JP6915311B2 - Bundling resin, toner and printing composition - Google Patents

Description

The present invention relates to binder resins, toners and textile printing compositions.

Bending resins are widely used in applications such as toner materials, printing materials, coating materials, adhesives, and films. The binder resin is required to have various properties depending on the application. For example, in toner applications and printing applications, it is required to have excellent heat resistance at high temperatures.

For example, Patent Document 1 discloses a binder resin for toner containing a polyester resin and an acrylic thermoplastic polymer as a binder resin having excellent hot offset resistance.

Japanese Unexamined Patent Publication No. 2006-276342

However, in the case of the binder resin described in Patent Document 1, the heat resistance at high temperature is not always sufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a binder resin having excellent heat resistance at high temperatures, and a toner and a printing composition containing the binder resin.

As a result of diligent studies, the present inventions have improved the storage elastic modulus (G') of the binder resin by using the polyester resin and the acrylic polymer in combination and defining the softening temperature of the binder resin, and at high temperatures. We have found that the heat resistance is improved, and have completed the present invention.

That is, the present invention has the following aspects.
[1] A binder resin containing a polyester resin (A) and an acrylic polymer (B), wherein the softening temperature of the binder resin is 130 ° C. or higher, and the polyester resin (A) / acrylic polymer. A binder resin having a mass ratio represented by (B) of 99.9 / 0.1 to 92/8.
[2] The binder resin according to [1], wherein the gel content of the binder resin is 5 to 40% by mass.
[3] The binder resin according to [1] or [2], wherein the polyester resin (A) has a softening temperature of 140 ° C. or higher.
[4] A toner containing the binder resin according to any one of [1] to [3].
[5] A printing composition containing the binder resin according to any one of [1] to [3].

According to the present invention, it is possible to provide a binder resin having excellent heat resistance at a high temperature, a toner containing the binder resin, and a composition for printing.

"Bound resin"
The binder resin of the present invention contains a polyester resin (A) and an acrylic polymer (B).

<Polyester resin (A)>
The polyester resin (A) (hereinafter, also referred to as “component (A)”) is synthesized using a polyvalent carboxylic acid and a polyhydric alcohol as raw materials. That is, the component (A) is a reaction product of a multivalent carboxylic acid and a polyhydric alcohol.

Examples of the polyvalent carboxylic acid include a divalent carboxylic acid and a trivalent or higher carboxylic acid.
Examples of the divalent carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids such as phthalic acid, sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid and adipic acid, and lower grades thereof. Examples include alkyl esters or acid anhydrides. Examples of the lower alkyl ester of these dicarboxylic acids include monomethyl ester, monoethyl ester, dimethyl ester and diethyl ester.
One of these may be used alone, or two or more thereof may be used in combination. In addition, it may be used in combination with a carboxylic acid having a valence of 3 or more, which will be described later.

Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and 1 , 2,5-Hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, and acid anhydrides thereof.
One of these may be used alone, or two or more thereof may be used in combination. It may also be used in combination with a divalent carboxylic acid.

Examples of the polyhydric alcohol include divalent alcohols and trihydric or higher alcohols.
Examples of the divalent alcohol include ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, and polyethylene. Diols such as glycol; bisphenol A, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-) Hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-Hydroxyphenyl) propane, polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-hydroxy) Examples thereof include bisphenol A alkylene oxide adducts such as phenyl) propane and polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane.
One of these may be used alone, or two or more thereof may be used in combination. In addition, it may be used in combination with a trihydric or higher alcohol described later.

Examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-Pentantriol, Glycerin, 2-Methyl-1,2,3-Propanetriol, 2-Methyl-1,2,4-Butantriol, Trimethylolpropane, 1,3,5-Trihydroxymethylbenzene And so on.
One of these may be used alone, or two or more thereof may be used in combination. It may also be used in combination with a divalent alcohol.

As a raw material for the component (A), a monovalent carboxylic acid or a monohydric alcohol may be used in combination in addition to the polyvalent carboxylic acid and the polyhydric alcohol as long as the object of the present invention is not impaired.
Examples of the monovalent carboxylic acid include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid; and aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid; Examples thereof include unsaturated carboxylic acids having one or more unsaturated double bonds in the molecule, such as oleic acid, linolenic acid, and linolenic acid.
Examples of the monohydric alcohol include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol; and aliphatic alcohols having 30 or less carbon atoms such as oleyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol.
One of these may be used alone, or two or more thereof may be used in combination.

