JP2023127453A - Binder resin composition for toner - Google Patents

Abstract

To provide a binder resin composition for toner which may obtain toner for electrostatic charge image development with excellent low-temperature fixability and image heat resistance.SOLUTION: There is provided a binder resin composition for toner which contains a resin composition (C-P) obtained by condensing a crystalline resin (C) having an acid group and an amine compound and an amorphous resin (A). A difference in a solubility parameter (SP value) of Fedors between the crystalline resin (C) and the amorphous resin (A) is equal to or greater than 1.40(cal/cm3)1/2.SELECTED DRAWING: None

Description

The present invention relates to a binder resin composition for toner.

In the field of electrophotography, with the development of electrophotographic systems, there is a need to develop toners for developing electrostatic images (hereinafter also simply referred to as "toners") that are compatible with higher image quality and faster speeds. For example, in order to cope with higher speed machines, toners are required to have excellent low-temperature fixability.
However, when a large amount of toner is printed with good low-temperature fixability, the toner fuses and/or sticks to the developing roll of an electrophotographic system, causing streaks in the printed image and reducing durability. Issues were likely to arise from this perspective as well. Therefore, there is a need for a toner that has both low-temperature fixability and durability.

For example, Patent Document 1 discloses that a polycondensation resin component obtained by polycondensing an alcohol component containing a specific aliphatic diol and a carboxylic acid component containing a specific aliphatic dicarboxylic acid compound, and a styrene-based Crystalline composite resin containing a resin component; Amorphous composite resin containing a polycondensation resin component obtained by polycondensing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid, and a styrene resin component and an electrophotographic toner containing a release agent and satisfying a specific average circularity, wherein the content of particles with a particle size of 3 μm or less in the toner is 5.0% by number or less Toner is listed.

Patent Document 2 describes a toner that contains a binder resin, is surface-modified with a polymeric amine, and is further surface-modified with a silicone-acrylic copolymer.

Further, Patent Document 3 describes a resin composition (CP) obtained by condensing a crystalline resin (C) having an acid group and a polyalkylene imine, and an amorphous resin (A). , a binder resin composition for toner in which the difference in Fedors solubility parameter (SP value) between the crystalline resin (C) and the amorphous resin (A) is 1.3 (cal/cm ³ ) ^1/2 or less is listed.

Japanese Patent Application Publication No. 2016-114829 Japanese Patent Application Publication No. 2017-58591 JP2020-24360A

Incidentally, in order to improve the low-temperature fixability of the toner, it is effective to use a crystalline resin that has a high affinity with the amorphous resin to lower the glass transition temperature of the toner. However, if the affinity between the amorphous resin and the crystalline resin is too high, the crystalline resin will be too compatible with the amorphous resin, which will lower the glass transition temperature of the toner and cause problems such as image heat resistance. In some cases, there may be a problem that the heat resistance performance of the material deteriorates, which is not sufficiently resolved in Patent Documents 1 to 3. Therefore, there is a demand for the development of toners that have excellent low-temperature fixability and image heat resistance.
One embodiment of the present invention relates to a binder resin composition for a toner, which provides a toner for developing electrostatic images having excellent low-temperature fixability and image heat resistance.

One embodiment of the present invention relates to the following [1].
[1] Binder resin for toner containing a resin composition (CP) obtained by condensing a crystalline resin (C) having an acid group and an amine compound and an amorphous resin (A) A composition,
A binder resin composition for toner, wherein the difference in Fedors solubility parameter (SP value) between the crystalline resin (C) and the amorphous resin (A) is 1.40 (cal/cm ³ ) ^1/2 or more. thing.

According to one embodiment of the present invention, it is possible to provide a binder resin composition for a toner, which provides a toner for developing electrostatic images having excellent low-temperature fixability and image heat resistance.

[Binder resin composition for toner]
A binder resin composition for toner according to an embodiment of the present invention (hereinafter also simply referred to as "binder resin composition") is a crystalline resin (C) having an acid group (hereinafter simply referred to as "crystalline resin (C)"). A resin composition (CP) obtained by condensing an amine compound (also referred to as "C)" or "resin (C)" (hereinafter also simply referred to as "resin composition (CP)") and an amorphous resin (A) (hereinafter also simply referred to as "resin (A)"), and the Fedors solubility parameters of the crystalline resin (C) and the amorphous resin (A) (hereinafter referred to as "resin (A)") (also simply referred to as "SP value") is 1.40 (cal/cm ³ ) ^1/2 or more. Note that the difference in SP value means the absolute value of the difference between the SP value of resin (C) and the SP value of resin (A).
According to the present embodiment, a toner for developing an electrostatic image that has excellent low-temperature fixability and image heat resistance is obtained, and a binder resin composition for a toner that contains the binder resin composition for an electrostatic image. A method for producing a toner and a binder resin composition for the toner can be provided.
Note that in the present invention, image heat resistance means that the occurrence of document offset is suppressed when printed matter on which images are provided are overlapped in a high-temperature environment.

The reason why the electrostatic image developing toner containing the toner binder resin composition according to the present embodiment has excellent low-temperature fixability and image heat resistance is not clear, but it is thought to be as follows.
First, in order to improve the low-temperature fixability of toner, it is common to use a crystalline resin that has a close SP value and high affinity with the amorphous resin, and the crystalline resin is finely dispersed in the amorphous resin. By compatibilizing the crystalline resin in the amorphous resin during fixing, the amorphous resin is plasticized and low-temperature fixability is developed.
In the binder resin composition for toner according to the present embodiment, the resin composition (CP) obtained by condensing the crystalline resin (C) having an acid group and the amine compound is the amorphous resin (A ) is considered to be able to be finely dispersed. In particular, when the amorphous resin (A) has acid groups, such as a polyester resin, the acid groups of the amorphous resin (A) and the resin composition (CP) may be introduced into the resin composition (CP). It is thought that the resin composition (CP) can be more finely dispersed due to the acid-base interaction with the basic groups contained in the resin composition. Therefore, even if the difference in SP value between the crystalline resin (C) and the amorphous resin (A) is greater than or equal to the lower limit above, the amorphous resin (A) and the resin composition (C-P ) becomes more compatible with each other, and as a result, it is thought that low-temperature fixing properties become better. On the other hand, during cooling, the compatibility between the amorphous resin (A) and the resin composition (CP) decreases, so the finely dispersed resin composition (C- It is thought that P) becomes easier to crystallize, and as a result, the image heat resistance becomes better.
For the above reasons, it is considered that the electrostatic image developing toner containing the toner binder resin composition according to the present embodiment can achieve both low-temperature fixability and image heat resistance.

The crystallinity of the resin is expressed by the crystallinity index defined as the ratio of the softening point to the maximum endothermic peak temperature measured by differential scanning calorimetry (DSC), ie, "softening point/maximum endothermic peak temperature." Generally, when this crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, crystallinity is low and there are many amorphous parts. In the present embodiment, "crystalline resin" has 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, and "amorphous resin" refers to a resin in which no endothermic peak is observed, or if it is observed, the crystallinity index is greater than 1.4 or less than 0.6.
The above-mentioned "maximum endothermic peak temperature" refers to the temperature of the peak with the largest peak area among the endothermic peaks observed under the conditions of the measurement method described in the Examples.
The crystallinity of the resin can be adjusted by the types and ratios of raw material monomers, manufacturing conditions (for example, reaction temperature, reaction time, cooling rate), and the like.
In this specification, "solubility parameter value" and "SP value" refer to the values proposed by Fedors et al. [POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. )]. A specific method for calculating the SP value of the resin will be described later.

<Resin composition (CP)>
The resin composition (CP) is obtained by condensing a crystalline resin (C) having an acid group with an amine compound.

(Crystalline resin (C) having acid groups)
Examples of the acid group of the resin (C) include a carboxy group and a sulfo group, with a carboxy group being preferred.
The resin (C) preferably contains a crystalline polyester resin from the viewpoint of further improving low-temperature fixability and image heat resistance.
From the viewpoint of further improving low-temperature fixability and image heat resistance, the resin (C) is more preferably a crystalline polyester resin such as a crystalline polyester or a crystalline composite resin having a polyester segment and an addition polymerized resin segment. Crystalline polyester is more preferred.
Crystalline polyester is a polycondensate of an alcohol component (c-al) and a carboxylic acid component (c-ac).
In addition, in this embodiment, the "polyester resin" may include polyester modified to such an extent that its properties are not substantially impaired. Examples of modified polyester include urethane-modified polyester in which polyester is modified with urethane bonds, epoxy-modified polyester in which polyester is modified with epoxy bonds, and composite resins having a polyester resin segment and an addition polymerization resin segment. Can be mentioned. Note that "polyester" means unmodified "polyester".

[Alcohol component (c-al)]
The alcohol component (c-al) preferably contains α,ω-aliphatic diol from the viewpoint of further improving low-temperature fixability and image heat resistance.
The number of carbon atoms in the α,ω-aliphatic diol is preferably 2 or more, more preferably 6 or more, still more preferably 11 or more, and preferably 16 or more, from the viewpoint of further improving low-temperature fixability and image heat resistance. Below, it is more preferably 14 or less, still more preferably 13 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, 1,14-tetradecanediol, etc. can be mentioned.
Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred from the viewpoint of further improving low-temperature fixability and image heat resistance. , 1,12-dodecanediol is more preferred from the viewpoint of obtaining a toner with better image heat resistance.

The content of α,ω-aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more, in the alcohol component (c-al) from the viewpoint of further improving low-temperature fixability and image heat resistance. More preferably, it is 95 mol% or more and 100 mol% or less, and still more preferably 100 mol%.

The alcohol component (c-al) may contain another alcohol component different from the α,ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α,ω-aliphatic diols, aromatic group-containing diols, alicyclic diols, and trihydric or higher polyhydric alcohols.
Examples of aromatic group-containing diols include bisphenols such as polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene adducts of 2,2-bis(4-hydroxyphenyl)propane. An alkylene (carbon number: 2 to 4) oxide (average number of added moles: 1 to 16, preferably 2 to 4) adducts of A can be mentioned.
Examples of alicyclic diols include hydrogenated bisphenol A [same as 2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxides having 2 to 4 carbon atoms in hydrogenated bisphenol A (average number of added moles of 1 12) adducts.
Examples of the trivalent or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sorbitan.
These alcohol components may be used alone or in combination of two or more. Note that from the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the alcohol component (c-al) may contain a monohydric alcohol as appropriate.

