JP2015200882A - toner binder and toner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder and a toner composition that can achieve both low-temperature fixability and hot-offset resistance, has excellent storage stability, and is environment friendly.SOLUTION: There is used a toner binder that contains a polycarbonate (A) comprising an epoxide and carbon dioxide, and a binder resin (B) other than (A), where the content of (A) based on the weight of the toner binder is 1 to 45 weight%, and the content of (B) is 55 to 99 weight%.

Description

  The present invention relates to a toner binder and a toner composition.

In an electrophotographic system, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is transferred onto a recording medium such as paper and then fixed by a method such as heating.
In this heat fixing method, a large amount of electric power is required in the process of thermally melting the toner and fixing it on a recording medium such as paper. From the viewpoint of energy saving and environmental protection in recent years, low-temperature fixability of toner is one of important characteristics.
In the electrophotographic process, in order to fix the toner transferred onto paper or the like, a contact heating type fixing machine [method using a heat roll, method using a film or belt between a heating body and paper] is used. Is widely adopted. In this method, the lower limit fixing temperature is preferably low (low temperature fixing property), and the temperature at which hot offset occurs on the heat roll surface, film or belt is preferably high (hot offset resistance). Further, since heat is generated from the fixing device or the like inside the copying machine or printer, the toner should not be aggregated by heat and the fluidity should not deteriorate (storage stability).

On the other hand, mankind burns large amounts of fossil fuels such as petroleum to obtain energy, raises the carbon dioxide concentration in the atmosphere, and causes environmental destruction. It is highly desirable to use the carbon dioxide as a carbon source, and some have been put into practical use. Some of them produce polycarbonate from carbon dioxide and epoxide, and several production methods have been reported (Patent Documents 1 and 2). It has also been shown that the obtained polycarbonate is applied to a toner binder (Patent Document 3). However, the polycarbonates shown are problematic in terms of storage stability for toner binder applications and further improvements are required.

WO2010-53110 WO2011-4730 Publication JP2013-50629A

  An object of the present invention is to provide a toner binder and a toner composition that are compatible with low-temperature fixability and hot offset resistance, have excellent storage stability, and are environmentally friendly.

As a result of intensive investigations to solve these problems, the present inventors have reached the present invention.
That is, the present invention relates to a toner binder containing a polycarbonate (A) composed of epoxide and carbon dioxide and a binder resin (B) other than (A), which is based on the weight of the toner binder (A). A toner binder having a content of 1 to 45% by weight and a content of (B) of 55 to 99% by weight; a toner composition containing the toner binder and the colorant.

  According to the present invention, it is possible to provide a toner binder and a toner composition that can achieve both low-temperature fixability and hot offset resistance, have excellent storage stability, are environmentally friendly and have no practical problems.

The present invention is described in detail below.
The polycarbonate (A) used for this invention should just consist of a carbon dioxide and an epoxide.
The epoxide is not particularly limited as long as it reacts with carbon dioxide to become polycarbonate. For example, aliphatic monoepoxides such as ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutylene oxide, 1-pentene oxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) Examples thereof include aliphatic polyepoxides such as ethers, aromatic monoepoxides such as glycidyl ethers of phenols, and aromatic polyepoxides such as bisphenol F diglycidyl ether and bisphenol A diglycidyl ether. Two or more epoxides may be used in combination.
Of the epoxides, aliphatic epoxy compounds are preferable, and ethylene oxide, propylene oxide, and combinations thereof are more preferable.

As catalysts and production conditions used when synthesizing the polycarbonate (A), those described in Patent Documents 1 to 3 can be used. 30-70 degreeC is preferable and, as for the glass transition point (henceforth Tg) of a polycarbonate (A), 35-65 degreeC is still more preferable.

The polycarbonate (A) may be modified with other compounds.
The compound used for modification is not particularly limited as long as it reacts with the polycarbonate (A), and examples thereof include carboxylic acids or anhydrides thereof, isocyanate compounds, and epoxy compounds.
Further, the polycarbonate (A) and the binder resin (B) are not limited to a mixture thereof, but may be a resin in which the polycarbonate (A) and the binder resin (B) are chemically bonded as a graft body or a block body.

