JPH0695423A - Toner for electrostatic developer - Google Patents

Abstract

PURPOSE:To provide a toner for an electrostatic developer excellent in stability of electrostatic charge characteristics to temp. and humidity and having releasability. CONSTITUTION:This toner for an electrostatic developer contains phosphorus- contg. organopolysiloxane represented by the general formula (where R<1> is a monovalent hydrocarbon group, R<2> is a divalent hydrocarbon group, R<3> is a monovalent hydrocarbon group, (a) is a positive number, (b) is 0 or a positive number, (c) is a positive number and (x) is 0, 1 or 2) and having <=200 deg.C softening point.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for an electrostatic developer, and more specifically, it contains phosphorus-containing organopolysiloxane and is excellent in stability of charging characteristics against temperature and humidity.
The present invention also relates to a toner for electrostatic developer having releasability.

[0002]

2. Description of the Related Art A toner for an electrostatic developer is mainly composed of a thermoplastic resin and a colorant, and if necessary, contains various additives such as a charge control agent, a fluidizing agent, a filler and a cleaning agent. Become. In the toner for electrostatic developer, the uniformity, charging property, fluidity, melting property and the like of the toner for electrostatic developer can be adjusted by combining the components.

However, the conventional toner for electrostatic developer has a problem that the charging characteristics greatly change with temperature and humidity. Further, the conventional toner for electrostatic developer has a problem that the releasability from the heating and fixing roll is poor, and the surface of the heating and fixing roll is contaminated with the toner for electrostatic developer. Further, since the heavy metal organic compounds used as conventional charge control agents are colored and toxic, the obtained toner for electrostatic developer is harmful to human body and causes environmental pollution. Further, the color copying toner has a problem that the hue of the toner is deteriorated.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for an electrostatic developer which has excellent stability of charging characteristics against temperature and humidity and has releasability.

[0005]

The present invention has the general formula:

[Chemical 2] (In the formula, R ¹ is a monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, a is a positive number, and b is 0 or a positive number. Is a number, c is a positive number, x is 0, 1 or 2) and contains an organopolysiloxane containing phosphorus having a softening point of 200 ° C. or lower. The present invention relates to a toner for a developer.

The toner for electrostatic developer of the present invention will be described in detail below.

The composition of the toner for electrostatic developer of the present invention is not particularly limited, and the main component is a thermoplastic resin and a colorant, and if necessary, a charge control agent, a fluidizing agent, a filler, and a cleaning agent. A toner for an electrostatic developer, which contains various additives such as

[Chemical 3] (In the formula, R ¹ is a monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, a is a positive number, and b is 0 or a positive number. Is a number, c is a positive number, x is 0, 1 or 2) and has a phosphorus-containing organopolysiloxane having a softening point of 200 ° C. or lower.

In the toner for electrostatic developer of the present invention, the kind of the thermoplastic resin as the main component is not particularly limited, and the thermoplastic resin generally used in the toner for electrostatic developer can be used. Specific examples of such a thermoplastic resin include polystyrene resin, α-methylstyrene resin, chlorostyrene resin, styrene-acryl copolymer, styrene-butadiene copolymer, styrene-butylmethacrylate copolymer, styrene- Divinylbenzene-butyl acrylate copolymer, styrene-maleic acid copolymer,
Acrylic resin, methacrylic resin, ethyl methacrylic resin, butadiene resin, isoprene resin, acrylonitrile resin, vinyl ether resin, vinyl acetate resin, polycarbonate resin, polyurethane resin, fluororesin, polyester resin, epoxy resin, polyamide resin, natural or synthetic wax, etc. As an example, the softening point of the thermoplastic resin is not particularly limited and is preferably 200 ° C. or lower. In the toner for electrostatic developer of the present invention, the blending amount of the thermoplastic resin is not particularly limited, but it is preferably in the range of 80 to 90% by weight in the toner for electrostatic developer.

