1 part, radical polymerization initiator (f): di-t-butyl It was polymerized in the same manner as in Production Example 1 except that 23 parts of peroxide and the polymerization temperature were changed to 200 ° C., and a xylene solution (Ra-) of a comparative copolymer composition (RA-2) containing a polymer (RA-2) 2) I got it. The peak molecular weight of the copolymer (RA-2) was 2900, the acid value was 1.5 mg KOH / g, and the glass transition point was 55 ° C.

Example 1
In an autoclave, 1114 parts of a xylene solution (a-1) of copolymer (A-1), 285 parts of polymer (B-1), 25 parts of polypropylene wax (Biscol 550-P manufactured by Sanyo Chemical Industries, Ltd.), melting point Thirty parts of paraffin wax at 75 ° C. was charged and uniformly dissolved under reflux of xylene. Next, the temperature was raised to 170 ° C. while distilling off xylene, and then the pressure was reduced. The solvent removal was continued at a pressure of 1 kPa or less, and it was confirmed by gas chromatography that the xylene content in the resin was 400 ppm or less, to obtain a toner binder (TB-1).

Example 2
1205 parts of a xylene solution (a-2) of copolymer (A-2), 360 parts of polymer (B-2), 20 parts of polypropylene wax (Biscol 440-P manufactured by Sanyo Chemical Industries, Ltd.), melting point 97 ° C. A toner binder (TB-2) was obtained in the same manner as in Example 1 except that 35 parts of Fischer-Tropsch wax was used.

Example 3
1360 parts of a xylene solution (a-3) of the copolymer (A-3), 270 parts of a polymer (B-1), 28 parts of a polypropylene wax (Biscol 660-P manufactured by Sanyo Chemical Industries, Ltd., melting point 138 ° C.) A toner binder (TB-3) was obtained in the same manner as in Example 1 except that 25 parts of paraffin wax having a melting point of 69 ° C. was used.

Example 4
1386 parts of a xylene solution (a-4) of the copolymer (A-4), 214 parts of a polymer (B-3), 40 parts of a polypropylene wax (Biscol 660-P manufactured by Sanyo Chemical Industries, Ltd., melting point 138 ° C.) A toner binder (TB-4) was obtained in the same manner as in Example 1 except that 30 parts of paraffin wax having a melting point of 97 ° C. was used.

Example 5
806 parts of the xylene solution (a-5) of the copolymer (A-5), 1034 parts of the xylene solution (b-4) of the copolymer (B-4), polypropylene wax (manufactured by Sanyo Chemical Industries, Ltd. Biscol 660) -P, 5 parts of polyethylene wax (Sanyo Kasei Kogyo Co., Ltd. Sun Wax 171 P melting point 103 ° C.), and 20 parts paraffin wax having a melting point of 69 ° C. Obtained (TB-5). Moreover, the copolymer (B-4) in 1034 parts of xylene solutions (b-4) of copolymer (B-4) was 390 parts.

Comparative Example 1
In an autoclave, 1109 parts of a xylene solution (Ra-1) of a copolymer solution (RA-1), 285 parts of a polymer (B-1), polypropylene wax (Biscol 550-P manufactured by Sanyo Chemical Industries, Ltd.) 55 A comparative toner binder (RTB-1) was obtained in the same manner as in Example 1 except that parts were charged.

Comparative Example 2
In an autoclave, 1239 parts of a xylene solution (Ra-2) of a copolymer solution (RA-2), 320 parts of a polymer (B-1), 20 parts of a polypropylene wax (Biscol 440-P manufactured by Sanyo Chemical Industries, Ltd.), A toner binder for comparison (RTB-2) was obtained in the same manner as in Example 1 except that 35 parts of Fischer-Tropsch wax having a melting point of 97 ° C. was charged.

<Creating a Toner>
Toner binders (TB-1) to (TB-5), (RTB-1), and (RTB-2) were each 88 parts of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) and 7 parts of a charge control agent After mixing 1 part of Tsuchiya chemical spirone black TRH) uniformly with a Henschel mixer [Nippon Coke Kogyo Co., Ltd. FM10B], it knead | mixes with a twin-screw extruder [resin Co., Ltd. product PCM-30] with a resin temperature of 140 degreeC. The cooled material is finely pulverized with a jet crusher [Labjet LJ manufactured by Nippon Pneumatic Mfg. Co., Ltd.], and classified with an elbow jet classifier [Model EJ-L-3 (LABO) made by Matsubo Co., Ltd.], Toner particles were obtained. Next, 100 parts of toner particles and 1.0 part of colloidal silica (Aerosil R972, manufactured by Nippon Aerosil) are uniformly mixed to obtain toners (T-1) to (T-5) of the present invention with a volume average particle diameter of 9 μm and comparison Toner (RT-1) and (RT-2) were obtained.
The volume average particle size was measured by Coulter Counter (Multisizer III, manufactured by Beckman Coulter, Inc.).

<Test example>
The evaluation results for each of the toners (T-1) to (T-5) and (RT-1) and (RT-2) are shown in Table 1.

  The toner binder of the present invention is extremely useful because it has a wide fixing temperature range as a toner and can form a high quality image.

Claims (6)

  A toner binder comprising a copolymer (A), a copolymer (B), a hydrocarbon wax (C) and a hydrocarbon wax (D), wherein the copolymer (A) essentially comprises a styrene monomer. A gel permeation chromatography measurement of the copolymer (A) having a segment (a1) composed of a polymer containing as a monomer and a segment (a2) derived from a polyolefin having a melting point of 101 to 160 ° C. The peak molecular weight in the molecular weight distribution curve obtained is 3000 to 30,000, and the peak molecular weight in the molecular weight distribution curve obtained by gel permeation chromatography of the copolymer (B) is 500,000 to 1,200,000, hydrocarbon wax Toner having a melting point of 65 ° C. to 100 ° C. for (C) and a melting point of hydrocarbon wax (D) of 101 to 160 ° C. Indah.   The toner binder according to claim 1, wherein the copolymer (A) and / or the copolymer (B) is a copolymer containing a styrene monomer and a carboxyl group-containing vinyl monomer as a constituent monomer.   The toner binder according to claim 1, wherein the acid value is 13 to 25 mg KOH / g.   The weight ratio ((A) / (B)) of the content of the copolymer (A) and the copolymer (B) is 60/40 to 80/20. Description toner binder.   The total proportion of the segment (a2), the hydrocarbon wax (C) and the hydrocarbon wax (D) of the copolymer (A) is 3 to 8% by weight based on the weight of the toner binder The toner binder as described in any one.   A toner comprising the toner binder according to any one of claims 1 to 5 and a colorant.