JP2002363425A - Resin composition, method for producing the same, toner resin composition and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner for an electrostatic charge image development having mechanical strength (as for brittleness) capable of bearing a practical use and grindability, excellent low-temperature fixing properaties and high- temperature offset resistance, a toner resin composition to be a toner binder for the toner, a resin composition to be a main component for the toner resin composition and to provide a method for producing the resin composition. SOLUTION: The resin composition comprises (A) a low-molecular weight resin containing at least an aromatic component and/or a functional group selected from an ester group and a hydroxy group and (B) a thermoplastic resin. The resin composition contains >=0.5 wt.% of an insoluble component when 1 g of the resin composition is dissolved in 100 ml of methylene chloride (25 deg.C). The toner comprises the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic latent image which is used in a resin composition and a method for producing the same and a toner jet method, or formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. Regarding the toner and toner resin composition used for developing an image, in particular, having a mechanical strength and pulverizability that can withstand practical use, a toner for developing an electrostatic charge image having excellent low-temperature fixing property and high-temperature offset resistance, The present invention relates to a toner resin composition serving as a toner binder, a resin composition as a main component thereof, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, low-temperature fixing type toners have been developed in order to achieve colorization and energy saving of electrophotographic copying machines and printers. To achieve the low-temperature fixing, a toner using a polyester resin as a binder resin is generally used. However, the polyester resin has a very high mechanical strength as a characteristic, and when pulverization is required in the toner production process, there is a problem that the productivity is poor. For the same reason, when trying to obtain a toner having a smaller particle size, poor grindability has been a major problem. Further, since the polyester resin has a polar group (ester), good chargeability can be obtained when used as a negatively chargeable toner, but application to a positively chargeable toner has been difficult. Similarly, by having a polar group, environmental stability of charging may be deteriorated. As a method for improving low-temperature fixability and pulverizability, a toner using a petroleum resin is known. For example, Japanese Patent Application Laid-Open No. 53-118050 discloses a toner having a good pressure fixing property in which an aromatic petroleum resin is added in an amount of 1 to 30% by weight to a resin mixture containing wax as a main component. There is no description about the case where the toner is used for heat roll fixing. When the composition described in this publication is applied to hot roll fixing, the glass transition temperature of the composition becomes extremely low, so that the blocking property may be deteriorated. Further, in the combination of the wax, the petroleum resin, and the ethylene-vinyl acetate copolymer described in the examples, the melt viscosity is remarkably reduced by heating, and the offset property may be deteriorated.

JP-A-54-48556 describes that a composition comprising a petroleum resin, an ethylene copolymer, and a polyvinyl acetal resin has a low fixing temperature as a heat fixing toner and has good pulverizability. There is. However, the fixing conditions disclosed in this publication are extremely high at 400 ° C., which is much higher than the general fixing temperature (about 130 to 230 ° C.) in the hot roll fixing which is currently mainstream, and It is considered that the required low-temperature fixing level has not been reached. JP-A-50-99740 and JP-A-50-99742 describe examples in which a petroleum resin having an unknown structure is added to a polyester having a specific structure in an amount of 44% by weight of the entire binder resin. Is an invention relating to heat fixing,
There is no description about low-temperature fixability when the toner is applied to hot roll fixing. In addition, since there is little information for specifying the chemical structure of the petroleum resin, it is completely unpredictable whether the material has excellent low-temperature fixability, pulverizability, and chargeability. JP-A-11-72956 discloses a toner containing a binder resin, an aliphatic hydrocarbon-an aromatic hydrocarbon copolymer petroleum resin having 9 or more carbon atoms, and a bisphenol A-alkylene oxide type polyester. But
The content of the petroleum resin with respect to the total amount of the binder resin and the petroleum resin was 2 to 33% by weight, and the minimum fixing temperatures of Comparative Example 3 in which no petroleum resin was used and Examples 3 to 9 in which petroleum resin was used. As is clear from the comparison, there is no remarkable difference, and the improvement in low-temperature fixability is insufficient.

Japanese Patent Application Laid-Open No. 8-278658 discloses a toner containing a hydrogenated petroleum resin having a hydrogenation amount of 50% or more of the whole petroleum resin, and a polyester resin or a styrene acrylic resin. As a petroleum resin, a hydrogenated petroleum resin using dicyclopentadiene and a C6-C8 aromatic hydrocarbon as raw materials is mentioned. However, the hydrogenated petroleum resin is poor in compatibility with other binder resins, waxes and the like as compared with an unhydrogenated resin, so that a toner composed of a composition of another resin and a hydrogenated petroleum resin causes Problems such as filming on a photoreceptor and the like, spent on a carrier, contamination in a developing device, and contamination in a device during pulverization may occur, which is not preferable. Further, none of the resins described in the above documents have a crosslinked structure, and thus there is a problem that high-temperature offset is likely to occur. JP-A-2000-131883 discloses a polyester containing a THF-insoluble content of 10 to 30%, a release agent, a colorant, and an aliphatic hydrocarbon-aromatic hydrocarbon copolymer resin having 9 or more carbon atoms. An electrostatic image developing toner is disclosed. However, the content ratio of the petroleum resin in this publication is in a low range of 2 to 50 parts by weight with respect to 100 parts by weight of the binder resin, so that there is a problem that the effect of improving the pulverizability is not sufficient.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has mechanical strength (brittleness) and pulverizability enough to withstand practical use, low-temperature fixability and high-temperature resistance. An object of the present invention is to provide a toner for developing an electrostatic image having excellent offset properties, a toner resin composition as a toner binder thereof, a resin composition as a main component thereof, and a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that at least an aromatic component and / or a low-molecular compound having a functional group selected from an ester group and a hydroxyl group. The above object is achieved by a toner for developing an electrostatic image using a resin composition comprising a molecular weight resin and (B) a thermoplastic resin, wherein the resin composition contains 0.5% by weight or more of a component insoluble in methylene chloride. The present invention has been completed by finding that it can be achieved.

That is, the gist of the present invention is as follows. [1]. A resin composition comprising (A) at least an aromatic component and / or a low molecular weight resin having a functional group selected from an ester group and a hydroxyl group, and (B) a thermoplastic resin, wherein 1 g of the resin composition is 100 ml. 0.5% by weight of insoluble components when dissolved in methylene chloride (25 ° C)
A resin composition comprising the above. [2]. The resin composition according to the above [1], wherein the low molecular weight resin (A) is at least one selected from the group consisting of a terpene resin, a rosin resin, a coumarone-indene resin, and a styrene oligomer. [3]. The resin composition according to the above [1], wherein the low molecular weight resin (A) comprises an aromatic petroleum resin.

[4]. When the low molecular weight resin (A) is aromatic-
The resin composition according to the above [1], comprising an aliphatic copolymerized petroleum resin and / or an aromatic-dicyclopentadiene copolymerized petroleum resin. [5]. The above [2] to wherein the content of aromatic hydrocarbon units in the low molecular weight resin (A) is 30% by weight or more.
The resin composition according to any one of [4]. [6]. When the weight average molecular weight of the low molecular weight resin (A) is 30
The resin composition according to any one of the above [1] to [5], which is 0 to 12,000. [7]. The softening temperature of the low molecular weight resin (A) is 70 to 13
The resin composition according to any one of the above [1] to [6], wherein the temperature is 0 ° C. [8]. The resin composition according to any one of the above [1] to [7], wherein the low-molecular-weight resin (A) has a half outflow temperature in a flow tester of 80 to 140 ° C.

[9]. The resin composition according to any one of the above [1] to [8], wherein the thermoplastic resin (B) comprises a styrene-based resin. [10]. The resin composition according to any one of the above [1] to [9], wherein the thermoplastic resin (B) comprises a polyester resin. [11]. The weight average molecular weight of the thermoplastic resin (B) is
[1] to [1] having a number average molecular weight of 5,000 to 1,000,000 and a number average molecular weight of 2,000 to 500,000.
0].

[12]. The resin composition according to any one of the above [1] to [11], wherein the weight ratio of the low molecular weight resin (A) to the thermoplastic resin (B) is 35/65 to 90/10. [13]. The above [1] to wherein the component insoluble in methylene chloride is 0.5% by weight or more due to crosslinking of the styrene resin.
The resin composition according to any one of [12]. [14]. The above-mentioned [1] to which the component insoluble in methylene chloride is 0.5% by weight or more due to crosslinking of the polyester resin.
The resin composition according to any one of [13].