In the toner for electrostatic developer of the present invention, the colorant which is the main component is a component for determining the hue of the toner for electrostatic developer, and the kind of the colorant is not particularly limited. Specific examples of such colorants include black dyes and pigments such as carbon black, oil black, and graphite.
Organic dyes such as quinoline yellow, phthalocyanine blue, and malachide green oxalate; C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3,
C. I. Pigment Yellow 74, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 98
Acetoacetic acid arylamide-based monoazo yellow pigments such as;
C. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14
Acetoacetic acid arylamide-based diazo yellow pigments such as C.I.
I. Solvent Yellow 19, C.I. I. Solvent
Yellow 77, C.I. I. Solvent Yellow 79,
C. I. Yellow dyes such as Disperse Yellow 164,
C. I. Pigment Red 48, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Red 53:
1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 81, C.I. I. Pigment Red 1
22, C.I. I. Pigment Red 5 and other red or red pigments; C.I. I. Solvent Red 52, C.I. I. Solvent Red 58, C.I. I. Solvent Red 8
Red dyes such as C.I. I. Pigment Blue 15:
3, blue-based dyes and pigments such as copper phthalocyanine and derivatives or modified products thereof, C.I. I. Pigment Green 7,
C. I. Pigment Green 36 and other green pigments, colored or colorless sublimable dyes, and the like. In the toner for electrostatic developer of the present invention, the blending amount of the colorant is not particularly limited, but it is 1 to 20% by weight in the toner for electrostatic developer.
Is preferred.

In the toner for electrostatic developer of the present invention, the phosphorus-containing organopolysiloxane has the general formula:

[Chemical 4] Indicated by. In the above formula, R ¹ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group. Aryl groups such as; vinyl groups,
Examples thereof include alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group. R ² is a divalent hydrocarbon group, and specific examples thereof include alkylene groups such as methylene group, ethylene group, propylene group and butylene group; and divalent hydrocarbon groups such as phenylene group. Also, R
³ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an aryl group such as a phenyl group, a tolyl group, and a xylyl group; Examples thereof include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group.

In the above formula, a is a positive number indicating the number of trifunctional siloxane units (T units) represented by the formula: R ¹ SiO _3/2 , and b is the formula: R ¹ ₂ is 0 or a positive number indicating the number of units of difunctional siloxane units (D units) represented by SiO _2/2, c has the formula: R ¹ R ² two represented by SiO _2/2 monofunctional siloxane units ( It is a positive number indicating the number of units (D unit). Further, x is 0, 1 or 2, and when x is 0, the phosphorus-containing organopolysiloxane of the present invention is a phosphate ester group (phosphate ester group) -containing organopolysiloxane, and x is 1
When the phosphorus-containing organopolysiloxane of the present invention is a phosphonate ester group (phosphonate ester group) -containing organopolysiloxane, and when x is 2, the phosphorus-containing organopolysiloxane of the present invention is a phosphonate. Innate ester group (phosphinic acid ester group)
The contained organopolysiloxane.

The method for producing such a phosphorus-containing organopolysiloxane is not particularly limited, and for example, the general formula: (R ¹ SiO _3/2 ) a (R ¹ ₂ SiO _2/2 ) b (R ¹ R ⁴ SiO _2/2 ) c (wherein R ¹ is a monovalent hydrocarbon group, R ⁴ is a haloalkyl group, a is a positive number, b is 0 or a positive number,
c is a positive number. ) And an organopolysiloxane containing a haloalkyl group represented by the general formula: R ³ _x (R ³ O) _(3-x) P═O (R ³ is a monovalent hydrocarbon group, x is 0, 1 or 2; It can be produced by reacting a phosphorus-containing organic compound represented by the formula (1) in the presence of a tertiary amine compound.

It is necessary that such a phosphorus-containing organopolysiloxane has a softening point of 200 ° C. or lower, and preferably a softening point of 150 ° C. or lower. This is because when the toner for an electrostatic developer of the present invention is manufactured, the thermoplastic resin and the phosphorus-containing organopolysiloxane can be softened and melted to be uniformly mixed. The softening point of the phosphorus-containing organopolysiloxane is preferably room temperature or higher, which means that the toner for an electrostatic developer of the present invention is stored at room temperature,
This is because the phosphorus-containing organopolysiloxane does not bleed out from the electrostatic developer toner.

