JP2021006870A - Binder resin composition for toner - Google Patents

Abstract

To provide a binder resin composition for toner excellent in low-temperature fixability, charge stability, and storage stability, and a toner for electrostatic charge image development containing the binder resin composition.SOLUTION: A binder resin composition for toner containing a crystalline polyester resin C that is a polycondensate C 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 is a binder resin composition for toner used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and a static charge image containing the binder resin composition. Regarding developing toner.

Patent Document 1 describes a resin (A) containing 1 to 50% by weight of a hydrocarbon group having 8 or more carbon atoms in a color toner composed of a toner binder (A), a wax (B), and a colorant (C). A color toner comprising D) and having a haze value of (A) of 70 or less is disclosed.

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.

Japanese Unexamined Patent Publication No. 2000-250264 Japanese Unexamined Patent Publication No. 2005-316378 JP-A-2019-008185

In the field of toner for electrophotographic, there is a need for high-speed printing and high image quality with the development of electrophotographic systems. Among them, the crystalline polyester resin is considered to have excellent low-temperature fixability, and it is known that the toner used in combination with the amorphous polyester resin exhibits excellent toner performance. However, since the crystalline polyester resin does not easily accumulate electric charges, there is a problem in charge stability.
Therefore, as a means for improving the charge stability of the crystalline polyester resin, for example, when terephthalic acid having an aromatic ring in which charge tends to accumulate is incorporated in the monomer structure, a certain charge stability can be obtained, but the crystalline polyester can be obtained. The crystal structure of the resin is broken and the crystallinity is lowered, so that the amorphous polyester resin is plasticized and the storage stability is lowered.
Further, as a means other than the introduction of terephthalic acid having an aromatic ring, as a crystalline monomer having an aromatic ring, a crystal having an alkyl group such as an acid-modified product of a polymer of an α-olefin having 2 or 3 carbon atoms. When the crystalline macromonomer was incorporated into the crystalline polyester resin, sufficient charge stability was not confirmed, probably because the crystalline macromonomer had poor dispersibility in the crystalline polyester resin (for example, Patent Document 2, Patent Document 2, 3). Further, when an amorphous monomer having an alkyl group such as dodecenyl anhydride is incorporated into the crystalline polyester resin, the crystal structure of the crystalline polyester resin is the same as when the terephthalic acid having an aromatic ring is incorporated. The amorphous polyester resin was plasticized and the storage stability was lowered due to the collapse of the resin and the decrease in crystallinity. (See, for example, Patent Document 1).

The present invention relates to a binder resin composition for toner, which is excellent in low temperature fixability, charge stability, and storage stability, and a toner for static charge image development containing the binder resin composition.

The present invention
[1] An alcohol component containing 95 mol% or more of a linear aliphatic diol having 2 or more and 12 or less carbon atoms, an acid-modified product A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms, and carbon. Contains a crystalline polyester resin C which is a polycondensate C of a linear aliphatic dicarboxylic acid compound having a number of 2 or more and 14 or less and a carboxylic acid component containing 90 mol% or more of the carboxylic acid components other than the acid modified product A. The present invention relates to a binder resin composition for toner, and [2] a toner for static charge image development, which contains the binder resin composition for toner according to the above [1].

The toner for static charge image development containing the binder resin composition of the present invention exerts excellent effects in low temperature fixability, charge stability, and storage stability.

The binder resin composition for toner of the present invention has one feature in that it contains a crystalline polyester resin C in which an acid-modified product A of an α-olefin polymer having 4 to 18 carbon atoms is used. The acid-modified product A is dispersed in the crystalline polyester resin to improve charge stability, and the hydrophobic polyolefin portion in the acid-modified product A is a crystalline polyester resin into which the acid-modified product A has been introduced. Probably because it is easy to crystallize inside, it does not lower the crystallinity of the crystalline polyester resin and does not lower the storage stability.

Further, the acid-modified product A is amorphous. By using the amorphous acid-modified product A, the crystalline polyester is compared with the acid-modified product of a crystalline α-olefin polymer such as a modified polypropylene-based polymer having a carboxylic acid group or an anhydrous carboxylic acid group. It has excellent charge stability, probably because it has good dispersibility in the resin.
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 C 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, further preferably 6 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 the α-olefin polymer having 4 to 18 carbon atoms include a polyisobutene polymer, a poly1-butene polymer, a poly1-pentene polymer, a poly1-hexene polymer, and a poly1-octene polymer. Examples thereof include coalescing, poly4-methylpentene-based polymer, poly1-dodecene-based polymer, poly1-hexadecene-based polymer, propylene-hexene copolymer and the like, and 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 1.5 parts by mass or more, more preferably 3 parts by mass, 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, from the viewpoint of charge stability. More than parts, more preferably 4.5 parts by mass or more, and from the viewpoint of storage stability, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, still more preferably 10 parts by mass. It is as follows.