[15]. [1] to [14], wherein the thermoplastic resin (B) is a styrene-based resin having at least one type of group selected from the group consisting of a carboxylic anhydride group, an acrylate group and a methacrylate group.
The resin composition according to any one of the above. [16]. The thermoplastic resin (B) is polystyrene and / or
Or the resin composition according to any one of the above [1] to [15], which is a substituted polystyrene. [17]. The thermoplastic resin (B) is composed of a trivalent or higher carboxylic acid, a trivalent or higher alcohol, a divalent or higher carboxylic acid containing a carbon-carbon double bond, and a divalent or higher alcohol containing a carbon-carbon double bond. The resin composition according to any one of the above [1] to [14], comprising a polyester resin using at least one kind selected from the group consisting of:

[18]. The resin composition according to any one of the above [1] to [17], wherein the resin composition further comprises at least one selected from the group consisting of a wax, a thermoplastic resin other than the thermoplastic resin (B), and an antioxidant. object. [19]. The glass transition temperature of the resin composition is 45 to 80
The resin composition according to any one of the above [1] to [18], which has a temperature of ° C. [20]. The method for producing a resin composition according to any one of [1] to [19], wherein the crosslinked thermoplastic resin (B) and the low molecular weight resin (A) are mixed. [21]. The method for producing a resin composition according to any one of the above [1] to [19], wherein the thermoplastic resin (B) and the low molecular weight resin (A) are crosslinked during mixing. [22]. The method for producing a resin composition according to any one of the above [1] to [19], wherein the thermoplastic resin (B) and the low molecular weight resin (A) are mixed and then crosslinked.

[23]. A toner resin composition comprising the resin composition according to any one of the above [1] to [19] as a main component. [24]. A toner containing the resin composition according to any one of the above [1] to [19]. [25]. The toner according to [24], wherein the toner further includes at least one selected from the group consisting of a colorant, a wax, a charge control agent, and a magnetic powder. [26]. The above [24] obtained by kneading and pulverizing the resin composition according to any one of the above [1] to [19], and at least one selected from the group consisting of a colorant, a wax, a charge control agent and a magnetic powder. ] Or the toner according to [25]. [27]. The above [2] having a volume average particle size of 5 to 15 μm.
4] The toner according to any one of [26].

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises (A) a low molecular weight resin having at least an aromatic component and / or a functional group selected from an ester group and a hydroxyl group;
A resin composition comprising a thermoplastic resin, wherein when 1 g of the resin composition is dissolved in 100 ml of methylene chloride (25 ° C.), the resin composition contains 0.5% by weight or more of an insoluble component. The low molecular weight resin (A) is preferably composed of at least one selected from the group consisting of petroleum resins, terpene resins, rosin resins, cumarone-indene resins, and styrene oligomers.

As the terpene resin, α-pinene,
β-pinene, limonene, dipentene, camphene, polymers made from terpene compounds such as deltasurikarene,
Copolymers of the terpene compound with other monomers and modified products of these polymers can be used. Among these, polymers and copolymers using α-pinene, β-pinene and dipentene as raw materials, and modified products thereof are preferable. As the copolymer, styrene, vinyl toluene, α
-Methylstyrene, β-methylstyrene, styrenes such as isopropenyltoluene, or indene, aromatic-terpene copolymer resin obtained by copolymerizing indene such as methylindene and terpene, phenol, alkylphenol and the like Phenols or terpene phenol resins obtained by copolymerizing terpenes with bisphenols such as bisphenol A, bisphenol F and bisphenol Z are preferably used. Among these, terpene phenol resins are preferable because they have good compatibility with the component (B). Further, as modified products of these resins, resins obtained by hydrogenating some or all of aliphatic unsaturated bonds and / or aromatic unsaturated bonds within a range that does not lose the effects of the present invention can be used. The weight average molecular weight of the terpene resin is preferably 400 to 5,000, more preferably 500 to 2,000, and the number average molecular weight is preferably 300 to 3,000, more preferably 400 to 1,
500.

As the rosin resin, gum rosin, wood rosin, tall oil rosin, and those obtained by processing and modifying these can be used. Modified rosins include metal salts with zinc, calcium, magnesium, etc., ester rubbers which are rosins esterified with alcohols such as glycerin, pentaerythritol and benzyl alcohol, rosin-maleic acid resins, rosin-modified phenol resins, rosin-modified alkyds Resin, hydrogenated rosin resin and the like can be used, and among them, ester rubber and rosin-maleic acid resin are preferable. The weight average molecular weight of the rosin resin is preferably 300-1,500, more preferably 300-900, and the number average molecular weight is preferably 300-1,500, more preferably 300-900.
It is.

Examples of the coumarone-indene resin include a coumarone-indene copolymer resin and a coumarone-indene-styrene copolymer resin. The weight average molecular weight of the coumarone-indene resin is preferably from 400 to 5,0.
00, more preferably 500 to 3,000, and the number average molecular weight is preferably 300 to 3,000, more preferably 400 to 2,000. The styrene oligomer has a weight average molecular weight of 1,000 to 12,000.
Those having a number average molecular weight of 0 to 500 to 7,000 are preferably used.

As the petroleum resin of the low molecular weight resin (A),
Aromatic petroleum resins, aliphatic-aromatic copolymerized petroleum resins and aromatic-dicyclopentadiene copolymerized petroleum resins are preferred. The aromatic monomer used as these petroleum resins is not limited as long as it is a polymerizable component, and includes, for example, styrene, alkyl-substituted styrene, α-methylstyrene, β-methylstyrene, allylbenzene, vinyltoluene, isopropenyltoluene, It is preferable to include at least one monomer selected from the group consisting of 1-propenyltoluene, 2-propenyltoluene, indene, methylindene, alkyl-substituted indene, and cumarone.

As a method for producing these petroleum resins, a fraction obtained from a petroleum refining process such as petroleum refining or naphtha pyrolysis as a polymerizable monomer as a raw material may be used as it is, or may be subjected to simple purification to obtain a single or a plurality of fractions. The fractions may be mixed and used for polymerization. After separation and purification for each monomer,
A single monomer or a mixture of plural monomers may be used for polymerization. Further, a raw material produced by a method other than petroleum refining may be used. The above-prepared C9 fraction or separately prepared aromatic monomer may be used together with other polymerization components such as C5 fraction, if necessary, for cationic polymerization, radical polymerization, thermal polymerization, anionic polymerization, ionic coordination polymerization, and bulk polymerization. It can be produced by appropriately selecting a method such as polymerization, suspension polymerization, emulsion polymerization, and polymerization using a transition metal complex catalyst. Among these, preferred polymerization methods include a Friedel-Crafts type cationic polymerization method using a Lewis acid and a thermal polymerization method. In the case of the Friedel-Crafts type cationic polymerization method, aluminum chloride, aluminum bromide, dichloroethylaluminum, titanium tetrachloride, tin tetrachloride, boron trifluoride, etc. are used as a catalyst, and toluene, xylene, Aromatic hydrocarbons such as ethylbenzene, mesitylene, cumene and cymene, or aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane and methylcyclohexane, and mixtures thereof are used. And the use ratio of the catalyst is 0.01 to 5 parts by weight per 100 parts by weight of the monomer,
Preferably, the polymerization temperature is 0.05 to 3 parts by weight, and the polymerization temperature is not uniform depending on the type of the monomer or the type of the catalyst.
The polymerization is carried out. The polymerization time is suitably from 0.5 to 5 hours. Further, after the polymerization, the catalyst is decomposed with an aqueous alkaline solution or methanol, washed with water, and a low-polymerized product, unreacted monomers and a solvent are removed under reduced pressure to obtain a purified petroleum resin.

The weight average molecular weight of the petroleum resin is preferably from 400 to 5,000, more preferably from 500 to 5,000.
3,000, the number average molecular weight is preferably 300 to 3,
000, more preferably 400-1,500.
The content of the aromatic hydrocarbon unit in the petroleum resin is preferably at least 30% by weight, more preferably at least 40% by weight. When the content of the aromatic hydrocarbon unit is 30;
If the amount is less than 10% by weight, the compatibility with the component (B) may be deteriorated. The petroleum resin has a hue according to JIS.
According to K5400, the Gardner color number measured under melting conditions is preferably 12 or less, more preferably 8 or less. The low molecular weight resin (A) preferably has a weight average molecular weight of 300 to 12,000, and
More preferably, it is 5,000. If the weight average molecular weight is less than 300, the mechanical strength of the resin composition comprising the components (A) and (B) is not sufficient, and if the weight average molecular weight exceeds 12,000, (A The toner obtained by using the resin composition comprising the component (B) and the component (B) may have insufficient low-temperature fixability.

