JP2020079346A - Crystalline polyester-based resin - Google Patents

Abstract

To provide a crystalline polyester-based resin that is excellent in recovery of crystallinity during production of a toner and can produce a toner excellent in low-temperature fixability and storage stability, to provide a resin composition for a toner and to provide a toner for electrostatic charge image development and the like.SOLUTION: [1] The crystalline polyester-based resin has a constituent portion derived from a polyester resin having crystallinity and a constituent portion derived from a modified polyolefin-based polymer A having a reactive functional group in which the constituent portion derived from a polyester resin and the constituent portion derived from the modified polyolefin-based polymer A has coupled through a covalent bond and the modified polyolefin-based polymer A has a number average molecular weight of 700 to 8,000; [2] the resin composition for a toner contains the crystalline polyester-based resin as described in [1] and an amorphous polyester-based resin; and [3] the toner for electrostatic charge image development contains the resin composition as described in [2].SELECTED DRAWING: None

Description

  The present invention relates to a crystalline polyester resin used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a resin composition for toner, a toner for developing an electrostatic image, and the like. ..

In the field of electrophotography, with the development of electrophotographic systems, it has been required to develop a toner for developing an electrostatic image corresponding to high image quality and high speed printing.
In Patent Document 1, condition (i): the number of functional groups (f) capable of reacting with an acid or an alcohol is 1.0 (mmol/g) or more, and (ii): a long chain having a branched carbon number of 30 or more A toner binder containing a polyester resin containing a compound (X) as a constituent unit, which contains an alkyl group (r) and (iii) has an endothermic amount when melted of 100 (J/g) or less. Resin compositions are described. It is described that the resin composition can provide a toner having good fixing performance, non-offset property, image stability, and durability.
Patent Document 2 discloses a toner having toner particles containing a crystalline polyester resin A, an amorphous polyester resin B, and a colorant, wherein (1) the crystalline polyester resin A has a terminal of a polyester molecular chain. Has a crystal nucleating agent site, and the crystalline polyester resin A has an SP value (Sa) ((cal/cm3)1/2) of 9.00 or more and 11.50 or less, and (2) the amorphous The polyester resin B is a group consisting of the following (a) to (c) ((a) an aliphatic hydrocarbon group having 8 or more and 50 or less carbon atoms, and (b) an aliphatic alcohol having 8 or more and 50 or less carbon atoms bonded by condensation. And at least one functional group selected from the group consisting of (c) a functional group formed by condensation of (c) an aliphatic carboxylic acid having 9 or more and 51 or less carbon atoms).
Patent Document 3 discloses a toner having toner particles containing a polyester resin A, a polyester resin B, a colorant, and a resin composition C, wherein (1) the polyester resin A is a polyester having a site capable of having a crystal structure. Part and a crystal nucleating agent part, and the crystal nucleating agent part is bonded to the end of the polyester part, and (2) the polyester resin B is a resin having no part capable of having a crystal structure. (3) The resin composition C is a resin composition in which a vinyl resin component and a polyolefin resin component are combined, and the SP value of the polyester part in the polyester resin A is Sa((cal/cm ³ ) ^{1 /2} ), the SP value of the polyester resin B is Sb ((cal/cm ³ ) ^1/2 ), and the SP value of the crystal nucleating agent part in the polyester resin A is Sc ((cal/cm ³ ) ^1/2 ). , When the SP value of the polyolefin resin component is Sd ((cal/cm ³ ) ^1/2 ) and the SP value of the vinyl resin component is Se ((cal/cm ³ ) ^1/2 ), the Sa, The Sb, the Sc, the Sd, and the Se have the following relationships (9.0≦Sa≦12.5, 0≦|Sc−Sd|≦1.8, −2.0≦Sb−Sa≦0. A toner characterized by satisfying 8) is described. According to the toner, the toner has a good fixing property even in a high-speed fixing process having a double-sided printing mechanism, maintains a stable toner image even after a conveying process after fixing, and does not cause winding around a fixing roller even on thin paper. Is listed.

JP, 2009-014820, A Japanese Unexamined Patent Application Publication No. 2005-04851 JP, 2014-026273, A

Conventionally, a crystalline resin has been used for the purpose of improving the low-temperature fixability of the toner. When a crystalline resin is used, there is a problem in that the crystallized state of the resin is impaired in the toner manufacturing process, and the original performance as a crystalline resin cannot be obtained.
Furthermore, when a crystalline resin is added, low-temperature fixability is improved, but when the toner is stored under high temperature and high humidity conditions, there is a problem that the toner aggregates.
For example, Patent Document 1 only describes a resin obtained by compounding an addition polymer with an amorphous polyester resin, and mentions a relationship with the above problem when a crystalline resin is added. I didn't.
The toners of Patent Documents 2 and 3 have a problem from the viewpoint of storage stability because some toner particles aggregate after storage under conditions of relatively high temperature and high humidity.
One embodiment of the present invention is a crystalline polyester resin, a resin composition for a toner, and an electrostatic charge image development, which are capable of obtaining a toner having excellent crystal recovery properties during toner production, and excellent low-temperature fixability and storage stability. For toner etc.

The present inventors have found that when the crystalline polyester-based resin has a constituent site derived from the modified polyolefin-based polymer A having a reactive functional group, the resin has excellent crystal recoverability during toner production. ..
One embodiment of the present invention relates to the following [1] to [3].
[1] Having a constituent site derived from a polyester resin having crystallinity and a constituent site derived from a modified polyolefin-based polymer A having a reactive functional group, and the constituent site derived from the polyester resin and the modified polyolefin-based polymer A constituent site derived from A is linked via a covalent bond,
The crystalline polyester resin, wherein the modified polyolefin polymer A has a number average molecular weight of 700 or more and 8,000 or less.
[2] A resin composition for a toner, which contains the crystalline polyester resin according to the above [1] and an amorphous polyester resin.
[3] A toner for developing an electrostatic charge image, containing the resin composition according to the above [2].

