JP2008158502A - Binder resin composition for toner, method for manufacturing same, and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder resin composition for toner and a toner showing preferable fixing performance, offset resistance, image stability and durability. <P>SOLUTION: The binder resin composition for toner contains a polyester resin, wherein the composition contains a polyester resin having a structural unit derived from an oxidized polyolefin and an oxidized polyolefin. The method for manufacturing the binder resin composition for toner includes polymerization of an acid component and an alcohol component in the presence of an oxidized polyolefin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a binder resin composition for toner used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a method for producing the same, and a toner.

In the method of obtaining an image by the electrophotographic printing method and the electrostatic charge developing method, the electrostatic charge image formed on the photoreceptor is developed with toner charged in advance by friction and then fixed. As for the fixing method, there are a heat roller method in which a toner image obtained by development is fixed using a pressurized and heated roller, and a non-contact fixing method in which fixing is performed using an electric oven or flash beam light. In order to pass through these processes without any problem, the toner needs to maintain a stable charge amount first, and then needs to have good fixability to paper. In addition, the apparatus has a fixing unit which is a heating body, and the temperature in the apparatus rises, so that it is necessary that the toner does not block. Further, even during continuous printing, it is necessary that the apparatus is not soiled or fogged on the printing surface, that is, the durability of the toner is required.
Further, in the heat roller system, the temperature of the fixing unit has been lowered from the viewpoint of energy saving, and the toner has been strongly required to have a capability of fixing onto a paper at a lower temperature, that is, a low temperature fixability. In addition, as the apparatus becomes more compact, a roller that does not apply a release agent has been used, and there is an increasing demand for toner to be peelable from the heat roller, that is, non-offset.

  Binder resin for toner has a great influence on the toner characteristics as described above, and polystyrene resin, styrene acrylic resin, polyester resin, epoxy resin, polyamide resin, etc. are known, but recently, toughness, A polyester resin which is excellent in fixability at a low temperature and has a good performance balance has attracted particular attention.

However, polyester resins tend to have low non-offset properties due to poor releasability during fixing. Generally, a release component such as wax is blended in the toner in order to impart releasability at the time of fixing. However, since the polyester resin and the wax are poorly compatible, unevenness in the dispersion state of the wax component occurs. In the toner, a wax-rich part and a wax-poor part are generated, causing various problems.
For example, since the wax-rich part is easily pulverized, there is a problem that the toner is finely powdered. In order to obtain a toner product having a desired particle size, fine powder is usually cut. However, since wax-rich fine powder is cut, the amount of wax in the toner product is reduced below the design value, and the wax is peeled off. There was a problem that sufficient effects could not be obtained. Furthermore, during continuous printing, the toner in the cartridge is stressed and further crushed and pulverized, which adversely affects performance such as image stability and durability. Therefore, various studies have been made on the compatibility between the polyester resin and the wax (see, for example, Patent Documents 1 to 3).

Patent Document 1 or 2 discloses a technique of using an oxidized polyolefin having relatively good compatibility with a polyester resin as a wax used at the time of toner production. Patent Document 1 discloses a technique for preventing the occurrence of filming by defining the dispersion diameter of oxidized polyolefin in toner. Patent Document 2 discloses a technique for obtaining a toner having good fixing property and offset property without photoconductor filming by using both oxidized polyethylene and non-oxidized polypropylene.
However, the wax dispersibility of the toners described in Patent Documents 1 and 2 has been improved as compared with the prior art, but is still insufficient. In addition, since the types of wax are limited, there is a problem in that various waxes cannot be appropriately selected and used in consideration of toner releasability, storage stability, fixability, color development, and the like.
Patent Document 3 discloses a technique for providing a toner having excellent low-temperature fixability, offset resistance, environmental stability and the like by using a polyester resin modified with a long-chain alkyl group having a specific functional group at the terminal. It is disclosed.
In the technique relating to the toner obtained by using a polyester resin modified by using 5% by mass or more of a modifier having a terminal modified with a linear long chain alkyl group exemplified in Patent Document 3, the following There was a problem like this.
Since the linear modifier has a large heat of fusion, the fixing property is insufficient due to the imperfect residual modifier in the molten state, or it does not function sufficiently as a mold release agent during fixing and has a hot offset resistance. It becomes insufficient.
Furthermore, in order to obtain the expected effect, it is modified with a large amount of modifier, and because the polyester resin is designed to have a high acid value, the image stability becomes poor, or a large amount remains in the resin. Unreacted modifiers cause the color development and transparency of the toner to deteriorate and the toner blocking resistance to be insufficient.

JP-A-3-168649 JP 2002-72538 A JP-A-7-175263

  In view of such circumstances, the present invention provides a binder resin composition for toner that can provide a toner having good fixing performance, non-offset property, image stability, and durability, a method for producing the same, and a toner using the same. It is intended to provide.