JIS K-220 for low molecular weight resin (A)
The softening temperature measured by the ring and ball method according to 7 is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.
It is. When the softening temperature is higher than 130 ° C., the low-temperature fixability of the electrostatic image developing toner using the resin composition comprising the component (A) and the component (B) may be insufficient.
The low-molecular-weight resin (A) preferably has a 流出 outflow temperature of 80 to 140 ° C measured using a flow tester,
What is 90-130 degreeC is more preferable. A toner for developing an electrostatic image using a resin composition using the component (A) having a half outflow temperature of less than 80 ° C. easily causes toner blocking during storage, and the half outflow temperature is 140 ° C.
In the case of a toner using the component (A) exceeding (a), sufficient low-temperature fixability may not be obtained.

The thermoplastic resin (B) is preferably composed of a styrene resin or a polyester resin, and a component insoluble in methylene chloride of the resin composition is 0.5% by weight or more by crosslinking of the styrene resin or the polyester resin. It is preferred that Further, the thermoplastic resin (B) is selected from the group consisting of a styrene resin having at least one group selected from the group consisting of a carboxylic anhydride group, an acrylate group and a methacrylate group, a polystyrene and a substituted polystyrene. Preferably, at least one type is used. Further, the thermoplastic resin (B) is a trivalent or higher carboxylic acid, a trivalent or higher valent alcohol, a divalent or higher carboxylic acid containing a carbon-carbon double bond, and a divalent or higher valent containing a carbon-carbon double bond. It is preferable to use a polyester resin made from at least one material selected from the group consisting of alcohols.

As the polyester resin, the alcohol component is ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, Α, ω-alkylene diols (C2 to C12) such as 1,12-dodecanediol, polyalkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, neopentyl glycol, 1,4 -Aliphatic dihydric alcohols such as cyclohexanedimethanol, glycerin, 1,1,1-tris (4-hydroxyphenyl) ethane, trimethylolethane, trimethylolpropane, monosaccharide, disaccharide, ring-opening sugar, and modified sugar Polyhydric alcohols such as sugars, etc. , 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane , 2,2-bis (3-phenyl-4
Bisphenols such as -hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylether, and bis (4-hydroxyphenyl) diphenylmethane; and the hydroxyl groups of these bisphenols are converted to alkylene glycols such as polyethylene glycol and polypropylene glycol. And those obtained by hydrogenating the aromatic ring of these bisphenols. Further, as the acid component, succinic acid, adipic acid, azelaic acid, sebacic acid, saturated aliphatic carboxylic acids such as octylsuccinic acid, maleic acid, fumaric acid, unsaturated aliphatic carboxylic acids such as maleic anhydride,
1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-bicyclo [2,2
1] Cycloaliphatic carboxylic acids such as dicarboxylic acids, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride,
1,2,4-cyclohexanetricarboxylic acid,
2,4-cyclohexanetricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,4-butanetricarboxylic anhydride, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid,
A trivalent or higher polycarboxylic acid such as 4-naphthalenetricarboxylic acid is used. Here, the carboxylic acid may be an acid halide, ester, or acid anhydride.

The alcohol component and the acid component may be used alone or in combination of two or more. However, a resin containing a polyhydric alcohol component, a resin containing a polyvalent carboxylic acid component, And a resin containing an unsaturated aliphatic carboxylic acid component and a methylene chloride-insoluble component of the resin composition.
It is preferable for the content to be 5% by weight or more. The resin containing the unsaturated aliphatic carboxylic acid component may be used in the presence of a radical initiator such as benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, a comonomer such as a styrene monomer, if necessary, or a naphthene. A method in which the reaction is carried out in the presence of an accelerator such as cobalt acid or the like is preferred in order to make the methylene chloride-insoluble component of the resin composition 0.5% by weight or more.

When the thermoplastic resin (B) is a copolymer resin of a poly (meth) acrylate and a styrene monomer, the ester group may be a group derived from an alcohol having 1 to 18 carbon atoms. Used. Examples of the alkyl group having an ester portion include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. Examples include a stearyl group, a phenyl group, a benzyl group, a glycidyl group, and a 2-chloroethylphenyl group. Among these (meth) acrylates, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,
Preferred are ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. Each of these monomers may be used alone or in combination of two or more. Examples of the styrene monomer include styrene, alkyl-substituted styrene, α-methylstyrene, β-methylstyrene, allylbenzene, vinyltoluene, isopropenyltoluene, 1-
Examples include propenyltoluene, 2-propenyltoluene, indene, methylindene, and alkyl-substituted indene. Of these, styrene and vinyl toluene are preferred. Each of these monomer components may be used alone or in combination of two or more.

When the thermoplastic resin (B) is a substituted polystyrene, examples of the substituent include halogens such as chloro and bromo, and alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl and butyl. And a methoxy group, a butoxy group and the like, an alkoxyl group having 1 to 6 carbon atoms, a hydroxyl group and the like. These substituents may be used alone or in combination of two or more of any components. Examples of the styrene-based resin in which the thermoplastic resin (B) has a carboxylic anhydride group include a styrene-maleic anhydride copolymer. Styrene-based resins having a carboxylic anhydride group include dihydric or higher alcohols and amines. By reacting with a compound capable of reacting with a carboxylic anhydride group, such as an imine, amide, imide, carboxylic acid, or thiol, a component insoluble in methylene chloride of the resin composition can be 0.5% by weight or more.
In addition, these styrenic resins can be cross-linked by using a bifunctional or higher-functional vinyl monomer such as divinylbenzene or a polymerization initiator having three or more reaction initiation points. A method of performing a cross-linking treatment or the like is preferable to make the insoluble component in methylene chloride of the resin composition 0.5% by weight or more.

The solvent-soluble portion of the thermoplastic resin (B) is measured by gel permeation chromatography,
The weight average molecular weight calculated in terms of polystyrene is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000. Similarly, the number average molecular weight is preferably between 2,000 and 500,000
0, more preferably 5,000 to 300,000. When the weight average molecular weight is less than 5,000 or the number average molecular weight is less than 2,000, the mechanical strength of the resin composition comprising the component (B) and the component (A) decreases, and the A large amount of finely pulverized components are generated during the production, and the productivity of the toner may be reduced, or the storage stability of a printed image may be reduced when the toner is used as a toner for developing an electrostatic image. Moreover, the weight average molecular weight exceeds 1,000,000, or the number average molecular weight is 500,000.
In the case where it exceeds 1, the softening temperature of the resin composition comprising the component (B) and the component (A) becomes too high, so that low-temperature fixing becomes difficult, and the mechanical strength becomes too high.
In some cases, the pulverizability of the electrostatic image developing toner may be reduced. In addition, the thermoplastic resin (B) may contain a fluidity improver such as liquid paraffin.

The resin composition of the present invention has a weight ratio of the low molecular weight resin (A) to the thermoplastic resin (B) of 35/65 to 65/65.
90/10 is preferred, and 50/50 to 80/20
Is more preferable. Within this range, the low-temperature fixability is excellent, and the mechanical strength is not too strong, not too brittle, has a suitable strength to withstand practical use, and has good hot offset resistance. This is because a resin composition is obtained. If the content of the low molecular weight resin (A) is less than 35% by weight, the low-temperature fixability may be insufficient or the mechanical strength may be too strong, and if it exceeds 90% by weight, the hot offset resistance deteriorates. It is not preferable because it may occur.

The resin composition of the present invention is produced by kneading the low molecular weight resin (A) and the thermoplastic resin (B) using a melt kneading machine used for a usual thermoplastic resin molding process. be able to. The glass transition temperature of the resin composition of the present invention is preferably 45 to 80 ° C, more preferably 55 to 75 ° C, and particularly preferably 60 to 70 ° C. A toner manufactured using a resin composition having a glass transition temperature of less than 45 ° C. is likely to cause toner blocking that aggregates during storage.

The resin composition of the present invention may contain a wax as an optional component. By using the wax in combination, the releasability of the toner can be improved. The wax is not particularly limited, and any wax can be selected from conventionally known waxes. Examples of the wax include animal and vegetable waxes, carnauba wax,
Candelilla wax, rice wax, montan wax, ozokerite, ceresin, amide wax, hydrogenated castor oil, castor wax, wood wax, beeswax, spermaceti, mineral wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum, polyethylene wax, oxidation Preferred are polyethylene wax, polypropylene wax, oxidized polypropylene wax, higher fatty acid wax, higher fatty acid ester wax, Fischer-Tropsch wax and the like. Among them, polyethylene wax, polypropylene wax, polyethylene oxide wax, polypropylene oxide wax, and Fischer-Tropsch wax are particularly preferred. These waxes may be used alone or in combination of two or more. When the wax is used in combination, the content of the wax is preferably 30% by weight or less based on the total amount of the resin composition. If the content exceeds 30% by weight, the glass transition temperature may be lowered, and the blocking resistance may be deteriorated.