  According to one embodiment of the present invention, a crystalline polyester-based resin, a toner resin composition, and an electrostatic charge, which are excellent in crystal recovery during toner production, and which can provide a toner having excellent low-temperature fixability and storage stability, are obtained. An image developing toner and the like can be provided.

[Crystalline Polyester Resin (Resin A)]
The crystalline polyester resin (hereinafter, also simply referred to as “resin A”) according to one embodiment of the present invention is a modified polyolefin polymer having a crystalline polyester resin-derived constituent site and a reactive functional group. It has a constituent site derived from A (hereinafter, also simply referred to as “polymer A”), and the constituent site derived from the polyester resin and the constituent site derived from the modified polyolefin-based polymer A are linked via a covalent bond.
The modified polyolefin polymer A has a number average molecular weight of 700 or more and 8,000 or less.
With the above configuration, a crystalline polyester resin, a toner resin composition, and an electrostatic charge image developing toner that are excellent in crystal recovery during toner production, and that are excellent in low-temperature fixability and storage stability are obtained. can get. The reason is not clear, but it can be considered as follows.

  The resin A has a constituent site derived from a crystalline polyester resin, and further has a constituent site derived from a modified polyolefin-based polymer A having a reactive functional group. Then, the constituent part derived from these polyester resins and the constituent part derived from the modified polyolefin-based polymer A are linked via a covalent bond. It is considered that the use of such a resin in the production of the toner promotes the crystal recovery by using the constituent site derived from the modified polyolefin-based polymer A as the crystal nucleus. As a result, it is considered that a toner excellent in low-temperature fixability is obtained, and since fine domains of the resin A are formed in the toner, a toner excellent in storage stability can be obtained.

Definitions of various terms in the present specification are shown below.
Whether the constituent portion derived from the resin and the polyester resin is crystalline or amorphous is judged by the crystallinity index. The crystallinity index, in the case of the resin A having a crystalline polyester resin-derived constituent site and a polymer A-derived constituent site, is derived from the softening point of the resin and the polyester resin-derived resin in the measuring method described in Examples described later. It is defined as the ratio of the endothermic peak temperature of the constituent parts (softening point (°C)/endothermic peak temperature (°C)). In the case of resins other than resin A, the crystallinity index is the ratio of the softening point of the resin to the peak temperature of the endotherm of the resin (softening point (° C.)/peak temperature of the endotherm (in the measuring method described in Examples below) C))). The crystalline resin is a resin having a crystallinity index of 0.65 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. The amorphous resin is a resin having a crystallinity index of 1.4 or more or less than 0.65. The crystallinity index can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate. The peak derived from the constituent site derived from the polyester resin can be assigned by a conventional method, but usually, it appears at a temperature lower than the endothermic peak of the constituent site derived from the polymer A. When it is unknown which of the peaks should be attributed, the polyester resin alone and the polymer A alone were measured under the above conditions using a differential scanning calorimeter, and an endothermic peak at a temperature closer to each endothermic peak was obtained. It belongs to the endothermic peak of each constituent site.
The “carboxylic acid compound” includes not only the carboxylic acid but also an anhydride that decomposes to form an acid during the reaction, and an alkyl ester of a carboxylic acid (for example, an alkyl group having 1 to 3 carbon atoms). It is a concept.
When the carboxylic acid compound is an alkyl ester of carboxylic acid, the carbon number of the carboxylic acid compound does not include the carbon number of the alkyl group which is the alcohol residue of the ester.
The “resin component” means a resin component contained in a toner including resin A and resin B.

The resin A has a crystalline polyester resin-derived constituent site and a modified polyolefin-based polymer A-containing constituent site having a reactive functional group, and the polyester resin-derived constituent site and the modified polyolefin-based polymer The constituent site derived from the combination A is linked via a covalent bond.
The resin A may be a polyester resin that has been modified to such an extent that its properties are not substantially impaired. Examples of the modified polyester-based resin include a urethane-modified polyester-based resin in which a constituent part derived from a polyester resin is modified with a urethane bond, and an epoxy-modified polyester-based resin in which a constituent part derived from a polyester resin is modified with an epoxy bond. Be done.
Linking via a covalent bond means that the components are linked via a covalent bond.
Examples of the component parts linked via a covalent bond include an ester bond, an ether bond, an amide bond, a urethane bond, and a bond having these bonds and a linking group.
Examples of the linking group include a divalent or higher hydrocarbon group having 1 to 6 carbon atoms. Examples of the linking group include a methylene group, an ethylene group, a propylene group, a phenyl group and the like.
Among these, it is preferable to connect via an ester bond, and it is more preferable to connect directly via an ester bond.

[Structural site derived from crystalline polyester resin]
The constituent portion derived from the crystalline polyester resin is preferably a polycondensation product of an alcohol component containing 80 mol% or more of α,ω-aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid.
The “component part derived from the polyester resin” means a component part of the resin in which a part of the polyester resin is bonded to another molecular group.

(Alcohol component)
The alcohol component preferably comprises α,ω-aliphatic diols.
The α,ω-aliphatic diol is preferably an α,ω-straight chain aliphatic diol.
The carbon number of the α,ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, further preferably 6 or more, further preferably 8 or more, further preferably 10 or more, and preferably 16 or less, It is more preferably 14 or less, still more preferably 12 or less.
Examples of the α,ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol and 1,14-tetradecanediol Can be mentioned. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol and 1,12-dodecanediol are preferable, and 1,6-hexanediol and 1,12-dodecanediol are preferable. Is more preferable.

  The amount of α,ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and 100% in the alcohol component. It is at most mol%, more preferably at 100 mol%.

