JP2001092179A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having high light-transmitting property, excellent environmental durability and excellent picture quality with which high quality color printing is possible even on an OHP sheet. SOLUTION: The toner is obtained by mixing a resin having ethyleniably unsaturated monomer unit containing an alicyclic structure and other monomer unit containing in the molecular chain, a coloring agent, an electrification controlling agent and a release agent, melting and kneading the mixture, cooling, coaresly pulverizing, finely pulverizing by a jet mill, and clasifying to prepare particles of about 7 μm average particle diameter. Then the obtained toner is mixed with colloidal silica in a Henschel mixer to obtain a developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image, and more particularly to a toner for developing an electrostatic image capable of forming a clear image with excellent fixability, transparency and gloss. is there.

[0002]

2. Description of the Related Art With respect to copiers and printers, with the spread of office automation, demands for copied images of high quality, that is, excellent in coloring property, fixing property, transparency and glossiness are increasing. Colorability, fixability, light transmission,
One of the main factors for improving the glossiness is the binder resin which is a main component of the toner. In copiers and printers, toner is supplied to an electrostatic charge image on a latent image carrier to obtain a toner image, and then the toner image is converted to plain paper or OHP paper.
It is transferred to a film for use and fixed. At present, styrene / acrylic resin and polyester resin are often used as the binder resin. However, in the former case, the fixability, light transmittance and glossiness of the toner cannot be sufficiently obtained, and accordingly, on the OHP, In a situation where it is difficult to obtain a high-quality image, the latter can obtain light transmittance, but the toner characteristics are easily changed in accordance with a change in environment, and the environment resistance is unstable.

Therefore, it has been proposed to use a polyolefin resin having an alicyclic structure as a binder resin (Japanese Patent Application Laid-Open No. 9-101631). The polyolefin resin used here is a copolymer of an α-olefin and an alicyclic compound having a double bond. It is described that such a polyolefin is excellent in transparency, and a toner using the polyolefin is excellent in light transmittance.

By the way, Tg required for toner application is as follows:
Generally, it is 100 ° C. or less. In fact, the structure of the polyolefin, which is a copolymer of an α-olefin and an alicyclic compound, used in Examples of the above publication is completely unknown. The Tg of the copolymer of α-olefin and alicyclic compound is 100 ° C.
In order to achieve the following, the proportion of structural units derived from α-olefins must be considerably increased. In a polymer having a large number of units derived from an α-olefin, the α-olefin structure tends to be localized, and the polymer tends to be heterogeneous. The toner is generally a fine powder of 1 to 15 μm, and the heterogeneity of the polymer directly leads to the heterogeneity of the toner. Such a toner is by no means preferable in obtaining the fine image quality required in recent years, and may cause color unevenness in a color image using OHP or the like.

As described above, although many studies have been made as color toners having high light transmittance, excellent environmental resistance, and excellent image quality, and toners capable of high-quality printing on OHP films, At present, it has not always been possible to satisfy requirements that are increasing year by year.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a high-quality copy image or print image of a copying machine or a printer, that is, coloring, fixing, light transmission, and gloss. It is an object of the present invention to provide a two-component, non-magnetic one-component or magnetic one-component toner excellent in toner. We have:
In order to achieve the above-mentioned object, as a result of investigation, it has been found that a resin containing an alicyclic structure-containing ethylenically unsaturated monomer unit and other monomer units in a molecular chain is used as a binder resin constituting a toner. The higher quality of the copied or printed image of the copying machine and the printer, that is, the coloring property,
It has been found that a two-component, non-magnetic one-component or magnetic one-component toner having excellent fixability, light transmittance and glossiness can be obtained,
The present invention has been completed based on this finding.