[0031] The resin composition of the present invention may optionally contain a conventionally known thermoplastic resin other than the thermoplastic resin (B) as an optional component. Such thermoplastic resins include, for example, styrene-propylene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-α-methyl methacrylate copolymer, styrene-acrylonitrile- Acrylate copolymer, α-methylstyrene-α-chloromethyl acrylate copolymer, α-methylstyrene-acrylonitrile-acrylate copolymer, vinyl chloride resin, phenol resin, epoxy resin, polyethylene resin, polypropylene Resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins, polyvinyl butyral resins, and the like. These thermoplastic resins are 1
Species may be used, or two or more may be used in combination. The content of the thermoplastic resin other than the thermoplastic resin (B) may be within a range that does not impair the effects of the present invention, but is preferably 50% by weight or less based on the total amount of the resin composition.

The resin composition of the present invention may optionally contain an antioxidant in an amount of 5% by weight or less based on the total amount of the resin composition. As such an antioxidant, a hindered phenol antioxidant, an aromatic amine antioxidant, a hindered amine antioxidant, a sulfide antioxidant, an organic phosphorus antioxidant, and the like can be applied. Among them, hindered phenolic antioxidants are preferred. One of these antioxidants may be used, or two or more thereof may be used in combination.

Further, the resin composition of the present invention may further contain, as optional components, additives other than those described above, for example, an antioxidant, an antiozonant, an ultraviolet absorber, a light stabilizer, a softener, a reinforcing agent, a filler, Mastication accelerator, foaming agent, foaming aid, lubricant,
Internal release agent, flame retardant, antistatic agent for kneading, coloring agent,
A coupling agent, a preservative, a flavoring agent, and the like may be contained in an amount of 5% by weight or less based on the total amount of the resin composition.

The wax and the thermoplastic resin (B)
Other additives such as a thermoplastic resin, an antioxidant and an antioxidant may be added to the low-molecular-weight resin (A) and the thermoplastic resin (B) before the toner production step to form the resin composition of the present invention. Then, in the toner production process, it may be added independently of the resin composition.

The method for producing the resin composition of the present invention is not limited, but includes a method of mixing the crosslinked thermoplastic resin (B) and the low molecular weight resin (A), and a method of mixing the thermoplastic resin (B) and the low molecular weight resin (A). A) and a method of crosslinking after mixing the thermoplastic resin (B) and the low molecular weight resin (A). The toner resin composition of the present invention contains the resin composition of the present invention as a main component. The toner resin composition of the present invention can uniformly disperse the colorant and other materials constituting the toner, and can maintain the uniformity of the toner particles using the same. The toner for developing an electrostatic charge image of the present invention usually comprises 25 to 95% by weight of a resin composition, 0 to 10% by weight of a colorant, 0 to 70% by weight of a magnetic powder, 0 to 10% by weight of a charge control agent, and 0 of a release agent. -20% by weight and lubricant 0-10
% By weight, and as an external additive, a fluidizing agent 0 to 1.
5% by weight and / or 0 to 1.5% by weight of cleaning aids are added.

As the release agent, the above-mentioned wax,
Fluororesin fine particles are exemplified, and wax is preferable. The use amount is more preferably 0.5 to 10% by weight.
If the amount of the wax exceeds 30% by weight, the glass transition point may be reduced, and the blocking resistance may be reduced.

As the colorant, an organic or inorganic colorant such as carbon black, copper oxide, manganese dioxide, alinine black, activated carbon, non-magnetic ferrite,
Magnetic ferrite, magnetite, iron black, benzidine yellow, CI Pigment Yellow 17, CI Pigment Yellow 1
80, disazo yellow, quinacridone, naphthol azo pigment, carmine 6B, dimethylquinacridone, naphthol, CI Pigment Red 57: 1, CI Pigment Red 122,
CIPigment Red 146, CIPigment Red 184, CIPig
ment Blue 15: 3, CI Pigment Blue 61, rhodamine B, phthalocyanine, copper phthalocyanine, titanium white, zinc white, and the like. In the magnetic toner, when the magnetic powder itself is colored (black), the magnetic powder itself can be used as a colorant. Examples of the magnetic powder include iron, cobalt, nickel, magnetite,
Hematite, ferrite and the like are used. The particle size of the magnetic powder is usually 0.05 to 1 μm, preferably 0.1 to 1 μm.
０．５0.5 μm.

The charge control agent is a substance capable of giving a positive or negative charge by triboelectric charge. Examples of such a charge control agent include Nigrosine Base EX (manufactured by Orient Chemical Co., Ltd.) and P-51 (Orient Chemical Co., Ltd.). Kogyo Co., Ltd.), Copy Charge PXVP435 (Hoechst), alkoxylated amine, alkylamide, molybdate chelate pigment, PLZ1001 (Shikoku Chemicals), Bontron S-22 (Orient Chemical), Bontron S
-34 (manufactured by Orient Chemical Industries), Bontron E-8
1 (manufactured by Orient Chemical Industries), Bontron E-84
(Manufactured by Orient Chemical Industries), Spiron Black TRH
(Hodogaya Chemical Industry Co., Ltd.), thioindigo pigment, Copy Charge NXVP434, Bontron E-89 (Orient Chemical Industry Co., Ltd.), magnesium fluoride, carbon fluoride, oxycarboxylic acid metal complex, dicarboxylic acid metal complex, amino acid metal complex , Diketone metal complex, diamine metal complex, azo group-containing benzene-benzene derivative skeleton metal complex, azo group-containing benzene-naphthalene derivative skeleton metal complex, benzyldimethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, metal complex, nigrosine base , Nigrosine hydrochloride, safranin, crystal violet, quaternary ammonium salt, metal complex of alkyl salicylic acid, calixarene-based compound, boron compound, fluorinated quaternary ammonium salt, azo-based Metal complex, triphenylmethane dyes, such as dibutyltin oxide can be applied.

As the lubricant, for example, polytetrafluoroethylene, low molecular weight polyolefin, fatty acid and its metal salt and amide can be used. As the fluidizing agent used as the external additive, for example, inorganic fine particles having a particle size of several tens nm, specifically, colloidal silica,
Alumina, titanium oxide, zinc oxide, magnesium fluoride, silicon carbide, boron carbide, titanium carbide, zirconium carbide, boron nitride, titanium nitride, zirconium nitride,
Magnetite, molybdenum disulfide, aluminum stearate, magnesium stearate, zinc stearate and the like can be used. These fluidizing agents may be subjected to a hydrophobic treatment with a silane-based or titanium-based coupling agent, a higher fatty acid, a silicone oil, a surfactant, or the like.

As the cleaning aid used as an external additive, for example, fine particles such as polystyrene, polymethyl methacrylate, polyacrylate, polybenzoguanamine, silicone resin, polytetrafluoroethylene, polyethylene, and polypropylene are preferable. .

The method for preparing the toner of the present invention is not particularly limited, and conventionally known methods such as a mechanical pulverization method, a spray drying method, a chemical polymerization method, and a wet granulation method can be applied.
Of these, the mechanical pulverization method involves dry-blending the above-mentioned toner components, melt-kneading them, then coarsely pulverizing them, and finally pulverizing them with a jet pulverizer or the like. Therefore, this is a method of obtaining a particulate toner having a volume average particle size of about 5 to 15 μm by performing classification.

The thus-prepared toner for developing an electrostatic image is mixed with carrier particles and used as a developer for two-component development, or used alone as a developer for one-component development. Is done. Here, as the carrier, for example, a magnetic powder carrier, a magnetic powder resin-coated carrier, a binder carrier, glass beads and the like are used. The particle size of the carrier is usually about 20 to 500 μm.

Examples of the magnetic powder carrier include:
Metals such as iron, nickel, ferrite, magnetite, and cobalt, and the above metals and zinc, antimony, aluminum,
Lead, tin, bismuth, beryllium, manganese, selenium,
Alloys or mixtures with metals such as tungsten, zirconium and vanadium, or metal oxides such as iron oxide, titanium oxide and magnesium oxide, chromium nitride, nitrides such as vanadium nitride, or silicon carbide, tungsten carbide, etc. A mixture with a carbide is used.