As the binder resin (B) other than (A) used in the present invention, polyester resin (B1), styrene (co) polymer (B2), polyether polyester resin (B3), epoxy resin (B4) and the like are used. It is done. From the viewpoint of chargeability, (B1), (B2) and combinations thereof are preferred.

The polyester resin (B1) used in the present invention is obtained by polycondensation of one or more polyol components (x) and one or more polycarboxylic acid components (y).
Examples of the polyol component (x) include diols and 3 to 8 or more valent polyols, and examples of the polycarboxylic acid component (y) include dicarboxylic acids and 3 to 6 or more valent polycarboxylic acids. .

As the polyol component (x) of the polyester resin (B1) used in the present invention, the diol includes alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 -Butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc.); alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol and hydrogenated bisphenol A) ); (Poly) oxyalkylene of the above alicyclic diol (the same applies to polyoxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.) of the alkylene group) ether [oxyalkylene unit (hereinafter abbreviated as AO unit) )]; Divalent phenols [monocyclic divalent phenols (for example, hydroquinone), polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30)], and the like. Polyoxyalkylene ethers of bisphenols are usually obtained by adding alkylene oxide (hereinafter abbreviated as AO) to bisphenols. Examples of bisphenols include those represented by the following general formula (1).
OH-Ar-X-Ar-OH (1)
[Wherein X is an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond, Ar is substituted with halogen or an alkyl group having 1 to 30 carbon atoms. Represents a good phenylene group. ]
Specifically, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2 , 2′-diethylbisphenol F, and two or more of these may be used in combination. As AO added to these bisphenols, those having 2 to 4 carbon atoms are preferable. Specifically, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2 , 3-, 1,3- or iso-butylene oxide, tetrahydrofuran (hereinafter referred to as THF) and a combination of two or more thereof. Of these, EO and / or PO are preferred. The added mole number of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles.
Of the polyoxyalkylene ethers of bisphenols, EO and / or PO adducts of bisphenol A (average added mole number of 2 to 4, particularly 2 to 3) are preferable from the viewpoint of toner fixing properties.
Examples of the polyol having 3 to 8 valences or more include 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin and trimethylolethane). , Trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol); sugars and derivatives thereof such as sucrose and methylglucoside); (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols (of AO units) Polyoxyalkylene ethers of trisphenols (trisphenol PA and the like) (numbers of AO units 2 to 30); polyoxys of novolak resins (phenol novolac and cresol novolac, average degree of polymerization 3 to 60) Alkylene ether (A The number 2 to 30) or the like of the unit and the like.

  Among these, from the viewpoint of achieving both low-temperature fixability and hot offset resistance, preferred are alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 30 AO units), 3 to 8 Or higher aliphatic polyhydric alcohols, and polyoxyalkylene ethers of novolak resins (number of AO units 2 to 30), and more preferable from the viewpoint of storage stability are alkylene glycols having 2 to 10 carbon atoms. , Polyoxyalkylene ethers of bisphenols (2 to 5 of AO units), polyoxyalkylene ethers of novolac resins (2 to 30 of AO units), particularly preferably alkylene glycols having 2 to 6 carbon atoms, Bisphenol A polyoxyalkylene ether (number of AO units 2-5) Preferably, ethylene glycol, propylene glycol, a polyoxyalkylene ether of bisphenol A (number of AO units 2-3).

As the polycarboxylic acid component (y) of the polyester resin (B1) used in the present invention, the dicarboxylic acid may be an alkanedicarboxylic acid having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, repartic acid, and sebacin. Acid), alkene dicarboxylic acid having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and glutaconic acid), aromatic having 8 to 36 carbon atoms Dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10 , 000] (α-olefin / maleic acid copolymer, etc.)
Examples of the trivalent to hexavalent or higher polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid). Etc.), vinyl polymers of unsaturated carboxylic acids [Mn: 450 to 10,000] (styrene / maleic acid copolymers, styrene / acrylic acid copolymers, styrene / fumaric acid copolymers, etc.) and the like. It is done.
As the polycarboxylic acid component (y), anhydrides and lower alkyl (carbon number 1 to 4) esters (such as methyl ester, ethyl ester, and isopropyl ester) of these polycarboxylic acids may be used.