[0007]

Thus, according to the present invention, a binder resin and a colorant are the main components, and the binder resin has an alicyclic structure-containing ethylenically unsaturated monomer unit in a molecular chain. And a resin containing other monomer units, wherein the toner for developing an electrostatic image is provided. As a preferred embodiment, the glass transition temperature of the binder resin is 60 to 100 ° C.
Or a resin obtained by hydrogenating an aromatic ring of an aromatic vinyl polymer obtained by polymerizing a monomer containing an aromatic vinyl monomer as a binder resin. An electrostatic image developing toner is provided.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrostatic image developing toner of the present invention contains a binder resin and a colorant as main components.

The binder resin used as a component of the toner of the present invention contains an alicyclic structure-containing ethylenically unsaturated monomer unit and other monomer units in the molecular chain.

Examples of the alicyclic structure-containing ethylenically unsaturated monomer unit include a unit having a saturated cyclic hydrocarbon (cycloalkane) structure and a unit having an unsaturated cyclic hydrocarbon (cycloalkene) structure. Fixation, transparency,
Those having a unit having a cycloalkane structure are preferred from the viewpoint of glossiness. The proportion of the alicyclic structure-containing ethylenically unsaturated monomer unit is usually from 10 to 99% by weight, preferably from 30 to 95% by weight.

The binder resin used in the present invention has a glass transition temperature (hereinafter sometimes referred to as Tg) of usually 60 to 60.
100 ° C, preferably 60 to 90 ° C, particularly preferably 6 ° C.
It is in the range of 3-88 ° C. If the Tg is too low, the storage stability as a toner powder tends to decrease. If the Tg is too high, the toner is developed, and if the temperature at which the toner is transferred and fixed to paper is not increased, a fixing failure may occur. Here, Tg is a value measured using a differential scanning calorimeter.

Although the molecular weight of the binder resin is not particularly limited, it is usually 2,000 to 100,000, preferably 3 to 100, as polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of a cyclohexane solution. 50,000 to 50,000. When it is in this range, the coloring property, the fixing property, the transparency, and the glossiness are likely to be good. However, when the binder resin does not dissolve in cyclohexane, a toluene solution is used, and the weight average molecular weight in terms of polyisoprene is determined.

The volatile component in the binder resin is preferably 0.5% by weight or less based on the binder resin for reasons such as environmental safety and odor. Here, the amount of the volatile component is measured by a differential thermogravimeter (TG / DTA2 manufactured by Seiko Instruments Inc.).
00) is the amount of the component that evaporates when heated from 30 ° C to 350 ° C. The method for reducing the volatile component is not particularly limited, for example, a polymer coagulation method using a poor solvent,
Examples include a direct drying method, a steam stripping method, a vacuum stripping method, and a nitrogen stripping method.

The binder resin used in the present invention is not particularly limited depending on the production method, but is usually obtained by addition copolymerization of an alicyclic structure-containing ethylenically unsaturated monomer and other monomers, or It is obtained by addition-copolymerizing an aromatic vinyl monomer and other monomers, and then adding hydrogen to the aromatic ring.

The alicyclic structure-containing ethylenically unsaturated monomer is
A polymerizable alicyclic hydrocarbon having an ethylenically unsaturated bond, specifically, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, α-methylvinylcyclohexane, vinylmethylcyclohexane, vinylbutylcyclohexane, such as vinylbutylcyclohexane Alkanes;
Vinylcycloalkenes such as vinylcyclopentene, vinylcyclohexene, vinylmethylcyclohexane, and vinylcycloheptene; cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclohexyl (meth) acrylate;

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 9-
Ethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 9-
Ethylidenetetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 9-
Methyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 8-
Ethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 8-
Ethylidenetetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 8-
Methyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 8,
9-ethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecyl-3- (meth) acrylate, 8,
9-ethylidenetetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodecyl-3- (meth) acrylate,
8,9-methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodecyl-3- (meth) acrylate,
2,7-dimethyltetracyclo [4.4.0.
^12,5 . 1 ^7,10] dodecyl-3- (meth) acrylate, 2,10-dimethyl-tetracyclo [4.4.
0.1 ^2,5 . [ ^17,10 ] dodecyl-3- (meth) acrylate, 11,12-dimethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodecyl-3- (meth) acrylate,

