JP3026526B2 - Toner for electrostatic image development - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a negatively chargeable and positively chargeable electrostatic image developing toner for developing an electrostatic image in electrostatic printing or the like.

[0002]

2. Description of the Related Art Toners which have been widely used in the past have been used.
Are dry-blended with a colorant such as carbon black, an optional charge control agent and / or a magnetic material to a styrene / acrylate copolymer powder obtained by suspension polymerization, and then melt-kneaded with an extruder or the like. , Followed by pulverization and classification. (See JP-A-51-23354).

However, the conventional toner obtained by the above-described melt-kneading-pulverization method has a limit in controlling the particle size of the toner, and substantially has a particle size of 10 μm or less, particularly 8 μm or less, particularly 5 μm or less. Perhaps it is difficult to produce toner with an average particle size with good yield, or if you use a developer to make many copies,
It has been difficult to avoid the drawbacks of poor printing durability, such as reduced image density or increased fogging and toner scattering.

[0004]

SUMMARY OF THE INVENTION The present invention greatly improves the above-mentioned disadvantages of the toner which has been widely used in the past, and is less expensive than the conventional toner by using a novel manufacturing method. It is an object of the present invention to provide a toner having good printing durability.

[0005]

Means for Solving the Problems The present inventors have proposed an image density,
As a result of various studies on an excellent toner which has high resolution and printing durability and does not cause fogging, scattering, etc., it has been found that a toner having the above-mentioned disadvantages improved can be obtained.

[0006]

The toner of the present invention is characterized by comprising primary particles of a polymer having an acidic polar group, colorant particles, and secondary particles containing a quaternary ammonium salt represented by the formula (1). The toner is preferably a toner containing a carrier, and the toner is preferably a developer containing a carrier.

Further, a positively-chargeable electrostatic particle composed of primary particles and colorant particles of a polymer having a basic polar group and secondary particles containing a quaternary ammonium salt represented by the formula (1) is preferred. A toner for developing a charge image, and the toner is a toner for developing a positively chargeable electrostatic image, which is a developer containing a carrier.

Preferred examples of the above-mentioned toner are described above. Particularly preferred examples include primary particles and colorant particles of a polymer having an acidic polar group or a basic polar group, and an optional charge control agent. In producing the toner, which is an associated particle of the secondary particles contained therein, the polymer particles thereof,
In general, it is produced by an emulsion polymerization method, a suspension polymerization method, a precipitation polymerization method, an interfacial polymerization method, a mechanical pulverization method of a synthetic resin piece, an association method utilizing a ζ potential, a coacervate method, etc. A suspension polymerization method and an association method utilizing ζ potential or the like are preferable.

The form of the secondary particles constituting the associated particles which are the toner of the present invention is not limited as long as the secondary particles do not alienate the present invention. Agent particles are particles that are aggregated by ionic bonding, hydrogen bonding, metal bonding, or weak acid-weak base bonding force.

The form of the aggregated particles is not particularly limited as long as the polymer particles and the colorant are aggregated. The formation of such associated particles generally involves:
Potential, coacervate, association method such as interfacial polymerization, and method of pulverizing after thermal fusion of interface can be used,
Among them, the association method is preferably used.

The average particle diameter of the polymer particles is 0.1.
01-10 μm is preferable, 0.01-8 μm is more preferable, and 0.0
It is more preferably 1 to 5 μm, particularly preferably 0.01 to 3 μm.
The average particle size of the colorant is preferably 0.01 to 10 μm, more preferably 0.002 to 8 μm, further preferably 0.002 to 5 μm, and particularly preferably 0.002 to 3 μm.

The average particle diameter of the secondary particles is preferably 0.05 to 15 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 8 μm, and particularly preferably 0.5 to 5 μm. The toner of the present invention has an average particle size of 1.0 to 20 μm.
Is preferably 1.5 to 15 μm, more preferably 2.0 to 13 μm, and particularly preferably 2.5 to 12 μm.

The polymer having a polar group used in the present invention is generally produced by an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like. Is good.

Preferred examples of the polymer having a polar group used in the present invention include styrenes, alkyl (meth) acrylates and comonomers having an acidic polar group or a basic polar group (hereinafter referred to as "comonomers having a polar group"). ")).

