JP2021006866A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development excellent in low-temperature fixability, hot offset resistance, and storage stability.SOLUTION: A toner for electrostatic charge image development containing a binder resin containing an amorphous polyester resin and a crystalline polyester resin, and wax, wherein the crystalline polyester resin is a polycondensate of an alcohol component including a straight-chain aliphatic diol having 2 to 12 carbon atoms in an amount of 95 mol% or more, and a carboxylic acid component including an acid modified product A of an amorphous α-olefin polymer having 4 to 18 carbon atoms and a straight-chain aliphatic dicarboxylic acid compound having 2 to 14 carbon atoms in an amount of 90 mol% or more in a carboxylic acid component other than the acid modified product A.SELECTED DRAWING: None

Description

The present invention relates to an electrostatic charge image developing toner used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

In recent years, there has been a strong demand for improving low temperature fixability, hot offset resistance, and storage stability of toner from the viewpoint of energy saving and high reliability, as well as promoting miniaturization, high speed, and high image quality of printers.
In order to solve these problems, the use of wax and a crystalline polymer in crystalline polyester or toner has been studied.

Patent Document 1 describes a toner having toner particles containing a binder resin, a colorant, a fatty acid metal salt, and a crystalline resin having a crystalline polyester moiety, wherein the crystalline polyester moiety has 7 carbon atoms at the end. When the above alkyl group has the above alkyl group, the carbon number of the alkyl group is C1, and the carbon number of the fatty acid constituting the fatty acid metal salt is C2, C1 and C2 satisfy the following relational expression (1). Characteristic toners are disclosed.
0.25 ≤ C1 / C2 ≤ 3.90 Equation (1)

Patent Document 2 describes a toner that contains at least a binder resin made of polyester and a wax, which is a compatibilizer that makes the polyester and the wax compatible with each other, and is obtained by reacting the polyester with a maleic anhydride-modified polyolefin. A polyester-based resin composition for a toner, which comprises a compatibilizer, is disclosed.

Patent Document 3 has a constituent part derived from a polyester resin and a constituent portion derived from a modified polypropylene-based polymer A having a carboxylic acid group or an carboxylic acid anhydride group, and the constituent portion derived from the polyester resin and the modified polypropylene. A binder resin composition for toner containing an amorphous polyester resin in which constituent parts derived from the polymer A are covalently linked, and the polymer A has an unsaturated bond. It is a polypropylene-based polymer terminal-modified with a carboxylic acid compound or an anhydride thereof, and the amount of the structural unit derived from the polymer A in the polyester-based resin is the alcohol component and the carboxylic acid forming the constituent portion derived from the polyester resin. A binder resin composition for toner, which is 8 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of acid components, is disclosed.

JP-A-2019-020492 Japanese Unexamined Patent Publication No. 2005-316378 JP-A-2019-008185

It is known that by using a crystalline polyester resin in the toner, the melt viscosity at the time of fixing can be lowered and the low temperature fixability can be improved. On the other hand, the melt viscosity at a high temperature is also lowered, so that the hot offset resistance and the storage stability are improved. Getting worse.
In Patent Document 1, when a crystalline polyester resin is used, the melt viscosity at the time of fixing can be lowered and the low temperature fixability is improved, but the hot offset resistance and the storage stability are deteriorated.
In Patent Document 2, when a crystalline wax compatibilizer such as an α-olefin polymer having 2 or 3 carbon atoms is used, the wax dispersion is improved and the hot offset resistance is improved, but the low temperature fixability is deteriorated. ..
In Patent Document 3, when a crystalline polypropylene polymer is used, the hot offset resistance is improved but the low temperature fixability is deteriorated, as in Patent Document 2.

The present invention relates to an electrostatic charge image developing toner having excellent low temperature fixability, hot offset resistance and storage stability.

The present invention is a static charge image developing toner containing a binder resin containing an amorphous polyester resin and a crystalline polyester resin and a wax, wherein the crystalline polyester resin has 2 or more and 12 or less carbon atoms. An alcohol component containing 95 mol% or more of a chain aliphatic diol, an acid-modified A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms, and a linear aliphatic dicarboxylic acid having 2 or more and 14 or less carbon atoms. The present invention relates to a toner for developing an electrostatic charge image, which is a polycondensate of an acid compound with a carboxylic acid component containing 90 mol% or more of the carboxylic acid component other than the acid modified product A.

The toner for developing an electrostatic charge image of the present invention exerts excellent effects in low temperature fixability, hot offset resistance and storage stability.

The toner for static charge image development of the present invention contains a binder resin and a wax containing an amorphous polyester resin and a crystalline polyester resin, and the crystalline polyester resin has 4 or more and 18 or less carbon atoms which is amorphous. It has one characteristic that it is a polycondensate (hereinafter, also referred to as crystalline polyester resin C) in which the acid-modified product A of the α-olefin polymer of the above is used.
Since the crystalline polyester resin C is easily compatible with the amorphous polyester resin, the dispersibility of the crystalline polyester resin C in the amorphous polyester resin is good. Then, the portion of the crystalline polyester resin C derived from the acid-modified product A is easily compatible with the wax, and as a result, the wax is well dispersed in the amorphous polyester resin. Further, since the dispersibility of the wax is improved, the crystals of the crystalline polyester resin are easily recovered even when stored at a high temperature, so that the storage stability is also good.
Further, the acid-modified product A of the amorphous α-olefin polymer becomes an acid-modified product of the crystalline α-olefin polymer such as a modified polypropylene-based polymer having a carboxylic acid group or an anhydrous carboxylic acid group. In comparison, the dispersibility in the amorphous polyester resin is good, so the low-temperature fixability is also good.
From the above, it is presumed that the low temperature fixability, hot offset resistance, and storage stability of the toner are improved.