The component (A) is obtained by a known polymerization method. For example, first, raw materials such as polyvalent carboxylic acid and polyhydric alcohol are put into a reaction vessel, heated and heated to carry out an esterification reaction or a transesterification reaction, and water or alcohol generated in the reaction is removed. The polycondensation reaction is subsequently carried out to obtain the component (A).

The catalyst used in the esterification reaction, transesterification reaction, and depolymerization reaction is not particularly limited, and is, for example, titanium tetraalkoxide, tetrabutoxytitanium, titanium oxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, triad. Known polymerization catalysts such as antimony oxide, germanium dioxide, and magnesium acetate can be used.

The polymerization temperature is not particularly limited, but is preferably in the range of 180 to 280 ° C. When the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and when the polymerization temperature is 280 ° C. or lower, the decomposition of the resin and the by-production of volatile substances that cause odors tend to be suppressed. The polymerization temperature is more preferably 200 ° C. or higher, and even more preferably 220 ° C. or higher. Further, the polymerization temperature is more preferably 270 ° C. or lower.

The content of the polyhydric alcohol is 180 mol parts with respect to 100 mol parts of the polyvalent carboxylic acid because the balance between the softening temperature (T4) and the glass transition temperature (Tg) of the obtained component (A) is good. The following are preferable, 70 to 170 mol parts are more preferable, 80 to 160 mol parts are further preferable, and 90 to 150 mol parts are particularly preferable. In particular, when the content of the polyhydric alcohol is 90 mol parts or more, the production stability of the component (A) tends to be good, and when it is 150 mol parts or less, the glass transition temperature is higher than the softening temperature. It tends to be easy to be stored, and the storage stability tends to be better.

From the viewpoint of increasing productivity, it is preferable to use a trifunctional or higher functional monomer as a raw material for the component (A). Examples of the trifunctional or higher functional monomer include the trivalent or higher carboxylic acid exemplified above in the description of the polyvalent carboxylic acid, the trihydric or higher alcohol exemplified above in the description of the polyhydric alcohol, and the like. As a trifunctional or higher functional monomer, a trivalent or higher carboxylic acid and a trivalent or higher alcohol may be used in combination.
The content of the trifunctional or higher functional monomer is preferably 5 to 50 mol parts, more preferably 5 to 40 mol parts, still more preferably 5 to 35 mol parts with respect to 100 mol parts of the polyvalent carboxylic acid. When the content of the trifunctional or higher-functional monomer is within the above range, the storage elastic modulus (G') and the gel fraction of the binder resin can be set to desired values while maintaining good productivity of the component (A). It becomes easier to control.

The softening temperature of the component (A) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher. When the softening temperature of the component (A) is 140 ° C. or higher, the softening temperature of the binder resin also increases, and the heat resistance at a high temperature becomes better. The upper limit of the softening temperature of the component (A) is not particularly limited, but when the binder resin of the present invention is used for toner applications or printing applications, it has hot offset resistance during printing on paper and from paper to fabric. From the viewpoint of improving the resin transferability to the fabric during transfer (fabric resistance resin transferability), the softening temperature of the component (A) is preferably 170 ° C. or lower, more preferably 165 ° C. or lower. When the binder resin of the present invention is used for printing, if the softening temperature of the component (A) is 170 ° C. or lower, the peelability between the paper and the fabric is also improved.

The softening temperature of the component (A) was measured with a nozzle of 1 mmφ × 10 mm under the conditions of a load of 294 N (30 kgf) and a temperature rise rate of 3 ° C./min at a constant rate of temperature rise, and halved in 1.0 g of the sample. Is the temperature at which is spilled.
The softening temperature of the component (A) can be measured using a flow tester.

<Acrylic polymer (B)>
The acrylic polymer (B) (hereinafter, also referred to as “component (B)”) may be thermoplastic or thermosetting, but thermoplastic is preferable. That is, as the component (B), an acrylic thermoplastic polymer is preferable.
The component (B) preferably contains a monofunctional (meth) acrylic acid alkyl ester unit as a constituent component. This is because the monofunctional (meth) acrylic acid alkyl ester contains an ester group as a constituent unit, so that the compatibility with the component (A) is improved and the effect of using the monofunctional (meth) acrylic acid alkyl ester in combination with the component (A) is enhanced.
Here, "(meth) acrylate" is a general term for acrylate and methacrylate.

