JPH0695227B2 - Resin composition for electrophotographic toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a resin composition for a toner used in electrophotography, and in particular, an electrophotographic toner having a strong positive chargeability and not having an offensive odor peculiar to amine compounds. The present invention relates to a resin composition.

(Prior Art) As a method of developing an electrostatic image of electrophotography, there is, for example, a dry developing method using a powder developer called a toner in which a colorant such as carbon black is dispersed in a natural or synthetic resin. In the dry development method, toner is usually charged by friction with a carrier such as iron powder or glass beads. The charged toner adheres to the electrostatic latent image on the photoconductor by an electric attraction, is further transferred onto the paper, and then is fixed by a heat roll or the like to be a permanent visible image.

Generally, in toner, to adjust the amount of charge during friction,
A charge control agent is added. For example, a nigrosine dye is used as a charge control agent for imparting a positive charge. However, the charge control agent is expensive, and its addition increases the price of the toner. When the charge control agent bleeds,
It also causes deterioration of the charging characteristics of the toner.

In order to solve such a drawback, JP-A-48-102633 discloses a toner in which an amine monomer is introduced into the toner resin itself. Since this toner has a strong positive charging property, it is not necessary to add a charge control agent. However, since the amine compound is introduced into the toner resin, this toner has a peculiar odor peculiar to the amine compound. It is difficult to use as a color toner because it is colored by an amine compound. Therefore, it is not suitable for practical use.

(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned conventional problems, and an object of the present invention is to provide an electrophotography having a strong positive charging property and having no offensive odor peculiar to amine compounds. It is to provide a resin composition for a toner. Another object of the present invention is to provide a resin composition for electrophotographic toner which does not cause coloring due to an amine compound.

(Means for Solving Problems) According to the present invention, by adding a terpene-based vegetable essential oil as a deodorant to a conventional amine-based compound-containing toner resin,
It was completed based on the inventor's finding that the offensive odor peculiar to amine compounds can be eliminated.

(1) Acrylic or methacrylic tertiary amine monomer, styrene monomer, acrylic acid or methacrylic acid ester monomer, and vinyl group containing an acid group. It contains a copolymer having a monomer as a constitutional unit and (2) a terpene-based plant essential oil, thereby achieving the above object.

The mechanism for removing bad odors with deodorants includes masking bad odors,
There is odor neutralization and malodorous substance neutralization. Masking is to add a relatively pleasant odor to the human sense of smell, thereby making the bad odor inconspicuous. Odor neutralization is the addition of a certain odor to a certain malodor.
It is to reduce the peculiar odor. What is neutralization of malodorous substances?
It means adding a certain substance and reacting it with a foul-smelling substance to transform it into another substance with a foul-smelling or weak odor. In general, for terpene-based plant essential oils, a slight masking effect,
There is at least one of the action of neutralizing the odor peculiar to amine compounds and the action of neutralizing malodorous substances by the reaction with amine compounds, and as a result, the offensive odor peculiar to amine compounds is below the human threshold It is reduced / erased. In order to ensure the effect of removing the malodor by the addition of the terpene-based vegetable essential oil, the copolymer of the present invention contains
A vinyl monomer containing an acid group is introduced. The vinyl-based monomer containing an acid group has an action of preventing or reducing a bad odor caused by an amine-based compound. Therefore, the malodor can be almost eliminated by the synergistic effect of this monomer and the terpene-based plant essential oil. The effects of adding terpene-based plant essential oils and introducing vinyl monomers containing acid groups are not limited to the reduction and elimination of such malodors. It is also possible to prevent the coloring of the resin composition by the amine compound and the adhesion of the coloring scale to the reactor during the polymerization of the resin.

The terpene-based plant essential oil used in the present invention is an essential oil mainly composed of terpenes extracted from conifers and the like. Tempels include, for example, camphor, limonene,
There are citral, geraniol, α-terpineol, cineol and Δ ³ -carene. Terpenic plant essential oil is
Acrylic or methacrylic tertiary amine monomer 100
The content is preferably 1 to 5 parts by weight with respect to parts by weight. 1
When the amount is less than 5 parts by weight, the offensive odor peculiar to amine compounds is not sufficiently eliminated, and when the amount is more than 5 parts by weight, the slight fragrance peculiar to terpene-based plant essential oils tends to stand out.

Examples of the vinyl-based monomer having an acid group include a half-ester compound obtained by an esterification reaction of an acrylic acid or methacrylic acid derivative having a hydroxyl group with a dicarboxylic acid, acrylic acid, methacrylic acid, maleic acid, maleic anhydride. There is acid.

Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, and glutaric acid, and aromatic dicarboxylic acids such as phthalic acid. The dicarboxylic acid may be substituted with a halogen, a lower alkyl group, an alkoxy group or the like. Also, an acid anhydride may be used. Examples of the acrylic acid or methacrylic acid derivative containing a hydroxyl group include compounds obtained by adding one or more molecules of alkylene oxide such as ethylene oxide and propylene oxide to acrylic acid or methacrylic acid. Also, for acrylic acid or methacrylic acid,
A hydroxyalkyl ester obtained by esterifying a dihydric alcohol such as ethylene glycol or propylene glycol may be used. As the half-ester compound obtained by the esterification reaction of a hydroxyl group-containing acrylic acid or methacrylic acid derivative and a dicarboxylic acid,
There are compounds represented by formulas (I) to (IV).

Here, R ₁ and R ₂ are the same or different and are hydrogen or a methyl group, m is an integer of 1 to 14, and n is an integer of 0 to 8.

Here, R ₃ and R ₄ are the same or different and each is hydrogen or a methyl group, X is hydrogen, halogen, a lower alkyl group or an alkoxy group, and h is an integer of 1 to 14.

Here, R ₅ is hydrogen or a methyl group, j is an integer of 3 to 6, and k is an integer of 0 to 8.

Here, R ₆ is hydrogen or a methyl group, Y is hydrogen, halogen, a lower alkyl group or an alkoxy group, and l is an integer of 3 to 6.

Such compounds include, for example, succinic acid mono (meta)
Acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxypropyl ester, glutaric acid mono (meth) acryloyloxyethyl ester, phthalic acid mono (meth) acryloyloxyethyl ester,
There is mono (meth) acryloyloxypropyl ester of phthalic acid.

The vinyl monomer containing an acid group is introduced into the copolymer in the range of 0.2 to 2 mol per mol of the acrylic or methacrylic tertiary amine monomer. If it is less than 0.2 mol, the offensive odor peculiar to amine compounds is not sufficiently eliminated, and if it is more than 2 mol, the obtained toner tends not to have sufficient positive chargeability.

The acrylic or methacrylic tertiary amine monomer refers to a tertiary amine containing an acryloyl group or a methacryloyl group, and is, for example, a compound represented by the following formula.

Here, R ₁ ′ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ ′ and R ₃ ′ are alkyl groups having 1 to 5 carbon atoms, and R ₄ ′ is a carbon atom number. 1 to 5 alkylene groups.

Such compounds include, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate and dimethyl acrylamide are available. The acrylic or methacrylic tertiary amine monomer is contained in the copolymer in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. If it is less than 0.1% by weight, the obtained toner does not have sufficient positive charging property, and if it is more than 10% by weight, the moisture resistance of the copolymer decreases, so the obtained toner contains moisture. This is because it tends to be easier.

The styrene monomer is contained in the copolymer in an amount of 30% by weight or more, preferably 40% by weight or more. When it is less than 30% by weight, the pulverizability of the obtained toner is lowered. Examples of the styrene-based monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- (n
-Butyl) styrene, p- (tert-butyl) styrene, p-
(N-hexyl) styrene, p- (n-octyl) styrene, p- (n-nonyl) styrene, p- (n-decyl) styrene, p- (n-dodecyl) styrene, p-methoxystyrene, p- There are phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.

Styrene-based monomers and acrylic acid or methacrylic acid ester-based monomers are generally used in copolymers containing 80-99.5
It is contained in the range of% by weight. When it is less than 80% by weight, the pulverizability of the obtained toner is lowered, and when it is more than 99.5% by weight, the obtained toner tends not to have a sufficient positive charging property. Examples of acrylic acid or methacrylic acid ester-based monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, and acrylic acid 2 -Ethylhexyl, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
There are dodecyl methacrylate and stearyl methacrylate.

As the method for producing the copolymer used in the present invention, any known polymerization method such as suspension polymerization method, solution polymerization method and emulsion polymerization method is used, and in particular, suspension polymerization method and solution polymerization method are preferable. More preferably, the solution polymerization method is used. The terpene-based vegetable essential oil contained in the copolymer may be added at any time during the polymerization process of the above-mentioned polymerization method, and is preferably added after the completion of the polymerization reaction in the solution polymerization method.

To the resin for toner of the present invention, vinyl acetate, vinyl propionate, vinyl chloride, ethylene, etc. may be introduced as a copolymerization component within the range in which the object of the present invention can be achieved. May be blended. Waxes such as epoxy resin and low molecular weight polypropylene resin may be mixed.