The crystallinity of the acid-modified product is represented by the crystallinity index ([softening point / maximum endothermic temperature]), similar to the crystallinity of the resin described later. The amorphous acid-modified product has a crystallinity index of more than 1.4, preferably more than 1.5, more preferably more than 1.6, or less than 0.6, preferably 0.5 or less. In addition, those in which the maximum endothermic temperature is not detected are also judged to be amorphous.

The crystalline polyester resin C contains an alcohol component containing a linear aliphatic diol having 2 to 12 carbon atoms, an acid-modified product A of an amorphous α-olefin polymer having 4 to 18 carbon atoms, and a carbon number of carbon atoms. It is a polycondensate with a carboxylic acid component containing a linear aliphatic dicarboxylic acid of 2 or more and 14 or less.

The carbon number of the linear aliphatic diol contained in the alcohol component is 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and 12 or less from the viewpoint of low temperature fixability. It is preferably 10 or less.

Linear aliphatic diols having 2 or more and 12 or less carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-. Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14- Examples thereof include tetradecanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol or 1,12-dodecanediol are preferable, and 1,6-hexanediol or 1,12-dodecane is preferable. Diols are more preferred, and 1,6-hexanediols are even more preferred. These alcohols may be used alone or in combination of two or more.

The content of the linear aliphatic diol having 2 or more and 12 or less carbon atoms is 95 mol% or more, more preferably 100 mol%, in the alcohol component.

The alcohol component may contain an alcohol other than the linear aliphatic diol having 2 or more and 12 or less carbon atoms. Other alcohols include branched aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; trivalent or higher valents such as glycerin, pentaerythritol and trimethylolpropane. Alcohol and the like can be mentioned.

In the acid-modified product A of the α-olefin polymer having 4 or more and 18 or less carbon atoms contained in the carboxylic acid component, the α-olefin has 4 or more carbon atoms, and 18 or less, preferably 10 or less, more preferably. Is 7 or less, more preferably 5 or less, still more preferably 4.

Examples of α-olefin polymers having 4 or more and 18 or less carbon atoms include polyisobutene-based polymers, poly1-butene-based polymers, poly1-pentene-based polymers, poly1-hexene-based polymers, and poly1-octene-based weights. Examples thereof include coalescence, poly4-methylpentene-based polymer, poly1-dodecene-based polymer, 1-hexadecene-based polymer, propylene-hexene copolymer, etc. Among these, polyisobutene-based polymer is preferable. The α-olefin polymer may be a homopolymer of the α-olefin, or may be two or more copolymers selected from the α-olefin, and the α-olefin and other olefins. It may be a copolymer with. Further, the copolymer may be either a random copolymer or a block copolymer.

Examples of the polyisobutene-based polymer include polyisobutene, a copolymer of isobutene and other olefins, and the like. Other olefins include, for example, ethylene, butene, pentene, hexene, 2-ethylhexene. In the case of a copolymer, the proportion of isobutylene is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and less than 100% by mass.

On the other hand, as the acid-modified product A, from the viewpoint of reactivity with the polyester resin, the α-olefin polymer having 4 or more and 18 or less carbon atoms is composed of maleic acid, fumaric acid, itaconic acid, and anhydrides of these acids. An acid-modified product modified with at least one acid selected from the above group is preferable, and an acid-modified product modified with maleic anhydride is more preferable. Examples of the acid-modified product include a random graft-type acid-modified product in which an acid is randomly grafted onto the α-olefin polymer and modified, and a terminal-modified type in which the terminal of the α-olefin polymer is modified with an acid. In the present invention, a terminal-modified acid-modified product is preferable from the viewpoint of low-temperature fixability and storage stability, and one end of an α-olefin polymer having 4 to 18 carbon atoms is preferable. One-ended modified acid-modified products modified with acid are more preferable.

The random graft type acid-modified product is preferably modified by grafting one or more acids in one molecule of the polymer. Whether it is modified by acid can be defined by general spectral measurements. For example, in the case of a random graft type acid denatured product with maleic anhydride, when modified with maleic anhydride, the double bond of maleic anhydride changes to a single bond, which can be defined by measuring the spectral change.

The random graft-modified acid-modified product can be obtained, for example, by generating a radical in the molecule of the α-olefin polymer and reacting it with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.

The terminal-modified acid-modified product is preferably modified by one (single-ended) or two (both-ended) acids in one molecule of the polymer. Whether it is modified by acid can be defined by general spectral measurements. For example, in the case of a one-terminal acid-modified product with maleic anhydride, when modified with maleic anhydride, the double bond of maleic anhydride changes to a single bond, which can be defined by measuring the spectral change. Further, the connected portion of the α-olefin on the polymer side also undergoes a spectral change before and after the bond, and can be defined by measuring this.

The one-terminal type acid-modified product can be obtained, for example, by subjecting the α-olefin polymer having an unsaturated bond at one end to an acid Ene reaction. The α-olefin polymer having an unsaturated bond at one end can be obtained by a known method, and can be produced, for example, by using a vanadium-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, or the like.