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 polyvalent 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.

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 90 ° C. or lower, more preferably 90 ° C. or lower from the viewpoint of low temperature fixability. It is 85 ° C. or lower, 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 80 ° C. or lower, more preferably 75 ° C. from the viewpoint of low temperature fixability. It is below ° C.

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 12 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, and further, from the viewpoint of low-temperature fixability in the binder resin composition for toner. It is preferably 7% by mass 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.

From the viewpoint of hot offset resistance, the binder resin composition for toner of the present invention is a non-polycondensation product of an alcohol containing a divalent or higher alcohol and a carboxylic acid component containing a divalent or higher carboxylic acid compound. It preferably contains a crystalline polyester resin AH.

Examples of the alcohol component of the amorphous polyester resin A include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols or linear or branched aliphatic diols are preferable, and aromatic diols are more preferable.

As the aromatic diol, an alkylene oxide adduct of bisphenol A is preferable, and more preferably, 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 2/98 or more, more preferably 5 /. It is 95 or more, more preferably 8/92 or more, and preferably 60/40 or less, more preferably 40/60 or less, still more preferably 30/70 or less, still more preferably 20/80 or less.

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

As the linear or branched aliphatic diol, an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferable. The aliphatic diol having a hydroxyl group bonded to a secondary carbon atom preferably has 3 or 4 carbon atoms. Examples of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol.

Other linear or branched aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nandiol, Examples thereof include 1,10-decanediol and 1,12-dodecanediol.

As the alicyclic diol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and alkylene oxide having 2 or more and 4 or less carbon atoms of hydrogenated bisphenol A (average number of added moles 2 or more and 12 or less) Additives and the like can be mentioned.

Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.

The content of the divalent alcohol in the alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 100 mol%.

Examples of the carboxylic acid component of the amorphous polyester resin A include aromatic dicarboxylic acid compounds, linear or branched 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.

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.

The content of the aromatic dicarboxylic acid compound is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 80 mol% or more, still more preferably 85 mol% or more, and more preferably 85 mol% or more in the carboxylic acid component. , 100 mol% or less, preferably 98 mol% or less, more preferably 95 mol% or less.

The linear or branched aliphatic dicarboxylic acid compound has preferably 2 or more, more preferably 4 or more, still more preferably 8 or more, still more preferably 10 or more, and preferably 22 or less, more preferably. Is 16 or less.

Examples of linear or branched aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, and dodecanedioic acid. Examples thereof include tetradecanedioic acid, anhydrides of these acids, and alkyl esters having 1 to 3 carbon atoms in the alkyl group.

The content of the divalent carboxylic acid compound is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, and preferably 95 mol% or less in the carboxylic acid component. Is.

The trivalent or higher carboxylic acid compound is preferably a trivalent carboxylic acid compound, more preferably trimellitic acid or an anhydride thereof.

The content of the trivalent or higher carboxylic acid compound is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, still more preferably 7 mol% or more in the carboxylic acid component. , And preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 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.

The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxy group of the alcohol component (COOH group / OH group) is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less. is there.

In the amorphous polyester resin AH, 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.

The softening point of the amorphous polyester resin AH is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 120 ° C. or higher, and preferably 170 ° C. or lower, more preferably 150 ° C. or lower.

The glass transition temperature of the amorphous polyester resin AH is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower. ..

The acid value of the amorphous polyester resin AH is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 25 mgKOH / g or less.

When the amorphous polyester resin AH is contained, the content thereof is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more in the binder resin composition for toner. Then, it is preferably 98% by mass or less, more preferably 95% by mass or less, further preferably 93% by mass or less, still more preferably 90% by mass or less, still more preferably 85% by mass or less, still more preferably 80% by mass or less. ..

The binder resin composition for toner of the present invention may further contain an amorphous polyester resin AL having a softening point lower than that of the amorphous polyester resin AH.