  The alcohol component may contain another alcohol component different from the α,ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α,ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin, penta Examples thereof include trihydric or higher alcohols such as erythritol and trimethylolpropane. These alcohol components may use 1 type(s) or 2 or more types.

(Carboxylic acid component)
The carboxylic acid component preferably comprises an aliphatic dicarboxylic acid.
The aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid.
The carbon number of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid. Among these, sebacic acid or dodecanedioic acid is preferable, and sebacic acid is more preferable. These carboxylic acid components may be used alone or in combination of two or more.

  The amount of the aliphatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% in the carboxylic acid component. % Or less, and more preferably 100 mol%.

  The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of the other carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and polyvalent carboxylic acids having a valence of 3 or more. These carboxylic acid components may be used alone or in combination of two or more.

  The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl 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, It is preferably 1.2 or less.

[Constituent site derived from polymer A]
The resin A has a constituent site derived from the polymer A resin, from the viewpoint of obtaining a toner having excellent crystal recoverability during the production of the toner, excellent low-temperature fixability and storage stability.
The “polymer A resin-derived constituent part” means a constituent part of the resin in which a part of the polymer A is bonded to another molecular group.
The polymer A is preferably a modified polypropylene-based polymer from the viewpoint of being excellent in crystal recoverability at the time of producing a toner and further improving low-temperature fixability and storage stability. The reason why the modified polypropylene-based polymer is preferable is that the polypropylene skeleton has a property of low polarity, so that the molecules in the crystalline polyester-based resin are likely to be accumulated and easily serve as a crystal growth point of the crystalline polyester, and the polypropylene skeleton moiety is also present. The reason is that the toner itself is difficult to plasticize, and therefore the storage stability of the toner is excellent.
The reactive functional group is, for example, a functional group capable of forming an ester bond with a hydroxyl group or a carboxy group.
Examples of the reactive functional group include a carboxylic acid group, a carboxylic acid anhydride group, and a hydroxy group. Among these, a carboxylic acid group or a carboxylic acid anhydride group is preferable.
The polymer A is a polypropylene-based polymer modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof (hereinafter, also referred to as “acid-modified polypropylene-based polymer”).

Examples of the polypropylene-based polymer before modification include polypropylene and copolymers of propylene and other olefins.
Polypropylene is, for example, by-produced during the production of polypropylene used for general molding containers, for general molding containers, for general molding containers, and for thermal decomposition of polypropylene used for general molding containers. Polypropylene obtained by a method of separating and purifying a low-molecular-weight polypropylene having
Examples of the copolymer of propylene and other olefin include a copolymer obtained by polymerizing propylene and another olefin having an unsaturated bond copolymerizable with propylene. The copolymer may be either a random copolymer or a block copolymer.
Other olefins include, for example, ethylene and olefins having 4 to 10 carbon atoms. Examples of the other olefin include ethylene, butene, pentene, hexene, and 2-ethylhexene.

Examples of the acid-modified polypropylene-based polymer include a polypropylene-based polymer end-modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof (hereinafter, also simply referred to as “end-modified polypropylene-based polymer”), unsaturated Examples thereof include a polypropylene-based polymer in which a carboxylic acid compound having a bond or an anhydride thereof is randomly graft-modified (hereinafter, also simply referred to as “random graft-modified polypropylene-based polymer”).
Among these, polypropylene-based polymers terminal-modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof are preferable. The terminal-modified polypropylene-based polymer is preferably modified with a carboxylic acid compound or an anhydride thereof having an unsaturated bond only at one end, a polypropylene-based polymer (hereinafter, also referred to as “one-end-modified polypropylene-based polymer”). Say).
Examples of the carboxylic acid compound having an unsaturated bond or the anhydride thereof include maleic anhydride, fumaric acid, and itaconic acid. Among these, maleic anhydride is preferable from the viewpoint of further improving the crystal recoverability, low temperature fixability and storage stability.
Examples of the polypropylene-based polymer end-modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof include, for example, a polypropylene-based polymer having an unsaturated bond at the end, a carboxylic acid compound having an unsaturated bond or an anhydride thereof. It can be obtained by subjecting the product to an Ene reaction. The one-end modified polypropylene-based polymer can be obtained, for example, by subjecting a polypropylene-based polymer having an unsaturated bond at one end to an ene compound with a carboxylic acid compound having an unsaturated bond or an anhydride thereof. The polypropylene 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 catalyst, a titanium catalyst, a zirconium catalyst, or the like.

Examples of the polymer A include a maleic anhydride modified polypropylene and a copolymer of a maleic anhydride modified propylene and other olefin.
Among these, from the viewpoint of further improving the crystal recoverability, low-temperature fixability, and storage stability, terminal maleic anhydride modified polypropylene is preferable, and one terminal maleic anhydride modified polypropylene is more preferable. By introducing the maleic anhydride site into the polypropylene-based polymer, the two polyester-based resin-derived constituent sites can be linked via an ester bond. In particular, by using a maleic anhydride-modified polypropylene-based polymer having one terminal, a polyester-based resin having a structure in which two polyester-based resin-derived constituent sites are linked by the maleic anhydride site at the end of the polypropylene-based polymer is obtained. it is conceivable that. Therefore, it is considered that the crystal recoverability, low temperature fixability and storage stability can be further improved by using a maleic anhydride-modified polypropylene-based polymer with one terminal.

  Examples of commercially available end-modified polypropylene-based polymers include, for example, maleic anhydride-modified polypropylene with one terminal modified "X-10065" (Mn=1,000), maleic anhydride-modified polypropylene with one terminal modified "X-10088" (Mn=2). , 500), maleic anhydride modified polypropylene "X-10082" (Mn = 8,000), maleic anhydride modified propylene/hexene copolymer "X-10087" (Mn = 800), anhydrous one end. Maleic acid-modified propylene/hexene copolymer “X-10053” (Mn=2,000), maleic anhydride modified propylene/hexene copolymer “X-10052” (Mn=4,000) at one end (above, BAKER HUGHES).