From the above, as the acid-modified product A of the α-olefin polymer, polyisobutene succinic anhydride having one end modified with maleic anhydride is preferable.

The weight average molecular weight of the acid-modified product A is preferably 500 or more, more preferably 700 or more, still more preferably 900 or more, still more preferably 1,100 or more from the viewpoint of storage stability, and from the viewpoint of low temperature fixability. It is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less.

The content of the acid-modified product A is preferably 0.5 parts by mass or more from the viewpoint of low-temperature fixability and hot offset resistance with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A. It is more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, and from the viewpoint of hot offset resistance and storage stability, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass. It is not more than parts by mass, more preferably 15 parts by mass or less.

The linear aliphatic dicarboxylic acid compound contained in the carboxylic acid component has 2 or more carbon atoms, preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and from the viewpoint of low temperature fixability. Therefore, it is 14 or less, preferably 12 or less.

Examples of linear aliphatic dicarboxylic acid compounds having 2 to 14 carbon atoms include fumaric acid, sebacic acid, dodecanedic acid, tetradecanedioic acid, and alkyl esters having 1 to 3 carbon atoms in the alkyl groups of these acids. Can be mentioned. Among these, sebacic acid or dodecanedioic acid is preferable, and sebacic acid is more preferable. As these carboxylic acid compounds, one kind or two or more kinds may be used.

The content of the linear aliphatic dicarboxylic acid compound having 2 or more and 14 or less carbon atoms is 90 mol% or more, preferably 95 mol% or more, and more preferably 100 mol in the carboxylic acid components other than the acid modified product A. %.

The carboxylic acid component may contain an acid modified product A and a carboxylic acid compound other than the linear aliphatic dicarboxylic acid compound having 2 or more and 14 or less carbon atoms. Examples of other carboxylic acid compounds include aromatic dicarboxylic acid compounds such as terephthalic acid and isophthalic acid, and carboxylic acid compounds having a valence of 3 or more.

A monohydric alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component.

The crystalline polyester resin C contains, for example, an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification co-catalyst, a polymerization inhibitor, or the like. It can be produced by polycondensation at a temperature of preferably 130 ° C. or higher, more preferably 170 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.

Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropyrate bistriethanol aminate. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the carboxylic acid component other than the alcohol component and the acid-modified product A. It is 1.5 parts by mass or less, more preferably 1 part by mass or less. Examples of the esterification co-catalyst include gallic acid and the like. The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.01 part by mass or more, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid modified product A. Is 0.5 parts by mass or less, more preferably 0.1 parts by mass or less. Examples of the polymerization inhibitor include t-butylcatechol and the like. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.01 part by mass or more, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid modified product A. It is 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

The crystalline polyester resin C contains an alcohol component containing a linear aliphatic diol having 2 to 12 carbon atoms, an acid modified product A of an α-olefin polymer having 4 to 18 carbon atoms and 2 to 14 carbon atoms. Even if it is a polycondensate with a carboxylic acid component containing a linear aliphatic dicarboxylic acid compound, an alcohol component containing a linear aliphatic diol having 2 or more and 12 or less carbon atoms and an α-olefin having 4 or more and 18 or less carbon atoms A polycondensate obtained by polycondensing the acid modified product A with a polycondensate of a carboxylic acid component other than the acid modified product A of the polymer may be used, but from the viewpoint of storage stability, the latter polycondensate is used. preferable.

When the latter polycondensate is obtained, for example, a carboxylic acid other than the acid-modified product A of an alcohol component containing a linear aliphatic diol having 2 or more and 12 or less carbon atoms and an α-olefin polymer having 4 or more and 18 or less carbon atoms. Produced by reacting a polycondensate with an acid component and an acid modified product A at a temperature of preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and preferably 190 ° C. or lower, more preferably 240 ° C. or lower. can do.

In the present invention, the polyester resin may be a polyester resin modified with a substance other than an acid to the extent that its properties are not substantially impaired. Examples of the polyester resin modified with other than acid include grafts with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636 and the like. Examples thereof include modified and blocked polyester resins, and among the modified polyester resins, urethane-modified polyester resins obtained by urethane-stretching the polyester resin with a polyisocyanate compound are preferable.

The softening point of the crystalline polyester resin C is preferably 60 ° C. or higher, more preferably 65 ° C. or higher from the viewpoint of storage stability, and preferably 100 ° C. or lower, more preferably 100 ° C. or lower from the viewpoint of low temperature fixability. It is 90 ° C. or lower, more preferably 85 ° C. or lower, still more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower.

The crystallinity of a resin is represented by the crystallinity index defined by the ratio of the softening point to the maximum endothermic temperature measured by the differential scanning calorimeter, that is, the value of [softening point / maximum endothermic temperature]. The crystalline resin is an amorphous resin having a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less, more preferably 1.1 or less. Is a resin having a crystallinity index of more than 1.4, preferably more than 1.5, more preferably 1.6 or more, or less than 0.6, preferably 0.5 or less. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, the production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In the crystalline resin, the maximum peak temperature of endothermic is defined as the melting point.

The maximum endothermic temperature (melting point) of the crystalline polyester resin C is preferably 50 ° C. or higher from the viewpoint of storage stability, and preferably 90 ° C. or lower, more preferably 80 ° C. or higher from the viewpoint of low temperature fixability. ° C or lower, more preferably 75 ° C or lower.