  Among these polycarboxylic acid components (y), those preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance are alkanedicarboxylic acids having 2 to 50 carbon atoms, alkenedicarboxylic acids having 4 to 50 carbon atoms, carbon An aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aromatic polycarboxylic acid having 9 to 20 carbon atoms, and more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, and terephthalic acid from the viewpoint of storage stability. , Isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and combinations thereof, particularly preferably adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

In the present invention, each polyester resin (B1) can be produced in the same manner as in a normal polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, and particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.
At this time, an esterification catalyst can be used as needed. Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, Japanese Patent Application Laid-Open No. 2006-243715. Patent Documents [Titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolamate), titanylbis (triethanolaminate) and their intramolecular polycondensates, etc.], and JP2007- No. 11307 catalyst (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), and acetic acid Lead and the like. Among these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the polyol component (x) and the polycarboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 5/1 to 1 / 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

  The softening point (hereinafter referred to as Tm) of the polyester resin (B1) used in the present invention is preferably 80 to 170 ° C., more preferably 85 to 160 ° C., from the viewpoint of achieving both hot offset resistance and low temperature fixability. Especially preferably, it is 90-150 degreeC.

In the present invention, Tm of the polyester resin (B1) can be measured by the following method.
<Method for measuring Tm of polyester resin (B1)>
Using a Koka-type flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent (flow value)” and “temperature”, and set the temperature corresponding to 1/2 of the maximum plunger descent Read from the graph and Tm is this value (temperature when half of the measurement sample flows out).

The acid value of the polyester resin (B1) can be measured by a method specified in JIS K0070 (1992 edition).

  The acid value of the polyester resin (B1) is preferably 10 to 50 mgKOH / g, more preferably 12 to 45 mgKOH / g, and particularly preferably 15 to 40 mgKOH / g. When the acid value is 50 mgKOH / g or less, the charging characteristics when used as a toner are good.

  The hydroxyl value of the polyester resin (B1) is preferably 0 to 60 mgKOH / g, more preferably 0 to 55 mgKOH / g, and particularly preferably 0 to 50 mgKOH / g. When the hydroxyl value is 60 mgKOH / g or less, the hot offset resistance when used as a toner becomes better.

The Tg of the polyester resin (B1) is preferably 45 to 75 ° C. The lower limit is more preferably 48 ° C, particularly preferably 50 ° C, and the upper limit is more preferably 72 ° C, particularly preferably 70 ° C.
In addition, in the above and below, Tg can be measured by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Instruments Co., Ltd. DSC20 and SSC / 580.

  The peak top molecular weight (hereinafter referred to as Mp) of the THF-soluble component of the polyester resin (B1) is preferably 2,000 to 20,000, more preferably 2 from the viewpoint of compatibility between toner durability and low-temperature fixability. , 500 to 19,000.

In the present invention, the molecular weight [Mp, Mn, weight average molecular weight (hereinafter referred to as Mw)] of the resin can be measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh Co., Ltd. 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)
The molecular weight is measured by dissolving the resin in THF and filtering the insoluble matter with a glass filter.

  The polyester resin (B1) may be used in combination of two or more types having different Tm from the viewpoint of the fixing temperature range. When two or more types are used in combination, they may be mixed with a colorant or the like when powder mixing, melt mixing, or toner.

Examples of the styrene (co) polymer (B2) in the present invention include a styrene monomer polymer or a copolymer having a styrene monomer and a (meth) acrylic monomer as essential constituent units.
Examples of the styrene monomer include styrene and alkyl styrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methyl styrene, p-methyl styrene). Styrene is preferred.

Examples of (meth) acrylic monomers include alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Alkyl ester having 1 to 18 carbon atoms; hydroxyl group-containing (meth) acrylate having 1 to 18 carbon atoms of alkyl group such as hydroxylethyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) C1-C18 amino group-containing (meth) acrylates of alkyl groups such as acrylates; Acrylonitrile, methacrylonitrile, methacrylonitrile methyl group-containing (meth) acrylic compounds having 1-18 carbon atoms and (meth Acry Mention may be made of the acid and the like.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid and a mixture of two or more thereof are preferred.