As the magnetic powder resin-coated carrier,
The magnetic powder particles used as the core material are coated with the following resin. As the coating resin, for example, polyethylene, silicone resin, fluorine resin, styrene resin,
Acrylic resin, styrene-acrylic resin, polyvinyl acetate, cellulose derivative, maleic acid resin, epoxy resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinylidene bromide, polycarbonate, polyester, polypropylene, phenol resin , Polyvinyl alcohol, fumaric acid ester resin, polyacrylonitrile, polyvinyl ether, chloroprene rubber, acetal resin, ketone resin, xylene resin, butadiene rubber, styrene-butadiene copolymer, polyurethane and the like. The magnetic powder resin-coated carrier includes conductive fine particles (carbon black, conductive metal oxide, metal powder), inorganic fillers (silica, silicon nitride, boron nitride, alumina, zirconia, silicon carbide, boron carbide,
Titanium oxide, clay, talc, glass fiber), the charge control agent exemplified above, and the like may be contained as necessary. The thickness of the resin coating on the carrier core material is preferably about 0.1 to 5 μm.

The toner of the present invention is used after being transferred and fixed to a toner image support such as paper or an OHP film such as polyester. As the fixing method, for example, pressure fixing, heat fixing (SURF fixing, fixing with a hot plate, oven fixing, infrared lamp fixing, etc.), contact heating pressure fixing, flash fixing, solvent fixing, etc. can be applied. Pressure fixing is preferred. When the contact heating pressure fixing method is adopted, a toner having a minimum fixing temperature of 145 ° C. or lower is preferable, and a toner capable of fixing at a low temperature of 130 ° C. or lower is particularly preferable.

The toner of the present invention can be applied to any type of magnetic one-component development, non-magnetic one-component development, two-component development, liquid development, and toner jet printing. , Two-component development and non-magnetic one-component development.

The toner of the present invention can be applied to various developing methods. For example, a magnetic brush developing method, a cascade developing method, a method using a conductive magnetic toner described in US Pat. No. 3,909,258,
JP-A-54-42121 and JP-A-55-42121 disclose a method using a high-resistance magnetic toner described in JP-A-31136.
Methods described in JP-A-18656, JP-A-54-43027, etc., fur brush development method, powder cloud method, impression development method, microtoning method, contact development method, touchdown development method, magnetodynamic development method , Jumping development method, FEED
(Floating Electrode Effect Development)
MT (Fine Micro Toning System) development method, NSP (No
n Magnetic Single Component Development Process) It can be applied to the development method and the like.

The toner of the present invention can be applied to an image forming apparatus using any charging method of corona charging (corotron type, scorotron type, etc.) and contact charging (charging roll type, charging brush type, etc.). Further, the present invention can be applied to a developing method without a cleaning step or a developing method having a cleaning step by a blade method, a fur brush method, a magnetic brush method, or a roller method, but a developing method having a cleaning step by a blade method or a fur brush method. Further, a developing method having no cleaning step is preferable.

The toner of the present invention can be applied to any of organic electrophotographic photoreceptors (laminated type, single layer type) and inorganic photoreceptors (amorphous silicon, amorphous selenium, selenium type photoreceptor, germanium type photoreceptor). It is particularly preferable to apply the present invention to an organic electrophotographic photoreceptor or an inorganic photoreceptor using amorphous silicon.

The toner of the present invention can be applied to either (1) a reversal development process or a normal development process.
(2) Applicable to both positively and negatively charged toners; (3) Applicable to both monochrome and color printing presses; (4) Applicable to both analog and digital printing presses (5) Applicable to copiers, printers (laser beam printers, liquid crystal shutter printers, etc.), facsimile machines, and multifunction machines having these features. Further, the present invention is applicable to a toner jet printing machine.

[0051]

Next, the present invention will be described in more detail with reference to examples. Example 1 [1] Production of resin composition As the low molecular weight resin (A) component, the softening temperature was 96 ° C,
6 kg of a petroleum resin (aromatic petroleum resin manufactured by Tosoh: Petcol 100T) having a Gardner color number of 6 measured under melting conditions in accordance with JIS K 5400 was used. Further, as the thermoplastic resin (B) component, the weight average molecular weight is 23.
Styrene having a glass transition temperature of 66 ° C.
Butyl acrylate copolymer (manufactured by Sanyo Chemical: Hymer SB)
-101) 2 kg and a polystyrene resin (made by Idemitsu Petrochemical Co .: HH32) are used, and after mixing these components in a pellet state, a twin-screw extruder [manufactured by Nippon Steel Works:
TEX-30; screw diameter · 30 mm] and melt-kneaded at a screw barrel temperature of 160 ° C. to obtain a resin composition. This resin composition contained 20% by weight of a component insoluble in methylene chloride.

[2] Evaluation of resin composition (A) Measurement of glass transition temperature (Tg) The resin composition obtained in the above [1] was measured according to JIS K 7121 by a differential scanning calorimeter (manufactured by Seiko Instruments Inc.). The temperature was raised at a rate of 10 ° C./10 minutes, and the extrapolated glass transition onset temperature was determined. (B) Measurement of Softening Temperature (Ti) The resin composition obtained in the above [1] was measured with a flow tester softening temperature measuring device manufactured by Shimadzu Rika Kikai Co., Ltd. The measurement conditions were as follows: load: 20 kgf, orifice diameter: 1.0 mm,
Length: 1.0 mm, plunger area: 1.0 cm ² ,
5. Sample amount: 1.0 g, starting temperature: 60 ° C., heating rate:
0 ° C./min, preheating: 200 seconds. The outflow start temperature and 1/2 outflow temperature (T (1/2)) were read from a measurement time-temperature chart and a measurement time-piston displacement chart. Table 1 shows the evaluation results.

[3] Production of electrostatic image developing toner (negatively charged non-magnetic toner) A chromium-containing metal dye [Orient Chemical Industry Co., Ltd.] as a charge control agent was added to 100 parts by weight of the resin composition obtained in the above [1]. Manufactured by Bontron S-34] 2
Parts by weight, 3 parts by weight of a polypropylene wax [manufactured by Sanyo Chemical Co .; Viscol 550P] as a wax, and carbon black [manufactured by Mitsubishi Chemical Corporation; MA-10]
0], and kneaded with a Labo Plastomill at a set temperature of 160 ° C. Next, the kneaded material was coarsely pulverized by a Henschel mixer, the obtained coarsely pulverized material was pulverized by a jet mill, and classified by an airflow classifier,
Toner particles having a volume average particle size of 9 μm were obtained. Next, 0.5 parts by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity-imparting agent is added to 100 parts by weight of the toner particles obtained here, and mixed with a Henschel mixer to obtain a non-chargeable non-chargeable toner. A magnetic toner was obtained. When this toner was evaluated as a toner for a two-component developing system, a ferrite carrier (manufactured by Powder Tech) was used as a carrier.

(Positively Charged Non-Magnetic Toner) 2 parts by weight of a nigrosine-based charge control agent (manufactured by Orient Chemical Industries; Bontron N21) as a charge control agent was added to 100 parts by weight of the resin composition obtained in the above [1]. Was mixed with 3 parts by weight of polypropylene wax (manufactured by Sanyo Chemical Co .; Viscol 550P) and 6 parts by weight of carbon black (manufactured by Cabot Corporation; REGAL330R) as a colorant, and kneaded by a Labo Plastomill at a set temperature of 160 ° C. Next, the kneaded material was roughly pulverized by a Henschel mixer,
The resulting coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle size of 9 μm. To 100 parts by weight of the toner particles, 0.5 parts by weight of silica fine particles (HVK-2150 manufactured by Clariant Japan Co., Ltd.) surface-treated with a polysiloxane having an ammonium salt as a structural unit as a fluidity imparting agent was added, and a Henschel mixer was added. To obtain a non-magnetic toner for positive charging. When this toner was evaluated as a toner for a two-component developing system, a ferrite carrier (manufactured by Powder Tech) was used as a carrier.

(Negatively Charged Magnetic Toner) To 100 parts by weight of the resin composition obtained in the above [1] was added magnetic powder [manufactured by Toda Kogyo Co .;
100 parts by weight of EPT1000], 2 parts by weight of a chromium-containing metal dye (manufactured by Orient Chemical Industries, Inc .; Bontron S-34) as a charge control agent, and 3 parts by weight of polypropylene wax (manufactured by Sanyo Chemical Industries; Viscol 550P) are mixed. At a set temperature of 160 ° C. using a Labo Plastomill. Next, the kneaded product was coarsely pulverized by a Henschel mixer, and the obtained coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle diameter of 7 μm. The toner particles 100
1.0 part by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity-imparting agent was added to the parts by weight, and mixed with a Henschel mixer to obtain a magnetic toner for negative charging.

