JPH0695226B2 - 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, charge control agents are expensive and their addition increases the price of the toner. This may cause the charge control agent to bleed and deteriorate 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 bad 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 electrophotographic apparatus which has a strong positive charging property and does not have a malodor 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 an odor eliminating agent to a conventional amine-based compound-containing toner resin,
It was completed based on the inventor's finding that the malodor peculiar to amine compounds can be removed.

The resin composition for an electrophotographic toner of the present invention is a copolymer containing (1) an acrylic or methacrylic tertiary amine monomer, a styrene monomer and an acrylic acid or methacrylic acid ester monomer as constituent units. It contains the combined product and (2) a terpene-based plant essential oil, whereby the above object is achieved.

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 to weaken an inherent malodor by adding a certain odor to a certain malodor. Neutralization of malodorous substances means adding a certain substance and reacting it with the malodorous substance.
To change to another substance that is odorless or has a weak odor.
In general, terpene-based plant essential oil has at least one of a subtle masking effect, an effect of neutralizing an odor peculiar to an amine compound, and an effect of neutralizing a malodorous substance due to a reaction with an amine compound. As a result, the offensive odor peculiar to amine compounds is reduced to below the human threshold.
Erased. The effects of adding terpene-based plant essential oils are not limited to the reduction and elimination of such offensive odors. 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 reaction vessel 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. Terpenes include, for example, camphor, limonene,
There are citral, geraniol, α-terpineol, cineol and Δ ³ -carene. Tempel 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.

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 1 to 5 carbon atoms. Is an alkylene group.

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. When the amount is less than 0.1% by weight, the obtained toner does not have a sufficient positive charging property, and when the amount is more than 10% by weight, the moisture resistance of the polymer decreases, so that the obtained toner tends to contain moisture. Because it tends to become.

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, 112.5 g of n-butyl acrylate and 37.5 g of dimethylaminoethyl acrylate. 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 the system to the boiling point of toluene, the above monomer solution was added dropwise for 2.5 hours with stirring to carry out polymerization. After completion of the dropping, 0.5 g of terpene-based plant essential oil containing at least one of camphor, limonene, citral, geraniol, cineol, α-terpineol and Δ ³ -carene was added, and the mixture was aged at the boiling temperature of toluene for 1 hour. . 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 copolymer and a terpene-based vegetable oil was obtained. This resin composition was cooled and pulverized into flakes.

The obtained resin composition was scarcely 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.

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 scarcely 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.

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 scarcely 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.

Example 4 A resin composition was obtained in the same manner as in Example 1 except that 137.5 g of n-butyl acrylate and 12.5 g of dimethylaminoethyl acrylate were used. The obtained resin composition was scarcely 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.

Example 5 A resin composition was obtained in the same manner as in Example 1 except that 125.0 g of n-butyl acrylate and 25.0 g of dimethylaminoethyl acrylate were used. The obtained resin composition was scarcely 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.

Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that the terpene-based plant essential oil was not used. 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. Moreover, this resin composition had an offensive odor peculiar to amine compounds.

Comparative Example 2 A resin composition was obtained in the same manner as in Example 1 except that terpene-based plant essential oil was not used and diethylaminoethyl acrylate was used instead of dimethylaminoethyl acrylate. 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. Moreover, this resin composition had an offensive odor peculiar to amine compounds.

(Effect of the Invention) The resin composition for an electrophotographic toner of the present invention is thus
Strong positive chargeability and amine compounds, especially tertiary amine,
It has no peculiar offensive odor. Moreover, there is almost no coloring of the resin composition by the amine compound and adhesion of the coloring scale to the reaction vessel during the polymerization of the resin. Therefore, the resin composition of the present invention can be effectively used for electrophotographic toner. It is particularly suitable for use in color toner.

Claims (10)

[Claims] 1. A copolymer having (1) an acrylic or methacrylic tertiary amine monomer, a styrene monomer, and an acrylic acid or methacrylic acid ester monomer as a constituent unit, and (2) a terpene. A resin composition for an electrophotographic toner, comprising a vegetable essential oil. 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 electrophotographic toner according to claim 1, wherein the acrylic or methacrylic tertiary amine monomer is contained in the copolymer in the range of 0.1 to 10% by weight. Resin composition. 5. 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 1 to 5 carbon atoms. Is an alkylene group. 6. The acrylic or methacrylic third
The resin composition for electrophotographic toner according to claim 1, wherein the amine monomer is at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylacrylamide. 7. 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. 8. 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-
Claims which are at least one of (n-decyl) styrene, p- (n-dodecyl) styrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene and 3,4-dichlorostyrene. Item 1. The resin composition for electrophotographic toner according to Item 1. 9. 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 a range of 80 to 99.5% by weight. The resin composition for electrophotographic toner as described above. 10. 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.