If necessary, the styrene (co) polymer (B2) may be used in combination with other vinyl ester monomers or aliphatic hydrocarbon vinyl monomers as constituent units.
Examples of vinyl ester monomers include aliphatic vinyl esters (4 to 15 carbon atoms such as vinyl acetate, vinyl propionate, isopropenyl acetate, etc.), unsaturated carboxylic acid polyvalent (2 to 3) alcohol esters (8 to 200 carbon atoms, such as Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6 hexanediol diacrylate, polyethylene glycol di (meth) acrylate, etc. ), Aromatic vinyl esters (carbon number 9-15, such as methyl-4-vinylbenzoate) and the like, and aliphatic hydrocarbon vinyl monomers include olefins (2-10 carbon atoms, such as ethylene, propylene, etc.). Emissions, butene, octene, etc.), dienes (number 4-10 such as butadiene carbon, isoprene, 1,6-hexadiene and the like) and the like.

The Mw of the styrene (co) polymer (B2) used in the present invention is preferably from 100,000 to 300,000, more preferably from 130,000 to 280,000, particularly preferably from 150,000 to 50,000 from the viewpoint of the fixing temperature range. 250,000.
The ratio of Mw to Mn (Mw / Mn) is preferably 10 to 70, more preferably 15 to 65, and particularly preferably 20 to 60 from the viewpoint of the fixing temperature range.

The Tg of the styrene (co) polymer (B2) is preferably 50 to 75 ° C., more preferably 50 to 70 ° C., and particularly preferably 53 to 65 ° C. from the viewpoints of storage stability and low-temperature fixability. .

It is preferable to use two or more types of styrene (co) polymers (B2) having different molecular weights from the viewpoint of the fixing temperature range.

The styrene (co) polymer (B2) can be synthesized by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization using the above-mentioned monomer with a radical polymerization initiator. A solution polymerization method and a bulk polymerization method or a combination thereof are preferable.
The polymerization temperature is preferably 60 to 230 ° C, more preferably 70 to 220 ° C.
The polymerization time is preferably 1 to 30 hours, more preferably 2 to 20 hours.
Examples of radical polymerization initiators include azo polymerization initiators (for example, azobisisobutyronitrile, azobisvaleronitrile, and azobiscyanovaleric acid) and organic peroxide polymerization initiators (for example, benzoyl peroxide, di-t-butyl). And peroxides and t-butyl peroxybenzoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane).
Of these, di-t-butyl peroxide and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane are preferred.
The amount of the polymerization initiator used is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and particularly preferably 0.3 to 6% by weight based on the total amount of monomers.

As a solvent in the case of solution polymerization, a cycloalkane solvent having 5 to 12 carbon atoms (such as cyclohexane and methylcyclohexane); an aromatic solvent having 6 to 12 carbon atoms (such as benzene, toluene, xylene, ethylbenzene and cumene); Ester solvents (such as ethyl acetate and butyl acetate); ether solvents (such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve) are used.
Among these, preferred are aromatic solvents, and more preferred are toluene, xylene and ethylbenzene.

  Moreover, when performing suspension polymerization, it can superpose | polymerize in water using inorganic acid salt dispersing agents (such as calcium carbonate and calcium phosphate) and organic dispersing agents (such as polyvinyl alcohol and methyl cellulose).

The content of the polycarbonate (A) based on the weight of the toner binder in the toner binder of the present invention is 1 to 45% by weight, preferably 2 to 40% by weight.
When the content of (A) is less than 1% by weight, the amount of carbon dioxide used is small, so the effect of reducing the environmental load is small. When it exceeds 45% by weight, the storage stability of the toner composition is lowered, which is not preferable. .
The content of the binder resin (B) based on the weight of the toner binder in the toner binder of the present invention is 55 to 99% by weight, preferably 60 to 98% by weight.
When the content of (B) is less than 55% by weight, the storage stability of the toner composition is lowered, and when it exceeds 99% by weight, the amount of carbon dioxide used is small and the effect of reducing the environmental load is small, which is not preferable. .

The method of mixing the polycarbonate (A) and the binder resin (B) may be any method, a method of mixing (A) during the production of (B), a kneader or the like using (A) and (B). There are a method of using and mixing, and a method of mixing powders of (A) and (B). When (A) is mixed during the production of (B), (A) and (B) may react to form a bond.