The random graft-modified polypropylene-based polymer is preferably a polypropylene-based polymer in which maleic anhydride is randomly grafted and modified (hereinafter, also referred to as “random-grafted maleic anhydride-modified polypropylene-based polymer”).
The random graft maleic anhydride-modified polypropylene polymer is preferably modified by grafting one or more maleic anhydride in one molecule. Whether or not it has been modified by maleic anhydride can be defined by general spectral measurement. When modified with maleic anhydride, the double bond of maleic anhydride changes into a single bond, which can be defined by measuring its spectral change.
The random graft modified polypropylene-based polymer is obtained, for example, by generating a radical in the polypropylene-based polymer molecule and reacting it with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.

  Examples of commercially available products of the random graft modified polypropylene polymer include, for example, random graft maleic anhydride modified polypropylene polymers such as "M-100", "M-300" and "M-310" in the "TOYO-tac" series. , "PMA H1000A", "PMA H1100A", "PMA H3000A", "PMA-T", "PMA-F2", "PMA-L" (above, Toyobo Co., Ltd.), "1001" of "Yumex" series. , “1010”, “100TS”, “110TS” (above, manufactured by Sanyo Kasei Co., Ltd.), and “Kayaburit” series “003”, “006” (above, manufactured by Akzo Nobel Co., Ltd.).

  The melting point of the polymer A is preferably 10° C. or higher, more preferably 20° C. or higher, further preferably 40° C. or higher, further preferably 60° C. or higher, and further preferably 70° C. or higher, from the viewpoint of further improving low-temperature fixability. , More preferably 80° C. or higher, and from the viewpoint of further improving low temperature fixability, preferably 170° C. or lower, more preferably 150° C. or lower, further preferably 140° C. or lower, further preferably 120° C. or lower, It is preferably 100° C. or lower.

  The acid value of the polymer A is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, further preferably 100 mgKOH/g or less, further preferably 80 mgKOH/g or less, and preferably 0.1 mgKOH/g. The above is more preferably 1 mgKOH/g or more, further preferably 5 mgKOH/g or more, and further preferably 10 mgKOH/g or more.

The hydroxyl value of the polymer A is preferably 70 mgKOH/g or less, more preferably 30 mgKOH/g or less, further preferably 10 mgKOH/g or less, and 0 mgKOH/g or more, preferably 0 mgKOH/g.
The melting point, acid value, and hydroxyl value are measured by the methods described in the examples.

The number average molecular weight of the polymer A is 700 or more, preferably 800 or more, more preferably 900 or more, from the viewpoint of obtaining a toner having excellent crystal recoverability at the time of production of the toner, and excellent low-temperature fixing property and storage stability. And 8,000 or less, preferably 6,000 or less, more preferably 4,000 or less, still more preferably 3,000 or less, still more preferably 2,000 or less.
The number average molecular weight is measured by gel permeation chromatography using polystyrene as a standard sample.

In the resin A, the amount of the constituent site derived from the polymer A is preferably 5% by mass or more, more preferably 8% by mass or more, from the viewpoint of further improving the crystal recovery property, the low temperature fixing property and the storage stability. From the viewpoint of further improving low-temperature fixability and storage stability, it is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 20% by mass. Hereafter, it is more preferably 15% by mass or less.
In the above amount, the amount of the resin A is the total amount of the polymer A and the raw material monomers, and is the amount excluding the dehydration amount due to polycondensation.

[Method for producing resin A]
Resin A is, for example,
(A) a method comprising polycondensing a raw material monomer containing an alcohol component and a carboxylic acid component in the presence of a modified polyolefin-based polymer A having a reactive functional group, or (b) a polyester resin having a reactive functional group It can be obtained by a method including reacting a modified polyolefin-based polymer A having a group.
Examples of the reaction (b) include dehydration condensation and transesterification when the reactive functional group is a carboxylic acid group or a carboxylic acid anhydride group. The reaction conditions are preferably such that the carboxylic acid group or carboxylic acid anhydride group of the polymer A and the alcohol component, carboxylic acid component or the like are dehydrated and condensed or transesterified.

  The polycondensation of the alcohol component and the carboxylic acid component is carried out, for example, in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst, a polymerization inhibitor, etc., at a temperature of about 180° C. to 250° C. You can Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolaminate. Examples of the esterification promoter that can be used together with the esterification catalyst include gallic acid and the like. 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 1 with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is less than or equal to parts by mass, more preferably less than or equal to 0.8 parts by mass. 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, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component, and preferably The amount is 0.5 parts by mass or less, more preferably 0.1 parts by mass or less.

[Physical properties of resin A]
The softening point of the resin A is preferably 50° C. or higher, more preferably 60° C. or higher, further preferably 65° C. or higher, from the viewpoint of further improving storage stability, and from the viewpoint of further improving low temperature fixability. , Preferably 100° C. or lower, more preferably 90° C. or lower, further preferably 80° C. or lower, further preferably 70° C. or lower.

  The melting point of the resin A is preferably 50° C. or higher, more preferably 55° C. or higher, further preferably 60° C. or higher, from the viewpoint of further improving storage stability, and from the viewpoint of further improving low temperature fixability. The temperature is preferably 120° C. or lower, more preferably 100° C. or lower, further preferably 80° C. or lower, further preferably 70° C. or lower.

[Resin composition for toner]
A toner resin composition according to an embodiment of the present invention contains a resin A and an amorphous polyester resin (hereinafter, also simply referred to as “resin B”).

  In the resin composition, the amount of the resin A is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, based on 100 parts by mass of the total amount of the amorphous polyester resin. It is preferably 8 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.