(Positively Charged Magnetic Toner) To 100 parts by weight of the resin composition obtained in the above [1] was added magnetic powder [manufactured by Toda Kogyo Co .;
90 parts by weight of EPT1000], 2 parts by weight of triphenylmethane lake pigment, 0.5 parts by weight of aluminum salicylate complex, and 3 parts by weight of polypropylene wax [manufactured by Sanyo Chemical Co .; Viscol 550P] as a wax,
At a set temperature of 160 ° C., the mixture was kneaded by a Labo Plastomill. Next, the kneaded product was coarsely pulverized by a Henschel mixer, and the obtained coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle diameter of 7 μm. To 100 parts by weight of the toner particles, 1.0 part by weight of positively charged hydrophobic colloidal silica fine particles (BET specific surface area: 95 m 2 / g) as a fluidity imparting agent was added, and mixed with a Henschel mixer to obtain a positive. A magnetic toner for charging was obtained.

(Non-Magnetic Toner for Color) Preparation of Masterbatch of Colorant (Yellow Masterbatch) Resin (200 parts by weight) obtained in the above [1] and CI Pigment Yellow 180
(100) parts by weight were mixed with a Henschel mixer, and the mixture was charged into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded for 0 minutes. After cooling the kneaded material, it was pulverized with a Henschel mixer to obtain a master batch Y. (Preparation of magenta masterbatch) CI Pigment Red 1 instead of CI Pigment Yellow 180
A master batch M was obtained in the same manner as described above except that No. 22 was used. (Preparation of cyan masterbatch) CI Pigment Blue 1 instead of CI Pigment Yellow 180
Masterbatch C was obtained in the same manner as above, except that 5: 3 was used. (Preparation of Black Masterbatch) Masterbatch B was obtained in the same manner as described above except that carbon black was used instead of CI Pigment Yellow 180 as a pigment.

Toner formulation of each color (yellow toner) Resin composition 8 obtained in the above [1]
2 parts by weight, 18 parts by weight of a master batch Y, 3 parts by weight of a zinc salt of a salicylic acid derivative, and 3 parts by weight of Fischer-Tropsch wax (manufactured by Sasol; Paraflint H1) were mixed and kneaded by a Labo Plastomill at a set temperature of 160 ° C. Next, the kneaded product was coarsely pulverized by a Henschel mixer, and the obtained coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain a volume average particle size of 9 μm.
Was obtained. To 100 parts by weight of the toner particles, 1 part by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity imparting agent was added and mixed with a Henschel mixer to obtain a non-magnetic toner for color (yellow).

(Magenta Toner) 82 parts by weight of the resin composition obtained in the above [1], 18 parts by weight of a master batch M,
3 parts by weight of a zinc salt of a salicylic acid derivative and 3 parts by weight of Fischer-Tropsch wax [manufactured by Sasol Co., Ltd .; paraflint H1] were mixed and kneaded by a Labo Plastomill at a set temperature of 160 ° C. Next, the kneaded product was coarsely pulverized by a Henschel mixer, and the obtained coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle diameter of 9 μm. The toner particles 100
1 part by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity-imparting agent was added to the parts by weight, and mixed with a Henschel mixer to obtain a non-magnetic toner for color (magenta).

(Cyan toner) 92 parts by weight of the resin composition obtained in the above [1], 9 parts by weight of a masterbatch C, 3 parts by weight of a zinc salt of a salicylic acid derivative, 3 parts by weight of Fischer-Tropsch wax (manufactured by Sasol Co .; Paraflint H1) Were mixed and kneaded at a set temperature of 160 ° C. using a Labo Plastomill. Next, the kneaded product was coarsely pulverized by a Henschel mixer, and the obtained coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle diameter of 9 μm. To 100 parts by weight of the toner particles, 1 part by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity-imparting agent was added and mixed with a Henschel mixer to obtain a non-magnetic toner for color (cyan).

(Black toner) 87 parts by weight of the resin composition obtained in the above [1], 18 parts by weight of a master batch B, 1.5 parts by weight of a master batch C, 3 parts by weight of a zinc salt of a salicylic acid derivative, Fischer-Tropsch wax [Sasol Co., Ltd.] 3 parts by weight of Paraflint H1] were mixed at a set temperature of 1
The mixture was kneaded at 60 ° C. using a Labo Plastomill. Next, the kneaded material was roughly pulverized by a Henschel mixer,
The resulting coarsely pulverized product was pulverized by a jet mill and classified by an airflow classifier to obtain toner particles having a volume average particle size of 9 μm. To 100 parts by weight of the toner particles, 1 part by weight of silica fine particles (manufactured by Nippon Aerogel) as a fluidity-imparting agent was added and mixed with a Henschel mixer to obtain a non-magnetic toner for color (black). When these toners were evaluated as toners for a two-component developing system, a ferrite carrier (manufactured by Powder Tech) was used as a carrier.

[4] Evaluation of Toner for Developing Electrostatic Charge Image (A) Evaluation of Mechanical Strength The pulverizing pressure by a jet mill at the time of pulverization in the above [3] and the fine powder component having a particle size of less than 5 μm removed by an airflow classifier The appropriateness of the mechanical strength (pulverizability) of the toner was evaluated based on the amount. Here, compared with the standard styrene acrylic resin X, those requiring a jet mill pulverization pressure of 10% or more to control the target particle size should be "too strong" and those having a large amount of fine powder components. "Too weak", other than "adequate". * Standard styrene acrylic: styrene (75% by weight) -butyl acrylate (25% by weight), weight average molecular weight (M
w) = 106,000, glass transition temperature (Tg) = 58
° C

(B) Evaluation of Low-Temperature Fixability and Offset Resistance (Negatively Charged Two-Component Toner) Four parts by weight of the negatively charged nonmagnetic toner and 100 parts by weight of a ferrite non-coated carrier were mixed to prepare a two-component developer. Produced. This was mounted on a commercially available printer (manufactured by Kyocera; FS-600) from which the fixing device was removed, and an unfixed image was output. Using an external fixing machine (using a soft roller coated with a fluorine resin for both the fixing roller and the press roller, and independently controlling the temperature of the upper and lower rollers), the obtained unfixed image is made variable in temperature, process speed, and nip width.
A fixing test was performed. Using this tester, the minimum fixing temperature and the offset occurrence temperature of the toner were measured, and the low-temperature fixing property and the offset resistance were evaluated. Here, as for the low-temperature fixing property, those having a minimum fixing temperature of 130 ° C. or less are excellent (）), those having a minimum fixing temperature in the range of 131 to 145 ° C. are good (○), and those having a minimum fixing temperature of 146 ° C. Those that were above were regarded as defective (x). Regarding the anti-offset property, those having a hot offset occurrence temperature of 225 ° C. or more are excellent (◎), and the hot offset occurrence temperature is 215 to 2
Those having a temperature of 24 ° C. were evaluated as good (○), those having a hot offset generation temperature of 205 to 214 ° C. were evaluated as poor (、), and those having a hot offset generation temperature of 204 ° C. or lower were evaluated as poor (×).

(C) Evaluation of Image Quality For the various toners described above, a fixed image was visually evaluated in a test using a machine without a fixing device, and an unfixed image was visually evaluated in a test with the fixing device removed. A case where there was no image defect such as fading, white spots, fog, carrier scattering, ghost, offset and insufficient density was evaluated as good (（), and a defect was evaluated as poor (×). (D) Evaluation of Transparency Those which have excellent color reproducibility of transmitted light when used as a color toner are good (）), there is little scattering of transmitted light and there is no problem in use as a color toner, but the image is slightly A dark sample was acceptable (△), and an image with turbidity or coloration and poor color reproducibility was evaluated as poor (x).