From the viewpoint of low-temperature fixability, the acid value of the crystalline polyester resin C is preferably 0.5 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, still more preferably 3 mgKOH / g or more, still more preferably 5 mgKOH / g or more. It is more preferably 7 mgKOH / g or more, and from the viewpoint of storage stability, it is preferably 15 mgKOH / g or less, more preferably 10 mgKOH / g or less, still more preferably 9 mgKOH / g or less.

The content of the crystalline polyester resin C is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass in the binder resin from the viewpoint of low-temperature fixability. % Or more, and from the viewpoint of storage stability, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 12% by mass or less.

As the amorphous polyester resin, an amorphous polyester resin which is a polycondensate of an alcohol component containing an alkylene oxide adduct of bisphenol A and a carboxylic acid component is preferable, and from the viewpoint of improving the dispersibility of wax, bisphenol A It is a polycondensate of an alcohol component containing an alkylene oxide adduct and a carboxylic acid component containing an acid-modified A of an α-olefin polymer having 4 to 18 carbon atoms, which is amorphous (hereinafter, amorphous). It is also preferably polyester resin A). By combining the amorphous polyester resin A and the crystalline polyester resin C using the amorphous acid modified product A, the amorphous polyester resin is compatible and plasticized when the acid modified product A is melted, so that the temperature is low. Fixability is further improved.

As an alkylene oxide adduct of bisphenol A, the formula (I):

(In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, x and y indicate the average number of moles of alkylene oxide added, which are positive numbers, respectively, and x and y. The value of the sum of is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less).
It is an alkylene oxide adduct of bisphenol A represented by. Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a propylene oxide adduct of bisphenol A in which R is a propylene group, an ethylene oxide adduct of bisphenol A in which R is an ethylene group, and the like. One or more of these can be used, and the combined use of the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A is preferable.

The molar ratio of the propylene oxide adduct of bisphenol A to the ethylene oxide adduct of bisphenol A (propylene oxide adduct of bisphenol A / ethylene oxide adduct of bisphenol A) is preferably 55/45 or more, more preferably 65 / It is 35 or more, more preferably 75/25 or more, and preferably 98/2 or less, more preferably 95/5 or less, still more preferably 92/8 or less.

The content of the alkylene oxide adduct of bisphenol A is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 95 mol% or more in the alcohol component. It is 100 mol%.

Examples of alcohol components other than the alkylene oxide adduct of bisphenol A include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6. -Hexandiol, 1,4-butanediol, 1,3-butanediol, aliphatic diols such as neopentyl glycol, and trihydric or higher alcohols such as glycerin can be mentioned. The content of these alcohols is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

Regarding the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms contained in the carboxylic acid component of the amorphous polyester resin A, the acid-modified product A used for the crystalline polyester resin C Is similar to. The acid-modified product A used in the crystalline polyester resin C and the amorphous polyester resin A may be the same or different.

However, the content of the acid-modified product A is preferably 0.5 parts by mass or more from the viewpoint of charge rise and hygroscopicity with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component other than the acid-modified product A. It is more preferably 1 part by mass or more, further preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 4 parts by mass or more, still more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more. From the viewpoint of storage stability, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, further preferably 40 parts by mass or less, further preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably. It is 20 parts by mass or less.

Examples of the carboxylic acid component other than the acid-modified product A of the amorphous polyester resin A include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and trivalent or higher valent carboxylic acid compounds. Can be mentioned. Among these, aromatic dicarboxylic acid compounds are preferable from the viewpoint of durability.

Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms in the alkyl group. Among these, isophthalic acid or terephthalic acid is preferable, and terephthalic acid is more preferable, from the viewpoint of low-temperature fixability.

The content of the aromatic dicarboxylic acid compound is preferably 60 mol% or more, more preferably 65 mol% or more, still more preferably 70 mol% or more in the carboxylic acid components other than the acid modified product A from the viewpoint of durability. From the viewpoint of low temperature fixability, it is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, still more preferably 80 mol% or less.

Examples of the aliphatic dicarboxylic acid compounds include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid, and anhydrides and alkyls of these acids. Examples thereof include alkyl esters having 1 to 3 carbon atoms in the group.

Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, anhydrides of these acids and alkyl groups. Examples thereof include alkyl esters having 1 to 3 carbon atoms, and among these, trimellitic acid-based compounds are preferable.

The content of the trivalent or higher carboxylic acid compound is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 10 mol% or more in the carboxylic acid components other than the acid modified product A from the viewpoint of hot offset resistance. From the viewpoint of low temperature fixability, it is preferably 25 mol% or less, more preferably 20 mol% or less.

A monohydric alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component.

In the amorphous polyester resin A, for example, a raw material monomer containing an alcohol component and a carboxylic acid component is subjected to the same reaction conditions as the crystalline polyester resin C in the presence of an esterification catalyst, an esterification auxiliary catalyst, etc., if necessary. , Obtained by the method of polycondensation.

From the viewpoint of storage stability, the softening point of the amorphous polyester resin A is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and a low temperature. From the viewpoint of fixability, the temperature is preferably 150 ° C. or lower, more preferably 140 ° C. or lower.

The glass transition temperature of the amorphous polyester resin A is preferably 40 ° C. or higher, more preferably 50 ° C. or higher from the viewpoint of storage stability, and preferably 80 ° C. or lower, more preferably from the viewpoint of low temperature fixability. It is preferably 70 ° C. or lower, more preferably 65 ° C. or lower.