The present invention relates to a binder resin composition for toner containing a polyester resin containing a structural unit derived from an oxidized polyolefin and an oxidized polyolefin.
Furthermore, the present invention relates to a method for producing a binder resin composition for toner, in which an acid component and an alcohol component are polymerized in the presence of an oxidized polyolefin.
Furthermore, the present invention relates to a toner containing the binder resin composition for toner.

  By using the binder resin composition for toner of the present invention, a toner having good fixability, non-offset property, image stability and durability can be provided.

  The binder resin composition for toner of the present invention needs to contain a polyester resin containing a structural unit derived from oxidized polyolefin.

The hydrocarbon skeleton of the oxidized polyolefin has the effect of improving the compatibility between the polyester resin and the wax and improving the wax dispersibility of the toner when the oxidized polyolefin is incorporated as a structural unit of the polyester resin.
In the case where the oxidized polyolefin is not taken in as a constituent component of the polyester resin, even if the oxidized polyolefin is contained in the toner, this action is insufficient.
In the present invention, the inclusion of the oxidized polyolefin in the binder resin composition for the toner further improves the wax dispersibility due to the synergistic effect with the polyester resin containing the structural unit derived from the oxidized polyolefin.
Furthermore, when the binder resin composition for toner of the present invention contains a polyester resin containing a structure derived from oxidized polyethylene obtained by oxidizing polyethylene having a branch as an oxidized polyolefin, and oxidized polyethylene obtained by oxidizing the polyethylene having branches. Therefore, it is more preferable because the fixing property of the obtained toner becomes good.

Oxidized polyolefin is obtained by oxidizing polyolefin by a method such as oxygen oxidation or chemical oxidation, and has functional groups such as hydroxyl, aldehyde, carboxyl, carbonyl, ester, and hydroperoxide groups in the polyolefin skeleton. It is contained in. Among these functional groups, a functional group (hydroxyl group, carboxyl group, ester group, etc.) capable of reacting with an acid or alcohol by a reaction such as a condensation reaction, an addition reaction, or a transesterification reaction is an acid or a raw material component of the polyester resin. By reacting with alcohol, the oxidized polyolefin can be incorporated into the polyester resin as a structural unit.
The polyolefin before the oxidation treatment is not particularly limited, but is a polymer mainly composed of an olefin skeleton, such as polyethylene, polypropylene, polyisoprene, polybutylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer. Etc. Of these, the polyolefin before the oxidation treatment is preferably a polyolefin mainly composed of an ethylene skeleton such as polyethylene or an ethylene-α-olefin copolymer from the viewpoint of thermal stability, and particularly preferably polyethylene.

  As polyethylene before the oxidation treatment, linear polyethylene produced by a low pressure polymerization method, branched polyethylene produced by a high pressure polymerization method, or the like, and a stereoregularity polyethylene produced by a metallocene catalyst are used. I can do it. Among these, it is preferable to use a branched polyethylene produced by a high pressure polymerization method. Oxidized polyethylene obtained by subjecting branched polyethylene to oxidation treatment has characteristics such as low melt viscosity and softness and low endotherm when melted, and tends to have good toner fixing properties. It is in.

  The acid value of the oxidized polyolefin is not particularly limited, but is preferably 10 (mgKOH / g) or more. When the acid value is 10 (mg KOH / g) or more, the amount of functional groups capable of reacting with acid or alcohol in the oxidized polyolefin increases, and the oxidized polyolefin tends to be easily incorporated into the polyester resin. The lower limit of the acid value of the oxidized polyolefin is more preferably 12 (mgKOH / g) or more, and further preferably 15 (mgKOH / g) or more. The upper limit of the acid value of the oxidized polyolefin is not particularly limited. From the viewpoint of controlling the reactivity when producing the polyester resin (P1) and the wax dispersibility of the toner when the oxidized polyolefin is incorporated into the polyester resin. To 100 (mg KOH / g) or less.

  The molecular weight of the oxidized polyolefin is not particularly limited, but the weight average molecular weight (Mw) is preferably 500 or more. When Mw is 500 or more, the wax dispersibility tends to be good. The lower limit value of the molecular weight of the oxidized polyolefin is more preferably 600 or more, further preferably 700 or more, and particularly preferably 800 or more. The upper limit of Mw of the oxidized polyolefin is not particularly limited, but is preferably 10,000 or less from the viewpoint of easy incorporation into the polyester resin. The upper limit of Mw of the oxidized polyolefin is more preferably 8000 or less, further preferably 6000 or less, and particularly preferably 5000 or less.