Examples of the monofunctional (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, propyl (meth) acrylate, and 2-ethyl. Xyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) Examples thereof include acrylate and glycidyl (meth) acrylate.
One of these may be used alone, or two or more thereof may be used in combination.

As the monofunctional (meth) acrylic acid alkyl ester, a monomer having a functional group (for example, an epoxy group) capable of reacting with the component (A) is preferable. Examples of such a monomer include glycidyl (meth) acrylate and the like.
When an acrylic polymer containing, for example, a monomer having an epoxy group as a constituent unit is used as the component (B), when mixed with the component (A), a part of the component (B) becomes a part of the component (A). It is thought that it will react. Specifically, the epoxy group in the component (B) reacts with the carboxy group or the hydroxy group at the end of the component (A), and the compound represented by the following general formula (1) or the following general formula (2) ( Reaction product) is considered to be formed. That is, when an acrylic polymer containing a monomer having a functional group capable of reacting with the component (A) as a constituent unit is used as the component (B), the component (A) and (B) are used as the binder resin. ) And the reaction products of the components (A) and (B). When the binder resin contains the reaction products of the component (A) and the component (B), the storage elastic modulus (G') of the binder resin tends to be further increased, and the heat resistance at high temperature tends to be further improved.
The compound represented by the following general formula (1) is a compound in which the epoxy group in the component (B) and the terminal carboxy group of the component (A) are reacted, and is represented by the following general formula (2). The compound is a compound in which the epoxy group in the component (B) and the hydroxy group at the end of the component (A) are reacted.

In formula (1), R ¹ is a hydrocarbon group, R ² is a hydrogen atom or a hydrocarbon group, R ³ and R ⁴ are independently hydrogen atoms or a methyl group, and R ⁵ is a polyester. It is a residue obtained by removing the terminal carboxy group from the resin.
In formula (2), R ⁶ is a hydrocarbon group, R ⁷ is a hydrogen atom or a hydrocarbon group, R ⁸ and R ⁹ are independently hydrogen atoms or methyl groups, and R ¹⁰ is a polyester. It is a residue obtained by removing the terminal hydroxy group from the resin.

The component (B) is a total of 100 parts by mass including 50 to 100 parts by mass of a monofunctional (meth) acrylic acid alkyl ester and 50 parts by mass or less of another vinyl monomer copolymerizable therewith, if necessary. It can be obtained by polymerizing parts.

Other vinyl monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-densyl styrene, pn-dodecyl styrene, p-phenyl styrene, 3, Styrene-based monomers such as 4-dicyclostyrene; unsaturated dicarboxylic acid diesters (specifically, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, etc.), unsaturated mono Styrene (specifically, (meth) acrylic acid, silicic acid, etc.), unsaturated dicarboxylic acid (specifically, maleic acid, fumaric acid, itaconic acid, etc.), unsaturated dicarboxylic acid monoester (specifically, malein) Examples thereof include carboxylic acid-containing vinyl-based monomers such as monomethyl acid, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, etc.; (meth) acrylonitrile; (meth) acrylamide and the like. One of these may be used alone, or two or more thereof may be used in combination.
Here, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, "(meth) acrylonitrile" is a general term for acrylonitrile and methacrylic acid, and "(meth) acrylamide" is a general term for acrylamide and methacrylamide. It is a generic term.

Furthermore, as another vinyl monomer, a polyfunctional vinyl monomer can also be used. Examples of the polyfunctional vinyl monomer include divinylbenzene, divinylnaphthalene, allyl methacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butylene glycol di (meth) acrylate. Examples thereof include 1,6-hexanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
One of these may be used alone, or two or more thereof may be used in combination.

As the polymerization method for producing the component (B), one-step polymerization or sequential multi-step polymerization by an emulsion polymerization method is preferable. However, the present invention is not particularly limited, and for example, it can be produced by emulsion suspension polymerization in which the outermost layer polymer is converted into a suspension polymerization system at the time of polymerization of the outermost layer polymer after emulsion polymerization.
In the production of the component (B), for example, the polymer latex produced by the emulsion polymerization method can be separated and recovered by various coagulants, or the solid content can be separated and recovered by spray drying to obtain the polymer powder. ..