[Carboxylic acid component (c-ac)]
From the viewpoint of further improving low-temperature fixability and image heat resistance, the carboxylic acid component (c-ac) preferably contains an α,ω-aliphatic dicarboxylic acid having 10 to 14 carbon atoms. As the α,ω-aliphatic dicarboxylic acid, α,ω-straight chain aliphatic dicarboxylic acid is preferred.
As the α,ω-aliphatic dicarboxylic acid having 10 to 14 carbon atoms, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferable from the viewpoint of further improving low-temperature fixability and image heat resistance.

The content of α,ω-aliphatic dicarboxylic acid having 10 to 14 carbon atoms is preferably 85 mol% or more, more preferably 90 mol% or more, and even more preferably 92 mol% in the carboxylic acid component (c-ac). % or more and 100 mol% or less.

The carboxylic acid component (c-ac) may include aliphatic dicarboxylic acids other than α,ω-aliphatic dicarboxylic acids having 10 to 14 carbon atoms, aromatic dicarboxylic acids, and fatty acids, as long as the effects of the present invention are not impaired. It may contain a cyclic dicarboxylic acid and a trivalent or higher polyhydric carboxylic acid.
Examples of aliphatic dicarboxylic acids other than α,ω-aliphatic dicarboxylic acids having 10 to 14 carbon atoms include oxalic acid, malonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, and succinic acid. Acids include adipic acid and azelaic acid.
Examples of the aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and polyhydric carboxylic acid having a valence of 3 or more are the same as those exemplified in the carboxylic acid component (a-ac) described below.

As mentioned above, these carboxylic acid components can be used alone or in combination of two or more. Note that from the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the carboxylic acid component (c-ac) may contain a monovalent carboxylic acid as appropriate.
The number of carbon atoms in the monovalent carboxylic acid is preferably 10 or more, more preferably 12 or more, and more preferably 10 or more, more preferably 12 or more, from the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, and from the viewpoint of further improving low-temperature fixability and image heat resistance. It is preferably 14 or more, and preferably 28 or less, more preferably 24 or less, and still more preferably 22 or less.
Examples of monovalent carboxylic acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and montanic acid. Among these, stearic acid and behenic acid are more preferred, and stearic acid is even more preferred, from the viewpoint of further improving low-temperature fixability and image heat resistance.
The content of monovalent carboxylic acid in the carboxylic acid component (c-ac) is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 3 mol% or more, and preferably 15 mol% or more. It is mol% or less, more preferably 10 mol% or less, still more preferably 8 mol% or less.
In this specification, the carboxylic acid component includes not only its compound, but also anhydrides that decompose to produce acids during the reaction, and alkyl esters of each carboxylic acid (alkyl groups having 1 to 3 carbon atoms). ) is also included. In addition, in this specification, when only the name of the carboxylic acid (free acid) is described for an exemplified carboxylic acid component (excluding examples), the anhydride of the carboxylic acid and the carbon number 1 The above description includes alkyl esters of 3 or less. That is, for example, when simply writing "trimellitic acid", "trimellitic acid, trimellitic anhydride (same as "trimellitic anhydride"), and alkyl having 1 to 3 carbon atoms in trimellitic acid" ester” is listed.

The equivalent ratio [COOH group/OH group] of the carboxy group (COOH group) of the carboxylic acid component (c-ac) to the hydroxy group (OH group) of the alcohol component (c-al) is preferably 0.7 or more, and more It is preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

The content of crystalline polyester in the resin (C) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, from the viewpoint of further improving low-temperature fixability and image heat resistance. The content is 100% by mass or less, more preferably 100% by mass.

The softening point of the resin (C) is preferably 60° C. or higher, more preferably 70° C. or higher, and still more preferably 80° C. or higher, from the viewpoint of further improving image heat resistance, and further improving low-temperature fixability. From this point of view, the temperature is preferably 150°C or lower, more preferably 120°C or lower, and still more preferably 100°C or lower.

The melting point of the resin (C) is preferably 50°C or higher, more preferably 65°C or higher, even more preferably 70°C or higher, and even more preferably 75°C or higher, from the viewpoint of further improving image heat resistance, and From the viewpoint of further improving fixing properties, the temperature is preferably 130°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 85°C or lower.

For example, the resin (C) has an acid value of 1 mgKOH/g or more.
The acid value of the resin (C) is preferably 2 mgKOH/g or more, more preferably 5 mgKOH/g or more, from the viewpoint of improving the reactivity with the amine compound and further improving the low-temperature fixability and image heat resistance. More preferably, it is 7 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less, and still more preferably 20 mgKOH/g or less.

The SP value of the resin (C) is preferably 8.50 (cal/cm ³ ) ^1/2 or more, more preferably 8.80 (cal/cm ³ ) from the viewpoint of further improving low-temperature fixability and image heat resistance. ) ^1/2 or more, more preferably 9.00 (cal/cm ³ ) ^1/2 or more, even more preferably 9.20 (cal/cm ³ ) ^1/2 or more, and preferably 10.50 ( cal/cm ³ ) ^1/2 or less, more preferably 10.00 (cal/cm ³ ) ^1/2 or less, even more preferably 9.80 (cal/cm ³ ) ^1/2 or less, even more preferably 9.60 (cal/cm ³ ) ^1/2 or less.

The softening point, melting point, acid value, and SP value of the resin (C) can be adjusted as appropriate depending on the types and ratios of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. These values, except for the SP value, are determined by the method described in Examples below. In addition, when using a combination of two or more types of resins (C), it is preferable that the softening point, melting point, and acid value obtained as a mixture thereof are each within the above ranges. In addition, when using two or more resins (C) in combination, the weighted average value of the SP values of each resin (C) is the SP value of the resin (C), and the weighted average value of the SP values of each resin (C) is preferably within the above range.

When the resin (C) is a crystalline polyester, the crystalline polyester can be obtained, for example, by polycondensing an alcohol component (c-al) and a carboxylic acid component (c-ac).
The polycondensation of the alcohol component (c-al) and the carboxylic acid component (c-ac) may be carried out in the presence of an esterification catalyst, an esterification promoter, a polymerization inhibitor, etc., if necessary.
Polycondensation may be carried out in an inert gas atmosphere such as nitrogen.

Examples of the esterification catalyst include tin catalysts such as dibutyltin oxide and tin(II) di(2-ethylhexanoate), and titanium compounds such as titanium diisopropylate bistriethanolaminate.
When using an esterification catalyst, the blending amount of the esterification catalyst is preferably 0.01 parts by mass or more per 100 parts by mass of the alcohol component (c-al) and the carboxylic acid component (c-ac). .5 parts by mass or less.

The temperature during polycondensation of the alcohol component (c-al) and the carboxylic acid component (c-ac) is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 180°C or higher, and preferably The temperature is 250°C or lower, more preferably 240°C or lower. Further, it is preferable to accelerate the reaction by reducing the pressure in the reaction system during the latter half of the polymerization, and adjust the resulting resin (C) so that the desired softening point and the like can be obtained.

(amine compound)
The amine compound is preferably a compound having an amino group (-NH ₂ , -NHR, -NRR'). Here, R and R' represent a hydrocarbon group having 1 or more and 5 or less carbon atoms. The amine compound is a compound that can undergo a condensation reaction with the acid group of the resin (C) and be incorporated into the molecular skeleton of the resin (C), and unreacted residual amine compounds and by-products derived from the amine compounds also affect the resin composition. It can be contained in a product (CP).
The amine compound may contain functional groups other than amino groups. Examples of the functional group include a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.

From the viewpoint of further improving low-temperature fixability and image heat resistance, the amount of the amine compound to be reacted with the resin (C) is determined based on the total amount of the resin composition (CP) and the amorphous resin (A). Preferably it is 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less. In this case, the amount of the amine compound to be reacted with the resin (C) is 100% by mass of the total amount of the resin composition (CP) and the amorphous resin (A) in the binder resin composition of the present invention. This is the percentage when .
Further, the amount of the amine compound to be reacted with the resin (C) is preferably 0.1 part by mass or more, and more preferably 0.1 part by mass or more, based on 100 parts by mass of the resin (C), from the viewpoint of further improving low-temperature fixability and image heat resistance. The amount is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less.
In addition, the amount of the amine compound to be reacted with the resin (C) includes, as described above, in addition to the amine compound incorporated into the molecular skeleton of the resin (C) through a condensation reaction with the acid group of the resin (C). It also includes the content of unreacted residual amine compounds and by-products derived from the amine compounds contained in the resin composition (CP). Therefore, the amount of the amine compound to be reacted with the crystalline resin (C) can also be calculated as the amount of the amine compound used in the condensation.

Examples of the amine compound include polyalkyleneimine, polyallylamine, (poly)ethylenepolyamine, alkanolamine, and alkylamine. Among these, from the viewpoint of further improving low-temperature fixability and image heat resistance, it is preferable to contain at least one selected from polyalkylene imine and (poly)ethylene polyamine, and polyalkylene imine is more preferable.
When the amine compound contains at least one selected from polyalkylene imine and (poly)ethylene polyamine, the total amount of at least one selected from polyalkylene imine and (poly) ethylene polyamine in the amine compound is preferably 70 The content is at least 80% by mass, more preferably at least 90% by mass, and is at most 100% by mass, even more preferably 100% by mass.

The polyalkylene imine is preferably a polyalkylene imine whose alkylene group has 2 or more carbon atoms and 5 or less carbon atoms, more preferably a polyalkylene imine whose alkylene group has 2 or more carbon atoms and 4 or less carbon atoms, and even more preferably polyethylene imine or polypropylene imine. , more preferably polyethyleneimine. These polyalkyleneimines may be used alone or in combination of two or more.
The number average molecular weight of the polyalkyleneimine is preferably 150 or more, more preferably 500 or more, still more preferably 800 or more, and even more preferably 1,000 or more, from the viewpoint of further improving low-temperature fixability and image heat resistance. And preferably it is 10,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, still more preferably 2,000 or less.
The value of the number average molecular weight is determined by the method described in Examples.