Specific examples of the oxidized polyolefin include the following, and any of them can be obtained commercially.
(1) Rico wax PED series manufactured by Clariant Co. (2) Sun wax E series manufactured by Sanyo Chemical Industries

Then, the manufacturing method of the binder resin composition for toners of this invention is demonstrated.
The method for producing the binder resin composition for toner of the present invention is not particularly limited, and examples thereof include a method of polymerizing an acid component and an alcohol component that are raw material components of a polyester resin in the presence of an oxidized polyolefin. By this production method, a binder resin for a toner containing a polyester resin containing a structural unit derived from oxidized polyolefin can be produced.
The polymerization method is not particularly limited, and examples thereof include a method in which the above-described components are introduced into a reaction vessel and polymerized through an esterification reaction or a transesterification reaction and a condensation reaction.

  In addition, since the oxidized polyolefin contains a carboxyl group and / or a hydroxyl group, it corresponds to an acid component and / or an alcohol component, but the acid component and alcohol component here refer to components other than the oxidized polyolefin. . In addition, when the molar part of the acid component and the alcohol component is shown, the oxidized polyolefin is not included in the calculation.

  The acid component is not particularly limited, but includes terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, and esters or acid anhydrides thereof. Aromatic dicarboxylic acid components; aliphatic dicarboxylic acid components such as phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, or esters or acid anhydrides thereof; trimellitic acid, pyro Merit acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8 -Octanetetracarboxylic acid or these esters Tricarboxylic or higher polycarboxylic acid component such as ether or anhydride, and the like.

  As the aromatic dicarboxylic acid, terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost. Trivalent or higher polyvalent carboxylic acid is preferably trimellitic acid or its acid anhydride.

  Although the usage-amount of an aromatic dicarboxylic acid component is not restrict | limited in particular, It is preferable to use 70 mol part or more in 100 mol part of all the acid components. When the amount of the aromatic dicarboxylic acid component used is 70 mol parts or more, the storage stability of the toner tends to be good and the resin strength tends to be improved. As for the lower limit of the usage-amount of an aromatic dicarboxylic acid component, 75 mol part or more is more preferable.

  When a trivalent or higher polyvalent carboxylic acid component is used, it is preferably used in an amount of 0.1 to 30 mol parts per 100 mol parts of the total acid components. When the amount of the trivalent or higher polyvalent carboxylic acid component is 0.1 mol part or more, the non-offset property of the toner tends to be good, and when it is 30 mol part or less, the toner has blocking resistance and fixing. Tend to be good. The lower limit value of the amount of the trivalent or higher polyvalent carboxylic acid component is more preferably 1 mol part or more, and the upper limit value is more preferably 28 mol parts or less.

The alcohol component is not particularly limited, and an aliphatic diol component or an aromatic diol component can be used.
The aliphatic diol component is not particularly limited, but ethylene glycol, neopentyl glycol, propylene glycol, butanediol, polyethylene glycol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1, Examples include 4-cyclohexanedimethanol.

The aromatic diol component is not particularly limited, but polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4- Aromatic diol components such as hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane. It is.
These can be used alone or in combination of two or more, and can also be used in combination of an aliphatic diol component and an aromatic diol component.

  In addition to these diol components, trihydric or higher polyhydric alcohol components can also be used. Although it does not restrict | limit especially as a polyhydric alcohol component more than trivalence, Although it is sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2 , 4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3 , 5-trihydroxymethylbenzene and the like. These can be used alone or in combination of two or more. Among these, pentaerythritol and trimethylolpropane are particularly preferable.

  Although the usage-amount of an aliphatic diol component is not specifically limited, 10 mol part or more is preferable with respect to 100 mol part of all the acid components. When the amount of aliphatic diol used is 10 mol parts or more, the degree of polymerization tends to increase and the non-offset property of the toner tends to be good, and polymerization is performed for a long time without using a large amount of polymerization catalyst. The polymerization degree tends to be increased even if it is not necessary, and this is preferable in terms of cost and environment. As for the usage-amount of an aliphatic diol component, 15 mol part or more is more preferable.

  When using a trihydric or higher polyhydric alcohol component, it is preferably contained in an amount of 0.1 to 30 mol parts per 100 mol parts of the total acid components. This is because the non-offset property of the toner tends to be good when the content is 0.1 mol part or more, and the blocking resistance and fixing property of the toner tend to be good when the content is 30 mol parts or less. Because it is in. More preferably, it is the range of 1-28 mol part. When the amount of the trihydric or higher polyhydric alcohol component is 0.1 mol part or more, the non-offset property of the toner tends to be good, and when it is 30 mol part or less, the toner has anti-blocking property or fixing property. Tends to be good. The lower limit value of the amount of the trihydric or higher polyhydric alcohol component is more preferably 1 mol part or more, and the upper limit value is more preferably 28 mol parts or less.