The acid value of the amorphous polyester resin A is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more from the viewpoint of low temperature fixability, and preferably 40 mgKOH / g or less from the viewpoint of hygroscopicity. More preferably, it is 35 mgKOH / g or less.

The content of the amorphous polyester resin A in the binder resin is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and preferably 98% by mass or less. It is more preferably 95% by mass or less, still more preferably 93% by mass or less.

The mass ratio of the crystalline polyester resin C to the amorphous polyester resin A (crystalline polyester resin C / amorphous polyester resin A) is preferably 1/99 or more, more preferably 2/98 or more, still more preferably 3 It is / 97 or more, and preferably 20/80 or less, more preferably 10/90 or less, and even more preferably 8/92 or less.

The total content of the crystalline polyester resin A and the amorphous polyester resin C is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more in the binder resin. It is 100% by mass or more, more preferably 100% by mass.

The binder resin may contain a resin other than the crystalline polyester resin and the amorphous polyester resin as long as the effects of the present invention are not impaired, and other resins include vinyl-based resins such as styrene-acrylic resin. Examples thereof include resins, epoxy resins, polycarbonates, polyurethanes, and composite resins containing two or more of these resins.

The content of the binder resin in the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more in the static charge image developing toner. Yes, and preferably less than 100% by mass, more preferably 98% by mass or less, still more preferably 95% by mass or less.

Examples of the wax include aliphatic hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax, or their oxides; carnauba wax, montane. Waxes or ester waxes such as deoxidizing waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, from the viewpoint of durability, at least one selected from the group consisting of Fisher Tropsch wax, polyethylene wax, polypropylene wax, and ester wax is preferable, and Fisher Tropsch wax is more preferable.

The melting point of the wax is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, still more preferably 90 ° C. or higher from the viewpoint of toner transferability, and preferably 130 ° C. or lower from the viewpoint of low temperature fixability. It is more preferably 125 ° C. or lower, still more preferably 120 ° C. or lower.

The wax content is preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the binder resin, from the viewpoint of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin. It is 0.8 parts by mass or more, more preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

In addition to the binder resin and wax, the toner for static charge image development of the present invention includes colorants, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, and oxidation. Additives such as an inhibitor and a cleaning property improver may be contained, and a colorant and a charge control agent are preferably contained.

As the colorant, dyes, pigments, magnetic substances and the like used as colorants for toner can be used. For example, carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment red 122, pigment green B, rodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindrin, disazoero And so on. In the present invention, the toner may be either black toner or color toner.

The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image concentration and low temperature fixability of the toner. It is preferably 40 parts by mass or less, more preferably 10 parts by mass or less.

The charge control agent is not particularly limited, and may contain either a positive charge control agent or a negative charge control agent.

Positive charge control agents include niglosin dyes such as "niglosin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industries, Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, for example. "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant Co., Ltd.), etc .; (Manufactured), etc .; imidazole derivatives such as "PLZ-2001", "PLZ-8001" (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc .; styrene-acrylic resin, for example "FCA-701PT" (Fujikura Kasei Co., Ltd.) (Manufactured) and the like.

As the negative charge control agent, metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" (Above, manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-" 147 ”,“ LR-297 ”(above, manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, for example,“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ Bontron E-304 "(above, manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 "(manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt, for example," COPY CHARGE NX VP434 " (Manufactured by Clariant), nitroimidazole derivatives and the like; organic metal compounds and the like can be mentioned.

The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.2 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of charge stability of the toner. Parts or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

The toner of the present invention may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, etc., but from the viewpoint of productivity and wax dispersibility, the melt-kneading method Grinding toner is preferable. In the case of crushed toner by the melt-kneading method, for example, raw materials such as binder resin, wax, colorant, and charge control agent are uniformly mixed with a mixer such as a Henschel mixer, and then a closed kneader, 1-axis or 2-axis. It can be manufactured by melt-kneading with an extruder, an open roll type kneader, etc., cooling, crushing, and classifying.

It is preferable to use an external additive for the toner of the present invention in order to improve transferability. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles. The above may be used together. Among these, silica is preferable, and from the viewpoint of toner transferability, hydrophobicized silica is more preferable.

Examples of the hydrophobizing agent for hydrophobicizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octylriethoxysilane (OTES), methyltriethoxysilane and the like. Be done.

The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and further, from the viewpoint of toner chargeability, fluidity, and transferability. It is preferably 150 nm or less, more preferably 90 nm or less.

From the viewpoint of the chargeability, fluidity, and transferability of the toner, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass, based on 100 parts by mass of the toner before being treated with the external additive. More than parts, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The volume median particle diameter (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle diameter of the toner particles before the toner is treated with the external additive is defined as the volume median particle diameter of the toner.

The toner of the present invention can be used as a one-component developer toner or as a two-component developer by mixing with a carrier.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical properties of the resin and the like can be measured by the following methods.

[Maximum endothermic temperature of acid-modified products]
Using the differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, and raise the temperature from room temperature (25 ° C) to 10 ° C. The temperature is raised to 200 ° C at / min, and then cooled to -10 ° C at a temperature lowering rate of 5 ° C / min. Next, the sample is heated to 180 ° C. at a heating rate of 10 ° C./min and measured. If the maximum endothermic temperature is not detected, it is amorphous. If it is detected, the softening point is measured by the same method as for resin, and the crystallinity index (softening point / maximum endothermic temperature) is calculated. To judge.