Examples of polyallylamine include polymers having amino groups in side chains, such as homopolymers or copolymers of allylamine compounds such as allylamine, dimethylallylamine, and diallylamine. These polyallylamines may be used alone or in combination of two or more.
The weight average molecular weight of the polyallylamine is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, and preferably 10 ,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less.
The value of the weight average molecular weight is determined by the method described in Examples.

Examples of the (poly)ethylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Among these, diethylenetriamine and triethylenetetramine are preferred from the viewpoint of further improving low-temperature fixability and image heat resistance. These (poly)ethylene polyamines may be used alone or in combination of two or more.

The alkanolamine is preferably an alkanolamine having 2 or more and 9 or less carbon atoms. Examples of alkanolamines include primary alkanolamines such as monoethanolamine, monopropanolamine, and monobutanolamine; monoalkanol secondary amines such as N-methylethanolamine and N-methylpropanolamine; diethanolamine and diisopropanolamine; secondary alkanolamines such as dialkanol secondary amines; monoalkanol tertiary amines such as N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-diethylethanolamine; N-methyldiethanolamine; Examples include tertiary alkanolamines such as dialkanol tertiary amines such as -ethyldiethanolamine, and trialkanol tertiary amines such as triethanolamine and triisopropanolamine. Among these, tertiary alkanolamines having 2 to 9 carbon atoms are preferred, monoalkanol tertiary amines having 2 to 9 carbon atoms are more preferred, and N,N-dimethylethanolamine is even more preferred. These alkanolamines may be used alone or in combination of two or more.

The alkylamine is preferably an alkylamine having 1 to 6 carbon atoms. Examples of the alkylamine include primary amines such as propylamine, butylamine, and hexylamine; and secondary amines such as diethylamine and dipropylamine. These alkylamines may be used alone or in combination of two or more.

As described above, the resin composition (CP) is obtained by condensing the crystalline resin (C) having an acid group with an amine compound.
The method for producing the resin composition (CP) is the same as the explanation regarding step 1 of the method for producing a binder resin composition for toner, which will be described later, and will therefore be omitted.

<Amorphous resin (A)>
The amorphous resin (A) is preferably an amorphous polyester, a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond, and has low-temperature fixability and image heat resistance. From the viewpoint of further improving properties, it is more preferable to include a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond.
The amorphous polyester and the polyester resin constituting the polyester resin segment of the composite resin may be a condensate of polyethylene terephthalate (PET) and a polycondensable raw material monomer (a). The polyester resin constituting the polyester resin segment of the composite resin is preferably a condensate of PET and a polycondensable raw material monomer (a) from the viewpoint of further improving low-temperature fixability and image heat resistance. .

When the amorphous resin (A) contains a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond, it is not clear why the low-temperature fixability and image heat resistance are better. , it can be considered as follows.
When heated, the resin composition (CP) that is finely dispersed in the amorphous resin (A) becomes more compatible with addition polymerized resin segments having similar SP values, resulting in low-temperature fixing. It is thought that the properties have improved. On the other hand, when the resin composition (CP) is cooled, it becomes easier to crystallize among the addition polymerized resin segments with similar SP values, and as a result, the effect of improving image heat resistance becomes more pronounced. Conceivable.

(Amorphous polyester)
From the viewpoint of further improving low-temperature fixability and image heat resistance, the amorphous polyester is preferably a polycondensate of a polycondensable raw material monomer (a), or a polycondensate of PET and a polycondensable raw material monomer (a). It is a condensate.

The raw material monomer (a) is a constituent component of the amorphous polyester, and preferably contains an alcohol component (a-al) and a carboxylic acid component (a-ac). That is, the amorphous polyester is a polyester resin that is a condensate of an alcohol component (a-al) and a carboxylic acid component (a-ac), or a polyester resin that is a condensate of PET, an alcohol component (a-al), and a carboxylic acid component (a-ac). Preferably, it is a polyester resin which is a condensate with ac).

[Alcohol component (a-al)]
Examples of the alcohol component (a-al) include diols such as aromatic group-containing diols, aliphatic diols, and alicyclic diols, and polyhydric alcohols having a valence of 3 or more.
Examples of aromatic group-containing diols include alkylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] (hereinafter also referred to as "BPA-AO"). Preferable examples of BPA-AO include BPA-AO represented by the following formula (I).

In formula (I), R ¹¹ O and R ¹² O each independently represent an alkyleneoxy group having 1 to 4 carbon atoms, preferably an ethyleneoxy group or a propyleneoxy group.
x and y are the average number of added moles of alkyleneoxy groups, and are each independently positive numbers. From the viewpoint of further improving low-temperature fixability and image heat resistance, the average value of the sum of x and y is preferably 1 or more and 16 or less.

Specifically, BPA-AO includes polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene (2.2)-2,2-bis(4- Examples include hydroxyphenyl)propane.
The numerical value in parentheses above corresponds to the average value of the sum of x and y in the above formula (I).

BPA-AO represented by formula (I) is preferably a propylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-PO") or an ethylene oxide adduct of bisphenol A (hereinafter also referred to as "BPA-EO"). ), more preferably at least BPA-EO is contained, and still more preferably BPA-EO and BPA-PO are used in combination. These BPA-AO may be used alone or in combination of two or more.

The number of carbon atoms in the aliphatic diol is preferably 2 or more, and preferably 18 or less, more preferably 14 or less, still more preferably 10 or less, and still more preferably 6 or less.
Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3- Butanediol, neopentyl glycol, 1,4-butenediol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1 ,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 3,3-dimethyl-1,2-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9 -nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, di Examples include propylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, from the viewpoint of further improving low-temperature fixability and image heat resistance, one or more selected from ethylene glycol, 1,2-propanediol, and 1,4-butanediol are preferred; From the viewpoint of further improving fixing properties, ethylene glycol and 1,2-propanediol are more preferred.

Examples of the alicyclic diol include 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and alkylene oxide adducts having 2 to 4 carbon atoms (average number of added moles of 2 to 12) of hydrogenated bisphenol A. It will be done.

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

These alcohol components may be used alone or in combination of two or more. In addition, from the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the alcohol component (a-al) may contain a monohydric alcohol as appropriate.

The alcohol component (a-al) is selected from alkylene oxide adducts of bisphenol A (BPA-AO) and aliphatic diols having 2 to 6 carbon atoms, from the viewpoint of further improving low-temperature fixability and image heat resistance. It is preferable to contain at least one selected from BPA-AO, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and neopentyl glycol. , BPA-AO, and even more preferably one or more selected from BPA-EO and BPA-PO.

When the alcohol component (a-al) contains BPA-AO, the content of BPA-AO in the alcohol component (a-al) is preferably 80 mol% or more, more preferably 90 mol% or more, and further The content is preferably 95 mol% or more, more preferably 98 mol% or more, and 100 mol% or less, and even more preferably 100 mol%.

[Carboxylic acid component (a-ac)]
Examples of the carboxylic acid component (a-ac) include dicarboxylic acids and polyvalent carboxylic acids of trivalent or higher valence.

Examples of dicarboxylic acids include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids, and one or more selected from aromatic dicarboxylic acids and aliphatic dicarboxylic acids are preferred.
The number of carbon atoms in the dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid, with isophthalic acid and terephthalic acid being preferred, and terephthalic acid being more preferred.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, 1,5-pentanedioic acid, and 1,12-dodecane. Examples include diacid, azelaic acid, succinic acid substituted with a hydrocarbon group having 1 to 20 carbon atoms, fumaric acid, adipic acid, and succinic acid substituted with a hydrocarbon group having 1 to 20 carbon atoms. At least one selected from the following is preferred, and adipic acid is more preferred.
Examples of the succinic acid substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms include n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-dodecenylsuccinic acid, -Octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, etc.
Examples of the alicyclic dicarboxylic acid include cyclohexanedicarboxylic acid and the like.

Examples of trivalent or higher polycarboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, it is preferable to include trimellitic acid.

Among these, the carboxylic acid component (a-ac) preferably includes an aromatic dicarboxylic acid, more preferably one or more aromatic dicarboxylic acids selected from terephthalic acid and isophthalic acid, and still more preferably contains terephthalic acid.
The content of the aromatic dicarboxylic acid in the carboxylic acid component (a-ac) is preferably 30 mol% or more, more preferably 35 mol% or more, and even more preferably is 40 mol% or more and 100 mol% or less.

When the carboxylic acid component (a-ac) contains a trivalent or higher polyvalent carboxylic acid, the content of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% in the carboxylic acid component (a-ac). The content is more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less.

These carboxylic acid components can be used alone or in combination of two or more. Note that from the viewpoint of adjusting the molecular weight and softening point of the obtained polyester, the carboxylic acid component (a-ac) may contain a monovalent carboxylic acid as appropriate.

The equivalent ratio of the carboxy group (COOH group) of the carboxylic acid component (a-ac) to the hydroxy group (OH group) of the alcohol component (a-al) [COOH group/OH group] is preferably 0.6 or more, and more It is preferably 0.7 or more, and preferably 1.3 or less, more preferably 1.2 or less.

〔polyethylene terephthalate〕
PET is a polycondensate of ethylene glycol, terephthalic acid, dimethyl terephthalate, etc., and is a component that is incorporated into a polyester resin by condensation of the terminal functional group of PET and the raw material monomer (a). During condensation with raw material monomer (a), PET may undergo depolymerization or transesterification, producing ethylene glycol, terephthalic acid, or decomposed polymer chains, which can become constituent components of polyester resins. .