  To the toner composition of the present invention, a hydrocarbon wax (w) having a melting point of 60 to 120 ° C. can be added in order to improve low-temperature fixability. The melting point of the hydrocarbon wax (w) is measured according to JIS K7122 using RDC-220 manufactured by Seiko Instruments Inc., and the maximum temperature of the maximum endothermic peak is defined as the melting point. The means for dispersing the hydrocarbon wax (w) in the binder resin is not particularly limited, but it is necessary that the temperature be equal to or higher than the temperature at which the hydrocarbon wax (w) melts. The timing of adding the hydrocarbon wax (w) may be during the synthesis reaction of the binder resin or after the synthesis reaction is completed. Further, it may be mixed with the toner binder of the present invention at the time of toner formation and uniformized at a temperature equal to or higher than the melting point.

The toner binder of the present invention contains a resin (AB) in which the polycarbonate (A) and the binder resin (B) are chemically bonded, not a mixture of the polycarbonate (A) and the binder resin (B). But you can.
Examples of the compound to be chemically bonded as a graft or block include carboxylic acids or anhydrides thereof, isocyanate compounds, and the like.
The content ratio of (A) and (B) in the resin (AB) in which the polycarbonate (A) and the binder resin (B) are chemically bonded is not particularly limited, but preferably (A) / (B) The weight ratio is 1/99 to 45/55.

  Examples of the hydrocarbon wax (w) having a melting point of 60 to 120 ° C. include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, carnauba wax, montan wax, rice wax, and low molecular weight polyethylene.

  The toner composition of the present invention contains the toner binder of the present invention and a colorant.

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian 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, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the toner binder of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 weight part, More preferably, it is 40-120 weight part.

The toner composition of the present invention may further contain one or more additives selected from the group consisting of a release agent, a charge control agent, and a fluidizing agent.

  As the release agent, polyolefin wax having a melting point of 120 to 170 ° C. can be used.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers and halogen-substituted aromatic ring-containing polymers.

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

  The composition ratio of the toner composition of the present invention is preferably from 30 to 97% by weight, more preferably from 40 to 95% by weight, and particularly preferably from 45 to 92% by weight, based on the weight of the toner composition. Colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, particularly preferably 0.5 to 50% by weight; among additives, a release agent is preferably 0 -30 wt%, more preferably 0.5-20 wt%, particularly preferably 1-10 wt%; charge control agent is preferably 0-20 wt%, more preferably 0.1-10 wt%, especially Preferably 0.5 to 7.5% by weight; the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, particularly preferably 0.1 to 4% by weight. The total content of additives is preferably 2 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

  Examples of the method for producing the toner composition of the present invention include known kneading and pulverizing methods and chemical toner production methods. For example, after dry blending the components constituting the above toner excluding the fluidizing agent, melt kneading, then coarsely pulverizing, and finally finely pulverizing using a jet mill pulverizer, etc. After the volume average particle diameter (D50) is preferably 5 to 20 μm, it can be produced by mixing a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].

  The toner composition of the present invention is mixed with 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.) as necessary. Used as a developer for a latent image. The weight ratio of the toner composition to the carrier particles is preferably 1/99 to 100/0. Further, instead of the carrier particles, it can be rubbed with a member such as a charging blade to form an electric latent image.

  The toner composition of the present invention is fixed on a support (paper, polyester film, etc., preferably paper) by a copying machine, a printer, or the like to form a recording material. As a method for fixing to a support, a known heat roll fixing method, flash fixing method, or the like can be applied.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

<Production Example 1> [Synthesis of Polycarbonate (A) Consisting of Epoxide and Carbon Dioxide]
Polypropylene carbonate (A) was obtained by the method described in Patent Document 2 using carbon dioxide and propylene oxide. The Tg of (A) was 40 ° C.

<Production Example 2> [Synthesis of polyester resin (B1-1)]
In the reaction vessel, 100 parts by weight of a bisphenol A · PO2 molar adduct, 630 parts by weight of a bisphenol A · PO3 molar adduct, 222 parts by weight of terephthalic acid, 20 parts by weight of adipic acid, and titanium diisopropoxybistriethanolamine as a condensation catalyst. 3 parts by weight of the nate was added, and the reaction was performed for 4 hours while distilling off the generated water under a nitrogen stream at 230 ° C., and then the reaction was performed for 4 hours under a reduced pressure of 0.5 to 2.5 kPa. Thereafter, 81 parts by weight of trimellitic anhydride was added at 210 ° C. and reacted for 1 hour under normal pressure, then reacted under reduced pressure of 0.5 to 5 kPa, and taken out when Tm reached 138 ° C. The obtained resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B1-1).
Tg of (B1-1) was 65 ° C., Tm was 140 ° C., Mp was 11,500, the hydroxyl value was 2 mgKOH / g, and the acid value was 21 mgKOH / g.