[Weight average molecular weight (Mw) of acid-modified product of α-olefin polymer]
(1) Preparation of sample solution The sample was dissolved in tetrahydrofuran so that the concentration was 0.5 g / 100 mL. Next, this solution is filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular weight distribution measurement Using the following measuring device and analytical column, flow tetrahydrofuran as an eluent at a flow rate of 1 mL per minute to stabilize the column in a constant temperature bath at 40 ° C. Inject 100 μL of the sample solution into it and measure. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, the calibration curve includes several types of monodisperse polystyrene (A-500 (Mw 5.0 × 10 ² ), A-1000 (Mw 1.01 × 10 ³ ), A-2500 (Mw 2.63 × 10) manufactured by Toso Co., Ltd.). ³ ), A-5000 (Mw 5.97 × 10 ³ ), F-1 (Mw 1.02 × 10 ⁴ ), F-2 (Mw 1.81 × 10 ⁴ ), F-4 (Mw 3.97 × 10 ⁴ ), F-10 (Mw 9.64 × 10 ⁴ ), F-20 (Mw 1.90 × 10 ⁵ ), F-40 (Mw 4.27 × 10 ⁵ ), F-80 (Mw 7.06 × 10 ⁵ ), F-128 (Mw 1.09 × 10 ⁶⁾ )) Is used as a standard sample. The molecular weight is shown in parentheses.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[Resin softening point]
Using the flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C / min, a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Push out from the nozzle. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is used as the softening point.

[Maximum peak temperature of endothermic resin]
Using the differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, and cool down from room temperature (25 ° C) to 10 ° C. Cool to 0 ° C at / min and maintain at 0 ° C for 1 minute. Then, the temperature is measured at a heating rate of 10 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the maximum endothermic temperature.

[Resin glass transition temperature]
Using the differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, raise the temperature to 200 ° C, and then use that temperature. Cool to 0 ° C at a temperature lowering rate of 10 ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line indicating the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition temperature.

[Acid value of resin]
Measure based on the method of JIS K 0070: 1992. However, only the measurement solvent is from the mixed solvent of ethanol and ether specified in JIS K 0070, the amorphous resin is the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)), and the crystalline resin is chloroform. : Change to a mixed solvent of dimethylformamide (chloroform: dimethylformamide = 7: 3 (volume ratio)).

[Melting point of wax]
Using the differential scanning calorimeter "DSC Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan and 200 at a heating rate of 10 ° C / min. The temperature is raised to ℃, and then cooled to -10 ℃ at a temperature lowering rate of 5 ℃ / min. Next, the sample is heated to 180 ° C. at a heating rate of 10 ° C./min and measured. The maximum peak temperature of endothermic observed from the melt endothermic curve obtained there is defined as the melting point of the wax.

[Average particle size of external additive]
The average particle size refers to the number average particle size, and the particle size of 500 particles (the average value of the major axis and the minor axis) is measured from a scanning electron microscope (SEM) photograph and used as the number average value thereof.

[Medium particle size of toner]
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter Co., Ltd.)
Aperture diameter: 50 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter Co., Ltd.)
Electrolyte: Isoton II (manufactured by Beckman Coulter Co., Ltd.)
Dispersion: Emulgen 109P (manufactured by Kao Co., Ltd., polyoxyethylene lauryl ether, HLB (griffin): 13.6) was dissolved in an electrolytic solution to adjust the content to 5% by mass. Was added and dispersed with an ultrasonic disperser (machine name: US-1, manufactured by SND Co., Ltd., output: 80 W) for 1 minute, then 25 mL of the electrolytic solution was added, and the mixture was further added to the ultrasonic disperser. Disperse for 1 minute to prepare a sample dispersion.
Measurement conditions: Add the sample dispersion to 100 mL of the electrolytic solution so that the particle size of 30,000 particles can be measured in 20 seconds, measure 30,000 particles, and measure the volume from the particle size distribution. Determine the medium particle size (D ₅₀ ).

Resin production example 1
The alcohol components shown in Table 1 are placed in a dehydration tube equipped with a nitrogen introduction tube, a 10-liter four-necked flask equipped with a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 1. Was added, the temperature was raised to 160 ° C, the esterification catalyst and esterification auxiliary catalyst shown in Table 1 were added, the temperature was raised to 235 ° C, the reaction was carried out at 235 ° C for 10 hours, and then the temperature was adjusted to 235 ° C and 8.0 kPa. After reacting for 1 hour, cooling to 200 ° C., adding trimellitic anhydride shown in Table 1, polycondensation reaction at 200 ° C. for 5 hours, and further reaching the softening point shown in Table 1 at 200 ° C. and 8.0 kPa. The reaction was carried out until an amorphous polyester resin (resin A1) was obtained.

Resin production example 2
The alcohol components shown in Table 1 are placed in a dehydration tube equipped with a nitrogen introduction tube, a 10-liter four-necked flask equipped with a stirrer and a thermocouple, heated to 100 ° C., and then terephthalic acid shown in Table 1. Was added, the temperature was raised to 160 ° C, the esterification catalyst and esterification co-catalyst shown in Table 1 were added, the temperature was raised to 235 ° C, the reaction was carried out at 235 ° C for 10 hours, and then the temperature was adjusted to 235 ° C and 8.0 kPa. It was allowed to react for 1 hour. The mixture was cooled to 160 ° C., the acid-modified product shown in Table 1 was added, the temperature was raised again to 235 ° C., a polycondensation reaction was carried out at 235 ° C. for 5 hours, and the reaction was further carried out at 235 ° C. and 8.0 kPa for 1 hour. Then, the mixture is cooled to 200 ° C., trimellitic anhydride shown in Table 1 is added, and the polycondensation reaction is carried out at 200 ° C. for 5 hours, and further reacted at 200 ° C. and 8.0 kPa until the softening point shown in Table 1 is reached. Amorphous polyester resin (resin A2) was obtained.