The intrinsic viscosity (hereinafter also referred to as "IV value") of PET is preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.55 from the viewpoint of further improving low-temperature fixability and image heat resistance. or more, and preferably 0.8 or less, more preferably 0.75 or less, and even more preferably 0.7 or less. The IV value is an indicator of molecular weight. The IV value of PET can be adjusted by adjusting the molar ratio of raw material monomers, polycondensation time, etc.
To measure the IV value, for example, dissolve the sample in a mixed solvent of phenol/tetrachloroethane = 60/40 (mass ratio) at a concentration of 0.4 g/dL, measure with an Ubbelohde viscometer, and use the following formula: It can be calculated according to

[In the formula, k is Huggins' constant, C is the concentration of the sample solution (g/dL), η = (t ₁ /t ₀ )-1, and t ₀ is the number of seconds in which the solvent only falls. t ₁ is the number of seconds the sample solution falls. Let k be 0.33. ]

PET manufactured according to a conventional method or a commercially available product can be used.
Commercially available PET products include, for example, "RAMAPET BF3067" (IV value: 0.64), "RAMAPET L1" (IV value: 0.60), and "RAMAPET N2G" (IV value: 0.64) manufactured by Indorama Ventures. 75); Examples include "TRN-NTJ" (IV value: 0.53) and "TRN-RTJC" (IV value: 0.64) manufactured by Teijin Ltd.

(composite resin)
A composite resin is a resin in which an addition polymerization resin segment and a polyester resin segment are bonded via covalent bonds.

[Polyester resin constituting the polyester resin segment]
The polyester resin constitutes the polyester resin segment of the composite resin, and is preferably a polycondensate of a polycondensable raw material monomer (a), or a polycondensate of polyethylene terephthalate (PET) and a polycondensable raw material monomer (a). It is a condensate, more preferably a condensate of polyethylene terephthalate (PET) and a polycondensable raw material monomer (a).
The raw material monomer (a) is a constituent component of the polyester resin, and preferably contains an alcohol component (a-al) and a carboxylic acid component (a-ac). That is, the polyester resin is preferably a polyester resin that is a condensate of an alcohol component (a-al) and a carboxylic acid component (a-ac), or a polyester resin that is a condensate of PET, an alcohol component (a-al), and a carboxylic acid component (a-ac). -ac), more preferably a polyester resin that is a condensate of PET, an alcohol component (a-al), and a carboxylic acid component (a-ac).
Here, the example of the raw material monomer (a) of the polyester resin and PET is the same as the example of the amorphous polyester described above.

When the polyester resin contains a PET component, the amount of the PET component is 100 parts by mole in total of the PET component and alcohol component (a-al) from the viewpoint of further improving low-temperature fixability and image heat resistance. , preferably 5 mole parts or more, more preferably 10 mole parts or more, still more preferably 15 mole parts or more, still more preferably 20 mole parts or more, and preferably 50 mole parts or less, more preferably 40 mole parts or more. The amount is not more than mol parts, more preferably not more than 30 mol parts. However, the number of moles of the PET component is calculated as the number of moles of condensation units of ethylene glycol and terephthalic acid.

[Addition polymerization resin constituting the addition polymerization resin segment]
The addition polymerization resin constitutes the addition polymerization resin segment of the composite resin, and is an addition polymerization product of the addition polymerizable raw material monomer (b). One kind or two or more kinds of raw material monomers (b) may be used. That is, the addition polymerization resin may be a homopolymer using only one type of raw material monomer (b), or a copolymer using two or more types of raw material monomer (b). , a copolymer is preferred.
Examples of the raw material monomer (b) include (meth)acrylic monomers and styrene monomers.

Examples of (meth)acrylic monomers include acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylate. n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid isooctyl, decyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Glycidyl (meth)acrylate, 2-chloroethyl (meth)acrylate, phenyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, α- Examples include (meth)acrylic acid and (meth)acrylic acid esters such as methyl chloroacrylate.
Note that "(meth)acrylic ester" includes both acrylic ester and methacrylic ester.
Among these, (meth)acrylic monomers give addition polymerization resins a desired acid value, allow sufficient compositing with polyester resins constituting polyester resin segments, and improve low-temperature fixability and image heat resistance. From the viewpoint of further improving the properties, it is preferable to contain one or more selected from acrylic acid and methacrylic acid.

Examples of styrenic monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-chlorostyrene, vinylnaphthalene, etc. Examples include styrene and styrene derivatives, with styrene and α-methylstyrene being preferred.

The raw material monomer (b) may contain monomers other than the (meth)acrylic monomer and the styrene monomer.
Other monomers include, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; diolefins such as butadiene; halobinyls such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinyl acetate; Examples include vinyl esters such as vinyl propionate, vinyl formate, and vinyl caproate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrole and N-vinylpyrrolidone. It will be done.

The raw material monomer (b) preferably contains at least one selected from (meth)acrylic monomers and styrene monomers, more preferably contains (meth)acrylic monomers, and still more preferably contains at least one selected from acrylic acid and methacrylic acid. Contains one or more selected (meth)acrylic monomers, and further includes one or more styrenic monomers selected from styrene and α-methylstyrene, or methyl acrylate, methyl methacrylate, butyl acrylate, or acrylic acid. It may also contain one or more other (meth)acrylic monomers selected from 2-ethylhexyl, 2-ethylhexyl methacrylate, stearyl acrylate, methyl methacrylate, n-butyl methacrylate, and 2-hydroxyethyl methacrylate. good.

The content of the (meth)acrylic monomer in the raw material monomer (b) constituting the addition polymerization resin or the content of the structural unit derived from the (meth)acrylic monomer in the addition polymerization resin segment depends on the low temperature fixability and From the viewpoint of further improving image heat resistance, the content is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, and preferably 100% by mass or less.
When the raw material monomer (b) constituting the addition polymerization resin contains one or more selected from acrylic acid and methacrylic acid, the total content of acrylic acid and methacrylic acid in the raw material monomer (b) or the addition polymerization resin The total content of structural units derived from acrylic acid and structural units derived from methacrylic acid in the segment is preferably 0.5% by mass or more, more preferably 3% by mass, from the viewpoint of further improving low-temperature fixability and image heat resistance. % or more, more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less.
When the raw material monomer (b) constituting the addition polymerization resin contains a styrene monomer, the content of the styrene monomer in the raw material monomer (b) constituting the addition polymerization resin or the styrene type in the addition polymerization resin segment The content of the monomer-derived structural unit is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, even more preferably 87% by mass or more, and preferably 98% by mass or less, more preferably 96% by mass or less, even more preferably is 94% by mass or less.

The total content of the (meth)acrylic monomer and styrene monomer in the raw material monomer (b) constituting the addition polymerization resin, or the structural unit derived from the (meth)acrylic monomer and the styrene monomer in the addition polymerization resin segment From the viewpoint of further improving low-temperature fixing properties and image heat resistance, the total content of the structural units derived from the above is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more, and , 100% by mass or less, more preferably 100% by mass.

The acid value of the addition polymerization resin is preferably 40 mgKOH/g or more, from the viewpoint of ensuring sufficient compositing with the polyester resin constituting the polyester resin segment and further improving low temperature fixability and image heat resistance. Preferably 45 mgKOH/g or more, more preferably 48 mgKOH/g or more, and preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, still more preferably 100 mgKOH/g or less. be.

The weight average molecular weight of the addition polymerization resin is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more, and even more preferably 7,500 or more, and preferably 100,000 or less, more preferably 50,000 or less, even more preferably 20,000 or less, still more preferably 15,000 or less, and even more preferably 13,000 or less.
The weight average molecular weight of the addition polymerization resin can be adjusted by adjusting the polymerization temperature and polymerization time.

The glass transition temperature of the addition polymerization resin is preferably 40°C or higher, more preferably 45°C or higher, and preferably 120°C or lower, more preferably The temperature is 90°C or lower, more preferably 70°C or lower.
The softening point of the addition polymerization resin is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, from the viewpoint of further improving low-temperature fixability and image heat resistance. From the viewpoint of further improving the temperature, the temperature is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower.
The acid value, weight average molecular weight, glass transition temperature, and softening point of the addition polymerization resin can be measured by the methods described in Examples.

The amount of the addition polymerization resin in the composite resin is preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the polyester resin, from the viewpoint of further improving low-temperature fixability and image heat resistance. The amount is more preferably 3 parts by weight or more, still more preferably 4 parts by weight or more, and preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less.

In addition, the total content of the composite resin in which the amorphous polyester and the addition polymerized resin segment and the polyester resin segment are bonded via covalent bonds in the resin (A) further improves low-temperature fixability and image heat resistance. From the viewpoint of increasing the carbon content, the content is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less, and preferably 100% by mass.

The softening point of the resin (A) is preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, from the viewpoint of further improving low-temperature fixability and image heat resistance. From the viewpoint of further improving the temperature, the temperature is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower.

The glass transition temperature of the resin (A) is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher, from the viewpoint of further improving low-temperature fixability and image heat resistance. From the viewpoint of further improving properties, the temperature is preferably 90°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower.

The acid value of the resin (A) is preferably from the viewpoint of interaction with the structure and components derived from the amine compound in the resin composition (CP), and from the viewpoint of further improving low-temperature fixability and image heat resistance. 0.5 mgKOH/g or more, more preferably 0.8 mgKOH/g or more, even more preferably 1 mgKOH/g, still more preferably 3 mgKOH/g or more, even more preferably 5 mgKOH/g, and preferably 40 mgKOH/g. g or less, more preferably 30 mgKOH/g or less, still more preferably 20 mgKOH/g or less.

The hydroxyl value of the resin (A) is preferably from the viewpoint of interaction with the structure and components derived from the amine compound in the resin composition (CP), and from the viewpoint of further improving low-temperature fixability and image heat resistance. It is 3 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, and preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, and even more preferably 60 mgKOH/g or less.

The SP value of the resin (A) is preferably 10.00 (cal/cm ³ ) ^1/2 or more, more preferably 10.50 (cal/cm ³ ) from the viewpoint of further improving low-temperature fixability and image heat resistance. ) ^1/2 or more, more preferably 10.80 (cal/cm ³ ) ^1/2 or more, and preferably 12.50 (cal/cm ³ ) ^1/2 or less, more preferably 12.30 ( Cal/cm ³ ) ^1/2 or less, more preferably 12.00 (cal/cm ³ ) ^1/2 or less, even more preferably 11.80 (cal/cm ³ ) ^1/2 or less.