[Amorphous polyester resin B (Resin B)]
The resin B may be a polyester resin composed of a polycondensation product of an alcohol component and a carboxylic acid component, or may be a polyester resin modified so as not to substantially impair its properties. Examples of the modified polyester-based resin include a urethane-modified polyester-based resin in which a constituent part derived from a polyester resin is modified with a urethane bond, and an epoxy-modified polyester-based resin in which a constituent part derived from a polyester resin is modified with an epoxy bond. Be done. Among these, a polyester resin composed of a polycondensate of an alcohol component and a carboxylic acid component is preferable.
Hereinafter, the alcohol component and the carboxylic acid component of the resin B will be described.

(Alcohol component)
The alcohol component contains, for example, a divalent or higher alcohol.
The content of the divalent or higher alcohol is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
Examples of the dihydric or higher alcohols 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.

The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(In the formula, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, and x and y represent the average number of moles of alkylene oxide added, and each is positive. And the value of the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). Is an alkylene oxide adduct of
Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. These may use 1 type(s) or 2 or more types. Among these, a combination of a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A is preferable.
The molar ratio of the propylene oxide adduct of bisphenol A and the ethylene oxide adduct of bisphenol A [the propylene oxide adduct of bisphenol A/the ethylene oxide adduct of bisphenol A] is preferably 20/80 or more, more preferably 30/ It is 70 or more, more preferably 40/60 or more, and preferably 80/20 or less, more preferably 70/30 or less, still more preferably 60/40 or less.
The amount of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, and It is preferably 100 mol %.

  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 the secondary carbon atom preferably has 3 or more and 4 or less 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.

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

Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and hydrogenated bisphenol A alkylene oxide having 2 to 4 carbon atoms (average added mole number of 2 to 12). The following) include adducts.
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components may use 1 type(s) or 2 or more types.

(Carboxylic acid component)
The carboxylic acid component contains, for example, a divalent or higher carboxylic acid compound.
The content of the divalent or higher carboxylic acid compound is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
Examples of the divalent or higher carboxylic acid compound include aromatic dicarboxylic acid compounds, linear or branched aliphatic dicarboxylic acid compounds, alicyclic dicarboxylic acid compounds, and trivalent or higher polyvalent carboxylic acid compounds. Among these, aromatic dicarboxylic acid compounds are preferable.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid or terephthalic acid is preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, and 100 mol% in the carboxylic acid component. % Or less.

The carbon number of the linear or branched aliphatic dicarboxylic acid is 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 16 or more. It is below.
Examples of the linear or branched aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid. Examples thereof include acids, succinic acids substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or their anhydrides or alkyl esters having 1 to 3 carbon atoms.
Examples of succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an anhydride thereof is preferable.
The amount of the linear or branched aliphatic dicarboxylic acid in the carboxylic acid component is preferably 2 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 30 mol%. It is preferably 25 mol% or less, more preferably 20 mol% or less, still more preferably 20 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, more preferably trimellitic acid or an anhydride thereof.
When a polyvalent carboxylic acid having a valence of 3 or more is contained, the amount of the polyvalent carboxylic acid having a valence of 3 or more is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% in the carboxylic acid component. The above is more preferably 15 mol% or more, and preferably 35 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less.
These carboxylic acid components may be used alone or in combination of two or more.

  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, It is more preferably 1.2 or less.

[Method for producing resin B]
The resin B is obtained, for example, by a method including polycondensing a raw material monomer containing an alcohol component and a carboxylic acid component.
The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, under the conditions shown in the above-mentioned method for producing the resin A.

[Physical properties of resin B]
The softening point of the resin B is preferably 80° C. or higher, more preferably 90° C. or higher, further preferably 100° C. or higher, and preferably 170° C. or lower, more preferably 150° C. or lower, further preferably 120° C. or lower. , And more preferably 110° C. or lower.

  The glass transition temperature of the resin B 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.

  In the resin composition, the amount of the resin B is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and preferably 98% by mass based on the total amount of the resin components. % Or less, more preferably 95% by mass or less, further preferably 93% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less.

[Amorphous polyester resin (resin B')]
The resin composition may include an amorphous polyester resin having a softening point different from that of the resin B by 5° C. or more (hereinafter, also simply referred to as “resin B′”).
The resin B′ preferably has a softening point 10° C. or higher higher than that of the resin B, more preferably 15° C. or higher higher than that of the resin B, and further preferably It has a softening point higher by 20° C. or more than the softening point.
The resin B'is a polycondensate of an alcohol component and a carboxylic acid component. The alcohol component and the carboxylic acid component are as exemplified in the resin B.

(Physical properties of resin B')
The softening point of the resin B′ is preferably 90° 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, further preferably 140° C. Hereafter, it is more preferably 132° C. or less.

  The glass transition temperature of the resin B′ is preferably 40° C. or higher, more preferably 50° C. or higher, even more preferably 55° C. or higher, and preferably 80° C. or lower, more preferably 75° C. or lower, further preferably 70. It is below ℃.

  The softening point and the glass transition temperature of the resin B′ can be appropriately adjusted depending on the kinds of raw material monomers and the amount thereof, and the production conditions such as reaction temperature, reaction time, and cooling rate, and the values thereof are It is determined by the method described in the examples.

  The resin B'is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the polycondensation conditions, for example, the reaction conditions shown in the above-mentioned method for producing the resin A can be applied.

  When the resin B′ is contained, the mass ratio [resin B/resin B′] of the resin B and the resin B′ is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40/60 or more. And preferably 90/10 or less, more preferably 70/30 or less, still more preferably 60/40 or less.

  When the resin composition contains the resin B′, the content of the resin B′ in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably It is 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and further preferably 50% by mass or less.