Preferred examples of such a copolymer include styrenes, alkyl (meth) acrylates and comonomers having an acidic polar group or a basic polar group (hereinafter referred to as "comonomers having a polar group"). Copolymers can be mentioned. In such a copolymer, if the total amount of styrenes and alkyl (meth) acrylate is 100 parts by weight, styrenes are preferably 95 to 20 parts by weight, and 90 to 90 parts by weight.
-30 parts by weight are more preferred. The amount of the alkyl (meth) acrylate is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight. The comonomer having a polar group has a total of styrenes and alkyl (meth) acrylate of 10%.
It is preferably added in an amount of 0.05 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 0 parts by weight. Also,
If necessary, comonomers copolymerizable with the above monomers can be added to the above copolymer as required, in addition to the above monomers, as long as the properties of the toner of the present invention are not impaired.

The styrenes include, for example,
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-di Chlorostyrene, p-chloromethylstyrene and the like can be mentioned.

Examples of the above alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic Lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
N-butyl methacrylate, isobutyl methacrylate,
N-octyl methacrylate, dodecyl methacrylate,
Examples thereof include lauryl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Among them, those having 1 to 12 carbon atoms are preferable, and 3 to 8
Are more preferred, and aliphatic alcohol (meth) acrylates having 4 carbon atoms are particularly preferably used.

Examples of the comonomer having an acidic polar group include α, β-ethylenically unsaturated compounds having a carboxyl group and α, β-ethylenically unsaturated compounds having a sulfone group.

Examples of the α, β ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monobutyl maleate, and maleic acid. Examples thereof include acid monooctyl esters and metal salts thereof such as sodium and zinc.

Examples of the α, β ethylenically unsaturated compound having a sulfone group include sulfonated ethylene, its Na salt, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and its Na salt.

Examples of the comonomer having a basic polar group include an amine group or a quaternary ammonium group having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably (meta) having 2 carbon atoms. A) acrylates, also (meth) acrylic amides or optionally (meth) acrylic amides mono- or di-substituted with alkyl groups of 1 to 18 carbon atoms on N, also having N as a ring member Examples thereof include a vinyl compound substituted with a heterocyclic group and N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, aliphatic alcohol (meth) acrylate having an amine group or a quaternary ammonium group is preferably used as a basic comonomer.

The aliphatic alcohol (meth) acrylate having an amine group or a quaternary ammonium group is, for example, dimethylaminoethyl acrylate.
Dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, quaternary ammonium salts thereof, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyl Trimethyl ammonium salt and the like can be mentioned.

The above-mentioned (meth) acrylamide or optionally an alkyl group having 1 to 18 carbon atoms on N is a mono- or di-alkyl group.
Examples of the substituted (meth) acrylamide include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide, and N-octadecyl Acrylamide and the like can be mentioned.

Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member include vinyl pyridine, vinyl pyrrolidone, vinyl N-methylpyridinium chloride, and vinyl N-ethyl. Pyridinium chloride and the like can be mentioned.

Examples of the N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride and N, N-diallylethylammonium chloride.

The above-mentioned polar polymer preferably has a glass transition point of -90 to 100 ° C, and has a glass transition point of -30 to 80 ° C.
C is more preferable, and -10 to 70 C is more preferable. If the glass transition point exceeds 100 ° C., the low-temperature fixability tends to deteriorate, and if it is less than −90 ° C., the powder fluidity of the toner tends to decrease, which is not preferable.

Further, examples of the polymer having a polar group include a polyester resin and an epoxy resin. Examples of the polyester resin include, for example, a co-condensation polymer of a polyhydric alcohol such as etherified bisphenol A or glycols and a dibasic acid such as terephthalic acid, fumaric acid, and maleic acid; Alternatively, a three-dimensional or higher copolymer including trimellitic acid, pyromellitic acid and the like can be mentioned, and their molecular weight is preferably about 2,000 to 200,000. Examples of the epoxy resin include a resin obtained by reacting epichlorohydrin with bisphenol A or a polyhydric alcohol or a modified product thereof, and the softening point thereof is preferably 90 to 200 ° C.

Although the degree of polymerization of the above polymer is not particularly limited, it is generally 2,000 to 4,000 in number average degree of polymerization.
00 is preferable, 5000 to 200,000 is more preferable, and 8000 is further preferable.
~ 100,000 is preferred. In addition, the weight average degree of polymerization is 3000
8800,000 is preferred, and 10,000〜400,000 is more preferred.