<Production Example 3> [Synthesis of polyester resin (B1-2)]
In a reaction vessel, 700 parts by weight of bisphenol A / PO2 molar adduct, 275 parts by weight of terephthalic acid, and 2 parts by weight of titanium diisopropoxybistriethanolamate as a condensation catalyst are produced at 230 ° C. in a nitrogen stream. The reaction was carried out for 4 hours while distilling off water, and then the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa. When the acid value became 2 mgKOH / g or less, the mixture was cooled to 175 ° C. Thereafter, 37 parts by weight of trimellitic anhydride was added and held for 1 hour, and the resulting resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (B1-2).
Tg of (B1-2) was 63 ° C., Tm was 95 ° C., Mp was 5,200, the hydroxyl value was 45 mgKOH / g, and the acid value was 21 mgKOH / g.

<Production Example 4> [Production of xylene solution of styrene copolymer (B2-1)]
The autoclave was charged with 250 parts by weight of xylene and replaced with nitrogen, and then heated to 185 ° C. in a sealed state with stirring. A mixed solution of 495 parts by weight of styrene, 5 parts by weight of n-butyl acrylate, 13 parts by weight of di-t-butyl peroxide and 100 parts by weight of xylene was added dropwise over 3 hours while controlling the temperature in the autoclave at 185 ° C. for polymerization. I let you. Furthermore, the polymerization was completed at the same temperature for 1 hour to obtain a xylene solution of a styrene copolymer (B2-1).

<Production Example 5> [Production of xylene solution of styrene copolymer (B2-2)]
After replacing the autoclave with nitrogen, 378 parts by weight of styrene, 115 parts by weight of n-butyl acrylate, 7 parts by weight of acrylic acid, 0.05 part by weight of 1,6-hexanediol diacrylate and 2,2-bis (4,4 -Di-t-butylperoxycyclohexyl) propane (4 parts by weight) was charged, the temperature was raised to 95 ° C. over 1 hour, and bulk polymerization was carried out at the same temperature for 4 hours. Subsequently, 120 parts by weight of xylene was added dropwise over 1 hour, the temperature was raised to 110 ° C. over 1 hour, and polymerization was performed at the same temperature for 2 hours. Further, a mixture of 70 parts by weight of xylene and 1 part by weight of 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was added dropwise over 0.5 hours, and then polymerized at the same temperature for 4 hours. . Thereafter, the temperature was raised to 150 ° C. and polymerized at the same temperature for 1 hour, and then diluted by adding 700 parts by weight of xylene to obtain a xylene solution of a styrene copolymer (B2-2).

<Production Example 6> [Production of styrene copolymer (B2-4)]
950 parts of water and 50 parts of a 2% aqueous solution of polyvinyl alcohol [PVA235 manufactured by Kuraray Co., Ltd.] are added to a four-necked flask, and 380 parts of styrene, 120 parts of n-butyl acrylate, 1,1-di-t-butyl par A mixed solution consisting of 1.5 parts of oxycyclohexane was added and stirred to obtain a suspension. After sufficiently replacing the flask with nitrogen, the temperature was raised to 87 ° C. to initiate polymerization. Polymerization was continued at the same temperature, and after confirming that the conversion rate was 98% after 24 hours, the temperature was raised to 100 ° C. and kept at the same temperature for 2 hours to complete the polymerization. As a post-treatment, the product was filtered, washed with water and dried to obtain a styrene copolymer (B2-4).

<Production Example 7> [Production of styrene copolymer (B2-5)]
After charging 100 parts of xylene in an autoclave and replacing with nitrogen, the temperature was raised to 140 ° C. in a sealed state with stirring. A mixed solution of 360 parts of styrene, 133 parts of n-butyl acrylate, 7 parts of acrylic acid, 0.8 part of di-t-butyl peroxide and 50 parts of xylene was taken over 3 hours while controlling the temperature in the autoclave at 140 ° C. The solution was dropped and polymerized. Furthermore, after maintaining at the same temperature for 1 hour, the temperature was raised to 175 ° C. to complete the polymerization. Thereafter, xylene was distilled off to obtain a styrene copolymer (B2-5).