[Toner for developing electrostatic image]
The electrostatic image developing toner (hereinafter, also simply referred to as “toner”) according to the embodiment of the present invention contains, for example, the above resin composition.
The content of the above-mentioned resin composition in the toner is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 99% by mass or less, more preferably It is 98 mass% or less, more preferably 95 mass% or less.
Then, the toner contains, for example, toner particles and an external additive.
<Toner particles>
The toner particles preferably contain resin A and resin B, and more preferably resin A, resin B and resin B′.
Toner particles include other colorants, waxes, charge control agents, magnetic powders, fluidity improvers, conductivity adjusters, reinforcing fillers such as fibrous substances, antioxidants, antiaging agents, cleaning improvers, etc. It may contain the additive of.

[Colorant]
The toner may contain a colorant.
As the colorant, any of dyes, pigments and the like used as a colorant for toner can be used, and examples thereof include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment green B and rhodamine-B. Examples include base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. The toner may be black toner or any other color toner.

  The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and preferably 40 parts by mass with respect to 100 parts by mass of the total amount of the resin component of the toner. The amount is not more than 10 parts by mass, more preferably not more than 20 parts by mass, further preferably not more than 10 parts by mass.

〔Release agent〕
The toner may contain a release agent.
Wax is mentioned as a mold release agent.
Examples of the wax include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sazol wax, or oxides thereof; carnauba wax. , Ester waxes such as montan wax or deoxidized waxes thereof and fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. These may use 1 type(s) or 2 or more types.

  The melting point of the release agent is preferably 60°C or higher, more preferably 70°C or higher, and preferably 160°C or lower, more preferably 140°C or lower, further preferably 120°C or lower, further preferably 110°C or lower. Is.

  The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more based on 100 parts by mass of the total amount of the resin component of the toner. And it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and further preferably 5 parts by mass or less.

(Charge control agent)
The toner may contain a charge control agent.
The charge control agent may be either a positively chargeable charge control agent or a negatively chargeable charge control agent.
Examples of the positively chargeable charge control agent include nigrosine dyes such as “Nigrosine base EX”, “Oil black BS”, “Oil black SO”, “Bontron N-01”, “Bontron N-04”, and “Bontron N-07”. , "Bontron N-09", "Bontron N-11" (above, manufactured by Orient Chemical Industry Co., Ltd.), etc.; triphenylmethane dye containing a tertiary amine as a side chain, quaternary ammonium salt compound, for example, " Bontron p-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant Co., Ltd.) and the like; polyamine resins such as "AFP-B" (manufactured by Orient Chemical Co., Ltd.) and the like. Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (above, manufactured by Shikoku Chemicals Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.). .

  Examples of the negatively chargeable charge control agent include 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 Co., Ltd.), “Aizen spirone black TRH”, “T-77” (above, manufactured by Hodogaya Chemical Co., Ltd.), etc.; metal compound of benzylic acid compound, 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" (manufactured by Orient Chemical Co., Ltd.), "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.), etc.; copper phthalocyanine dye; quaternary ammonium salt such as "COPY CHARGE NX VP434" (Clariant Co., Ltd.) Manufactured), nitroimidazole derivatives and the like; organometallic compounds and the like.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less, based on 100 parts by mass of the total amount of the resin component of the toner. , More preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and further preferably 2 parts by mass or less.

The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 3 μm or more, more preferably 4 μm or more, still more preferably 6 μm or more, and preferably 15 μm or less, more preferably 10 μm or less.
In the present specification, the volume median particle diameter (D ₅₀ ) means a particle diameter at which the cumulative volume frequency calculated by volume fraction becomes 50% when calculated from the smaller particle diameter.

  The content of the toner particles in the toner is preferably 90% by mass or more, more preferably 93% by mass or more, further preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less. Is.

<External additive>
It is preferable to use an external additive for the toner in order to improve storage stability. Examples of the external additive include inorganic particles such as silica, alumina, titania, zirconia, tin oxide and zinc oxide, and organic particles such as melamine resin particles and resin particles such as polytetrafluoroethylene resin particles. These may use 1 type(s) or 2 or more types.
Examples of silica include hydrophobic silica that has been hydrophobized.
Examples of the hydrophobizing agent for hydrophobizing the surface of the silica fine particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Can be mentioned. These may use 1 type(s) or 2 or more types.
The number average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 200 nm or less, more preferably 120 nm or less, still more preferably 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and 100 parts by mass of the toner particles, and It is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

[Toner manufacturing method]
The toner may be a toner obtained by any known method such as a melt kneading method, an emulsion phase inversion method, a polymerization method, and an aggregation fusion method, but from the viewpoint of productivity and dispersibility of a colorant, Pulverized toner obtained by a melt-kneading method is preferable. In the case of pulverized toner by the melt-kneading method, for example, raw materials such as a binder resin, a colorant, a release agent, and a charge control agent are uniformly mixed with a mixer such as a Henschel mixer, and then a closed type kneader, uniaxial or 2 It can be produced by melt-kneading with a shaft extruder, open roll type kneader, etc., cooling, pulverizing and classifying.

  The toner can be used as a one-component developing toner or as a two-component developer by mixing with a carrier.

  Each property was measured by the following methods.

[Measuring method]
[Melting Point (Mp) of Crystalline Polyester Resin and Polymer A]
A differential scanning calorimeter “DSC210” (manufactured by Seiko Instruments Inc.) was used to raise the temperature to 200° C., and a sample cooled from that temperature to 0° C. at a temperature lowering rate of 10° C./min was heated at a rate of 10° C./min. Raise the temperature. The maximum peak temperature of the heat of fusion is the melting point.

[Acid Value of Resin and Polymer A]
It is measured based on the method of JIS K 0070:1992. However, only the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K 0070:1992 to a mixed solvent of chloroform and dimethylformamide (hereinafter also referred to as “DMF”) (chloroform:DMF=7:3 (volume ratio)). change.