The polar group has an acid value of 2 to 50 and an amine value of 1 to 15
It is preferred that On the other hand, the colorant has coloring properties that can be added to the electrostatic image developer to give a necessary color as the electrostatic image developer, and other than the colorant such as a magnetic material such as magnetite. Is included in the colorant if it imparts colorability to the developer.

Examples of the colorant include inorganic pigments, organic pigments and organic dyes. Inorganic pigments and organic pigments are preferably used, and one or more pigments and / or one or more pigments are used. Can be used in combination.

Examples of the inorganic pigments include metal powder pigments, metal oxide pigments, carbon pigments, sulfide pigments, chromate pigments, and ferrocyanide pigments.

Examples of the metal powder pigment include zinc powder, iron powder, copper powder and the like.

Examples of the metal oxide pigment include, for example,
Magnetite, ferrite, red iron oxide, titanium oxide, zinc oxide, silica, chromium oxide, ultramarine, cobalt blue, celerian blue, Milanel violet,
Trilead tetroxide and the like can be mentioned.

Examples of the above-mentioned carbon pigments include carbon black, thermotomic carbon, furnace black and the like.

Examples of the sulfide pigments include zinc sulfide, cadmium red, selenium red, mercury sulfide, and cadmium yellow.

Examples of the chromate pigments include, for example,
Molybdenum red, barium yellow, strontium yellow, chrome yellow and the like can be mentioned. Examples of the ferrocyan compound pigments include, for example, miroribble.

Examples of the organic pigments include azo pigments, acid dye pigments and basic dye pigments, mordant dye pigments, phthalocyanine pigments, quinacdrine pigments, and dioxane pigments.

Examples of the azo pigments include benzidine yellow, benzidine orange, permanent red 4R, pyrazolone red, lithol red, brilliant scarlet G, and bommarnlite.

Examples of the acid dye-based pigment and the basic dye-based pigment include Orange II, Acid Orange R,
Dyes such as eoxin, quinoline yellow, tartrazine yellow, acid green, peak blue, alkali blue, etc., precipitated with a precipitant, or
Examples thereof include those obtained by precipitating dyes such as damine, magenta, makalite green, methyl violet, and Victoria Bull with tannic acid, tartar, PTA, PMA, PTMA, and the like.

Examples of the mordant dye-based pigments include metal salts of hydroxyanthraquinones and alizarinmer.
Drake and the like can be mentioned.

Examples of the phthalocyanine pigment include phthalocyanine blue and sulfonated copper phthalocyanine.

Examples of the quinacridone pigments and dioxane pigments include quinacridone red, quinacridone violet, carbazole-dioxane violet and the like.

The other organic pigments include, for example, organic fluorescent pigments, aniline black, nigrosine dyes, aniline dyes and the like. The quaternary ammonium salt used in the present invention is represented by the following formula.

[0045]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group having 1 to ₃ carbon atoms, and R ₄ represents an alkyl group having 1 to 22 carbon atoms, a phenyl group and derivatives thereof. A ⁻ represents an anion, and represents a molybdate anion, a tungstate anion, or a heteropolyacid anion containing molybdenum or a tungsten atom.

Preferably, trimethyl-hexadecyl ammonium heptamolybdate and the like are mentioned as specific examples. More preferably, the anion such as trimethyl heptadecane ammonium heptamolybdate is a molybdate anion and the positively chargeable anion. It is preferable that the toner is contained in a toner for developing an electrostatic image.

The above-mentioned quaternary ammonium salts suitable for inclusion in the toner for developing electrostatic images include TP-302 and TP-302.
-415 (manufactured by Hodogaya Chemical Co., Ltd.).

[0049]

[0050]

The content of the quaternary ammonium salt in the toner is preferably 0.01 to 6 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the toner.

The toner of the present invention may contain a fluidizing agent and a release agent as required. Examples of the fluidizing agent include fine powders of hydrophobic silica, titanium oxide, aluminum oxide and the like. Such a fluidizing agent is preferably added in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the toner.