Since the toner for an electrostatic developer of the present invention contains the above-mentioned phosphorus-containing organopolysiloxane, the obtained toner for an electrostatic developer has excellent stability of charging characteristics against temperature and humidity. Further, the electrostatic developer toner itself can have excellent releasability, and more preferably, the phosphorus-containing organopolysiloxane is translucent or white and has a phosphorus-containing organic group bonded thereto. It can be added as a charge control agent for adjusting the polarity of the electrostatic developer toner to a high negative polarity, and does not deteriorate the hue of the obtained electrostatic developer toner for color copy.

The toner for electrostatic developer of the present invention comprises, in addition to the above components, a charge control agent, a fluidizing agent, a filler, if necessary.
A cleaning agent or the like can be added. Hereinafter, these components will be described.

The charge control agent is an optional component for controlling the charge amount of the electrostatic developer toner, and the type thereof is not particularly limited. Specific examples of the charge control agent include chromium complex salts of azo dyes, chromium complex salts of aromatic hydroxycarboxylic acids, aluminum complex salts of aromatic hydroxycarboxylic acids or aromatic carboxylic acids, aromatic hydroxycarboxylic acids or aromatics. Examples thereof include zinc complex salt of carboxylic acid, boron complex salt of aromatic hydroxycarboxylic acid or aromatic carboxylic acid. In the toner for an electrostatic developer of the present invention, the phosphorus-containing organopolysiloxane can act as a charge control agent, and therefore it is optional to add a charge control agent. In the toner for electrostatic developer of the present invention, the compounding amount of the charge control agent is not particularly limited, but generally 1 to 5% by weight in the toner for electrostatic developer.
It is preferably in the range of.

The fluidizing agent is an optional component for improving the fluidity of the electrostatic developer toner, and the type thereof is not particularly limited. Specific examples of such a fluidizing agent include colloidal silica, metal soaps, nonionic surfactants, and the like. Further, in the toner for electrostatic developer of the present invention, the blending amount of the fluidizing agent is not particularly limited, but in general, it is preferably in the range of 0.1 to 2% by weight in the toner for electrostatic developer. .

The type of filler is not particularly limited, and specific examples of the filler include silica, alumina, titanium dioxide,
Examples thereof include titanium barium, zinc oxide, silica sand, iron oxide, ferrite, calcium carbonate, clay and talc.
In the toner for electrostatic developer of the present invention, the compounding amount of the filler is not particularly limited, but it is generally preferably in the range of 1 to 5% by weight in the toner for electrostatic developer.

The type of cleaning agent is not particularly limited,
As the cleaning agent, specifically, metal salts of fatty acids,
Examples include fluorine-based surfactants and silicon oxide derivatives. In the toner for electrostatic developer of the present invention, the compounding amount of the cleaning agent is not particularly limited, but generally, it is preferably in the range of 0.1 to 1% by weight in the toner for electrostatic developer.

The toner for electrostatic developer of the present invention can be prepared by uniformly blending the above-mentioned components and optional components. The method for producing the toner for the electrostatic developer is not particularly limited, and a commonly used production apparatus such as a Ross mixer, a kneader mixer, a ball mill, a Henschel mixer can be used. Further, the temperature during the production needs to be equal to or higher than the softening point of the thermoplastic resin and the phosphorus-containing organopolysiloxane in the toner for electrostatic developer of the present invention.

Since the toner for electrostatic developer of the present invention contains phosphorus-containing organopolysiloxane, it has excellent stability of charging characteristics against temperature and humidity. Therefore, the copying machine can be operated in a bad environment. Useful for. Further, since the toner for electrostatic developer of the present invention has releasability, the roll cleaning mechanism such as fuser oil for fixing roll can be greatly simplified. Furthermore, since the above-mentioned phosphorus-containing organopolysiloxane can act as a white-based charge control agent, it is not necessary to further add a charge control agent, so that the composition of the toner for electrostatic developers can be simplified and various types can be used. It can be used as a charge control agent for an electrostatic developer for color copying, and can reduce toxicity to the human body and environmental pollution as compared with conventional toners for electrostatic developers.

[0022]

EXAMPLES The present invention will be described with reference to examples. The peel strength was measured using a peel tester (manufactured by Tester Sangyo Co., Ltd.), and the toner for electrostatic developer was heated thinly on a silicone rubber sheet (thickness: 6 mm) for a heat and pressure fixing roller for a copy machine After fixing, a commercially available adhesive tape having a width of 1.8 cm was applied from above, and a high-speed peeling test of 180 ° at a peeling speed of 100 m / min. Was performed.