The softening point, glass transition temperature, acid value, hydroxyl value, and SP value of the resin (A) can be adjusted as appropriate depending on the type and ratio of raw material monomers, and manufacturing conditions such as reaction temperature, reaction time, and cooling rate. can. These values, except for the SP value, are determined by the method described in Examples below. In addition, when using a combination of two or more types of resins (A), it is preferable that the values of the softening point, glass transition temperature, acid value, and hydroxyl value obtained as a mixture thereof are each within the above ranges. In addition, when using two or more resins (A) in combination, the weighted average value of the SP values of each resin (A) is the SP value of the resin (A), and the weighted average value of the SP values of each resin (A) is preferably within the above range.

When the resin (A) is an amorphous polyester, the amorphous polyester is prepared by, for example, polycondensing an alcohol component (a-al), a carboxylic acid component (a-ac), and, if necessary, PET. can get.
Polycondensation may be carried out in the presence of an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor, etc., if necessary.
Suitable embodiments of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor, as well as their suitable blending amounts, are the same as those described above for the method for producing resin (C). Moreover, the suitable temperature during polycondensation is also the same as that described above for the method for producing resin (C).
Polycondensation may be carried out in an inert gas atmosphere such as nitrogen.

In the case of a composite resin in which the resin (A) is a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond, the addition polymerization resin and the polyester resin are combined to a sufficient extent. From the viewpoint of achieving this, it is preferable to form a covalent bond via a compound that can react with either the addition polymerization resin or the polyester resin (hereinafter also referred to as a "bi-reactive compound"). The bireactive compound is preferably a compound that can react with both the raw material monomers constituting the addition polymerization resin and the polyester resin, more preferably an ethylenically unsaturated monocarboxylic acid, and one selected from acrylic acid and methacrylic acid. It is more preferable to use more than one species.
The bireactive compound can be introduced into the polymer skeleton as a raw material monomer for either an addition polymerization resin or a polyester resin before compounding, and then compounded with the other resin via the bireactive compound. Preferably, from the viewpoint of ensuring sufficient compositing, it is more preferable to introduce it into the polymer skeleton as a raw material monomer of the addition polymerization resin before compositing, and then to conjugate it with the polyester resin via the bireactive compound. preferable.
The amount of the bireactive compound capable of reacting with both the addition polymerization resin and the polyester resin is preferably 0.5% by mass or more, more preferably 0.5% by mass or more in the raw material monomer of the addition polymerization resin constituting the addition polymerization resin segment. is 3% by mass or more, more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, even more preferably 15% by mass or less. .

Methods for compounding addition polymerization resins and polyester resins include (i) a method using a polymer reaction between an addition polymerization resin and a polyester resin, and (ii) a method of forming a polyester resin in the presence of an addition polymerization resin. and (iii) a method in which PET and a part of the raw material monomer (a) are reacted, and then the addition polymerization resin and the remainder of the raw material monomer (a) are added and the reaction is carried out.

The addition polymerization resin used in methods (i) to (iii) may be produced by addition polymerization of the raw material monomer (b), or commercially available products may be used.
As the addition polymerization method for the raw material monomer (b), it can be produced by a known polymerization method such as a bulk polymerization method or a solution polymerization method. Among these polymerization methods, bulk polymerization is preferred from the viewpoint of controlling the molecular weight, molecular weight distribution, and copolymerizability of monomers, and further improving low-temperature fixability and image heat resistance. As used herein, "bulk polymerization" refers to addition polymerization carried out under conditions in which a solvent is substantially absent in the reaction system, ie, under solvent-free conditions.
The bulk polymerization is preferably carried out at a high temperature under pressure equal to or higher than normal pressure.
Here, the "pressurized state" refers to a state in which the contents are heated to a temperature higher than the boiling point under normal pressure in a closed container such as an autoclave.
Radicals generated by the thermally initiated reaction of the raw material monomer (b) at high temperatures under pressure above normal pressure function as polymerization initiators, allowing addition polymerization to proceed even under conditions where the amount of radical generator is relatively small. It is possible to obtain an addition polymerization resin with a narrow molecular weight distribution.
From the above point of view, the temperature of bulk polymerization is preferably 140°C or higher, more preferably 160°C or higher, even more preferably 180°C or higher, even more preferably 190°C or higher, and preferably 350°C or lower, more preferably is below 320°C.
As a commercially available addition polymer resin, for example, the JONCRYL series manufactured by BASF Japan Co., Ltd. can be used.

The production of the polyester resin used in method (i), the reaction of the constituent components of the polyester resin in method (ii), and the reaction of PET and raw material monomer (a) in method (iii) are performed in such a manner that the resin (A) described above is A method similar to that for amorphous polyester can be used.

Resin (A) is an amorphous resin (AL) having a low softening point and a softening point 5° C. or higher higher than that of the amorphous resin (AL), from the viewpoint of further improving low-temperature fixability and image heat resistance. , and an amorphous resin (AH) having a high softening point are preferably used together. From the same viewpoint as above, it is more preferable that the amorphous resin (AL) is a composite resin and the amorphous resin (AH) is a polyester resin.
The difference in softening point between the amorphous resin (AL) and the amorphous resin (AH) is preferably 10° C. or higher, more preferably 20° C. or higher, from the viewpoint of further improving low-temperature fixability and image heat resistance. The temperature is more preferably 30°C or higher, more preferably 80°C or lower, more preferably 60°C or lower, even more preferably 50°C or lower.
When amorphous resin (AL) and amorphous resin (AH) are used together, the mass ratio (AL/AH) of amorphous resin (AL) and amorphous resin (AH) is determined by the low temperature fixing property. And from the viewpoint of further improving image heat resistance, it is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.4 or more, even more preferably 0.8 or more, still more preferably 1 or more, And preferably it is 10 or less, more preferably 5 or less, still more preferably 2.5 or less.

The difference in SP value between the crystalline resin (C) and the amorphous resin (A) is 1.40 (cal/cm ³ ) ^1/2 or more, preferably 1.45 (cal/cm ³ ) ^1/2 or more. , more preferably 1.48 (cal/cm ³ ) ^1/2 or more, still more preferably 1.50 (cal/cm ³ ) ^1/2 or more, and preferably 2.50 (cal/cm ³ ) ^1/2 or less, more preferably 2.20 (cal/cm ³ ) ^1/2 or less, even more preferably 2.00 (cal/cm ³ ) ^1/2 or less, even more preferably 1.80 (cal/cm ^{3 )} ) ^1/2 or less, more preferably 1.60 (cal/cm ³ ) ^1/2 or less. Note that the difference in SP value means the absolute value of the difference between the SP value of resin (C) and the SP value of resin (A), as described above.
It is preferable that the SP value of the amorphous resin (A) is higher than the SP value of the crystalline resin (C).
When using two or more types of amorphous resins (A) as the amorphous resin (A), as mentioned above, the weighted average value of the SP values of each amorphous resin (A) is calculated as the amorphous resin (A). Let it be the SP value of resin (A).
In addition, when using two or more types of crystalline resins (C) in combination, as described above, similarly, the weighted average value of the SP values of each crystalline resin (C) is calculated as the SP value of the crystalline resin (C). shall be. Note that when using a crystalline resin alone in addition to the resin composition (CP) as a binder resin for the toner, the crystalline resin (C ) is the SP value of
Here, the SP value is calculated as the product of the SP value and the molar ratio of each monomer constituting the resin. The molar ratio of each monomer constituting the amorphous resin (A) and the crystalline resin (C) can be calculated from the molar ratio of the charged monomers or by analyzing the resin structure by NMR or the like. In addition, the types of monomers constituting the amorphous resin (A) and the crystalline resin (C) can be determined by analyzing the resin structure by, for example, NMR, if the monomers used are unknown.

In the binder resin composition for toner, the mass ratio [(A)/(CP)] of the amorphous resin (A) and the resin composition (CP) is determined by From the viewpoint of further improving the properties, the ratio is preferably 65/35 or more, more preferably 75/25 or more, and even more preferably 85/15 or more, and from the viewpoint of the temporal stability of the toner's low-temperature fixability and the image heat resistance. , preferably 95/5 or less, more preferably 94/6 or less, still more preferably 92/8 or less.

The total content of the amorphous resin (A) and the resin composition (CP) in the binder resin composition is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably It is 95% by mass or more and 100% by mass or less. The total content of the amorphous resin (A) and the resin composition (CP) is more preferably 100% by mass based on 100% by mass of the binder resin composition.

[Method for producing binder resin composition for toner]
The method for producing a binder resin composition for a toner according to the present embodiment includes the following steps from the viewpoint of obtaining a toner having excellent low-temperature fixability and image heat resistance.
Step 1: A step of condensing a crystalline resin (C) having an acid group and an amine compound to obtain a resin composition (CP), and Step 2: A resin composition (CP) and an amorphous resin (A) a step of mixing;
A method for producing a binder resin composition for toner, comprising:
The difference in Fedors solubility parameter (SP value) between resin (C) and resin (A) is 1.40 (cal/cm ³ ) ^1/2 or more.
In addition, the crystalline resin (C), the amine compound, the resin composition (CP), the amorphous resin (A), the difference in SP value between the resin (C) and the resin (A), and Since their preferred embodiments are the same as those described above for the binder resin composition for toner, their description will be omitted.

<Step 1>
Step 1 is a step of condensing the crystalline resin (C) having an acid group with an amine compound to obtain a resin composition (CP).
The temperature during condensation in step 1 is preferably 50°C or higher, more preferably 100°C or higher, even more preferably 130°C or higher, and preferably 235°C or lower, more preferably 200°C or lower, and even more preferably 170°C or lower. below ℃.

The condensation time in Step 1 can be changed as appropriate, but from the viewpoint of reactivity, it is preferably 10 minutes or more, more preferably 30 minutes or more, and preferably 10 hours or less, more preferably 5 hours or less.

The method for producing the resin composition (CP) may be as follows: After producing a crystalline resin (C) having an acid group, it may be condensed with an amine compound, or by producing a crystalline resin (C) having an acid group. During the process, an amine compound may be added for condensation.

The preferred range of the amount of the amine compound to be reacted with the resin (C) in Step 1 is the same as the description of the amine compound described above.