[Softening point, peak temperature and glass transition temperature of polyester resin]
(1) Using a softening point flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating 1 g of a sample at a temperature rising rate of 6° C./min. It is extruded from a 1 mm long nozzle. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half the sample flows out is taken as the softening point.
(2) Endothermic peak temperature of constituent part derived from polyester resin, endothermic peak temperature of resin From a room temperature (20°C) using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.) The sample cooled to 0° C. at a temperature lowering rate of 10° C./min is held for 1 minute as it is, and then the temperature is raised to 180° C. at a heating rate of 10° C./min for measurement. In the case of the resin A having a constituent site derived from a crystalline polyester resin and a constituent site derived from the polymer A, among the observed endothermic peaks, the temperature of the peak appearing on the lowest temperature side is the It shall be the peak temperature of endotherm.
The peak of the constituent site derived from the polyester resin can be assigned by a conventional method, but it usually appears on the lower temperature side than the endothermic peak of the constituent site derived from the polymer A. When it is unknown which of the peaks should be attributed, the polyester resin alone and the polymer A alone were measured under the above conditions using a differential scanning calorimeter, and an endothermic peak at a temperature closer to each endothermic peak was obtained. It belongs to the endothermic peak of each constituent site.
In the case of other polyester resins, the temperature of the peak on the highest temperature side among the observed endothermic peaks is the endothermic peak temperature.
The crystallinity index is calculated from the ratio between the softening point and the endothermic peak of the structural unit derived from the polyester resin.
(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed in an aluminum pan and heated to 200° C. Then, the temperature is cooled to 0° C. at a temperature decreasing rate of 10° C./min. Next, measurement is performed while raising the temperature to 150° C. at a temperature rising rate of 10° C./min.
The glass transition temperature is defined as the temperature at the intersection of the base line extension below the endothermic peak temperature and the tangent line showing the maximum slope from the peak rising portion to the peak apex.

[Dissolution endotherm]
Each sample was observed using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.) from room temperature (20°C) to 180°C at a heating rate of 10°C/min. The endothermic peak area derived from the crystalline polyester resin is taken as the melting endotherm. The melting endotherm of the resin before being made into a toner is shown in Table 1 as the melting endotherm B.

[Volume median particle diameter (D ₅₀ )]
The volume median particle diameter (D ₅₀ ) of the toner particles is measured by the following method.
Measuring machine: "Coulter Multisizer II" (manufactured by Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: "Coulter Multisizer AccuComp version 1.19" (manufactured by Beckman Coulter, Inc.)
Electrolyte: "Isoton II" (manufactured by Beckman Coulter, Inc.)
Dispersion liquid: "Emulgen 109P" (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolytic solution to a concentration of 5% by mass.
Dispersion conditions: 10 mg of a measurement sample was added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of the electrolytic solution was added, and further dispersed for 1 minute with an ultrasonic disperser, Prepare the sample dispersion.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolytic solution so that the particle size of 30,000 particles could be measured in 20 seconds, and 30,000 particles were measured. Determine the median particle size (D ₅₀ ).

[Production of resin]
[Production of Crystalline Polyester Resin A]
Production Example A1 (Production of Resin A-1)
The raw material monomer of polyester resin, the esterification catalyst, and the cocatalyst shown in Table 1 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser equipped with a dehydration tube, and a nitrogen introduction tube. The temperature was raised to 140° C. in a nitrogen atmosphere, and then the temperature was raised by 5° C. to 200° C. every hour. Then, after adding the reactive polyolefin, the reaction was carried out at 200° C. for 1 hour, and then the condensation reaction was carried out under the condition of 200° C. and 13 kPa until the softening point reached the softening point shown in Table 1. , Resin A-1 was obtained.

Production Examples A2 to A6, A81 to A82 (Production of Resins A-2 to A-6, A-81 to A-82)
Resins A-2 to A-6 and A-81 to A-82 were obtained in the same manner as in Production Example A1 except that the raw materials shown in Table 1 were used.

[Production of Amorphous Polyester Resin B and Resin B′]
Production Example B1 (Production of Resin B-1)
The raw material monomer of the polyester resin, the esterification catalyst, and the cocatalyst shown in Table 2 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless stir bar, a downflow condenser equipped with a dehydration tube, and a nitrogen introduction tube. After heating to 180° C. in a nitrogen atmosphere and then increasing the temperature to 230° C. by 5° C. every 1 hour, it was confirmed that the solid monomers were all melt-reacted, and then the pressure was reduced to 9.3 kPa for dehydration condensation to obtain a softening point. Resin B-1 was obtained by reacting until reaching the softening point shown in Table 2.

Production Example B2 (Production of Resin B-2)
Resin B-2 was obtained in the same manner as in Production Example B1 except that the raw materials shown in Table 2 were used.

Production Example B'1 (Production of Resin B'-1)
10 liters equipped with a raw material monomer of polyester resin other than trimellitic anhydride, an esterification catalyst, a co-catalyst, a thermometer, a stirring rod made of stainless steel, a downflow condenser equipped with a dehydration pipe, and a nitrogen introduction pipe shown in Table 2. In a four-necked flask, heated to 180° C. in a nitrogen atmosphere, and then heated every 5 hours to 230° C. by 5° C., and after confirming that all solid monomers were melted and reacted, the pressure was reduced to 9.3 kPa. It was dehydrated and condensed. The pressure is returned to normal pressure, the temperature is cooled to 190° C., trimellitic anhydride is added, heated to 210° C., reacted at normal pressure for 1 hour, and then reduced to 9.3 kPa for crosslinking dehydration condensation to obtain a softening point. Was reacted until the softening point shown in Table 2 was reached to obtain resin B'-1.

Production Example B'2 (Production of Resin B'-2)
Resin B'-2 was obtained in the same manner as in Production Example B'1 except that the raw materials shown in Table 2 were used.