<Production Example 8>
In the reaction vessel, 257 parts by weight of a bisphenol A · PO2 molar adduct, 217 parts by weight of a bisphenol A · PO3 molar adduct, 9 parts by weight of an EO5 molar adduct of phenol novolak (average polymerization degree of about 5), 111 parts of terephthalic acid Part by weight, 30 parts by weight of trimellitic anhydride and 3 parts by weight of titanium diisopropoxybistriethanolamate as a condensation catalyst, and reacted for 5 hours while distilling off the water produced at 220 ° C. under a nitrogen stream, Subsequently, it was made to react under the reduced pressure of 0.5-2.5 kPa for 6 hours. Thereafter, 30 parts by weight of trimellitic anhydride and 400 parts by weight of polypropylene carbonate (A) were added at 190 ° C. and reacted at normal pressure for 1 hour, and then reacted at a reduced pressure of 0.5 to 5 kPa. When it became, it took out. The obtained resin was cooled to room temperature and then pulverized into particles. This is called Resin (AB-1).
Resin (AB-1) had a Tg of 58 ° C. and a Tm of 140 ° C.

<Production Example 9>
In a reaction vessel, 270 parts by weight of a bisphenol A · PO2 molar adduct, 169 parts by weight of a bisphenol A · EO2 molar adduct, 165 parts by weight of terephthalic acid, and 2 parts by weight of potassium titanyl oxalate as a condensation catalyst were placed at 220 ° C. The reaction was performed at a pressure of 0.5 to 25 kPa, and the mixture was cooled to 180 ° C. when the acid value became 2 mgKOH / g or less. Thereafter, 19 parts by weight of trimellitic anhydride and 400 parts by weight of polypropylene carbonate (A) were charged, held at 180 ° C. for 1 hour, and then taken out. The obtained resin was cooled to room temperature and then pulverized into particles. This is called Resin (AB-2).
(AB-2) had a Tg of 61 ° C. and a Tm of 100 ° C.

<Example 1>
20 parts by weight of polypropylene carbonate (A), 40 parts by weight of polyester resin (B1-1), and 40 parts by weight of polyester resin (B1-2) are melt-mixed at a jacket temperature of 150 ° C. using a twin screw extruder, and a toner binder (TB -1) was obtained [content of (A) in (TB-1): 20 wt%, total content of (B1-1) and (B1-2): 80 wt%].

<Example 2>
In an autoclave, 810 parts by weight of a styrene copolymer (B2-1) xylene solution and 1,210 parts by weight of a styrene copolymer (B2-2) xylene solution were charged and mixed. A small sample was collected, xylene was distilled off with a vacuum dryer, and the physical properties of the mixture (B2-3) of (B2-1) and (B2-2) were measured. Tg was 64 ° C. and Mw was 25. It was ten thousand.
Next, 100 parts by weight of polypropylene carbonate (A) was added and mixed at 140 ° C. for 1 hour. The temperature was raised to 170 ° C. while distilling off xylene, and then held at 1 kPa for 2 hours under reduced pressure to obtain a toner binder (TB-2) [content of (A) in (TB-2): 10 wt. %, (B2-3) content: 90% by weight].

<Example 3>
In an autoclave, 945 parts by weight of a styrene copolymer (B2-1) xylene solution, 150 parts by weight of a styrene copolymer (B2-4), and 250 parts by weight of a styrene copolymer (B2-5) were charged and mixed. A small sample was collected, xylene was distilled off with a vacuum dryer, and the physical properties of the mixture (B2-6) of (B2-1), (B2-4) and (B2-5) were measured. 59 degreeC and Mw were 260,000.
Next, 50 parts by weight of polypropylene carbonate (A) was added and mixed at 140 ° C. for 1 hour. The temperature was raised to 170 ° C. while distilling off xylene, and then held at 1 kPa for 2 hours under reduced pressure to obtain a toner binder (TB-3) [content of (A) in (TB-3): 5 wt. %, (B2-6) content: 95% by weight].