  In the polymerization of the polyester resin, for example, a polymerization catalyst such as titanium tetrabutoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium oxide or the like can be used.

  The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 280 ° C. When the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and when it is 280 ° C. or lower, the decomposition of the resin and the by-product of volatile components that cause odor tend to be suppressed. The lower limit of the polymerization temperature is more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit of the polymerization temperature is more preferably 270 ° C. or less.

  In the present invention, if necessary, a polyester resin can be polymerized by adding a release agent component together with the above components within a range not impairing the effects of the present invention. By adding a release agent component and polymerizing, the toner fixing property and wax dispersibility tend to be improved. As the release agent component, the same waxes that can be used as a toner formulation described later can be used as appropriate, for example, carnauba wax, rice wax, beeswax, synthetic ester wax, paraffin wax, fatty acid amide, silicone wax and the like. Can be mentioned.

The procedure for adding the oxidized polyolefin when the oxidized polyolefin is added in the process of producing the polyester resin is not particularly limited, but it is charged into the reaction vessel together with the acid component and the alcohol component described above, and polymerized in the presence of the oxidized polyolefin. It is preferable to produce a resin. By polymerizing in this way, the oxidized polyolefin tends to be incorporated as a structural unit in the polyester resin, and the dispersibility of the wax added externally during toner production tends to be good. It is not always necessary for the oxidized polyolefin to be incorporated into the polyester resin (P1) as a constituent unit, and it is preferable that a part of the oxidized polyolefin is dispersed in the polyester resin as it is without reacting.
In particular, when oxidized polyethylene obtained by oxidizing a branched polyethylene as an oxidized polyolefin is used, the oxidized polyolefin dispersed without reacting becomes oxidized polyethylene obtained by oxidizing the branched polyethylene, and the fixing characteristics of the resulting toner Is more preferable because it becomes favorable.

  The content of the oxidized polyolefin dispersed without reacting is not particularly limited, but is preferably 0.1 to 8% by mass in the total amount of the binder resin composition for toner. When the content of the oxidized polyolefin dispersed without reacting is 0.1% by mass or more, the hot offset resistance and the fixability tend to be good. When the content is 8% by mass or less, the resulting binder is obtained. The blocking resistance, image stability and durability of the resin tend to be good. The lower limit of the content of the oxidized polyolefin dispersed without reacting is more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more. Further, the upper limit of the content of the oxidized polyolefin dispersed without reacting is more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

The polyester resin obtained by the above-described method may be at least a part of the polyester resin (P1). In addition to the polyester resin (P1), the polyester resin includes a polyester resin (P0) that does not contain a structural unit derived from oxidized polyolefin. May be.
The content of the structural unit derived from the oxidized polyolefin is not particularly limited, but is preferably 0.2 to 10% by mass in the total amount of the polyester resin.

The content of the structural unit derived from the oxidized polyolefin here is an oxidized polyolefin as a structural unit of the polyester resin, and is an average content in the polyester resin. Generally, the polyester resin obtained by the above-mentioned method has a composition distribution, and the content of the structural unit derived from the oxidized polyolefin is different for each molecular chain. Therefore, the content of the structural unit derived from the oxidized polyolefin referred to here is an average content of the entire polyester resin, and the polyester resin also includes a polyester resin (P0) that does not have the oxidized polyolefin as a structural unit. Is an average value of the whole including the polyester resin (P0).
In the present invention, the term “content of component derived from oxidized polyolefin” refers to the total content of oxidized polyolefin dispersed without reacting with the content of structural units derived from oxidized polyolefin (that is, reaction) Thus, the total amount of the components that remain as they are without reacting with the components incorporated in the polyester resin as structural units).

  When the content of the structural unit derived from the oxidized polyolefin is 0.2% by mass or more, the dispersibility of the wax added at the time of toner formation tends to be good, and when it is 10% by mass or less, blocking resistance and image stability are improved. Tend to be good in durability and durability. The lower limit of this content is more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Moreover, the upper limit of this content is more preferably 8% by mass or less, and particularly preferably 7% by mass or less.

  The content of the polyester resin (P1) and the polyester resin (P0) in the binder resin composition for toner is not particularly limited, but is preferably 50 to 99.9% by mass in the total amount of the binder resin composition for toner. When the content of the polyester resin (P1) and the polyester resin (P0) is 50% by mass or more, the dispersibility of the wax added at the time of toner formation tends to be good while maintaining the advantages of the polyester resin as a toner binder. In the case of 99.9% by mass or less, the hot offset resistance and the fixability tend to be good. The lower limit of the content of the polyester resin (P1) and the polyester resin (P0) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 92% by mass or more, and particularly preferably 93% by mass or more. 95 mass% or more is the most preferable. Further, the upper limit of the content of the polyester resin (P1) and the polyester resin (P0) is more preferably 99.9% by mass or less, further preferably 99.8% by mass or less, and particularly preferably 99.7% by mass or less. .