Hexacyclo [6.6.1.1]^3,6. 1
^10,13. 0^2,7. 0^9,14Heptadecyl-4
-(Meth) acrylate, 12-methylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,14Heptadecyl-4- (meth) acrylate,
11-methylhexacyclo [6.6.1.1^3,6. 1
^10,13. 0^2,7. 0^9,14Heptadecyl-4
-(Meth) acrylate, 12-ethylhexacyclo
[6.6.1.1^3,6. 1^10,13. 0^2,7. 0
^9,14Heptadecyl-4- (meth) acrylate,
11-ethylhexacyclo [6.6.1.1^3,6. 1
^10,13. 0^2,7. 0^9,14Heptadecyl-4
-(Meth) acrylate, octacyclo [8.8.
^{Two, three}. 1^{4, 7}. 1^11,18. 1^13,15. 0.
0^3,8. 0^12,17Docosyl-5- (meth) ac
Relevant, 15-methyloctacyclo [8.8.
^{Two, three}. 1^{4 , 7}. 1^11,18. 1^13,15. 0.
0^3,8. 0^12,17Docosyl-5- (meth) ac
Related,

Pentacyclo [6.6.1.1]^3,6. 0
^2,7. 0^9,14Hexadecyl-4- (meth) ac
Lylate, 1,6-dimethylpentacyclo [6.6.
1.1 ^3,6. 0^2,7. 0^9,14Hexadecyl-
4- (meth) acrylate, 15,16-dimethyl pen
Tacyclo [6.6.1.1^3,6. 0^2,7. 0^9,1
4] Hexadecyl-4- (meth) acrylate, 1,3
-Dimethylpentacyclo [6.6.1.1^3,6. 0
^2,7. 0^9,14Hexadecyl-4- (meth) ac
Related, pentacyclo [6.5.1.1^3,6. 0
^2,7. 0^9,13Pentadecyl-4- (meth) ac
Lylate, 1,6-dimethylpentacyclo [6.5.
1.1^3,6. 0^2,7. 0^9,13Pentadecyl-
4- (meth) acrylate, 1,3-dimethylpentane
Black [6.5.1.1^3,6. 0^2,7. 0^9,13]
Pentadecyl-4- (meth) acrylate, 15,16
-Dimethylpentacyclo [6.5.1.1^3,6. 0
^2,7. 0^9,13Pentadecyl-4- (meth) ac
Normetane ring structure-containing (meth) acryl
Relate and the like.

As the aromatic vinyl monomer, styrene,
α-methylstyrene, p-methylstyrene, t-butylstyrene, vinylnaphthalene and the like.

The other monomer is not limited as long as it can be copolymerized with the alicyclic structure-containing ethylenically unsaturated monomer and / or the aromatic vinyl monomer.
Α-olefins such as propylene and 4-methyl-1-pentene; conjugated diene monomers such as butadiene and isoprene; methyl (meth) acrylate and ethyl (meth)
Ethylenically unsaturated carboxylic esters such as acrylate, 2-ethylhexyl (meth) acrylate and butyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and itaconic acid; acrylonitrile, methacrylonitrile And ethylenically unsaturated carboxylic amides such as acrylamide and methacrylamide; and cyclic diene monomers such as norbornadiene and cyclohexadiene. Among these, a conjugated diene monomer or an ethylenically unsaturated carboxylic acid ester is preferred from the viewpoint of improving the fixability of the binder resin.

The amount of the alicyclic structure-containing ethylenically unsaturated monomer and / or the aromatic vinyl monomer is usually from 10 to 99% by weight, preferably from 30 to 95% by weight, based on all monomers used for polymerization.
% By weight.