The average particle size of the component (B) is preferably 500 μm or less. When the average particle size of the component (B) is 500 μm or less, it is easy to control the particle size to monodisperse. The lower limit of the average particle size of the component (B) is not particularly limited, but the average particle size of the component (B) is preferably 0.01 μm or more from the viewpoint of improving the productivity when separated as particles.
Of the particle sizes with an average particle size of 500 μm or less, the suspension polymerization method is preferably used when particles larger than 5 μm are desired, and an emulsion polymerization method or dispersion polymerization is selected when particles of 5 μm or less are desired to be obtained. It is preferable to do so. If the storage stability of the toner becomes low due to the influence of the emulsifier, emulsifier-free polymerization may be used.
The average particle size of the component (B) is a particle size corresponding to a cumulative 50% based on the volume distribution measured by using a laser diffraction method. Specifically, the measurement is performed as follows.

The particle size distribution of the component (B) is measured using a laser diffraction type particle size measuring machine (manufactured by HORIBA, Ltd., “LA-920”). According to the operation manual of the device, using a flow cell for measurement, distilled water is added into the cell, the relative refractive index is selectively set to 1.20, the particle size reference is set as the volume reference, the optical axis is adjusted, and the optical axis is adjusted. Perform fine adjustment and blank measurement. Next, the component (B) is added to a concentration in the range of 70 to 90% of the transmittance, ultrasonic treatment is carried out at an intensity of 5 for 1 minute, and the particle size distribution measurement of the resin particles is carried out. From the measured particle size distribution, the particle size (median diameter) corresponding to the cumulative 50% of the volume distribution standard is defined as the average particle size.

As the component (B), a commercially available product can be used, and examples thereof include trade names: Metabrene P-1900 and P-1901 manufactured by Mitsubishi Rayon Co., Ltd.

The mass ratio represented by the polyester resin (A) / acrylic polymer (B) (hereinafter, also referred to as “A / B ratio”) is 99.9 / 0.1 to 92/8, and 99. 9 / 0.1-94 / 6 is preferable. If the amount of the component (A) is too large, the softening temperature of the binder resin tends to decrease. On the other hand, if the amount of the component (A) is too small, when the component (A) and the component (B) are kneaded using a kneader or the like to produce a binder resin, the mixture solidifies in the kneader and condenses. It becomes difficult to take out the resin. When the A / B ratio is within the above range, it becomes easy to control the softening temperature of the binder resin to a desired value while maintaining good productivity of the binder resin.

<Manufacturing method>
The binder resin is obtained by mixing the component (A) and the component (B).
A known kneader can be used for mixing the component (A) and the component (B). Specific examples of the kneader include a single-screw extruder, a twin-screw extruder, a continuously sealed mixer, a gear extruder, a disc extruder, a roll mill extruder, a static mixer, and other continuous melt mixers; Examples thereof include a batch closed-type melt-mixer such as a mixer and a harke mixer.

The mixing temperature when the component (A) and the component (B) are mixed is preferably 100 to 200 ° C. When the mixing temperature is within the above range, a decrease in productivity during mixing can be suppressed.

<Physical characteristics>
The softening temperature of the binder resin is 130 ° C. or higher, preferably 140 ° C. or higher. When the softening temperature of the binder resin is 130 ° C. or higher, the heat resistance at a high temperature is good. The upper limit of the softening temperature of the binder resin is not particularly limited, but when the binder resin of the present invention is used for toner applications or printing applications, it has hot offset resistance during printing on paper and transfer from paper to fabric. From the viewpoint of improving the transferability of the fabric resin at the time, the softening temperature of the binder resin is preferably 240 ° C. or lower, more preferably 230 ° C. or lower. When the binding resin of the present invention is used for printing, if the softening temperature of the binding resin is 240 ° C. or lower, the peelability between the paper and the fabric is also improved.
The softening temperature of the binder resin can be controlled by adjusting the softening temperature of the component (A) and the A / B ratio. For example, by using a polyester resin having a softening temperature of 140 to 170 ° C. as the component (A) and setting the A / B ratio within the above range, the softening temperature of the binder resin can be easily controlled to 130 to 240 ° C.