Resin production example 3
The alcohol components shown in Table 2 are placed in a dehydration tube equipped with a nitrogen introduction tube, a 10-liter four-necked flask equipped with a stirrer and a thermocouple, heated to 100 ° C., and then sebacic acid shown in Table 2. Was added, the temperature was raised to 140 ° C, the reaction was carried out at 140 ° C for 6 hours, the temperature was raised to 200 ° C over 6 hours, and then the esterification catalyst and esterification co-catalyst shown in Table 2 were added to 200 ° C. , 8.0 kPa for 1 hour. Cool to 160 ° C, add the acid modified product shown in Table 2, raise the temperature to 200 ° C again, carry out a polycondensation reaction at 200 ° C for 5 hours, and further raise to 235 ° C to 235 ° C, 8.0 kPa. The reaction was carried out for 1 hour to obtain crystalline polyester resins (resins C1 to C8).

Resin production example 4
The alcohol components shown in Table 2 are placed in a dehydration tube equipped with a nitrogen introduction tube, a 10-liter four-necked flask equipped with a stirrer and a thermocouple, heated to 100 ° C., and then sebacic acid shown in Table 2. Was added, the temperature was raised to 140 ° C, the reaction was carried out at 140 ° C for 6 hours, the temperature was raised to 200 ° C over 6 hours, and then the esterification catalyst and esterification auxiliary catalyst shown in Table 2 were added to 200 ° C. , 8.0 kPa for 1 hour to obtain a crystalline polyester resin (resin C9).

Resin production example 5
The alcohol components shown in Table 2 are placed in a dehydration tube equipped with a nitrogen introduction tube, a 10-liter four-necked flask equipped with a stirrer and a thermocouple, heated to 100 ° C., and then sebacic acid shown in Table 2. And the acid-modified product was added, the temperature was raised to 140 ° C, the reaction was carried out at 140 ° C for 6 hours, the temperature was raised to 200 ° C for 6 hours, and then the esterification catalyst and esterification auxiliary catalyst shown in Table 2 were added. Then, the reaction was carried out at 200 ° C. and 8.0 kPa for 1 hour to obtain crystalline polyester resins (resins C10 and C11).

Examples 1 to 11 and Comparative Examples 1 to 3
100 parts by mass of binder resin shown in Table 3, 2 parts by mass of wax "SP-105" (manufactured by Hiroyuki Kato, Fischer-Tropsch wax, melting point: 105 ° C), colorant "ECB-301" (manufactured by Dainichi Seika Co., Ltd., After stirring 3.0 parts by mass of phthalocyanine blue (PB15: 3)) and 0.5 parts by mass of the charge control agent "Bontron E-304" (manufactured by Orient Chemical Industry Co., Ltd.) for 1 minute using a Henschel mixer, the conditions shown below It was melt-kneaded with.

[Melting and kneading conditions]
A biaxially rotating twin-screw extruder "PCM-30" (manufactured by Ikegai Co., Ltd., shaft diameter 2.9 cm, shaft cross-sectional area 7.06 cm ² ) was used. The operating conditions are barrel set temperature 120 ° C, shaft rotation speed 200r / min (shaft rotation peripheral speed 0.30m / sec), mixture supply speed 10kg / h (mixture supply amount per unit cross-sectional area of the shaft 1.42kg / h).・ It was cm ² ).

The obtained kneaded product is cooled and roughly crushed by a crusher "Rotoplex" (manufactured by Hosokawa Micron Co., Ltd.), and a coarsely crushed product having a medium volume particle diameter of 2 mm or less is obtained using a sieve having a mesh size of 2 mm. It was. The obtained coarsely pulverized product was finely pulverized using a DS2 type air flow classifier (collision plate type, manufactured by Nippon Pneumatic Co., Ltd.) by adjusting the pulverization pressure so that the volume median particle diameter was 8.0 μm. The obtained finely pulverized material is classified using a DSX2 type airflow classifier (manufactured by Nippon Pneumatic Co., Ltd.) by adjusting the static pressure (internal pressure) so that the volume median particle size is 6.5 μm. , Toner particles were obtained.

100 parts by mass of the obtained toner particles, 0.8 parts by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle size: 16 nm) as an external additive, and Hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size: 40 nm) 1.2 parts by mass, using a Henshell mixer (manufactured by Nippon Coke Industries Co., Ltd.) at 2100 r By mixing at / min (peripheral speed 29 m / sec) for 3 minutes, an external additive treatment was performed to obtain toner.