  The binder resin composition for toner according to the present invention is not limited to the polyester resin (P1), the polyester resin (P0), and the oxidized polyolefin dispersed without reacting, and other resins are used as long as the effects of the present invention are not impaired. For example, you may contain a styrene resin, a styrene-acrylic resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy resin, etc.

The glass transition temperature (hereinafter referred to as Tg) of the binder resin composition for toner is not particularly limited, but is preferably 45 to 65 ° C. When Tg is 45 ° C. or higher, the blocking resistance of the toner tends to be good, and when it is 65 ° C. or lower, the fixability of the toner tends to be good. As for the lower limit of Tg, 50 degreeC or more is more preferable.
The softening temperature of the toner binder resin composition is not particularly limited, but is preferably 90 to 200 ° C. When the softening temperature is 90 ° C. or higher, the non-offset property of the toner tends to be good, and when it is 200 ° C. or lower, the toner fixability tends to be good. The lower limit value of the softening temperature is more preferably 100 ° C. or higher, and the upper limit value is more preferably 180 ° C. or lower.
The acid value of the toner binder resin composition is not particularly limited, but is preferably 20 mgKOH / g or less. When the acid value is 20 mgKOH / g or less, the image density of the toner tends to be stable. The upper limit of the acid value of the polyester resin (P) is more preferably 15 mgKOH / g or less, and particularly preferably 12 mgKOH / g or less.

The toner of the present invention contains the toner binder resin described above. The toner of the present invention can be blended with additives such as a colorant, a charge control agent, a release agent, and a flow modifier, a magnetic material, and the like as necessary.
The colorant is not particularly limited, but carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo And disazo dyes, condensed azo dyes or pigments. These dyes and pigments can be used alone or in admixture of two or more. In the case of a full-color toner, benzidine yellow, monoazo dyes and condensed azo dyes are used as yellow, quinacridone, rhodamine dyes, and monoazo dyes are used as magenta, and phthalocyanine blue is used as cyan.
The content of the colorant is not particularly limited, but is preferably 2 to 10% by mass in the toner from the viewpoint of the toner color tone, image density, and thermal characteristics.

The charge control agent is not particularly limited, and examples of the positive charge control agent include quaternary ammonium salts and basic or electron-donating organic substances. Negative charge control agents include metal chelates, metal-containing dyes, and acidic substances. Or an electron withdrawing organic substance etc. are mentioned. In the case of color toners, it is important that the charge control agent is colorless or light color and does not cause any color tone problems on the toner. Examples include metal salts of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, metal complexes, amides A compound, a phenol compound, a naphthol compound, etc. are mentioned. Furthermore, a vinyl polymer having a styrene, acrylic acid, methacrylic acid or sulfonic acid group may be used as the charge control agent.
The content of the charge control agent is not particularly limited, but is preferably 0.5 to 5% by mass in the toner. When the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be a sufficient level, and when the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. Tend to.

The release agent is not particularly limited, and carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester type in consideration of toner releasability, storage stability, fixability, color developability, etc. Wax, paraffin wax, fatty acid amide, silicone wax and the like can be appropriately selected and used. These can be used alone or in combination of two or more.
The melting point of the release agent is not particularly limited, and can be appropriately selected and used in consideration of the toner performance. The content of the release agent is not particularly limited, but is preferably 0.3 to 15% by mass in the toner because it affects the toner performance. The lower limit of the content of the release agent is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Further, the upper limit value of the content of the release agent is more preferably 13% by mass or less, and particularly preferably 12% by mass or less.
Since the binder resin composition for toner of the present invention contains the polyester resin (P1) containing a structural unit derived from oxidized polyolefin, it is excellent in compatibility with various release agents. Therefore, even if any of the above-mentioned release agents is blended at the time of toner production, the dispersibility is good and the effect expected from the release agent can be sufficiently imparted.

Additives such as flow modifiers are not particularly limited, but fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive titania and other inorganic fine powders , Resistance adjusting agents such as styrene resin and acrylic resin, lubricants and the like, and these are used as an internal additive or an external additive.
The content of these additives is not particularly limited, but is preferably 0.05 to 10% by mass in the toner. When the content of these additives is 0.05% by mass or more, a toner performance-modifying effect tends to be sufficiently obtained, and when it is 10% by mass or less, the image stability of the toner tends to be good. is there.

The toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.
When used as a magnetic one-component developer, it contains a magnetic substance. Examples of the magnetic substance include ferromagnetic alloys including iron, cobalt, nickel, etc., including ferrite and magnetite, as well as compounds and strong substances. Alloys that do not contain magnetic elements but exhibit ferromagnetism by appropriate heat treatment, such as so-called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, and chromium dioxide Is mentioned.
The content of the magnetic substance is not particularly limited, but is preferably 3 to 70% by mass in the toner because it greatly affects the pulverizability of the toner. When the content of the magnetic material is 3% by mass or more, the charge amount of the toner tends to be a sufficient level, and when it is 70% by mass or less, the toner fixing property and pulverization property tend to be good. The lower limit of the content of the magnetic material is more preferably 3% by mass or more, and particularly preferably 3% by mass or more. Further, the upper limit of the content of the magnetic material is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

  When used as a two-component developer, it is used in combination with a carrier. As the carrier, a known material such as a magnetic substance such as iron powder, magnetite powder, or ferrite powder, a resin coating on the surface thereof, or a magnetic carrier can be used. As coating resins for resin coating carriers, generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, mixtures of these resins, etc. Can be used.

  The method for producing the toner of the present invention is not particularly limited, but after mixing the binder resin composition and the compound described above, the mixture is melt-kneaded with a twin screw extruder or the like, coarsely pulverized, finely pulverized, and classified. According to the method of manufacturing by external addition of inorganic particles (grinding method), the above binder resin and compound are dissolved and dispersed in a solvent, and after granulating in an aqueous medium, the solvent is removed. Examples include a method (chemical method) in which toner particles are obtained by washing and drying, and the inorganic particles are externally added as necessary.

  Although the Example of this invention is shown below, the embodiment of this invention is not limited to this. The evaluation methods for the resin and toner shown in this example are as follows.

(1) Evaluation method of binder resin composition 1) Glass transition temperature (Tg)
Intersection of the base line on the low temperature side of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured with a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation at a heating rate of 5 ° C / min The temperature of was determined.
2) Softening temperature When using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm at a load of 294 N (30 Kgf) and a temperature increase rate of 3 ° C./min, a sample was measured. The temperature at which 1/2 of 1.0 g flowed out was determined.

3) Acid value (AV)
About 0.2 g of the sample was precisely weighed in a branched Erlenmeyer flask (A (g)), 10 ml of benzyl alcohol was added, and the resin was dissolved by heating in a nitrogen atmosphere for 15 minutes with a 230 ° C. heater. After cooling to room temperature, 10 ml of benzyl alcohol, 20 ml of chloroform and a few drops of a phenolphthalein solution were added and titrated with a 0.02N KOH solution (titrate = B (ml), titer of KOH solution = p). . A blank measurement was performed in the same manner (titer amount = C (ml)), and calculation was performed according to the following formula.
Acid value (mgKOH / g) = (BC) × 0.02 × 56.11 × p ÷ A
4) Content (% by mass) of oxidized polyolefin dispersed in the binder resin composition without reacting
Measured under the same conditions as in 1), the endothermic amount of the oxidized polyolefin itself (J / g) and the endothermic amount of the oxidized polyolefin dispersed in the binder resin composition (J / g) It calculated | required from the area from the base line of the endothermic peak in a chart, and calculated | required content of the oxidation polyolefin currently disperse | distributed in the binder resin composition from the following formula | equation.
Content (% by mass) of oxidized polyolefin dispersed in binder resin composition
= {Endothermic amount of oxidized polyolefin dispersed in binder resin composition (J / g)}
/ {Endothermic amount of oxidized polyolefin itself (J / g)} × 100 (mass%)

(2) Toner Evaluation Method 1) Hot Offset Resistance Using a printer having a fixing roller not coated with silicone oil and capable of changing the roller temperature set to a roller speed of 30 mm / s, 0. When a solid image of 4.5 cm × 15 cm is printed at a roller temperature of 5 ° C. at a toner concentration of 5 mg / cm ² , the minimum temperature when the toner moves to the fixing roller due to a hot offset phenomenon at the time of fixing is the temperature at which hot offset occurs. The hot offset resistance was judged using the following criteria.
◎ (Very good): Hot offset occurrence temperature exceeds 200 ° C ○ (Good): Hot offset occurrence temperature exceeds 180 ° C to 200 ° C or less × (Inferior): Hot offset occurrence temperature is 180 ° C or less

2) Cold offset resistance When using the same equipment as the hot offset resistance evaluation, setting the roller speed to 100 mm / s and printing the image in the same way, the maximum when toner moves to the fixing roller due to the cold offset phenomenon during fixing The temperature was defined as the cold offset generation temperature, and the cold offset resistance was judged using the following criteria.
◎ (very good): Cold offset occurrence temperature is less than 135 ° C ○ (Good): Cold offset occurrence temperature is 135 ° C or more and less than 145 ° C × (Inferior): Cold offset occurrence temperature is 145 ° C or more

3) Fixability Using the same apparatus as in the hot offset resistance evaluation, the above test pattern image fixed with a roller speed of 100 mm / s and a fixing roller temperature of 140 ° C. was fixed with a sand eraser of JIS512. The image density before and after the test was measured with a Macbeth image densitometer, and the fixing ratio was calculated by the following formula and evaluated according to the following criteria.
Fixing rate = image density after test / image density before test × 100 (%)
◎ (Very good): Fixing rate of 80% or more ○ (Good): Fixing rate of 75% or more and less than 80% △ (Available): Fixing rate of 70% or more and less than 75% × (Inferior): Less than 70% Fixation rate or cold offset phenomenon occurs at 145 ° C. and cannot be measured.