<Example 4>
500 parts by weight of the resin (AB-1) and 500 parts by weight of the resin (AB-2) were melt-mixed at a jacket temperature of 150 ° C. with a twin screw extruder to obtain a toner binder (TB-4) [(TB-4 ) Content in (A): 40 wt%, total content of polyester resin: 60 wt%].

<Comparative Example 1>
A toner binder (RTB-1) is obtained in the same manner as in Example 1 except that 50 parts by weight of polypropylene carbonate (A), 25 parts by weight of polyester resin (B1-1), and 25 parts by weight of polyester resin (B1-2) are used. [Content of (A) in (RTB-1): 50% by weight, total content of (B1-1) and (B1-2): 50% by weight].

<Examples 5 to 8, Comparative Example 2>
The toner binders (TB-1), (TB-2), (TB-3), (TB-4), (RTB-1), the colorant, the release agent, and the charge control agent are mixed in the mixing ratio shown in Table 1 ( The toner composition was obtained according to the following method.
First, premixing was performed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], and then kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet pulverizer Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and a particle size D50 is obtained. 8 μm toner particles were obtained. Next, 100 parts by weight of toner particles are mixed with 0.5 parts by weight of colloidal silica [Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.] using a sample mill, and the toner compositions (T-1) to (T-) of the present invention are mixed. 4) and a comparative toner composition (RT-1) were obtained.

The colorants, release agents, and charge control agents listed in Table 1 are as follows.
Colorant: “Carbon Black MA-100” [Mitsubishi Chemical Corporation]
Mold release agent: “Biscol 550-P” [manufactured by Sanyo Chemical Industries, Ltd.]
Charge control agent: “T-77” [Hodogaya Chemical Co., Ltd.]

  The toner compositions (T-1) to (T-4) and (RT-1) obtained by the above methods were evaluated for low temperature fixability, hot offset resistance and storage stability by the following methods. The evaluation results are shown in Table 1.

[1] Low-temperature fixability An unfixed image developed using a commercial copier [AR5030; manufactured by Sharp Corporation] using the toner composition described above is transferred to a commercial copier [AR5030; manufactured by Sharp Corporation]. Evaluation was performed using a fixing machine. After the fixed image was rubbed with a pad, the fixing roll temperature at which the residual ratio of the image density measured using a Macbeth reflection densitometer RD-191 (manufactured by Macbeth Co., Ltd.) was 70% or more was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property.

[2] Hot offset resistance Fixing evaluation was performed in the same manner as the above-described evaluation method for low-temperature fixability, and the presence or absence of hot offset on a fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature. The higher the hot offset generation temperature, the better the hot offset resistance.

[3] Storage stability After leaving the toner composition in a constant temperature water bath at 50 ° C. for 8 hours, constant vibration on a 42-mesh sieve for 10 seconds [using a Pider Teste PT-E manufactured by Hosokawa Micron Co., Ltd., frequency 1600 The storage stability was evaluated based on the following evaluation criteria from the amount of toner remaining on the screen.
[Evaluation criteria]
○: Residual toner composition amount on the sieve is less than 10% by weight Δ: Residual toner composition amount on the sieve is 10% by weight to less than 20% by weight X: Residual toner composition amount on the sieve is 20% by weight or more

  The toner binder and toner composition of the present invention can achieve both low-temperature fixability and hot offset resistance, have excellent storage stability, and are environmentally friendly, so that it can be used for electrophotography, electrostatic recording, electrostatic printing, and the like. It is useful as a toner binder and a toner composition for developing an electrostatic image to be used.

Claims (5)

  A toner binder (TB) containing a polycarbonate (A) obtained from a reaction between an epoxide and carbon dioxide, and a binder resin (B) other than (A), and containing (A) based on the weight of the toner binder A toner binder, wherein the ratio is 1 to 45% by weight and the content of (B) is 55 to 99% by weight.   A toner binder containing a resin (AB) obtained by chemically bonding a polycarbonate (A) and a binder resin (B) obtained from a reaction between an epoxide and carbon dioxide.   The toner binder according to claim 1, wherein the binder resin (B) is a polyester resin and / or a styrene (co) polymer.   The toner binder according to claim 1, wherein the epoxide is propylene oxide and / or ethylene oxide. A toner composition comprising the toner binder according to claim 1 and a colorant.