<Step 2>
Step 2 is a step of mixing the resin composition (CP) obtained in Step 1 and the amorphous resin (A).
In step 2, the mass ratio [(A)/(CP)] of the amorphous resin (A) and the resin composition (CP) is 65/35 or more and 95/5 or less. It is preferable to mix it with
A more preferable range of the mass ratio [(A)/(CP)] is also the same as the range described above for the binder resin composition for toner.
There are no particular restrictions on the method of mixing the resin composition (CP) and the amorphous resin (A), and they can be mixed uniformly using, for example, a Henschel mixer.
Further, various additives described in connection with the electrostatic image developing toner described later may be mixed in advance before being added, or may be mixed simultaneously with the various additives.
When mixed with various additives at the same time, a method similar to the mixing method described below in the method for producing a toner for developing an electrostatic image can be used.

Further, the mixing in step 2 may be performed at the same time as the melt-kneading described in the method for producing toner for developing an electrostatic image, which will be described later. Melt-kneading can be carried out using a kneader such as a closed kneader, a single-screw or twin-screw extruder, or a continuous open-roll kneader, but the dispersibility of colorants and other substances in the binder resin as described below From the viewpoint of improving the storage stability of the toner, it is preferable to use a twin-screw extruder or a continuous open roll kneader, and from the viewpoint of further improving the storage stability of the toner, it is more preferable to use a twin-screw extruder.

The mixing temperature in step 2 is preferably 80°C or higher, more preferably 90°C or higher, and preferably 160°C or lower, more preferably 150°C or lower.

[Toner for developing electrostatic images]
The electrostatic image developing toner according to the present embodiment contains the toner binder resin composition according to the present embodiment described above.
The binder resin composition for toner according to the present embodiment can preferably be used as a binder resin for the toner for developing an electrostatic image. The toner may contain a binder resin other than the binder resin composition according to the present embodiment, for example, another resin such as a crystalline resin having no acid group, as long as the effects of the present invention are not impaired. .
The content of the binder resin composition according to the present embodiment is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass, based on the total amount of binder resin in the toner for developing electrostatic images. or more, and 100% by mass or less. The content of the binder resin composition according to the present embodiment is more preferably 100% by mass based on the total amount of binder resin in the electrostatic image developing toner.

<Colorant>
The toner according to this embodiment may contain a colorant.
As the colorant, any of the dyes, pigments, etc. used as colorants for toners can be used.

Examples of dyes include azine dyes, anthraquinone dyes, perinone dyes, and rhodamine dyes, such as C.I. I. Solvent Black 5, C. I. Solvent Black 7, Spirit Black SB, Toluidine Blue, C. I. Solvent Blue 11, C. I. Solvent Blue 12, C. I. Solvent Blue 35, C. I. Solvent Blue 59, C. I. Solvent Blue 74, 1-aminoanthraquinone, 2-aminoanthraquinone, hydroxyethylaminoanthraquinone, C.I. I. Examples include Solvent Violet 47, Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, Solvent Red 179, and Rhodamine-B Base.

The pigment may be either an inorganic pigment or an organic pigment.
Examples of inorganic pigments include carbon black and metal oxides.
Examples of organic pigments include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and quinophthalone pigments. The organic pigment is preferably C.I. I. pigment yellow, C. I. pigment red, C. I. pigment orange, C. I. pigment violet, C. I. pigment blue, and C.I. I. One or more types of product numbers selected from Pigment Green may be mentioned.
The hue of the colorant is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, blue, red, orange, or green can be used. These colorants may be used alone or in combination of two or more.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass or more, based on 100 parts by mass of the total amount of the binder resin. It is not more than 20 parts by mass, more preferably not more than 10 parts by mass.

<Release agent>
The toner according to this embodiment may contain a release agent.
Examples of mold release agents include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax; hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and Sasol wax; or their oxides; carnauba wax; , montan wax or their deoxidized waxes, ester waxes such as fatty acid ester wax; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc. These mold release agents can be used singly or in combination. You may use two or more types in combination.
The melting point of the release agent is preferably 60° C. or higher, more preferably 70° C. or higher, from the viewpoint of toner transferability, and preferably 150° C. or lower, more preferably 130° C., from the viewpoint of low-temperature fixability. The temperature is preferably below 120°C.

The content of the release agent is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the total binder resin, from the viewpoint of low-temperature fixing properties and anti-offset properties of the toner. , and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 7 parts by mass or less.

<Charge control agent>
The toner according to this embodiment may contain a charge control agent. The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.
As the positively chargeable charge control agent, nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron (registered trademark) N-01", "Bontron (registered trademark) N- 04”, “Bontron (registered trademark) N-07”, “Bontron (registered trademark) N-09”, “Bontron (registered trademark) N-11” (manufactured by Orient Chemical Industry Co., Ltd.), etc.; tertiary amines triphenylmethane dyes containing as a side chain, quaternary ammonium salt compounds such as "Bontron (registered trademark) P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" ( Polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.); imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); Styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.).

As the negatively chargeable charge control agent, metal-containing azo dyes such as "Varifast (registered trademark) Black 3804", "Bontron (registered trademark) S-31", "Bontron (registered trademark) S-32", "Bontron (registered trademark) S-34”, “Bontron (registered trademark) S-36” (manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH”, “T-77” (Hodogaya Chemical Co., Ltd.) Metal compounds of benzylic acid compounds, such as "LR-147" and "LR-297" (manufactured by Nippon Carlit Co., Ltd.); Metal compounds of salicylic acid compounds, such as "Bontron (registered trademark) E. -81", "Bontron (registered trademark) E-84", "Bontron (registered trademark) E-88", "Bontron (registered trademark) E-304" (manufactured by Orient Chemical Industry Co., Ltd.), "TN- Copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE PX VP434" (manufactured by Clariant), nitroimidazole derivatives, and organometallic compounds. These charge control agents may be used alone or in combination of two or more.

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 even more preferably The amount is 0.5 parts by mass or more, and from the viewpoint of low-temperature fixability, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less.

<Other additives>
The toner according to the present embodiment further includes other additives such as magnetic powder, a fluidity improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a cleaning property improver, etc. It may contain appropriate additives.
Note that, in this specification, the toner before adding external additives, which will be described later, is also referred to as "toner particles." The colorant, mold release agent, charge control agent, and other additives mentioned above are preferably added before mixing the external additives.

(external additive)
The toner according to this embodiment may further contain an external additive in order to improve fluidity. Examples of the external additive include inorganic particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic particles such as resin particles such as melamine resin particles and polytetrafluoroethylene resin particles. . The toner may contain one or more of these external additives. Among these external additives, silica is preferred, and hydrophobic silica subjected to hydrophobic treatment is more preferred.

Examples of hydrophobizing agents for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Can be mentioned. Among these, hexamethyldisilazane is preferred.

When surface-treating toner particles using an external additive, the content of the external additive is preferably 0.05 parts by mass per 100 parts by mass of toner particles from the viewpoint of toner chargeability and fluidity. It is at least 0.1 parts by mass, more preferably at least 0.1 parts by mass, and preferably at most 5 parts by mass, more preferably at most 3 parts by mass.

The volume median particle diameter (D ₅₀ ) of the toner according to the present embodiment is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, More preferably, it is 10 μm or less. In this specification, the volume median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated from the volume fraction is 50% from the smallest particle size.
Furthermore, even when the toner is treated with an external additive, the preferred range of the volume median particle diameter (D ₅₀ ) of the toner treated with the external additive is the volume of the toner particles before being treated with the external additive. It is the same as the median particle size (D ₅₀ ). The value of the volume median particle diameter (D ₅₀ ) is determined by the method described in the Examples.

[Method for manufacturing toner for developing electrostatic image]
The toner for developing an electrostatic image according to the present embodiment may be a toner for developing an electrostatic image obtained by any conventionally known method, for example, the manufacturing method shown in (1) to (3) below. etc.
(1) A method of manufacturing a toner by melt-kneading a toner raw material mixture containing a binder resin composition and pulverizing the obtained melt-kneaded material (hereinafter also referred to as "melt-kneading pulverization method").
(2) Toner particles are obtained by agglomerating and fusing binder resin particles made of a binder resin composition in a toner raw material mixture containing a dispersion liquid in which the binder resin composition is dispersed in a water-soluble medium. (hereinafter also referred to as "agglomeration and fusing method")
(3) A method of manufacturing a toner by stirring a dispersion in which a binder resin composition is dispersed in an aqueous medium and a raw material for toner at high speed to obtain toner particles. From the viewpoint of further improving the low-temperature fixability and image heat resistance of the toner produced, the melt-kneading and pulverizing method (1) is preferred. Alternatively, the toner may be obtained by the aggregation and fusion method (2).

In the case of pulverized toner produced by the melt-kneading method, for example, raw materials such as a binder resin composition, a colorant, a mold release agent, and a charge control agent are uniformly mixed in a mixer such as a Henschel mixer, and then mixed in a closed kneader or a single-shaft kneader. Alternatively, it can be produced by melt-kneading with a twin-screw extruder, open roll kneader, etc., followed by cooling, pulverization, and classification.
The method for producing a toner preferably includes a step of melt-kneading a mixture containing a binder resin composition at a temperature within a range of 80° C. or higher and 160° C. or lower. The melt-kneading temperature is preferably 80°C or higher, more preferably 90°C or higher, and preferably 160°C or lower, more preferably 150°C or lower.
The method for producing toner preferably includes a step of pulverizing and classifying a mixture obtained by melt-kneading to obtain toner particles. The pulverization and classification can be performed by a known method.

When producing a toner using any of the above methods, the binder resin composition and its raw materials, as well as each additive such as a colorant, a release agent, and a charge control agent, are used as the binder for toner according to the present embodiment. The resin composition and toner for developing electrostatic images may be the same as those described above, and their preferred embodiments and blending amounts (same amounts as the above-mentioned contents and blending amounts) are also the same.

When producing a toner by any of the above methods, the amount of the binder resin composition used is preferably 5% by mass or more based on 100% by mass of the total amount of raw materials (in terms of solid content) contained in the resulting toner. , more preferably 50% by mass or more, still more preferably 70% by mass or more, and 100% by mass or less, preferably 97% by mass or less.