(Positively Charged Two-Component Toner) A two-component developer was prepared by mixing 4 parts by weight of the positively charged non-magnetic toner and 100 parts by weight of a silicon resin-coated ferrite carrier. This was removed from the fixing device, and mounted on a commercially available printer [FS-600 manufactured by Kyocera Corporation] in which the photoconductor was converted to a positively charged amorphous silicon photoconductor, and an unfixed image was output. The obtained unfixed image was evaluated in the same manner as described above. (Negatively charged magnetic one-component toner)
The image was mounted on a commercially available magnetic one-component printer (manufactured by Canon; LBP-930) without the fixing device, and an unfixed image was output. The obtained unfixed image was evaluated in the same manner as described above. (Positively-charged magnetic one-component toner)
The fixing device was removed, and the photoconductor was mounted on a commercially available magnetic one-component printer (manufactured by Canon Inc .; LBP-930) in which the photoconductor was converted to a positively charged amorphous silicon photoconductor, and an unfixed image was output. The obtained unfixed image was evaluated in the same manner as described above. (Negatively Charged Non-Magnetic One-Component Toner) The negatively-charged non-magnetic toner was mounted on a commercially available non-magnetic one-component printer (manufactured by Seiko Epson; LP-9200) without a fixing device, and an unfixed image was output. The obtained unfixed image was evaluated in the same manner as described above. (Positively Charged Non-Magnetic One-Component Toner) The positively charged non-magnetic toner was mounted on a commercially available positively charged non-magnetic one-component printer (manufactured by Brother Industries, Ltd .; HL730) without a fixing device, and an unfixed image was output. The obtained unfixed image was evaluated in the same manner as described above.

Example 2 The procedure of Example 1 was repeated, except that the amount of the styrene-butyl acrylate copolymer used in Example 1 was changed to 4 kg and polystyrene was not used. The obtained resin composition contained 44% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 3 The styrene-butyl acrylate copolymer used in Example 1 was replaced with a styrene-acrylic acid (2-ethylhexyl) copolymer (copolymer composition: styrene / acryl = 80).
/ 20, insoluble in methylene chloride, glass transition temperature 60
(° C., 流出 outflow temperature: 178 ° C.) 4 kg, the amount of PETCOL 100T used was changed to 4 kg, and the same procedure as in Example 1 was carried out except that polystyrene was not used. The obtained resin composition contains 30% by weight of a component insoluble in methylene chloride.
Was included. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 4 The low molecular weight resin used in Example 1 was
Softening temperature is 100 ° C from 00T, JIS K 5400
The amount of a styrene-butyl acrylate copolymer was changed to 6 kg of a petroleum resin [Aromatic-aliphatic petroleum resin: High Resin NX manufactured by Toho Chemical Co., Ltd.] having a Gardner color number of 7 measured under melting conditions according to Was changed to 4 kg, and the same procedure as in Example 1 was carried out except that polystyrene was not used. The obtained resin composition contained 38% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 5 The low molecular weight resin used in Example 1 was
From 00T, the softening temperature was 90 ° C., and the weight was changed to 6 kg of a coumarone resin (coumarone-indene-styrene copolymer resin: Esculon, manufactured by Nippon Steel Chemical Co., Ltd.) having a Gardner color number of 12 measured under melting conditions in accordance with JIS K 5400. Example 1 was repeated except that the amount of the styrene-butyl acrylate copolymer was changed to 4 kg and polystyrene was not used. The obtained resin composition contained 41% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 6 The low molecular weight resin used in Example 1 was
From 00T, the softening temperature is 125 ° C and the glass transition temperature is 68
The temperature was changed to 8 kg of a terpene phenolic resin (manufactured by Yasuhara Chemical Co., Ltd .: Mighty Ace G125), and the same procedure as in Example 1 was carried out except that polystyrene was not used.
The obtained resin composition contains 2 components insoluble in methylene chloride.
1% by weight. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 7 The low molecular weight resin used in Example 1 was
Softening temperature is 100 ° C from 00T, JIS K 5400
Ester group-containing petroleum resin having a Gardner color number of 6, a number average molecular weight of 420, and a saponification value of 175 mgKOH / g [Quinton, an ester group-containing dicyclopentadiene petroleum resin manufactured by ZEON CORPORATION] 1
500], the amount of styrene-butyl acrylate copolymer used was changed to 4 kg, and no polystyrene was used. The obtained resin composition contained 41% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 8 The low molecular weight resin used in Example 1 was
From 00T, softening temperature is 103 ° C, Hazen color tone is 75,
A rosin resin having an acid value of 12 and a hydroxyl value of 44 [Rosin resin manufactured by Arakawa Chemical Industries: Pine Crystal KE-359]
And the amount of the styrene-butyl acrylate copolymer was changed to 4 kg, and the same procedure as in Example 1 was carried out except that polystyrene was not used. The resulting resin composition contained 42% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 9 Except that the styrene-butyl acrylate copolymer used in Example 1 was changed to 2 kg of polystyrene crosslinked with divinylbenzene (melt flow rate according to JIS K 7210: 2 g / 10 min) In the same manner as in Example 1. The obtained resin composition contained 20% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 10 The amount of the petroleum resin used in Example 1 was 4 kg, and the amount of the styrene-butyl acrylate copolymer was 4 kg.
kg, and replace polystyrene with Dick Era Styrene (made by Dainippon Ink and Chemicals, Inc.) instead of HH32.
Except that 2 kg was used, the procedure was the same as in Example 1. The obtained resin composition contained 39% by weight of a component insoluble in methylene chloride.
Was included. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 11 The styrene-butyl acrylate copolymer used in Example 1 was converted to a polyester resin (raw material: 2,2-bis (4-
(Hydroxyphenyl) propane-ethylene oxide adduct / 2,2-bis (4-hydroxyphenyl) propane-propylene oxide adduct / terephthalic acid / isophthalic acid / dodecenylsuccinic acid / trimellitic acid, glass transition temperature 62 ° C., 1/2 The flow rate was changed to 4 kg (outflow temperature: 172 ° C.), and the same procedure as in Example 1 was carried out except that polystyrene was not used. The obtained resin composition contained 21% by weight of a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Example 12 The styrene-butyl acrylate copolymer used in Example 1 was converted to a polyester resin (raw material: 2,2-bis (4
-Hydroxyphenyl) propane-ethylene oxide adduct / 2,2-bis (4-hydroxyphenyl) propane-propylene oxide adduct / terephthalic acid / isophthalic acid / dodecenylsuccinic acid / maleic acid / fumaric acid; glass transition temperature 62 ° C. (1/2 outflow temperature 155 ° C)
The resin was kneaded in the same manner as in Example 1 except that the weight was changed to 4 kg and polystyrene was not used. After adding styrene and di-tert-butyl peroxide to this composition and heating to 150 ° C., a resin composition containing 4% by weight of a component insoluble in methylene chloride could be obtained. The production of a toner using the resin composition obtained here was performed by the following two methods. Except that the crosslinked resin was used as a raw material, the same method as in Example 1 was used (Example 12-). The resin before crosslinking, the other toner materials described in Example 1, and a crosslinking agent (styrene), Reaction catalyst (di-tert
-Butyl peroxide), and a reaction is performed in the process of kneading to obtain a toner comprising a component containing 4% by weight of a component insoluble in methylene chloride (Example 12-).
Table 1 shows the evaluation results of the resin composition and the toner obtained here.
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Example 13 The amount of PETCOL 100T used in Example 1 was changed to 7 kg, and the styrene-butyl acrylate copolymer was melted at a melt flow rate of 2.0 g / 10 min (230 ° C., 230 ° C.
2.16 kg) of styrene-maleic anhydride resin (manufactured by Nova Chemical Co .; DYLARKD232) was changed to 3 kg, and the same procedure as in Example 1 was carried out except that polystyrene was not used. To this composition, p-phenylenediamine was added to resin 1
After adding 0.3 parts by weight to 00 parts by weight, the mixture was heated to 150 ° C. to obtain a resin composition containing 35% by weight of a component insoluble in methylene chloride. The production of a toner using the resin composition obtained here was performed by the following two methods. Except that the crosslinked resin was used as a raw material, the same method as in Example 1 was used (Example 13-). The resin before crosslinking, the other toner materials described in Example 1, and the crosslinking agent (p-phenylene) After mixing diamine), a reaction is performed in a kneading process to obtain a toner composed of a component containing 30% by weight of a component insoluble in methylene chloride (Example 13-). Resin composition and toner obtained here Table 1 shows the evaluation results of
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Example 14 The low molecular weight resin used in Example 1 was
The temperature was changed from 00T to 6 kg of an aromatic petroleum resin having a softening temperature of 83 ° C. and a Gardner color number of 7 measured under melting conditions in accordance with JIS K 5400, and the styrene-butyl acrylate copolymer was replaced with a styrene-maleic anhydride resin. [Dylark232 manufactured by Nova Chemical Co., Ltd.] The procedure was the same as in Example 1 except that the weight was changed to 4 kg and polystyrene was not used. After adding 10 parts by weight of polytetramethylene glycol (molecular weight 650) to 100 parts by weight of the resin, the resin composition is heated to 150 ° C., thereby containing 2% by weight of a component insoluble in methylene chloride. Could be obtained. The production of a toner using the resin obtained here was performed by the following two methods. Except that the crosslinked resin was used as a raw material, the same method as in Example 1 was used (Example 14-). The resin before crosslinking, the other toner materials described in Example 1, and the crosslinking agent (polytetramethylene) Glycol), a reaction is carried out in the course of kneading, and a method for obtaining a toner comprising a component containing 1% by weight of a component insoluble in methylene chloride (Example 14-). Resin composition and toner obtained here Table 1 shows the evaluation results of
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Example 15 The low molecular weight resin used in Example 1 was
From 00T, the softening temperature is 125 ° C and the glass transition temperature is 68
The temperature was changed to 8 kg of a terpene phenol resin (Mighty Ace G125, manufactured by Yasuhara Chemical Co., Ltd.), and the styrene-butyl acrylate copolymer was changed to a styrene-maleic anhydride resin (manufactured by Nova Chemical Company; DYLARKD23).
2] Same as Example 1 except that the weight was changed to 2 kg and polystyrene was not used. After adding 0.3 parts by weight of hexamethylenediamine to 100 parts by weight of the resin, the mixture is heated to 150 ° C. to obtain a resin composition containing 22% by weight of a component insoluble in methylene chloride. Was completed. The production of a toner using the resin composition obtained here was performed by the following two methods. Except that the crosslinked resin was used as a raw material, the same method as in Example 1 was used (Example 15-). The resin before crosslinking, the other toner materials described in Example 1, and the crosslinking agent (hexamethylenediamine) ) Is mixed and then reacted in a kneading process to obtain a toner consisting of a component containing 19% by weight of a component insoluble in methylene chloride (Example 15-). Table 1 shows the evaluation results.
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Comparative Example 1 The thermoplastic resin used in Example 1 was styrene-butyl acrylate having a weight average molecular weight of 220,000 and a glass transition temperature of 64 ° C. (manufactured by Sanyo Chemical Co., Ltd .: Hymer SB-3).
05) Same as Example 1 except that the weight was changed to 4 kg and polystyrene was not used. The obtained resin composition did not contain a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Comparative Example 2 The thermoplastic resin used in Example 1 was styrene-maleic anhydride resin (manufactured by Nova Chemical Co .; DYLARK).
D232] The same procedure as in Example 1 was carried out except that the weight was changed to 4 kg and polystyrene was not used. The obtained resin composition did not contain a component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