(Examples) The present invention will be described below with reference to Examples.

Example 1 40 g of azobisisobutyronitrile (AIBN) as a polymerization initiator was dissolved in 850 g of styrene, 92.5 g of n-butyl acrylate, 37.5 g of dimethylaminoethyl acrylate and 20 g of monoacryloyloxyethyl succinate. 400 g of toluene was placed in a 2-liter separable flask, and the inside of the flask was replaced with nitrogen gas. After heating this system to the boiling point of toluene, the above monomer solution was stirred while stirring.
The mixture was dropped and polymerized for 2.5 hours. After completion of the dropping, 0.5 g of terpene-based plant essential oil containing at least one of camphor, limonene, citral, geraniol, cineole, α-terpineol and Δ ³ -calene was added, and further aged at the boiling temperature of toluene for 1 hour. did. Then, while gradually raising the temperature of the system to 180 ° C, the toluene was removed under reduced pressure, and styrene-n-butyl acrylate-
A resin composition containing a dimethylaminoethyl acrylate-succinic acid monoacryloyloxyethyl ester copolymer and a terpene-based plant essential oil was obtained. This resin composition was cooled and pulverized into flakes.

The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask.

This resin composition was further finely pulverized with a jet mill to obtain a finely divided resin composition having an average particle size of 13 to 15 μm. After mixing this with an iron powder carrier, the charge amount was measured by a known method using a blow-off powder charge amount measuring device. The amount of charge was +17 μc / g, indicating a remarkably high positive chargeability. Moreover,
No offensive odor peculiar to amine compounds was felt in this resin composition. The results are shown in the table below.

Example 2 A resin composition was obtained in the same manner as in Example 1 except that dimethylaminoethyl methacrylate was used instead of dimethylaminoethyl acrylate. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +17 μc / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 3 A resin composition was obtained in the same manner as in Example 1 except that diethylaminoethyl methacrylate was used instead of dimethylaminoethyl acrylate. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +17 μc / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 4 A resin composition was obtained in the same manner as in Example 1 except that 117.5 g of n-butyl acrylate and 12.5 g of dimethylaminoethyl acrylate were used. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +16 μc / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 5 A resin composition was obtained in the same manner as in Example 1 except that 105.0 g of n-butyl acrylate and 25.0 g of dimethylaminoethyl acrylate were used. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +17 μc / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 6 A resin composition was obtained in the same manner as in Example 1 except that acrylic acid was used instead of succinic acid monoacryloyloxyethyl ester, and diethylaminoethyl acrylate was used instead of dimethylaminoethyl acrylate. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +19 μc / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 7 A resin composition was obtained in the same manner as in Example 1 except that acrylic acid was used instead of succinic acid monoacryloyloxyethyl ester. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +18 μc / g
Became. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Example 8 A resin composition was obtained in the same manner as in Example 1 except that array acid anhydride was used instead of monoacryloyloxyethyl succinate. The obtained resin composition was not colored, and the colored scale did not adhere to the upper part of the separable flask. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +16 μm.
It became c / g. Moreover, the resin composition did not have the offensive odor peculiar to amine compounds. The results are shown in the table below.

Comparative Example 1 Except that succinic acid monoacryloyloxyethyl ester was not used and terpene-based plant essential oil was not added,
A resin composition was obtained in the same manner as in Example 1. The obtained resin composition was colored dark brown, and adhesion of a colored scale to the upper part of the separable flask was observed. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +18 μc / g. Further, this resin composition had an offensive odor peculiar to amine compounds. The results are shown in the table below.

Comparative Example 2 Except that succinic acid monoacryloyloxyethyl ester was not used and terpene-based plant essential oil was not added,
A resin composition was obtained in the same manner as in Example 3. The obtained resin composition was colored dark brown, and adhesion of a colored scale to the upper part of the separable flask was observed. When the charge amount of this resin composition was measured by the same method as in Example 1, it was +17 μc / g. Further, this resin composition had an offensive odor peculiar to amine compounds. The results are shown in the table below.

As is clear from the table, the resin composition for an electrophotographic toner of the present invention containing a vinyl monomer having an acid group or a terpene vegetable essential oil has a strong positive charging property and a cumin compound,
In particular, it does not have a characteristic odor of tertiary amine. Moreover, there is no coloring of the resin composition by the amine compound or adhesion of the coloring scale to the reactor during the polymerization of the resin. The conventional resin composition has a strong positive charging property, but has an offensive odor peculiar to amine compounds and is colored dark brown. Moreover, the colored scale adheres to the reactor during the polymerization.