The amorphous polyester resin AL is a polycondensate of an alcohol containing a divalent or higher alcohol and a carboxylic acid component containing a divalent or higher carboxylic acid compound. Specific examples of the alcohol component and the carboxylic acid are amorphous. Quality Polyester resin AH is the same.

However, 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 10/90 or more, more preferably. It is 20/80 or more, more preferably 30/70 or more, still more preferably 40/60 or more, still more preferably 60/40 or more, and preferably 90/10 or less, more preferably 80/20 or less.

The content of the carboxylic acid compound having a valence of 3 or more is preferably 8 mol% or less, more preferably 5 mol% or less, and further preferably 0 mol% in the carboxylic acid component of the amorphous polyester resin AL. ..

The difference in softening points between the amorphous polyester resin AH and the amorphous polyester resin AL is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 15 ° C. or higher, still more preferably 20 ° C. or higher, and It is preferably 55 ° C. or lower, more preferably 45 ° C. or lower.

The softening point of the amorphous polyester resin AL is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, and preferably 125 ° C. or lower, more preferably 120 ° C. or lower, further preferably. Is 115 ° C. or lower, more preferably 110 ° C. or lower.

The glass transition temperature of the amorphous polyester resin AL is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 55 ° C. or higher, and preferably 80 ° C. or lower, more preferably 75 ° C. or lower, further. It is preferably 70 ° C. or lower.

The acid value of the amorphous polyester resin AL is preferably 0.2 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, and preferably 10 mgKOH / g or less, more preferably 8 mgKOH / g or less.

In the amorphous polyester resin AL, 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.

When the amorphous polyester resin AL is contained, the content thereof is preferably 10% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less in the binder resin composition for toner. , More preferably 70% by mass or less, further preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 30% by mass or less.

When the amorphous polyester resin AL is contained, the mass ratio of the amorphous polyester resin AH to the amorphous polyester resin AL (amorphous polyester resin AH / amorphous polyester resin AL) is preferably 60/40 or more. , More preferably 70/30 or more, still more preferably 80/20 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 85/15 or less.

The mass ratio of the crystalline polyester resin C to the amorphous polyester resin (crystalline polyester resin C / amorphous polyester resin) is preferably 2/98 or more, more preferably 4/96 or more, still more preferably 6/94. The above, and preferably 20/80 or less, more preferably 16/84 or less, still more preferably 12/88 or less.

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

The binder resin composition of the present invention may contain a resin other than the crystalline polyester resin C, the amorphous polyester resin AH, and AL as long as the effects of the present invention are not impaired, and other resins may be used. , Vinyl-based resins such as styrene-acrylic resin, epoxy resins, polycarbonates, polyurethanes, composite resins containing two or more of these resins, and the like.

The content of the binder resin composition of 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 in the static charge image developing toner. And preferably less than 100% by mass, more preferably 98% by mass or less, still more preferably 95% by mass or less, still more preferably 92% by mass or less.

In addition to the binder resin (the binder resin composition of the present invention), the toner for developing an electrostatic charge image of the present invention includes a colorant, a mold release agent, a charge control agent, a magnetic powder, a fluidity improver, and a conductivity adjustment. Additives such as agents, reinforcing fillers such as fibrous substances, antioxidants, and cleaning improvers may be contained, and it is preferable that a colorant, a mold release agent, and a charge control agent are 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.

As the release agent (wax), aliphatic hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystallin wax, paraffin wax, Fishertropch wax, and sazole wax, or oxides thereof; Ester waxes such as carnauba wax, montan wax or their deoxidizing waxes and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., which may be used alone or in combination of two or more. Can be used.

The melting point of the release agent 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 higher from the viewpoint of low temperature fixability. Below, it is more preferably 125 ° C. or lower, still more preferably 120 ° C. or lower.

The content of the release agent is preferably 0.5 parts by mass or more with respect to 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 preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, further preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less. More preferably, it is 7 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 dispersibility of the colorant, the toner is melt-kneaded. Grinded toner by the method is preferable. In the case of crushed toner by the melt-kneading method, for example, raw materials such as a binder resin, a colorant, a mold release agent, and a charge control agent are uniformly mixed with a mixer such as a Henshell mixer, and then a closed kneader, 1 shaft or 2 It can be manufactured by melt-kneading with a shaft 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 mold release agent]
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 taken as the melting point of the release agent.