The toner for developing an electrostatic image according to this embodiment and the toner for developing an electrostatic image obtained by the manufacturing method according to this embodiment are a toner for two-component development that is used as a toner for one-component development or mixed with a carrier. They can be used in image forming apparatuses of a one-component development method or a two-component development method, respectively.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples in any way. Each property of the raw materials etc. was measured and evaluated by the following method.
In addition, in the description such as "alkylene oxide (X)", the numerical value X in parentheses means the average number of moles of alkylene oxide added.

[Weight average molecular weight (Mw) of addition polymerization resin]
Molecular weight distribution was measured by gel permeation chromatography (GPC) to determine weight average molecular weight.
(1) Preparation of sample solution A sample was dissolved in tetrahydrofuran at 25°C so that the concentration was 0.5 g/100 mL. Next, this solution was filtered using a fluororesin filter "DISMIC-25JP" (manufactured by ADVANTEC) with a pore size of 0.2 μm to remove insoluble matter, and a sample solution was obtained.
(2) Molecular weight measurement Using the measuring device and analytical column described below, tetrahydrofuran was flowed as an eluent at a flow rate of 1 mL per minute, and the column was stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution was injected thereto for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodisperse polystyrene "A-500" (5.0 x 10 ² ), "A-1000" (1.01 x 10 ³ ), and "A-2500" (2.63 ×10 ³ ), “A-5000” (5.97×10 ³ ), “F-1” (1.02×10 ³ ), “F-2” (1.81×10 ⁴ ), “F- 4” (3.97×10 ⁴ ), “F-10” (9.64×10 ⁴ ), “F-20” (1.90×10 ⁵ ), “F-40” (4.27×10 ⁵ ), "F-80" (7.06×10 ⁵ ), and "F-128" (1.09×10 ⁶ ) (manufactured by Tosoh Corporation) were used as standard samples.
Measuring device: “HLC-8220CPC” (manufactured by Tosoh Corporation)
Analysis column: “GMHXL” + “G3000HXL” (manufactured by Tosoh Corporation)

[Number average molecular weight (Mn) of polyalkylene imine]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method shown below, and the number average molecular weight was determined.
(1) Preparation of sample solution Polyalkyleneimine was dissolved at 0.15 mol/L in a solution of Na ₂ SO ₄ dissolved in 1% by mass acetic acid aqueous solution so that the concentration was 0.2 g/100 mL. . Next, this solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 0.2 μm to remove insoluble components, and a sample solution was obtained.
(2) Molecular weight measurement Using the following measuring device and analytical column, a solution of 0.15 mol/L of Na ₂ SO ₄ dissolved in a 1% by mass acetic acid aqueous solution was flowed as an eluent at a flow rate of 1 mL/min. The column was stabilized in a constant temperature bath at 40°C. There, 100 μL of the sample solution was injected and measurements were performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time included several types of standard pullulan "P-5" (5.9×10 ³ ), "P-50" (4.73×10 ⁴ ), and "P-200" (2.12× 10 ⁵ ) and "P-800" (7.08×10 ⁵ ) (manufactured by Showa Denko Co., Ltd.) prepared as standard samples were used. The molecular weight is shown in parentheses.
Measuring device: “HLC-8320GPC” (manufactured by Tosoh Corporation)
Analysis column: "α" + "α-M" + "α-M" (manufactured by Tosoh Corporation)

[Softening point of resin and resin composition]
Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of sample was heated at a heating rate of 6°C/min while applying a load of 1.96 MPa with a plunger to a diameter of 1 mm and a length of 1 mm. It was extruded from the nozzle. The fall of the plunger of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was defined as the softening point.

[Glass transition temperature of resin and resin composition]
Using a differential scanning calorimeter "Q-20" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then The temperature was cooled down to 0°C at a cooling rate of 10°C/min. Next, the sample was heated at a heating rate of 10°C/min, and the temperature at the intersection of the extension line of the baseline below the highest endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the top of the peak was determined. It was taken as the glass transition temperature.

[Melting point of crystalline resin]
Using a differential scanning calorimeter "Q-100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, and the temperature was lowered from room temperature at a rate of 10°C/min. The mixture was cooled to −10° C. and the temperature was maintained for 1 minute. Next, the sample was heated to 200°C at a heating rate of 10°C/min, and then cooled from that temperature to -30°C at a cooling rate of 10°C/min. Next, the temperature of the sample was raised at a heating rate of 10° C./min, and among the endothermic peaks observed, the peak temperature on the highest temperature side was taken as the melting point.

[Acid value and hydroxyl value of resin and resin composition]
The acid value and hydroxyl value of the resin were measured based on the method of JIS K0070:1992. However, the measurement solvent should be a mixed solvent of ethanol and ether specified in JIS K0070:1992, or a mixed solvent of acetone and toluene for amorphous polyester resins and resin compositions [acetone:toluene = 1:1 (volume ratio)] ], in the case of crystalline polyester resin, chloroform was used.

[Melting point of mold release agent]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then lowered from 200°C. It was cooled to 0°C at a rate of 10°C/min. Next, the sample was heated at a heating rate of 10° C./min, and the amount of heat was measured. The maximum peak temperature of the endotherm obtained was taken as the melting point.

[Volume median particle size (D ₅₀ ) of toner particles]
The volume median particle diameter (D ₅₀ ) of the toner particles was measured as follows.
・Measuring device: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50μm
・Analysis software: “Coulter Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
・Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
・Dispersion liquid: "Emulgen (registered trademark) 109P" [polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance, Griffin method) = 13.6] was dissolved in the electrolyte, and the concentration was 5 mass. % dispersion was obtained.
・Dispersion conditions: Add 10 mg of the measurement sample to 5 mL of the dispersion liquid, disperse for 1 minute with an ultrasonic disperser, then add 25 mL of electrolyte, and further disperse for 1 minute with an ultrasonic disperser, A sample dispersion was prepared.
・Measurement conditions: Add the sample dispersion to 100 mL of the electrolyte in a beaker to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then measure 30,000 particles. Then, the volume median particle diameter (D ₅₀ ) was determined from the obtained particle size distribution.

[SP values of resin (A) and resin (C)]
The SP value is calculated as the product of the SP value and the molar ratio of each monomer constituting the resin.
For example, when a resin is formed from two types of monomers, X and Y, if the mass ratio of each monomer is x and y (mass%), the molecular weight is Mx and My, and the SP value is SPx and SPy, then this resin The SP value is expressed by the following formula (1).
SP value = {(x×SPx/Mx)+(y×SPy/My)}×{1/(x/Mx+y/My)} (1)
The SP value of a monomer was proposed by Fedors et al. for the atoms or atomic groups in the molecular structure of the monomer [POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. 147-154)], the evaporation energy (Δei) and molar volume (Δvi) are determined from the following formula (2). However, for double bonds that are cleaved during polymerization, the molecular structure is defined as the cleaved state.
σ=(ΣΔei/ΣΔvi)1/2 (2)
If it is not possible to calculate the SP value of the monomer using the above formula (2), use literature such as Polymer Handbook (published by Wiley Publishing) 4th edition or the information provided by the National Institute for Materials Science (NIMS) as a specific value. The solubility parameter items described in the database PolyInfo (http://polymer.nims.go.jp) can be referred to.

[Example of resin production]
(Production examples A-1, A-2)
The raw material monomer (b) for addition polymerization resin containing acrylic acid or methacrylic acid as a bireactive compound shown in Table 1 was placed in an autoclave equipped with a stainless steel stirring rod, and heated under pressure and heating conditions (300°C) for 2 hours. The raw material monomer (b) was polymerized by bulk polymerization. Addition polymerization resins A-1 and A-2 were obtained by recovering the precipitated addition polymerization resins by returning the mixture to normal pressure and room temperature. Various physical properties are shown in Table 1.

(Production examples AX-1, AL-1)
The alcohol component, carboxylic acid component, esterification catalyst, and esterification cocatalyst shown in Table 2 were transferred to a dehydration tube, a cooling tube, and a nitrogen introduction tube equipped with a thermometer, a stainless steel stirring bar, a fractionating column, a flowing-down condenser, and a nitrogen inlet tube. The mixture was placed in a 10 liter four-necked flask equipped with a nitrogen atmosphere, heated to 235° C. in a mantle heater, and reacted at normal pressure for 7 hours. Thereafter, a reduced pressure reaction was performed at 235° C. and 8 kPa to a desired acid value and softening point to obtain resins AX-1 and AL-1, which are amorphous polyester resins. Various physical properties were measured and shown in Table 2.

(Manufacturing example AL-2)
The alcohol component, carboxylic acid component, esterification catalyst, and esterification cocatalyst shown in Table 2 were added to a 10-liter tube equipped with a thermometer, stainless steel stirring rod, fractionator, dehydration tube, cooling tube, and nitrogen introduction tube. The mixture was placed in a four-necked flask, heated to 235° C. in a mantle heater in a nitrogen atmosphere, and reacted at normal pressure for 2.5 hours, and then at reduced pressure of 8 kPa for 1 hour. Thereafter, the mixture was cooled to 190°C under normal pressure, addition polymerization resin A-1 was added, and then the temperature was raised to 235°C. Thereafter, the reaction was carried out at 10 kPa to a desired softening point to obtain resin AL-2. Various physical properties were measured and shown in Table 2.

(Production examples AL-3, AL-4)
The alcohol component, carboxylic acid component, polyethylene terephthalate, esterification catalyst, and esterification cocatalyst shown in Table 2 were equipped with a thermometer, stainless steel stirring rod, fractionator, dehydration tube, cooling tube, and nitrogen introduction tube. The mixture was placed in a 10-liter four-necked flask, heated to 235° C. in a mantle heater in a nitrogen atmosphere, and reacted at normal pressure for 2 hours. Thereafter, it was cooled to 180°C, addition polymerization resin A-1 or A-2 was added, and then the temperature was raised stepwise to 235°C at a rate of 10°C/h. Thereafter, the reaction was carried out to a desired softening point to obtain resins AL-3 and AL-4. Various physical properties were measured and shown in Table 2.