The softening temperature of the binder resin was measured with a nozzle of 1 mmφ × 10 mm under the conditions of a load of 294 N (30 kgf) and a temperature rise rate of 3 ° C./min at a constant rate of temperature rise, and 1/2 of 1.0 g of the sample was measured. It is the temperature at the time of spillage.
The softening temperature of the binder resin can be measured using a flow tester.

The gel fraction of the binder resin is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, based on the total mass of the binder resin. When the gel fraction of the binder resin is within the above range, the heat resistance at high temperature becomes better.
The gel fraction of the binder resin can be adjusted by the composition of the component (A) and the component (B).

The gel fraction of the binder resin is obtained as follows.
First, about 0.5 g of the binder resin is weighed in a 100 mL Erlenmeyer flask (X1 (g)), and 50 mL of tetrahydrofuran (THF) is added to dissolve the binder resin.
Separately, the glass filter is filled with Celite from 6 to 7 minutes, and after sufficiently drying, the dried glass filter is weighed (X2 (g)).
Next, the THF solution in which the binder resin is dissolved is transferred into a dry glass filter and suction filtered. After continuing suction so that no solvent remains in the filter, the glass filter is sufficiently dried in a vacuum dryer, the dried glass filter is weighed (X3 (g)), and the gel fraction is according to the following formula (i). (THF insoluble matter) is calculated.
Gel fraction (mass%) = {(X3-X2) / X1} x 100 ... (i)

<Effect>
The binder resin of the present invention described above contains the component (A) and the component (B) in a specific mass ratio, and has a softening temperature of 130 ° C. or higher, so that it is excellent in heat resistance at high temperatures. Specifically, the binder resin of the present invention tends to have a storage elastic modulus (G') at 200 ° C. of 150 Pa or more, and is excellent in heat resistance at high temperatures. In particular, if the binder resin contains the reaction products of the components (A) and (B) described above, the storage elastic modulus (G') of the binder resin tends to increase, and the heat resistance at high temperatures tends to increase. The sex is improved. The storage elastic modulus (G') of the binder resin is preferably 1,000 Pa or more. The upper limit of the storage elastic modulus (G') of the binder resin is not particularly limited, but when the binder resin of the present invention is used for toner applications or printing applications, it has a hot offset resistance during printing on paper. From the viewpoint of improving the fabric resin transferability during transfer from paper to fabric, the storage elastic modulus (G') of the binder resin is preferably 10,000 Pa or less, more preferably 8,000 Pa or less. When the binding resin of the present invention is used for printing, if the storage elastic modulus (G') of the binding resin is 10,000 Pa or less, the peelability between the paper and the fabric is also improved.

The storage elastic modulus of the binder resin is 200 ° C. when measured from 80 ° C. to 240 ° C. under the conditions of a thickness of 1 mm, a frequency of 1 Hz, a strain of 1%, and a heating rate of 3 ° C./min using a parallel plate of 25 mmφ. It is the storage elastic modulus in.
The storage elastic modulus of the binder resin can be measured using a rotary rheometer.

<Use>
The binder resin of the present invention can be used for applications such as toner materials, printing materials, coating materials, adhesives, and films. In particular, it is suitable for toner applications and printing applications.

"toner"
The toner of the present invention contains the above-mentioned binder resin of the present invention.
The content of the binder resin of the present invention is preferably 5 to 95% by mass with respect to the total mass of the toner.

The toner of the present invention contains, in addition to the binder resin of the present invention, a colorant and, if necessary, an optional component.
Examples of the colorant include colorants such as known pigments used for toner.
Examples of the optional component include various known additives used for toner, and specific examples thereof include a charge control agent, a mold release agent, and a flow modifier.
Further, the toner may contain a resin other than the binder resin of the present invention (for example, a styrene resin, a cyclic olefin resin, an epoxy resin, etc.) as long as the effect of the present invention is not impaired.

The method for producing the toner of the present invention is not particularly limited, but the binder resin of the present invention, a colorant, and if necessary, an arbitrary component are mixed, and then melt-kneaded with a twin-screw extruder or the like to coarsen the mixture. A method of pulverizing, finely pulverizing, classifying, and externally treating inorganic particles as necessary (crushing method); the binder resin of the present invention, a colorant, and an optional component if necessary. Is dissolved and dispersed in a solvent, granulated in an aqueous medium, the solvent is removed, washed and dried to obtain toner particles, and if necessary, inorganic particles are externally added to produce the particles. (Chemical method) and the like.