[0023]

[Reference Example 1] 100 g of water, 100 g of isopropyl alcohol and 400 g of toluene were put into a 2 liter round bottom flask equipped with a stirrer, a thermometer and a dropping funnel, and 297 g (about 1.4 mol) of phenyltrichlorosilane was added to this system while stirring. A mixed solution of 76 g (about 0.3 mol) of diphenylodichlorosilane and 39 g (about 0.3 mol) of dimethyldichlorosilane was added dropwise over 1 hour. After completion of the dropping, the system was heated, heated under reflux for 2 hours, and then cooled. After standing, the lower layer was taken out, 600 g of a 10% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for 30 minutes and left standing to take out the lower layer. The pH of the lower layer was 10. Further, 600 g of water was added, the mixture was stirred for 30 minutes, allowed to stand and the lower layer was removed, and this operation was repeated twice. Toluene and water were distilled off from the obtained toluene solution by an evaporator to obtain 1
It was adjusted so that the volatile content at 50 ° C. was 50%. The viscosity of the obtained toluene solution was 6 centipoise at 25 ° C.

Next, 25 g of 3-chloropropyl (methyl) dimethoxysilane was added to 500 g of this toluene solution, and the mixture was heated and stirred at a reflux temperature for 5 hours to give a compound of the general formula:

[Chemical 5] A toluene solution of a 3-chloropropyl group-containing organopolysiloxane represented by was prepared.

Then, in a 1 l round-bottomed flask equipped with a stirrer, a thermometer and a dropping funnel, 525 g of the toluene solution of the above-mentioned organopolysiloxane containing 3-chloropropyl group, 25 g of dimethylmethylphosphonate and 2 of triethylamine were added.
g was added, and the mixture was heated with stirring at the toluene reflux temperature for 6 hours.
After confirming that the generation of methyl chloride was completed from this system, the low boiling point component was distilled off at 150 ° C / 5 mmHg by an evaporator, and immediately after the distillate was no longer produced, a viscous liquid substance was formed in the metal vat. It was taken out and cooled to room temperature. After cooling, a solid phosphorus-containing organopolysiloxane represented by the following formula was obtained. This phosphorus-containing organopolysiloxane is slightly yellow and transparent and has a softening point of 75-85.
It was ℃.

[Chemical 6]

[0026]

[Reference Example 2] 100 g of water, 100 g of isopropyl alcohol and 400 g of toluene were put into a 2 liter round bottom flask equipped with a stirrer, a thermometer and a dropping funnel, and 297 g (about 1.4 mol) of phenyltrichlorosilane was added to this system while stirring. A mixed solution of 76 g (about 0.3 mol) of diphenylodichlorosilane and 39 g (about 0.3 mol) of dimethyldichlorosilane was added dropwise over 1 hour. After completion of the dropping, the system was heated, heated under reflux for 2 hours, and then cooled. After standing, the lower layer was taken out, 600 g of a 10% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for 30 minutes and left standing to take out the lower layer. The pH of the lower layer was 10. Further, 600 g of water was added, the mixture was stirred for 30 minutes, allowed to stand and the lower layer was removed, and this operation was repeated twice. Toluene and water were distilled off from the obtained toluene solution by an evaporator to obtain 1
It was adjusted so that the volatile content at 50 ° C. was 50%. The viscosity of the obtained toluene solution was 6 centipoise at 25 ° C.

Next, 25 g of 3-chloropropyl (methyl) dimethoxysilane was added to 500 g of this toluene solution, and the mixture was heated and stirred at a reflux temperature for 5 hours to give a compound of the general formula:

[Chemical 7] A toluene solution of a 3-chloropropyl group-containing organopolysiloxane represented by was prepared.