The polymerization is carried out by using a polymerization initiator such as a radical polymerization catalyst or an ionic polymerization catalyst, by bulk polymerization, emulsion polymerization,
It can be performed by a method such as suspension polymerization or solution polymerization.

The method of adding hydrogen to the aromatic ring of the aromatic vinyl polymer can be carried out by using a known hydrogenation method. Specifically, for example, in the presence of a hydrogenation catalyst, hydrogen is introduced into a melt or solution, preferably a solution of the aromatic vinyl polymer, and hydrogen is added to the aromatic ring portion to cause an addition reaction.

Examples of the hydrogenation catalyst include fine powders of noble metals such as ruthenium, rhodium, palladium, platinum and nickel; And the like obtained by reducing a complex of a transition metal element solubilized in an organic solvent with an alkyl metal compound.

The solvent used for the solution of the aromatic vinyl polymer may be any solvent that can dissolve the binder resin obtained by the hydrogenation reaction and does not poison the catalyst.
Specific examples of the solvent include cycloalkanes such as cyclohexane; alkanes such as n-hexane. Polar compounds such as alcohols and ketones may be added to the solvent in order to adjust the viscosity and reaction rate of the solvent.

The binder resin of the present invention is not particularly limited by the hydrogenation rate of the aromatic ring. Usually 50-100
%, Preferably 80 to 100%, particularly preferably 90 to 100%.
100%.

Further, by introducing a carboxyl group into the above-mentioned binder resin by a melt air oxidation method or a modification with maleic anhydride within a range that does not impair the environmental dependency, compatibility with other toner components and dispersion of the pigment can be obtained. Performance can be improved. The same improvement can be realized by introducing a hydroxyl group and an amino group by a known method. Furthermore, a metal such as zinc, copper, or calcium is added to a binder resin obtained by copolymerizing a diene monomer such as norbornadiene or cyclohexadiene, or a binder resin into which a carboxyl group is introduced, to form a crosslink. By forming the structure, the offset resistance can be improved.

The toner of the present invention can be used in addition to the above-mentioned binder resin, for example, a polyester, a polymer of a conjugated diene monomer, or a copolymer of a conjugated diene monomer and (meth) acrylate. A copolymer of an aromatic vinyl monomer and a (meth) acrylate, a polymer of a (meth) acrylate monomer, and the like, usually 50% by weight or less, based on the entire toner.
Preferably not more than 40% by weight, more preferably 30% by weight
Below, more preferably, it can be used in a range of 20% by weight or less.

The colorant used in the present invention includes a black colorant and a colorant for a color toner. Examples of the black colorant include carbon black, nigrosine-based dyes and pigments; magnetic particles such as cobalt, nickel, iron tetroxide, iron manganese oxide, iron zinc oxide, and nickel iron oxide; When carbon black is used, the primary particle size is 2
It is preferable to use a layer having a thickness of from 0 to 40 nm because good image quality can be obtained and the safety of the toner to the environment is enhanced. Examples of the colorant for a color toner include Neftor Yellow S, Hansa Yellow G, C.I. I. Pigment Yellow, C.I.
I. Bat Yello, Eosin Lake, C.I. I. Pigment red, C.I. I. Pigment violet, C.I. I.
Bat red, phthalocyanine blue, C.I. I. Pigment blue, C.I. I. Bat blue, C.I. I. Acid blue and the like. These colorants are used in the binder resin 10
It is used in a proportion of usually 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 0 parts by weight.

The toner of the present invention may contain a charge control agent (including a charge control resin), a release agent, and the like in addition to the binder resin and the colorant.