In the pulverization method, the component (A) and the component (B) may be mixed in advance to prepare a binder resin, and then mixed with a colorant and, if necessary, an arbitrary component. A) component, (B) component, a colorant, and an optional component may be mixed if necessary. From the viewpoint of suppressing dye sublimation while suppressing a decrease in productivity, the temperature at the time of mixing or melt-kneading is preferably 100 to 200 ° C.
In the chemical method, the component (A) and the component (B) may be mixed in advance to prepare a binder resin, and then dissolved / dispersed in a solvent together with a colorant and, if necessary, an arbitrary component. , (A) component, (B) component, a colorant, and if necessary, an arbitrary component may be dissolved / dispersed in a solvent.

The toner of the present invention can be used as any of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.
When the toner of the present invention is used as a magnetic one-component developer, the toner contains a magnetic substance. Examples of the magnetic material include known magnetic materials used for toner.
When the toner of the present invention is used as a two-component developer, the toner of the present invention is used in combination with a carrier. Examples of the carrier include known carriers used for toner.

Since the toner of the present invention contains the binder resin of the present invention described above, it has excellent heat resistance at high temperatures. In particular, when the softening temperature of the binder resin of the present invention is 240 ° C. or lower, the hot offset resistance during printing on paper is also excellent.

"Composition for printing"
The printing composition of the present invention contains the above-mentioned binding resin of the present invention.
The content of the binder resin of the present invention is preferably 5 to 95% by mass with respect to the total mass of the printing composition.

The printing composition of the present invention contains, in addition to the binder resin of the present invention, a colorant and, if necessary, an optional component.
Examples of the colorant include colorants such as known dyes used for printing toner.
Examples of the optional component include various known additives used for printing toner, and specific examples thereof include a charge control agent, a mold release agent, and a flow modifier.
The printing composition contains a resin other than the binder resin of the present invention (for example, a styrene resin, a cyclic olefin resin, an epoxy resin, etc.) as long as the effect of the present invention is not impaired. May be good.

The method for producing the printing composition of the present invention is not particularly limited, and examples thereof include a pulverization method and a chemical method exemplified above in the description of the toner.

Since the printing composition of the present invention contains the binding resin of the present invention described above, it is excellent in heat resistance at high temperatures. In particular, when the softening temperature of the binder resin of the present invention is 240 ° C. or lower, hot offset resistance during printing on paper, fabric resin transfer resistance during transfer from paper to fabric, sublimation resistance, and paper Excellent peelability of fabric.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.

[Measurement / evaluation method]
<Measurement of softening temperature>
The softening temperature of the polyester resin, the acrylic polymer and the binder resin is 1 mmφ × 10 mm nozzle, load 294 N, heating rate 3 ° C./using a flow tester (manufactured by Shimadzu Corporation, “CFT-500D”). The temperature at which 1/2 amount of 1.0 g of the resin sample flowed out was measured under a constant temperature rise of min, and this was taken as the softening temperature.

<Measurement of gel fraction>
The gel fraction of the binder resin was measured as follows.
About 0.5 g of the measurement sample was weighed in a 100 mL Erlenmeyer flask (X1 (g)), 50 mL of THF was added, and the measurement sample was immersed in a water bath set at 70 ° C. for 3 hours to dissolve the measurement sample in THF.
Separately, the glass filter 1GP100 was tightly filled with Celite 545 from 6 to 7 minutes, dried in a dryer at 105 ° C. for 3 hours or more, and the dried glass filter was weighed (X2 (g)).
Then, the THF solution in which the measurement sample was dissolved was transferred into a dry glass filter and suction filtered. Using acetone, all the contents remaining on the wall of the Erlenmeyer flask were transferred into a glass filter, and acetone was poured through the glass filter to drop the soluble components into a suction bottle, and suction was continued so that no solvent remained in the filter. Later, it was dried in a vacuum dryer at 80 ° C. for 1 hour or more, the dried glass filter was weighed (X3 (g)), and the gel fraction (THF insoluble matter) was calculated according to the following formula (i).
Gel fraction (mass%) = {(X3-X2) / X1} x 100 ... (i)