Test Example 1 [Low temperature fixability]
The printer "OKI MICROLINE 5400" (manufactured by Oki Data Corporation), which was modified to take unfixed images, was filled with toner and a 2 cm square solid image was printed. Using an external fixing device modified from "OKI MICROLINE 3010" (manufactured by Oki Data Corporation), the temperature of the fixing roll is raised by 5 ° C from 100 ° C to 200 ° C at a rotation speed of 150 mm / sec. The unfixed image was fixed at each temperature to obtain a fixed image. After attaching a mending tape (manufactured by Sumitomo 3M Ltd.) to the images obtained at each fixing temperature, the tape was sufficiently attached to the fixing image by placing a weight on a cylinder of 500 g. Then, the mending tape was slowly peeled off from the fixed image. The image density before and after peeling is measured using the image density measuring device "Gretag SPM50" (manufactured by Gretag Macbeth), and the image density ratio before and after rubbing ([image density after rubbing / image density before rubbing] x 100) is the first. The temperature exceeding 90% was set as the minimum fixing temperature, and was used as an index of low temperature fixing property. The results are shown in Table 3.

Test Example 2 [Hot offset resistance]
The fixing image of 100 ° C. to 200 ° C. obtained in the fixing property test of Test Example 1 was visually confirmed, and the maximum temperature of the fixing roll in which no hot offset was observed was defined as the maximum fixing temperature. The results are shown in Table 3.

Test Example 3 [Preservation]
5 g of toner was placed in a 20 mL polypropylene container. The container containing the toner was placed in a constant temperature and humidity chamber at 50 ° C. and stored for 24 hours with the lid of the container open. The degree of cohesion of the toner after being left to stand was measured and used as an index of heat-resistant storage stability. The results are shown in Table 3. The smaller this value is, the better the heat-resistant storage property is.

<Cohesion>
The degree of cohesion is measured using a powder tester (manufactured by Hosokawa Micron Co., Ltd.).
Stack 150 μm, 75 μm, and 45 μm open sieves, place 5 g of toner on top, and vibrate for 60 seconds with a vibration width of 1 mm. After the vibration, the amount of toner remaining on the sieve is measured, and the degree of cohesion is calculated using the following formula.

From the above results, the toners of Examples 1 to 11 contain a binder resin and a wax containing an amorphous polyester resin and a crystalline polyester resin, and the crystalline polyester resin has 4 carbon atoms which are amorphous. Since it is a polycondensate using the acid-modified product A of the α-olefin polymer of 18 or less, it can be seen that all of the low temperature fixability, the hot offset resistance and the storage stability are good.
From the comparison between Example 1 and Comparative Example 1, by including the acid-modified product in the crystalline polyester resin, the dispersibility of the crystalline polyester resin and the wax is improved, and the hot offset resistance and the storage stability are improved. I understand.
By controlling the compatibility between the amorphous polyester resin and the crystalline polyester resin from the comparison of Examples 1 to 2 to 6 in which the chain length of the aliphatic diol of the crystalline polyester resin was changed, the crystalline polyester resin and the wax It can be seen that the dispersibility of the resin can be controlled and the performance can be satisfied at a high level of low temperature fixability, hot offset resistance, and storage stability.
From the comparison of Examples 1 and 6 to 8, by increasing the acid-modified product used for the crystalline polyester resin, the dispersibility of the crystalline polyester resin and the wax is improved, and both low temperature fixability and hot offset resistance are achieved. be able to.
From the comparison between Examples 1 and 9, the increase in the amount of crystalline polyester resin improves the dispersibility of the wax, makes it possible to achieve both low-temperature fixability and hot offset resistance, and has good storage stability. I understand.
Further, in Comparative Examples 2 and 3 in which the crystallinity compatibilizer and the crystalline polyester resin are used in combination, the meltability of the crystalline polyester resin is lowered and the low temperature fixability is deteriorated.

The toner for static charge image development of the present invention is suitably used for developing a latent image formed by an electrostatic charge image development method, an electrostatic recording method, an electrostatic printing method, or the like.

Claims (7)

A binder resin containing an amorphous polyester resin and a crystalline polyester resin, and a toner for static charge image development containing wax, wherein the crystalline polyester resin is a linear aliphatic diol having 2 or more and 12 or less carbon atoms. An alcohol component containing 95 mol% or more of, an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms, and a linear aliphatic dicarboxylic acid compound having 2 or more and 14 or less carbon atoms. A toner for developing an electrostatic charge image, which is a polycondensate with a carboxylic acid component containing 90 mol% or more of the carboxylic acid component other than the acid-modified product A. The toner for static charge image development according to claim 1, wherein the acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms has a weight average molecular weight of 500 or more and 5,000 or less. The acid-modified product A of the amorphous α-olefin polymer having 4 to 18 carbon atoms and the α-olefin polymer having 4 to 18 carbon atoms are maleic acid, fumaric acid, itaconic acid, and these. The static charge image developing toner according to claim 1 or 2, which is an acid-modified product modified with at least one acid selected from the group consisting of acid anhydrides. The acid-modified product A of the amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms is an acid-modified product in which one end of the α-olefin polymer having 4 or more and 18 or less carbon atoms is modified with an acid. , The static charge image developing toner according to any one of claims 1 to 3. The weight of the amorphous polyester resin is the weight of the alcohol component containing the alkylene oxide adduct of bisphenol A and the carboxylic acid component containing the acid-modified product A of the amorphous α-olefin polymer having 4 to 18 carbon atoms. The toner for developing an electrostatic charge image according to any one of claims 1 to 4, which is a condensate. The toner for static charge image development according to any one of claims 1 to 5, wherein the wax is at least one selected from the group consisting of Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and ester wax. The toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein the wax has a melting point of 80 ° C. or higher and 130 ° C. or lower.