A 1 liter round bottom flask equipped with a stirrer, a thermometer and a dropping funnel was charged with 525 g of the toluene solution of the above-mentioned organopolysiloxane containing 3-chloropropyl group, 35 g of methylphenylmethylphosphonate and 2 g of dimethylbenzylamine, and the toluene reflux temperature. Heat to
The mixture was heated and stirred for 6 hours. After confirming that the generation of methyl chloride has ended, use an evaporator to remove the product at 150 ° C / 5mm.
The low boiling point component was distilled off with Hg, and immediately after the distillate was no longer produced, it was taken out as a viscous liquid into a metallic vat and cooled to room temperature. After cooling, a solid phosphorus-containing organopolysiloxane represented by the following formula was obtained. This phosphorus-containing organopolysiloxane was slightly yellow and transparent and had a softening point of 78 to 88 ° C.

[Chemical 8]

[0029]

Example 1 A composition prepared as follows was heated with a kneader mixer, melted and kneaded for 3 hours, pulverized and classified to prepare a toner for an electrostatic developer having an average particle size of 15 μm. Styrene-acrylic copolymer having a softening point of 150 ° C. 100 parts by weight Phosphorus-containing organopolysiloxane prepared in Reference Example 1 5 parts by weight Carbon black (# 40) 5 parts by weight

The obtained toner for electrostatic developer had good fluidity. Further, the toner for the electrostatic developer is SEM-XM
As a result of performing surface analysis on Si atoms using A,
It was confirmed that Si atoms were dispersed very uniformly. Next, 1.5 parts by weight of the obtained toner for electrostatic developer and 30 parts by weight of iron powder having an average particle diameter of 300 μm were shaken with a shaker.
After shaking for 0 minutes, the charge amount of the toner for electrostatic developer after 30 seconds of blow-off was measured by a blow-off powder charge amount measuring device. Also, to observe the effects of temperature and humidity,
The electrostatic developer toner after charging was spread on a glass petri dish, and the electrostatic charge of the electrostatic developer was measured immediately after standing in an atmosphere of 60 ° C. and 95% humidity for 24 hours. Next, the releasability of the obtained toner for electrostatic developer was measured. The results are shown in Table 1.

[0031]

Example 2 A composition prepared as follows was heated with a kneader mixer, melted and kneaded for 3 hours, pulverized and classified to prepare a toner for an electrostatic developer having an average particle size of 15 μm. Styrene-acrylic copolymer having a softening point of 150 ° C. 100 parts by weight Phosphorus-containing organopolysiloxane prepared in Reference Example 2 5 parts by weight Carbon black (# 40) 5 parts by weight

The obtained toner for electrostatic developer had good fluidity. Further, the toner for the electrostatic developer is SEM-XM
As a result of performing surface analysis on Si atoms using A,
It was confirmed that Si atoms were dispersed very uniformly. Next, 1.5 parts by weight of the obtained toner for electrostatic developer and 30 parts by weight of iron powder having an average particle diameter of 300 μm were shaken with a shaker.
After shaking for 0 minutes, the charge amount of the toner for electrostatic developer after 30 seconds of blow-off was measured by a blow-off powder charge amount measuring device. Also, to observe the effects of temperature and humidity,
The electrostatic developer toner after charging was spread on a glass petri dish, and the electrostatic charge of the electrostatic developer was measured immediately after standing in an atmosphere of 60 ° C. and 95% humidity for 24 hours. Next, the releasability of the obtained toner for electrostatic developer was measured. The results are shown in Table 1.

[0033]

Comparative Example 1 A toner for an electrostatic developer was prepared in the same manner as in Example 1 except that a commercially available azine type charge control agent was used instead of the phosphorus-containing organopolysiloxane. The obtained toner for electrostatic developer was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0034]

Comparative Example 2 A toner for an electrostatic developer was prepared in the same manner as in Comparative Example 1 except that 0.5 part by weight of dimethylpolysiloxane having a viscosity of 500 centistokes was added. The electrostatic developer toner thus obtained was evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

The toner for an electrostatic developer of the present invention contains a phosphorus-containing organopolysiloxane, so that
It is characterized by excellent stability of charging characteristics against humidity and releasability.

Claims (1)

[Claims] 1. A toner having a general formula: (In the formula, R ¹ is a monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, a is a positive number, and b is 0 or a positive number. Is a number, c is a positive number, x is 0, 1 or 2) and contains an organopolysiloxane containing phosphorus having a softening point of 200 ° C. or lower. Toner for developer.