4) Blocking resistance About 5 g of the toner was weighed and put into a sample bottle, which was left in a dryer kept at 50 ° C. for about 24 hours, and the degree of aggregation of the toner was evaluated as an index of blocking resistance. . The evaluation criteria were as follows.
◎ (Very good): Disperse just by inverting the sample bottle.
○ (Good): Dispersed when the sample bottle is turned upside down and tapped 2-3 times.
X (Inferior): Dispersed when the sample bottle is turned upside down and hit four times or more.

5) Image stability When 10,000 sheets were printed under the same conditions as the non-offset evaluation method, the image stability was evaluated based on the toner charge amount.
A (very good): There is no change in the initial charge amount and the final charge amount.
○ (Good): The amount of charge is slightly changed, but the image density is less affected.
Δ (usable): The charge amount (image density) varies, but can be improved by additives.
X (Inferior): Image density greatly changes.

6) Durability After printing 10,000 sheets in the same manner as the image stability, durability was evaluated based on blade fusion and fogging of the printed surface.
A (very good): Blade fusion and fogging are not recognized.
○ (Good): Blade fusion and fog are only slightly visible.
Δ (Available): Some blade fusion and fogging are observed, but can be improved by additives.
X (Inferior): Blade fusion and fog are greatly observed.

Production Example of Polyester Resin A 1500 ppm of antimony trioxide with respect to the acid component, the alcohol component, and the total acid component having the charging composition shown in Table 1 was put into a reaction vessel equipped with a distillation tower. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. And stirring was stopped when the predetermined torque was shown, the reaction system was returned to normal pressure, and the reaction product was taken out by pressurizing with nitrogen to obtain a polyester resin A. The characteristic values of the obtained polyester resin A are shown in Table 2.

Example 1
1500 ppm of antimony trioxide with respect to the acid component, alcohol component, polyethylene oxide, and all acid components (excluding oxidized polyolefin) having the charged composition shown in Table 1 was charged into a reaction vessel equipped with a distillation column. In addition, as for polyethylene oxide, content of the component derived from polyethylene oxide in a binder resin composition (the total amount of the components which remain as it is without reacting with the component which reacts and is taken in as a structural unit in a polyester resin) is binder resin composition. It charged so that it might become 3 mass% in a thing.
Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. And stirring was stopped when the predetermined torque was shown, the reaction system was returned to normal pressure, the reaction product was taken out by pressurizing with nitrogen, and the binder resin composition 1 was obtained.
The physical property values of the obtained binder resin composition 1 are shown in Table 1.

Next, the binder resin composition 1 obtained above was used to make a toner. To blend the toner, 93 parts by mass of binder resin composition 1, 3 parts by mass of quinacridone pigment (HOSTAPARM PIN E, CI No .: Pigment Red 122 manufactured by Clariant), polyethylene wax (manufactured by Sanyo Chemical Industries, Sunwax 171-P melting point 101 ° C.) 3 parts by mass and negatively chargeable charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) 1 part by mass were mixed for 5 minutes with a Henschel mixer. Next, the obtained mixture was melt-kneaded with a biaxial kneader. The melt kneading was performed by setting the internal temperature to the softening temperature of the resin. After kneading, the toner soul was obtained by cooling, finely pulverized to 10 μm or less with a jet mill fine pulverizer, and fine particles of 3 μm or less were cut with a classifier to adjust the particle size. To 100 parts by mass of the fine powder obtained, 0.25 part by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added, mixed and adhered with a Henschel mixer, and finally a toner was obtained.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1.

Examples 2-7
Binder resin compositions 2 to 7 were obtained in the same manner as in Example 1 except that the acid component, alcohol component, and oxidized polyolefin were changed as shown in Table 1. Table 1 shows the characteristic values of the obtained binder resin composition.
Next, a toner was obtained in the same manner as in Example 1 except that the binder resin composition 1 (93 parts by mass) was changed as shown in Table 1.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1.