As the charge controlling agent, a nigrosine compound,
Examples include triphenylmethane, quaternary ammonium salts, and hydrogen halide salts of alkylamines. More specifically, Bontron N1, N4, N21, (Nigrosine, manufactured by Orient Chemical), Nigrosine EX (manufactured by Orient Chemical), Copy Blue PR (manufactured by Hoechst), quaternary ammonium salt-containing resin (Fujikura Kasei) FCA-201-
PS), a charge control resin such as a charge control resin having a nitrogen-containing group having a positive charge, a metal complex of an organic compound which is a negative charge control agent, a metal-containing dye, for example, Spiron Black T
RH (Hodogaya Chemical), T-77 (Hodogaya Chemical), Bontron S-34 (Orient Chemical), Bontron E-84 (Orient Chemical), sulfonic acid group-containing resin (Fujikura Kasei) Manufactured by FCA-1001-NS)
And the like. The charge control agent is used usually in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin.

Examples of the release agent include low-molecular-weight polyolefin waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, and low-molecular-weight polybutylene, low-molecular-weight oxidized polypropylene having low molecular weight, and low-molecular-weight terminal-modified polypropylene having a molecular terminal substituted by an epoxy group. And terminal-modified polyolefin waxes such as block copolymers of these and low-molecular-weight polyethylene, molecular-end-oxidized low-molecular-weight polyethylene, low-molecular-weight polyethylene having a molecular terminal substituted by an epoxy group, and block polymers of these and low-molecular-weight polypropylene; candelilla, carnauba, rice Wax, wood wax, jojoba, etc .; natural waxes; petroleum waxes such as paraffin, microcrystalline, petrolactam and their modified waxes; montan, ceresin, ozokerite Synthetic waxes such as Fischer-Tropsch wax; mineral waxes pentaerythritol myristate, one such multifunctional ester compounds such as pentaerythritol tetra palmitate or two or more can be exemplified.

Of these, synthetic wax (particularly Fischer-Tropsch wax), synthetic polyolefin, low molecular weight polypropylene wax, microcrystalline wax and the like are preferable. The release agent is a binder resin 10
Usually, 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight is used based on 0 parts by weight.

[0034] Formulations of the above-mentioned binder resin, colorant, and if necessary, a charge control agent, a release agent, and the like are blended and mixed using a Henschel mixer or the like to obtain a blend. 100-2
The mixture is melt-kneaded using a kneader such as a two-roll twin screw extruder or a buscon kneader heated to 00 ° C. The kneaded compound is cooled, pulverized and classified to obtain a toner having a target particle size. After that, inorganic particles, organic resin particles,
External additives such as silica particles, titanium oxide particles, and particularly preferably silica particles that have been subjected to hydrophobic treatment may be mixed.

The volume average particle diameter of the toner of the present invention is usually
It is 1 to 10 μm, preferably 3 to 8 μm. If it is smaller than 1 μm, manufacturing is difficult, and if it is larger than 10 μm, the resolution is reduced. The particle size distribution (volume average particle diameter / number average particle diameter) is usually 1.7 or less, preferably 1.5 or less, and more preferably 1.3 or less. 1.
If it is larger than 7, the transferability decreases.

The toner of the present invention can be used as a one-component toner or a two-component toner. Further, the toner of the present invention can be used as a magnetic toner by mixing magnetic powder, or can be used as a full-color toner.

[0037]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to only these examples. Parts and percentages are by weight unless otherwise specified. The methods for measuring physical properties in Examples and Comparative Examples are as follows.

(1) Toner (particle size) The volume average particle size (Dv) and the number average particle size (Dp) of the toner particles are measured using a Multisizer (manufactured by Coulter Inc.)
Was measured. The measurement by this multisizer is
The measurement was performed under the conditions of an aperture diameter: 100 μm, a medium: Isoton II, a concentration: 10%, and the number of measured particles: 50,000.

(Weight Average Molecular Weight) The detailed conditions for measuring the weight average molecular weight (hereinafter, referred to as Mw) are as follows. Apparatus: HLC8020 manufactured by Tosoh Corporation Column: TSKgel manufactured by Tosoh Corporation triple use Temperature: 20 ° C Solvent: cyclohexane Flow rate: 1.0 ml / min. Sample: 0.4 ml of a sample having a concentration of 0.15% In calculating the molecular weight, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used.