[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 sebacic acid shown in Table 1. After reacting at 140 ° C for 6 hours, the temperature was raised to 200 ° C for 6 hours, the esterification catalyst and esterification co-catalyst shown in Table 1 were added, and the temperature was 200 ° C for 1 hour at 8.0 kPa. It was reacted. After cooling to 160 ° C., the acid-modified product shown in Table 1 is added, and the polycondensation reaction is carried out again at 200 ° C. for 5 hours, and further reacted at 200 ° C. and 8.0 kPa for 1 hour to obtain a crystalline polyester resin (resin C1). ~ C4) 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 sebacic acid shown in Table 1. After reacting at 140 ° C for 6 hours, the temperature was raised to 200 ° C over 6 hours, the esterification catalyst and esterification co-catalyst shown in Table 1 were added, and the temperature was 200 ° C for 1 hour at 8.0 kPa. The reaction was carried out to obtain a crystalline polyester resin (resin C5).

Resin production example 3
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 the cebasic acid shown in Table 1 is used. And terephthalic acid were added and reacted at 140 ° C for 6 hours, then the temperature was raised to 200 ° C over 6 hours, and then the esterification catalyst and esterification co-catalyst shown in Table 1 were added to 200 ° C and 8.0 kPa. The reaction was carried out for 1 hour to obtain a crystalline polyester resin (resin C6).

Resin production example 4
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 sebacic acid shown in Table 1. And acid-modified products were added and reacted at 140 ° C for 6 hours, then the temperature was raised to 200 ° C for 6 hours, and then the esterification catalyst and esterification co-catalyst shown in Table 1 were added, and the temperature was 200 ° C. The reaction was carried out in 1 hour to obtain a crystalline polyester resin (resin C7).

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 terephthalic acid shown in Table 2. Was added, the temperature was raised to 160 ° C., the esterification catalyst and the esterification co-catalyst shown in Table 2 were added, and the mixture was reacted at 235 ° C. for 10 hours and then reacted at 235 ° C. and 8.0 kPa for 1 hour. After cooling to 200 ° C., trimellitic anhydride shown in Table 2 is added, and the polycondensation reaction is carried out at 200 ° C. for 1 hour, and further reacted at 200 ° C. and 8.0 kPa until the softening point shown in Table 2 is reached. Amorphous polyester resin (resin AH) was obtained.

Resin production example 6
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 terephthalic acid shown in Table 2. Was added, the temperature was raised to 160 ° C, the esterification catalyst and esterification co-catalyst shown in Table 2 were added, and the mixture was reacted at 235 ° C for 10 hours and then reacted at 235 ° C and 8.0 kPa for 1 hour. An amorphous polyester resin (resin AL) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 3
Table 3 shows 100 parts by mass of binder resin, 6 parts by mass of colorant "Fastgen Super Magenta R" (CI Pigment Red 122, manufactured by Dainippon Ink and Chemicals Co., Ltd.), charge control agent "LR-147" (Japan) 1 part by mass of Carlit) and 4 parts by mass of mold release agent "SP-105" (manufactured by Hiroyuki Kato, Fisher Tropschwax, melting point: 105 ° C) are thoroughly stirred with a Henschel mixer, and then the total length of the kneaded part is 1560 mm. , A screw diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the set heating temperature in the roll was 100 ° C., the temperature of the kneaded product was 160 ° C., the supply speed of the kneaded product was 10 kg / h, and the average residence time was about 18 seconds. After cooling, toner particles having a volume medium particle size (D ₅₀ ) of 6.5 μm were obtained by a jet mill.

To 100 parts by mass of the obtained toner particles, 2 parts by mass of "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle size: 16 nm) was added. , The mixture was mixed with a Henschel mixer at 3600 r / min for 5 minutes to treat with an external additive to obtain toner.

Test Example 1 [Low temperature fixability]
Toner was mounted on the color printer "C612dnw" (trade name, manufactured by Oki Data Corporation), and an image was output (printing area: 6 cm x 6 cm, 0.5 mg / cm ² ) without fixing.
The unfixed image was fixed by using the fixing machine of the printer offline and raising the temperature from 100 ° C. to 5 ° C. at 100 mm / sec. J paper (manufactured by Fuji Xerox, basis weight: 82 g / m ² , paper thickness: 97 μm) was used as the fixing paper.
"UNICEF cellophane" (Mitsubishi Pencil, width: 18 mm, JISZ-1522) was attached to the fixed image, passed through a fixing roller set at 30 ° C, and then the tape was peeled off. The optical reflection density before and after the tape was applied was measured using a reflection densitometer "RD-915" (manufactured by Macbeth), and the ratio of the two (after peeling / before applying) first exceeded 90%. The temperature of the roller was set as the minimum fixing temperature, and the low temperature fixing property was evaluated. The results are shown in Table 3.