[Production of toner]
Examples 1-10 and Comparative Examples 1-3 (Production of Toners 1-10, 81-83)
100 parts by weight of the amorphous polyester-based resin shown in Table 3, 100 parts by weight of the crystalline polyester-based resin shown in Table 3, and a negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Industry Co., Ltd.) 1 part by mass, 5 parts by mass of colorant "Pigment Blue 15:3" (manufactured by Dainichiseika Kogyo Co., Ltd.), and mold release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 80°C). ) After thoroughly mixing 2 parts by mass with a Henschel mixer, using a co-rotating twin-screw extruder having a kneading portion with a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm, a roll rotation speed of 200 r/min and a heating temperature of 100 in the roll. Melt kneading was performed at ℃. The feed rate of the mixture was 20 kg/h and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized by a jet mill and classified to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the obtained toner particles, 2.0 parts by mass of an external additive "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 16 nm) was added, and the mixture was mixed with a Henschel mixer. By mixing at 3600 r/min for 5 minutes, external additive treatment was performed, and toners 1 to 10 and 81 to 83 were obtained.

[Evaluation methods]
[Crystal recovery]
The crystal recoverability was defined by the following method as to how much the crystalline polyester resin in the toner originally had the crystallization ability.
Each of the toners is measured according to the above-described method for measuring the dissolution endotherm, and the observed endothermic peak area derived from the crystalline polyester resin is defined as the dissolution endotherm A.
On the other hand, the temperature of each resin before toner production is also raised under the same conditions, and the observed endothermic peak area derived from the crystalline polyester resin is taken as the melting endothermic amount B.
The crystal recoverability is defined by the following formula using the melting endotherm A and the melting endotherm B.
Crystal recoverability (%)=(A/B)×100
The crystal recoverability is represented by a numerical value of 100 to 0, and the larger the numerical value is, the more the crystallization of the crystalline polyester resin in the toner is promoted. The results are shown in Table 3.

[Low temperature fixability]
3 parts by mass of each toner was mixed with 97 parts by mass of styrene/methylmethacrylate resin-coated ferrite powder (manufactured by Kanto Denka Kogyo Co., Ltd., average particle diameter 100 μm) to obtain a two-component developer. A two-component developer is mounted on a copying machine "AR-505" (manufactured by Sharp Corporation) that is modified so that it can be fixed outside the apparatus, and a paper "CopyBond SF-70NA" (Sharp Corporation) is mounted. Manufactured, 75 g/m ² ) to give a toner adhesion amount of 0.5 mg/cm ^2, and a printed matter was obtained in an unfixed state. Using a fixing machine (fixing speed of 200 mm/sec) adjusted so that the total fixing pressure is 40 kgf, the temperature of the fixing roller is gradually increased from 90° C. to 240° C. in 5° C. increments at each temperature, and the unfixed state is obtained. The fixing test of the printed matter was performed. A sand eraser with a bottom of 15 mm×7.5 mm with a load of 500 g was applied, and the image fixed through the fixing device was rubbed 5 times back and forth, and the optical reflection density before and after rubbing was measured by a reflection densitometer “RD-915” (manufactured by Macbeth Co.). ) Was used to determine the low-temperature fixability by setting the temperature of the fixing roller whose ratio (after rubbing/before rubbing) exceeds 70% first as the minimum fixing temperature. The results are shown in Table 3. The lower the minimum fixing temperature, the better the low-temperature fixing property, and the minimum fixing temperature is preferably 145°C or lower, more preferably 135°C or lower, and further preferably 125°C or lower.

[Storage stability]
5 g of each toner was put in a 50 mL volume polybin and left in an environment of a temperature of 50° C. and a relative humidity of 60% for 48 hours. Then, the toner was sieved with a mesh having an opening of 100 μm, the residual toner on the mesh was weighed, and the storability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
A: Residual toner is less than 0.5 g B: Residual toner is 0.5 g or more and less than 1 g C: Residual toner is 1 g or more

  As described above, it can be seen that the toner of the example is superior to the toner of the comparative example in the crystal recovery property, the low-temperature fixing property, and the storage stability.

Claims (11)

Having a constituent site derived from a polyester resin having crystallinity and a constituent site derived from a modified polyolefin-based polymer A having a reactive functional group, the constituent site derived from the polyester resin and the modified polyolefin-based polymer A derived from Linked to the component site via a covalent bond,
The crystalline polyester resin, wherein the modified polyolefin polymer A has a number average molecular weight of 700 or more and 8,000 or less.   The crystalline polyester resin according to claim 1, wherein the crystalline polyester resin has a crystallinity index of 0.6 or more and less than 1.4.   The constituent part derived from the polyester resin having crystallinity is a polycondensation product of an alcohol component containing 80 mol% or more of α,ω-aliphatic diol and a carboxylic acid component containing aliphatic dicarboxylic acid. 2. The crystalline polyester resin according to item 2.   The crystalline polyester resin according to claim 1, wherein the reactive functional group is a functional group capable of forming an ester bond with a hydroxyl group or a carboxy group.   The crystalline polyester resin according to claim 1, wherein the reactive functional group is a carboxylic acid group or a carboxylic acid anhydride group.   The crystalline polyester resin according to claim 1, wherein the modified polyolefin polymer A is modified with a carboxylic acid compound having an unsaturated bond or an anhydride thereof.   The crystalline polyester resin according to claim 6, wherein the carboxylic acid compound having an unsaturated bond or its anhydride is maleic anhydride.   The crystalline polyester resin according to any one of claims 1 to 7, wherein the constituent portion derived from the polyester resin and the constituent portion derived from the modified polyolefin polymer A are linked by an ester bond.   A resin composition for a toner, comprising the crystalline polyester resin according to any one of claims 1 to 8 and an amorphous polyester resin.   The resin composition for toner according to claim 9, wherein the content of the crystalline polyester-based resin is 2 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the total amount of the amorphous polyester-based resin.   A toner for developing an electrostatic charge image, containing the resin composition according to claim 9.