Examples 8 and 9
Binder resin compositions 8 and 9 were obtained in the same manner as in Example 1 except that the acid component, alcohol component, and oxidized polyolefin were changed as shown in Tables 1 and 2. Table 1 shows the characteristic values of the obtained binder resin composition.
Subsequently, it replaced with the binder resin composition 1 (93 mass parts), and it was the same method as Example 1 except using the binder resin composition 8 or 9 and the polyester resin A in the ratio of Table 1 and 2. A toner was obtained.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Tables 1 and 2.

Example 10
Instead of the binder resin composition 1, a toner was obtained in the same manner as in Example 1 except that the binder resin composition 2 and the polyester resin A were used in the proportions shown in Table 2.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.

Examples 11-13
In place of the binder resin composition 1, the binder resin composition 6 was used, and the wax used at the time of toner was changed to sun wax 171-P, and as shown in Table 2, polywax 500 (polyethylene wax, manufactured by Toyo Petrolite Co., Ltd.), A toner was obtained in the same manner as in Example 1 except that biscol 660-P (polypropylene wax manufactured by Sanyo Chemical Industries, Ltd.) and carnauba wax were used.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.

Comparative Example 1
A toner was obtained in the same manner as in Example 1 except that the polyester resin A was used in place of the binder resin composition 1.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.

Comparative Example 2
Example 1 except that polyester resin A is used in place of binder resin composition 1 and lycowax PED822 (oxidized polyethylene wax manufactured by Clariant) is used in place of sun wax 171-P as the wax used in the toner formation. A toner was obtained in the same manner as above.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.
Whether or not the oxidized polyethylene wax used at the time of toner formation is a constituent component of the polyester resin was confirmed by the following method.
The toner obtained in Comparative Example 2 was dissolved in THF, shaken, and then centrifuged at 12000 rpm for 30 minutes. Subsequently, the THF soluble component was taken out, concentrated, purified by reprecipitation with chloroform-n-hexane, and vacuum dried at 60 ° C. for 8 hours to separate only the polyester resin component in the toner. The obtained resin content was analyzed by IR, and it was confirmed that no polyethylene skeleton was detected as a constituent component of the polyester resin.

Comparative Example 3
A binder resin composition B was obtained in the same manner as in Example 1 except that the oxidized polyolefin was changed to polyethylene (Licowax PE820) shown in Table 1. Table 2 shows the characteristic values of the obtained binder resin composition B.
Next, a toner was obtained in the same manner as in Example 1 except that binder resin composition B was used in place of binder resin composition 1.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.

From the above examples and comparative examples, the following was found.
(1) Examples 1 to 13 using a binder resin composition containing a polyester resin in which at least a part of the polyester resin is a polyester resin (P1) containing a structural unit derived from oxidized polyolefin have all toner performances. It was excellent.
(2) Examples 1 and 2 using a binder resin composition containing a polyester resin containing a polyester resin (P1) containing a structural unit derived from oxidized polyethylene obtained by oxidizing a branched polyethylene produced by a high pressure polymerization method 5 to 13 were particularly excellent in fixability.

(3) In Comparative Example 1 in which the polyester resin (P1) containing a structural unit derived from oxidized polyolefin is not used, since the dispersibility of the wax is poor, the hot offset resistance and the durability are inferior, the fixability, Image stability remained at a usable level.
(4) Although Comparative Example 2 which uses polyethylene oxide at the time of toner formation but does not have a structural unit of polyester resin, the dispersibility of the wax is insufficient, so that the durability is inferior and the fixability is low. The image stability remained at a usable level.
(5) In Comparative Example 3 using the binder resin composition B to which polyethylene wax that has not been subjected to oxidation treatment was added during polymerization, since the dispersibility of the wax is poor, hot offset resistance and durability are inferior. In addition, the fixing property and the image stability remained at a usable level.

For the examples and comparative examples described in Tables 1 and 2, the materials described below were used.
Diol A: 2.3 mol adduct of bisphenol A propylene oxide Diol B: 2.0 mol adduct of bisphenol A ethylene oxide

Lycowax PED822: Oxidized polyethylene (manufactured by Clariant Co., Ltd.) obtained by oxidizing polyethylene having a branch produced by a high pressure polymerization method
Lycowax PED522: Polyethylene oxide produced by oxidation treatment of polyethylene produced by low-pressure polymerization method (manufactured by Clariant)
Lycowax PED136: Oxidized polyethylene obtained by oxidizing high density polyethylene (manufactured by Clariant)
Lycowax PE820: branched polyethylene produced by high pressure polymerization (Clariant)

Claims (4)

  A binder resin composition for a toner comprising a polyester resin containing a structural unit derived from an oxidized polyolefin and an oxidized polyolefin.   The binder resin composition for toner according to claim 1, wherein the oxidized polyolefin is oxidized polyethylene.   A method for producing a binder resin composition for a toner, wherein an acid component and an alcohol component are polymerized in the presence of an oxidized polyolefin.   A toner containing the binder resin composition for toner according to claim 1.