<Evaluation of heat resistance>
The storage elastic modulus (G') of the binder resin at 200 ° C. was measured using a rotary rheometer (“HAAKE MARS III” manufactured by Thermo Fisher Scientific Co., Ltd.). The measurement conditions are as follows. The higher the storage elastic modulus (G'), the better the heat resistance at high temperatures.
・ Geometry: 25mmφ parallel plate ・ GAP: 1mm
・ Frequency: 1Hz
・ Strain: 0.01
-Measurement temperature: 80 to 240 ° C (heated at 3 ° C / min)

<Evaluation of productivity>
In the production of the binder resin, the state when the polyester resin (A) and the acrylic polymer (B) were kneaded with a kneader was visually judged, and the productivity was evaluated according to the following evaluation criteria.
◯: The kneaded product does not solidify, and the binder resin can be taken out from the kneading machine.
X: The kneaded product is solidified and the binder resin cannot be taken out from the kneading machine.

[Manufacturing of polyester resin (A)]
A-1 to A-5 were produced as shown below.
The polyvalent carboxylic acid, the polyhydric alcohol, and the catalyst having the charged compositions shown in Table 1 were charged into a reaction vessel equipped with a distillation column. As the bisphenol A alkylene oxide adduct, a propylene oxide derivative of bisphenol A (PO2.3 molar adduct) was used.
Next, the rotation speed of the stirring blade in the reaction vessel was maintained at 200 rpm, the temperature was started, the temperature in the reaction system was heated to 265 ° C., and the esterification reaction was carried out while maintaining this temperature. After the distillation of water from the reaction system disappeared and the esterification reaction was completed, the temperature inside the reaction system was maintained at 230 ° C., the pressure inside the reaction system was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and the reaction system was set to 133 Pa. The condensation reaction was carried out while distilling out the polyhydric alcohol.
The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase in viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating the desired softening temperature. Then, when a predetermined torque was exhibited, stirring was stopped, the reaction system was returned to normal pressure, and the reaction product was taken out by pressurizing with nitrogen to obtain polyester resins (A-1) to (A-5). The polymerization end points of the polyester resins (A-1) to (A-5) were determined by measuring the softening temperature by sampling during the polymerization.
The softening temperature of the obtained polyester resin (A) was measured. The results are shown in Table 1.

[Acrylic polymer (B)]
The following compounds were used as the acrylic polymer (B).
B-1: A homopolymer of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., "P-1900", softening temperature 140 ° C.).
B-2: homopolymer of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., "P-1901", softening temperature 170 ° C.).

[Examples 1 to 4, Comparative Examples 1 to 4]
According to the compounding composition shown in Tables 2 and 3, the polyester resin (A) and the acrylic polymer (B) were melt-kneaded with a twin-screw kneader to obtain a binder resin.
The softening temperature and gel fraction of the obtained binder resin were measured, and the heat resistance and productivity were evaluated. These results are shown in Tables 2 and 3.

As is clear from the results in Table 2, the binder resin obtained in each example had a high storage elastic modulus (G') of 210 Pa or more, and was excellent in heat resistance at high temperatures. The productivity was also good.
On the other hand, as is clear from the results in Table 3, the binder resin of Comparative Example 1 which did not contain the acrylic polymer (B) and had a softening temperature of less than 130 ° C. was inferior in heat resistance.
The binder resin of Comparative Example 2 having a softening temperature of less than 130 ° C. was inferior in heat resistance.
The binder resin of Comparative Example 3 in which the proportion of the acrylic polymer (B) was small and the softening temperature was less than 130 ° C. was inferior in heat resistance.
In the case of Comparative Example 4 in which the proportion of the acrylic polymer (B) was large, the kneaded product solidified in the kneading machine during kneading, and the binder resin could not be taken out. Therefore, the heat resistance could not be evaluated.

Claims (4)

A binder resin containing a polyester resin (A) and an acrylic polymer (B).
The softening temperature of the polyester resin (A) is 150 to 170 ° C.
The softening temperature of the binder resin is 130 to 240 ° C.
The acrylic polymer (B) is a homopolymer of glycidyl methacrylate.
A binder resin having a mass ratio of 99.9 / 0.1 to 92/8 represented by the polyester resin (A) / acrylic polymer (B). The binder resin according to claim 1, wherein the gel content of the binder resin is 5 to 40% by mass. A toner containing the binder resin according to claim 1 or 2. A composition for printing, which comprises the binder resin according to claim 1 or 2.