(2) Evaluation of Image Quality (Environment Dependency) Using a printer modified so as to be able to change the temperature of the fixing roll section of a commercially available non-magnetic one-component developing system printer (eight-sheet machine), 35 ° C. × 80 RH% (H
/ H) environment and each environment of 10 ° C. × 20 RH% (L / L), continuous printing is performed from the beginning, and the print density is 1.3 or more with a reflection densitometer (manufactured by Macbeth) and a whiteness meter ( The number of continuous printed sheets capable of maintaining an image quality of 10% or less of fog in the non-image area measured by Nippon Denshoku Co., Ltd. was examined, and the environmental dependency of image quality due to toner was evaluated based on the following criteria. ：: The number of continuous prints that can maintain the above image quality is 1000 or more, Δ: The number of continuous prints that can maintain the above image quality is 500 or more 1
Less than 000, ×: The number of continuous prints that can maintain the above image quality is less than 500.

(Durability) With the above-mentioned modified printer, 23
Under an environment of 50 ° C. × 50 RH%, continuous printing was performed from the beginning, and the printing density measured by a reflection densitometer (manufactured by Macbeth) was 1.3.
The value calculated from the whiteness before and after printing of the non-image part measured by a whiteness meter (manufactured by Nippon Denshoku) and the value of continuous printing that can maintain an image quality of 10% or less is determined based on the following criteria. The durability of the image quality by the toner was evaluated. ：: The number of continuous prints capable of maintaining the above image quality is 10,000 or more, Δ: The number of continuous prints capable of maintaining the above image quality is 5,000 or more and less than 10,000, ×: The number of continuous prints capable of maintaining the above image quality is less than 5000.

(Measurement of Print Density (ID)) Print density (I)
The evaluation of D) was performed by measuring the “solid portion” using a Macbeth reflection densitometer.

(Measurement of fog) Whiteness meter (manufactured by Nippon Denshoku)
It is calculated from the following equation from the whiteness before and after printing of the non-image part measured in the above. Fog, F = ((W ₀ −W ₁ ) / W ₁ ) × 100 W ₀ : Whiteness of non-image portion before printing W ₁ : Whiteness of non-image portion after printing

(Fixing Temperature) A fixing test was performed using the above-mentioned modified printer. The fixing test was performed by changing the temperature of the fixing roll of the modified printer, measuring the fixing rate of the toner at each temperature, and determining the relationship between the temperature and the fixing rate. The fixing rate was calculated from the ratio of the image density before and after the tape peeling operation in the solid image area on the test paper printed by the modified printer. That is, the image density before peeling the tape is the ID, and the image density after the tape is peeled is I.
Assuming that after D, the fixing rate can be calculated from the following equation. Fixing rate (%) = (after ID / before ID) × 100

Here, the tape peeling operation means that an adhesive tape (Scotch Mending Tape 810-3-18 manufactured by Sumitomo 3M) is applied to the measurement portion of the test paper, adhered by pressing at a constant pressure, and then at a constant speed. Is a series of operations for peeling off the adhesive tape in the direction along the paper. The image density was measured using a reflection type image densitometer manufactured by McBeth. In this fixing test, the fixing roll temperature at a fixing rate of 80% was evaluated as the fixing temperature of the toner.

(Offset Temperature) The solid temperature was changed in the same manner as the fixing temperature to print solid black. At that time, it was judged from the presence or absence of occurrence of offset.

(Specular Gloss; Gloss in the Table) Specular gloss (gloss) was measured by printing a solid image using a gloss meter GM-26D (Murakami Color Research Laboratory). The fixing temperature was fixed at 170 ° C., and the incident angle of light on the printed image was 75 degrees. Printing density of 1.3 or more was used.