(Production example AH-1)
The alcohol components shown in Table 3, terephthalic acid, esterification catalyst, and esterification cocatalyst were mixed into a 10 liter cell equipped with a thermometer, a stainless steel stirring rod, a fractionating column, a dehydration tube, a cooling tube, and a nitrogen introduction tube. The mixture was placed in a neck flask, heated to 235° C. in a mantle heater in a nitrogen atmosphere, and reacted at normal pressure for 4 hours, and then at reduced pressure of 8 kPa for 1 hour. Thereafter, the mixture was cooled to 190° C. under normal pressure, adipic acid and trimellitic anhydride were added, and then the temperature was raised stepwise to 210° C. at a rate of 10° C./h. Thereafter, the reaction was carried out at 8 kPa to a desired softening point to obtain resin AH-1. Various physical properties were measured and shown in Table 3.

(Production examples C-1, C-2, C-3)
The alcohol component, carboxylic acid component, esterification catalyst, and polymerization inhibitor shown in Table 4 were added to a thermometer, stainless steel stirring bar, fractionator, dehydration tube, cooling tube equipped with a flowing condenser, and nitrogen introduction tube. The mixture was placed in an equipped 10 liter four-necked flask, heated to 140°C in a mantle heater in a nitrogen atmosphere, reacted for 5 hours, and then raised stepwise to 200°C at a rate of 10°C/h. I took a warm bath. Thereafter, the reaction was carried out at 8 kPa to a desired softening point to obtain crystalline polyester resins C-1, C-2, and C-3. Various physical properties were measured and shown in Table 4. Note that since Resin C-1 was insoluble in the measurement solvent, the acid value could not be measured.

(Production example CP-1)
5306 g of crystalline polyester resin C-3 was placed in a 2 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a dehydration tube with a falling condenser, and a nitrogen introduction tube, and the mixture was placed in a mantle heater in a nitrogen atmosphere. After raising the temperature to 150°C, 53.1g of "Polyethyleneimine 300" (manufactured by Junsei Kagaku Co., Ltd.) was added, and the reaction was carried out at 150°C for 3 hours to form a mixture between crystalline polyester resin C-3 and the polyethyleneimine. A resin composition CP-1 was obtained by condensing the following. Various physical properties were measured and shown in Table 5.

(Manufacturing example CP-2)
In Production Example CP-1, crystalline polyester resin C- A resin composition CP-2 was obtained by condensing No. 3 with the polyethyleneimine. Various physical properties were measured and shown in Table 5.

(Manufacturing example CP-3)
In Production Example CP-1, the crystalline polyester resin C-3 and the diethylene triamine were condensed in the same manner as Production Example CP-1, except that "polyethyleneimine 300" was changed to "diethylenetriamine". A resin composition CP-3 was obtained. Various physical properties were measured and shown in Table 5.

(Manufacturing example CP-4)
In Production Example CP-1, crystalline polyester resin C-3 and the triethylenetetramine were prepared in the same manner as Production Example CP-1, except that "polyethyleneimine 300" was changed to "triethylenetetramine". A resin composition CP-4 was obtained by condensing the following. Various physical properties were measured and shown in Table 5.

[Manufacture of toner]
(Example 1)
100 parts by mass of the binder resin composition shown in Table 6, 5 parts by mass of the colorant "ECB-301" (manufactured by Dainichiseika Kagyo Co., Ltd.), 1 mass of the charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.) and 2 parts by mass of the mold release agent "HNP-9" (manufactured by Nippon Seiro Co., Ltd., paraffin wax, melting point: 75 ° C.) were thoroughly stirred with a Henschel mixer, and the total length of the kneaded part was 1560 mm, the screw diameter was 42 mm, The mixture was melt-kneaded using a co-rotating twin-screw extruder with a barrel inner diameter of 43 mm. The rotational speed of the screw was 200 r/min, the heating temperature inside the screw was 90°C, the temperature of the kneaded material was 140°C, the feeding rate of the kneaded material was 10 kg/h, and the average residence time was about 18 seconds. The obtained kneaded material was cooled from 140°C to 50°C in 1.5 hours, rolled and cooled at 50°C with a cooling roller, and then left to stand at 45°C for 4 hours, crushed with a jet mill, classified, and divided by volume. Toner particles having a particle size (D ₅₀ ) of 5.5 μm were obtained.
To 100 parts by mass of the obtained toner particles, 1.0 parts by mass of external additive "AEROSIL NAX 50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica, hydrophobic treatment agent: HMDS, number average particle diameter: 30 nm) was added. The external additive treatment was carried out by adding and mixing for 5 minutes at 3600 r/min using a Henschel mixer to obtain a toner.
The obtained toner was evaluated by the method described below. The results obtained are shown in Table 6.

(Examples 2 to 9 and Comparative Examples 1 to 5)
Toners were obtained in the same manner as in Example 1, except that the type of binder resin composition or the amount added thereof was changed as shown in Table 6.
Each of the obtained toners was evaluated by the method described below. The results obtained are shown in Table 6.

[Toner evaluation]
<Low temperature fixability>
The toner was installed in a fixing device of the copying machine "AR-505" (manufactured by Sharp Corporation) that had been modified to enable fixing outside the device, and printed matter was obtained in an unfixed state (print area: 2 cm). x 12 cm, adhesion amount: 0.5 mg/cm ² ). After that, using a fixing machine (fixing speed: 300 mm/sec) adjusted so that the total fixing pressure is 30 kgf, the temperature of the fixing roll is gradually increased by 5 degrees Celsius from 100 degrees Celsius to 240 degrees Celsius, and the temperature is not determined at each temperature. A fixation test was conducted on the printed matter in the worn state. A cellophane adhesive tape "UNICEF cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z 1522) was pasted on the image area of the obtained printed matter, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. Ta. The paper used for printing was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/m ² ).
The optical reflection density before applying the tape and after peeling it off was measured using a reflection densitometer "RD-915" (manufactured by Gretag Macbeth), and the ratio of both (after peeling/before pasting x 100) was 90% at first. The temperature of the fixing roller exceeding the above was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability of the toner.

<Image heat resistance>
The toner was installed in a fixing device of the copying machine "AR-505" (manufactured by Sharp Corporation) that had been modified to enable fixing outside the device, and printed matter was obtained in an unfixed state (print area: 2 cm). x 12 cm, adhesion amount: 0.5 mg/cm ² ). Thereafter, using a fixing machine (fixing speed: 300 mm/sec) adjusted to have a total fixing pressure of 30 kgf, and setting the temperature of the fixing roll to 140° C., the unfixed printed matter was fixed. The paper used for printing was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/m ² ).
The fixed images were superimposed on each other and left for one day under a load of 100 g/cm ² at a temperature of 60° C. and a humidity of 50%, and the presence or absence of document offset was visually observed when peeled off after one day. I confirmed it. The obtained results were evaluated according to the following criteria.
A: Document offset cannot be confirmed. B: Peeling of the fixed image cannot be confirmed, but slight sticking occurs when it is peeled off. C: Sticking occurs when it is peeled off, and the fixed image has slight peeling (white spots, etc.) D: Sticking occurs when peeled off, and white spots are clearly visible in the fixed image. E: Papers are stuck together, and the paper will be damaged when peeled off.

As shown in Table 6, the toner crystals of Examples 1 to 9 in which the difference in SP value between the crystalline resin (C) and the amorphous resin (A) was 1.40 (cal/cm ³ ) ^1/2 or more It can be seen that the toner using the resin-adsorbing composition has a low minimum fixing temperature and the resulting fixed image has excellent heat resistance.
On the other hand, as shown in Table 6, the difference in SP value between the crystalline resin (C) and the amorphous resin (A) is less than 1.40 (cal/cm ³ ) ^1/2 , and when an amine compound is used The binder resin compositions for toner of Comparative Examples 1 to 3 in which the difference in SP value between the crystalline resin (C) and the amorphous resin (A) is less than 1.40 (cal/cm ³ ) ^1/2 The toners using the toner binder resin compositions of Comparative Examples 4 and 5 had a higher minimum fixing temperature or the heat resistance of the obtained fixed images was poorer than the toners of Examples 1 to 9. It can be seen that
From the above, it can be seen from the results of Examples 1 to 9 and Comparative Examples 1 to 5 that according to the present invention, a toner having excellent low-temperature fixability and image heat resistance can be obtained.

Claims (10)

A binder resin composition for a toner, comprising a resin composition (CP) obtained by condensing a crystalline resin (C) having an acid group and an amine compound, and an amorphous resin (A). There it is,
A binder resin composition for toner, wherein the difference in Fedors solubility parameter (SP value) between the crystalline resin (C) and the amorphous resin (A) is 1.40 (cal/cm ³ ) ^1/2 or more. thing. The binder resin composition for a toner according to claim 1, wherein the amorphous resin (A) includes a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond. 1 or 2, wherein the mass ratio [(A)/(CP)] of the amorphous resin (A) and the resin composition (CP) is 65/35 or more and 95/5 or less. 2. The binder resin composition for toner according to 2. The amount of the amine compound to be reacted with the crystalline resin (C) is 0.01% by mass or more based on the total amount of the resin composition (CP) and the amorphous resin (A).1. The binder resin composition for toner according to any one of claims 1 to 3, which has a content of 0% by mass or less. The binder resin composition for a toner according to any one of claims 1 to 4, wherein the amine compound contains at least one selected from polyalkyleneimine and (poly)ethylene polyamine. The binder resin composition for a toner according to any one of claims 1 to 5, wherein the crystalline resin (C) contains a crystalline polyester resin. A toner for developing an electrostatic image, comprising the binder resin composition for toner according to any one of claims 1 to 6. Step 1: A step of condensing a crystalline resin (C) having an acid group with an amine compound to obtain a resin composition (CP), and Step 2: A step of obtaining the resin composition (CP) and an amorphous resin composition. a step of mixing with resin (A);
A method for producing a binder resin composition for toner, comprising:
A binder resin composition for toner, wherein the difference in Fedors solubility parameter (SP value) between the crystalline resin (C) and the amorphous resin (A) is 1.40 (cal/cm ³ ) ^1/2 or more. How things are manufactured. 9. The production of the binder resin composition for a toner according to claim 8, wherein the amorphous resin (A) includes a composite resin in which an addition polymerization resin segment and a polyester resin segment are bonded via a covalent bond. Method. 9. The mass ratio [(A)/(CP)] of the amorphous resin (A) and the resin composition (CP) is 65/35 or more and 95/5 or less. 9. The method for producing a binder resin composition for toner according to 9.