Test Example 2 [Charging stability]
After leaving the toner in an environment with a temperature of 25 ° C and a relative humidity of 50% for 72 hours, for each toner, 0.6 g of toner and 19.4 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 90 μm) Toner in a 50 mL volume polyethylene container, mix at 250 r / min using a ball mill, and measure the amount of toner charge after mixing for 60 seconds and 3600 seconds by the following method, Q / M meter (manufactured by EPPING). Was measured using.
After the specified mixing time, the specified amount of toner and carrier mixture is put into the cell attached to the Q / M meter, and only the toner is sucked for 90 seconds through a sieve with a mesh opening of 32 μm (stainless steel, twill weave, wire diameter: 0.0035 mm). did. The voltage change on the carrier generated at that time was monitored, and the value of [total electricity amount (μC) after 90 seconds / suctioned toner amount (g)] was defined as the charge amount (μC / g).
The ratio of the charge amount after the mixing time of 60 seconds to the charge amount after the mixing time of 3600 seconds (the charge amount after the mixing time of 3600 seconds / the charge amount after the mixing time of 60 seconds) was calculated. The results are shown in Table 3. The closer the ratio of the charge amount is to 1, the better the charge stability is, and the less likely it is that printing defects due to development defects will occur.

Test Example 3 [Preservation]
Put 5 g of toner in a cylindrical container, leave it in a high temperature environment with a temperature of 50 ° C and a relative humidity of 50% for 72 hours, sieve it through a 200 mesh (opening: 75 μm), and weigh the percentage (mass%) of the passed toner. did. The heavier the mass of the passed toner, the better the storage stability, and the less likely it is that printing defects will occur due to the aggregation of the toner. The results are shown in Table 3.

From the above results, it can be seen that the toners of Examples 1 to 6 are excellent in both storage stability and charge stability while maintaining good low-temperature fixability. Among them, the toner of Example 2 in which the acid-modified product A was used in the crystalline polyester resin by 4.7 parts by mass 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 was sufficiently charged and stable. Since it maintains the amount of acid-modified material that can be obtained and the crystallinity that does not affect the storage stability of the crystalline polyester resin, it is particularly excellent in all aspects of low-temperature fixability, charge stability, and storage stability. I understand.
On the other hand, the toner of Comparative Example 1 containing a polyester resin that does not use an acid-modified product is excellent in low-temperature fixability because the charge easily leaks, but the charge stability is deteriorated. Further, although the toner of Comparative Example 2 in which terephthalic acid is introduced into the crystalline polyester resin has improved chargeability, the storage stability is deteriorated due to a decrease in the crystallinity of the resin. The toner of Comparative Example 3 containing a crystalline polyester resin using a crystalline acid-modified product has a remarkable decrease in charge stability because the dispersibility of the acid-modified product is insufficient.

The binder resin composition for toner of the present invention is suitably used for a toner for static charge image development used for developing a latent image formed by an electrostatic charge image developing method, an electrostatic recording method, an electrostatic printing method, or the like. It is something that can be done.

Claims (5)

An alcohol component containing 95 mol% or more of a linear aliphatic diol having 2 or more and 12 or less carbon atoms, an acid-modified A of an amorphous α-olefin polymer having 4 or more and 18 or less carbon atoms, and 2 or more carbon atoms. A toner containing a crystalline polyester resin C which is a polycondensate C of 14 or less linear aliphatic dicarboxylic acid compounds with a carboxylic acid component containing 90 mol% or more of the carboxylic acid components other than the acid modified product A. Bending resin composition for use. The binder resin composition for toner 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 or more and 18 or less carbon atoms and the α-olefin polymer having 4 or more and 18 or less carbon atoms are maleic acid, fumaric acid, itaconic acid, and these. The binder resin composition for 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 to 18 carbon atoms is an acid-modified product in which one end of the α-olefin polymer having 4 to 18 carbon atoms is modified with an acid. , The binder resin composition for toner according to any one of claims 1 to 3. A toner for developing an electrostatic charge image, which contains the binder resin composition for toner according to any one of claims 1 to 4.