(Effect of the Invention) The resin composition for an electrophotographic toner of the present invention is thus
It has a strong positive charging property and does not have an amine compound, especially a tertiary amine, and a peculiar offensive odor. Moreover, there is no coloring of the resin composition by the amine compound or adhesion of the coloring scale to the reactor during the polymerization of the resin. Therefore, the resin composition of the present invention can be effectively used for electrophotographic toner. In particular,
It is suitable for use in color toners.

Claims (14)

[Claims] 1. A constitutional unit comprising (1) an acrylic or methacrylic tertiary amine monomer, a styrene monomer, an acrylic acid or methacrylic acid ester monomer, and a vinyl monomer containing an acid group. And (2) a terpene-based vegetable essential oil, and a resin composition for an electrophotographic toner. 2. The terpene-based essential oil is camphor,
The resin composition for electrophotographic toner according to claim 1, which contains at least one of limonene, citral, geraniol, α-terpineol, cineol and Δ ³ -carene. 3. The acrylic or methacrylic third
The resin composition for electrophotographic toner according to claim 1, wherein the terpene-based vegetable oil is contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the amine monomer. 4. The acrylic or methacrylic third
The resin for an electrophotographic toner according to claim 1, wherein the vinyl-based monomer containing an acid group is introduced into the copolymer in an amount of 0.2 to 2 mol per 1 mol of the amine monomer. Composition. 5. A half-ester compound obtained by an esterification reaction of a vinyl-based monomer having an acid group with a hydroxyl group-containing acrylic acid or methacrylic acid derivative, dicarboxylic acid, acrylic acid, methacrylic acid, maleic acid. The resin composition for electrophotographic toner according to claim 1, which is at least one of maleic anhydride and maleic anhydride. 6. The half-ester compound is represented by formulas (I) to (I)
The resin composition for electrophotographic toner according to claim 5, which is at least one of the compounds represented by the formula (V). Here, R ₁ and R ₂ are the same or different and are hydrogen or a methyl group, m is an integer of 1 to 14, and n is an integer of 0 to 8. Here, R ₃ and R ₄ are the same or different and each is hydrogen or a methyl group, X is hydrogen, halogen, a lower alkyl group or an alkoxy group, and h is an integer of 1 to 14. Here, R ₅ is hydrogen or a methyl group, j is an integer of 3 to 6, and k is an integer of 0 to 8. Here, R ₆ is hydrogen or a methyl group, Y is hydrogen, a halogen, a lower alkyl group or an alkoxy group, and l is an integer of 3 to 6. 7. The half-ester compound is succinic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxypropyl ester, glutaric acid mono (meth) acryloyloxyethyl ester, phthalic acid mono (meth). The resin composition for an electrophotographic toner according to claim 5, which is at least one of acryloyloxyethyl ester and mono (meth) acryloyloxypropyl phthalate. 8. The electrophotographic toner according to claim 1, wherein the acrylic or methacrylic tertiary amine monomer is contained in the copolymer in a range of 0.1 to 10% by weight. Resin composition. 9. The acrylic or methacrylic third
The resin composition for electrophotographic toner according to claim 1, wherein the amine monomer is a compound represented by the following formula. Here, R ₁ ′ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₂ ′ and R ₃ ′ are alkyl groups having 1 to 5 carbon atoms, and R ₄ ′ is a carbon atom. It is an alkylene group of the numbers 1 to 5. 10. The acrylic or methacrylic tertiary amine monomer is at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylacrylamide. The resin composition for an electrophotographic toner according to 1. 11. The resin composition for electrophotographic toner according to claim 1, wherein the styrene-based monomer is contained in the copolymer in an amount of 30% by weight or more. 12. The styrenic monomer is styrene, o-
Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- (n-butyl) styrene, p- (tert-
Butyl) styrene, p- (n-hexyl) styrene, p-
(N-octyl) styrene, p- (n-nonyl) styrene, p- (n-decyl) styrene, p- (n-dodecyl) styrene, p-methoxystyrene, p-phenylstyrene, p-
The resin composition for an electrophotographic toner according to claim 1, which is at least one of chlorostyrene and 3,4-dichlorostyrene. 13. The copolymer according to claim 1, wherein the styrene-based monomer and the acrylic acid or methacrylic acid ester-based monomer are contained in the copolymer in an amount of 80 to 99.5% by weight. The resin composition for electrophotographic toner as described above. 14. The acrylic acid or methacrylic acid ester-based monomer is methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
The resin composition for an electrophotographic toner according to claim 1, which is at least one of dodecyl methacrylate and stearyl methacrylate.