Comparative Example 3 The thermoplastic resin used in Example 1 was replaced with a polyester resin (raw material: 2,2-bis (4-hydroxyphenyl)
Propane-ethylene oxide adduct / 2,2-bis (4-hydroxyphenyl) propane-propylene oxide adduct / terephthalic acid / isophthalic acid / dodecenylsuccinic acid, glass transition temperature 62 ° C., 1/2 outflow temperature 1
72 ° C.) The procedure was the same as in Example 1 except that the weight was changed to 4 kg and polystyrene was not used. The obtained resin composition is
There was no component insoluble in methylene chloride. Table 1 shows the evaluation results of the resin composition and the toner thus obtained.

[0083]

[Table 1]

[0084]

As described in detail above, the resin composition of the present invention can be fixed at a low temperature and has good pulverizability.
For developing an electrostatic image used to develop an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., or for a toner binder resin used in a toner jet method printing. Are suitable. Further, a toner obtained by adding an appropriate amount of a coloring material, a charge control agent, and a wax to the resin composition has excellent low-temperature fixing property and high-temperature offset resistance, has appropriate mechanical strength, and is excellent as a toner. .

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) G03G 9/097 G03G 9/08 331 344 101 F-term (Reference) 2H005 AA01 AA02 AB02 CA03 CA14 CA15 CA17 DA01 EA03 EA05 EA06 EA07 FA06 4J002 AE03Y AF02W BA01W BB03Y BB07Y BB12Y BB23Y BB25Y BC01X BC03W BC04Y BC06Y BC07X BC08X BC09X BC11X BC12X BD04Y BE06Y BK00W CC01Y CC04Y CD00Y CE00W CE00Y CF01X CF03 EV08 CF02CK02 CF02X

Claims (27)

[Claims] 1. A resin composition comprising: (A) a low molecular weight resin having at least an aromatic component and / or a functional group selected from an ester group and a hydroxyl group; and (B) a thermoplastic resin. A resin composition containing 0.5% by weight or more of an insoluble component when 1 g of the composition is dissolved in 100 ml of methylene chloride (25 ° C.). 2. The low molecular weight resin (A) is a terpene resin,
The resin composition according to claim 1, comprising at least one selected from the group consisting of a rosin resin, a cumarone-indene resin, and a styrene oligomer. 3. The resin composition according to claim 1, wherein the low molecular weight resin (A) comprises an aromatic petroleum resin. 4. The resin composition according to claim 1, wherein the low molecular weight resin (A) comprises an aromatic-aliphatic copolymerized petroleum resin and / or an aromatic-dicyclopentadiene copolymerized petroleum resin. 5. The low molecular weight resin (A) has an aromatic hydrocarbon unit content of 30% by weight or more in the low molecular weight resin (A).
5. The resin composition according to any one of items 1 to 4. 6. The resin composition according to claim 1, wherein the low-molecular-weight resin (A) has a weight average molecular weight of 300 to 12,000. 7. The softening temperature of the low molecular weight resin (A) is 70.
The resin composition according to any one of claims 1 to 6, wherein the temperature is from 130 to 130 ° C. 8. The resin composition according to claim 1, wherein the low-molecular-weight resin (A) has a 流出 outflow temperature of 80 to 140 ° C. in a flow tester. 9. The resin composition according to claim 1, wherein the thermoplastic resin (B) comprises a styrene resin. 10. The resin composition according to claim 1, wherein the thermoplastic resin (B) comprises a polyester resin. 11. The thermoplastic resin (B) has a weight average molecular weight of 5,000 to 1,000,000 and a number average molecular weight of 2,000 to 500,000.
0. The resin composition according to any one of 0. 12. The resin composition according to claim 1, wherein the weight ratio of the low molecular weight resin (A) to the thermoplastic resin (B) is 35/65 to 90/10. 13. The component insoluble in methylene chloride due to crosslinking of the styrenic resin is at least 0.5% by weight.
13. The resin composition according to any one of items 12 to 12. 14. The resin composition according to claim 1, wherein a component insoluble in methylene chloride is 0.5% by weight or more due to crosslinking of the polyester resin. 15. The thermoplastic resin (B) is a styrene resin having at least one group selected from the group consisting of a carboxylic anhydride group, an acrylate group and a methacrylate group. The resin composition according to any one of the above. 16. The resin composition according to claim 1, wherein the thermoplastic resin (B) is polystyrene and / or substituted polystyrene. 17. The thermoplastic resin (B) comprises a trivalent or higher carboxylic acid, a trivalent or higher alcohol, a divalent or higher carboxylic acid containing a carbon-carbon double bond, and a dicarboxylic acid containing a carbon-carbon double bond. The resin composition according to any one of claims 1 to 14, comprising a polyester resin using at least one selected from the group consisting of alcohols having a valency of at least one. 18. The resin composition according to claim 1, further comprising at least one selected from the group consisting of a wax, a thermoplastic resin other than the thermoplastic resin (B), and an antioxidant.
18. The resin composition according to any one of 17. 19. The glass transition temperature of the resin composition is 45.
The resin composition according to any one of claims 1 to 18, wherein the temperature is from 80 to 80 ° C. 20. The method for producing a resin composition according to claim 1, wherein the crosslinked thermoplastic resin (B) and the low molecular weight resin (A) are mixed. 21. The method for producing a resin composition according to claim 1, wherein the thermoplastic resin (B) and the low molecular weight resin (A) are crosslinked during mixing. 22. The method for producing a resin composition according to claim 1, wherein crosslinking is performed after mixing the thermoplastic resin (B) and the low molecular weight resin (A). 23. A toner resin composition comprising the resin composition according to claim 1 as a main component. 24. A toner comprising the resin composition according to claim 1. 25. The toner according to claim 24, wherein the toner further includes at least one selected from the group consisting of a colorant, a wax, a charge control agent, and a magnetic powder. 26. A method comprising kneading and pulverizing the resin composition according to claim 1 and at least one selected from the group consisting of a colorant, a wax, a charge control agent, and a magnetic powder. Item 29. The toner according to Item 24 or 25. 27. The toner according to claim 24, wherein the volume average particle size is 5 to 15 μm.