(Light transmission) A solid image was printed in the same manner as in the specular gloss. However, the transfer material was changed from paper to OHP paper. Images formed on OHP paper are OH
A color image was projected on a P machine and evaluated according to the following evaluation criteria. ：: excellent in transparency, no uneven brightness, and excellent in color reproducibility. Δ: There is slight unevenness in brightness, but there is no practical problem. X: There is uneven brightness and poor color reproducibility. However, a print density of 1.0 or more was used.

Example 1 After 70 parts of styrene and 30 parts of butyl acrylate were polymerized, hydrogen was added to the aromatic ring to obtain a resin A having a hydrogenation ratio of 99.8%. Mw of resin A
Was 5,600 and Tg was 69 ° C. Sulfonic acid group-containing charge control resin (trade name "FCA-10" manufactured by Fujikura Kasei Co., Ltd.)
01-NS "), 2 parts of a release agent (manufactured by Sasol Co., trade name" Paraflint H1 "), yellow pigment (manufactured by Clariant, trade name" toner yellow HG ")
VP2155 ") 5 parts and resin A 88 parts,
After melt-kneading at 140 ° C. with two rolls, the mixture was cooled and coarsely pulverized. Then, the toner was refined by a jet mill and classified to prepare a toner having an average particle diameter of about 8 μm. The toner and 0.5% colloidal silica (trade name “RX-200” manufactured by Nippon Aerosil Co., Ltd.) with respect to the toner were mixed with a Henschel mixer to obtain a developing toner.

Example 2 A polymer was synthesized in the same manner as in Example 1 except that 70 parts of styrene and 30 parts of butyl acrylate were used instead of 85 parts of styrene and 15 parts of isoprene, and hydrogen was added. Resin B with 99.9% hydrogenation
I got The Mw of the resin B was 12,500 and the Tg was 67 ° C. A resin B was used in place of the resin A, and a magenta pigment (manufactured by Clariant, trade name "toner magenta E-02") was used instead of the yellow pigment.
Instead of colloidal silica, silica (made by Degussa, R-
8 μm in the same manner as in Example 1 except that 202) was used.
A toner having an m particle size was produced.

Example 3 Resin C was obtained by copolymerizing 80 parts of vinylcyclohexane and 20 parts of ethylene. Mw of the resin C was 21,000 and Tg was 76 ° C. 8 μm particle size in the same manner as in Example 1 except that resin C was used in place of resin A, and 5 parts of a cyan pigment (manufactured by Sumika Color Co., Ltd., product name “GN-X”) was used instead of the yellow pigment. Was manufactured.

Comparative Example 1 Instead of resin A, resin D (ethylene-norbornene addition polymer (MW = 24,000
0, Tg = 72 ° C., norbornene content 47%), except that toner was produced in the same manner as in Example 1. Table 1 shows the evaluation results of the examples and the comparative examples.

[0053]

[Table 1]

From the above results, by using a resin containing an alicyclic structure-containing ethylenically unsaturated monomer unit and another monomer unit as a binder resin, heat resistance, fixability, light transmittance, It can be seen that a toner for developing an electrostatic charge image which provides a toner having excellent gloss, excellent durability of image quality, and excellent resolution can be obtained.

[0055]

The toner of the present invention has a fixing property, a light transmittance,
Excellent gloss and can be used as color toner. Also,
Using the toner of the present invention, clear high-quality images can be
It is also obtained in sheets.

Claims (3)

[Claims] 1. A resin comprising a binder resin and a colorant as main components, wherein the binder resin contains an alicyclic structure-containing ethylenically unsaturated monomer unit and other monomer units in a molecular chain. A toner for developing electrostatic images. 2. The binder resin has a glass transition temperature of 60 to 10.
2. The toner for developing an electrostatic image according to claim 1, wherein the temperature is 0.degree. 3. An aromatic ring of an aromatic vinyl polymer having a binder resin and a colorant as main components, wherein the binder resin is obtained by polymerizing a monomer mixture containing an aromatic vinyl monomer. For developing an electrostatic image, which is a resin obtained by adding hydrogen to a toner.