Examples of the release agent include Cd, Ba, Ni, Co, Si, Cu, Mg and Ca salts of stearic acid, and Zn, Mn, Fe, Co, Cu, Pb and Mg salts of oleic acid. , Z of palmitic acid
n, Co, Cu, Mg, Si, Ca salt, Zn, Co, Ca of linoleic acid
Metal salts of higher fatty acids such as salts, Zn and Cd salts of ricinoleic acid, Pb salts of caprylic acid, Pb salts of caproic acid, natural and synthetic paraffins and fatty acid esters or partially saponified products thereof, alkylenebis Fatty acid amides and the like are used, and one or a combination of two or more of these compounds is used as appropriate.

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[Comparative Example 1] 92.5 parts by weight (styrene-butyl acrylate (80:20) resin) carbon black (Regal 330R Cabot) by Nicalite S NC-6157 (manufactured by Nippon Carbide Industrial Co., Ltd.) 7)
Parts by weight are melt-kneaded, pulverized and classified to obtain a toner having an average particle size of 10 μm.
I got To 100 parts by weight of the obtained toner, 0.5 part by weight of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added and mixed as a fluidizing agent to obtain a toner for testing. The test toner was mixed with a commercially available ferrite carrier (FL-150) in a ball mill for 1 hour so as to have a toner concentration of 4% to obtain a test developer. Table 1 shows the results of a copy test performed using the same copying machine as in Example 1.

[0065]

[0066]

[0067]

[0068]

Example 1 Preparation of basic polar group-containing resin Styrene monomer (ST) 75 parts by weight Butyl acrylate (BA) 25 parts by weight 2-hydroxypropyl-NNN-trimethylammonium chloride acrylate (BQA) 5 parts by weight 100 parts by weight of the above monomer mixture 100 parts by weight of water Nonionic emulsifier (Emulgen 950) 3 parts by weight Cationic emulsifier (Sanisol B-50) 5 parts by weight V-50 Add 1 part by weight to an aqueous solution mixture, and stir at 80 ° C. For 8 hours to obtain a basic polar group-containing resin emulsion having a solid content of 50%.

Preparation of toner 186 parts by weight of basic polar group-containing resin emulsion Carbon black (Regal 330R) 100 parts by weight Quaternary ammonium salt (trimethylpeptadecane ammonium heptamolybdate) 1 part by weight Water 139 Parts by weight The above mixture was dispersed with a slasher and stirred for about 30 minutes.
C. for 2 hours. After that, 95 ° C with further stirring
And kept for 3 hours. Observe with a microscope during this time,
It was confirmed that the complex of the resin particles and the carbon black particles grew. After cooling, the resulting liquid dispersion was washed with water and washed with water, and dried in vacuum at 50 ° C. for 10 hours to obtain a toner having an average particle diameter of 7 μm. To the resulting toner-100 parts by weight silica R-972, 0.3 parts by weight was added and mixed,
A test toner was used. The test toner was mixed with a commercially available ferrite carrier (FL-150) in a ball mill for 1 hour so as to have a toner concentration of 3% to form a test developer. -2085 manufactured by Mita Industries Co., Ltd.). Table 1 shows the results.

The test developer was used in a commercially available copying machine (SF-730).
0: manufactured by Sharp Corporation). Table 1 shows the results.

Evaluation Method of Image Density of Copy Image The density of the image (solid black portion of Test Chart NO1-R1975 of the Electrographic Society of Japan) is measured and determined using a Macbeth reflection densitometer RD-914.

The whiteness is measured using a color difference meter ND-504DE manufactured by JEOL Ltd. The color differences L, a, and b are obtained and the whiteness of natural paper before copying K ₀ = 100 − [(100−L) ² + a ² + b ² ] ^1/2 The whiteness of the non-image portion after copying K = 100 − [( ^{100-L) 2 + a 2} + b 2 ] head (% seeking ^1/2 from the head by the following formula) = K / K ₀ × 100 head may as low numbers, good at 0.3 or less, can be judged as defective by 0.5 or more .

The resolution electrophotographic society test chart NO1-R1
975 was copied, and the resolution pattern of 8.0 points was magnified 100 times with an optical microscope and visually judged as follows.

5. The fine lines are reproduced, and there is almost no fogging between the thin lines. 4. The fine lines are reproduced, but the fogging is slightly recognized between the fine lines. Slightly large 2. Poor reproduction of fine lines, many fogging between fine lines 1. Fine lines are not reproduced, and they are one line. The higher the number, the better the resolution. Can be determined.

[0075]

[Table 1]

[0076]

Industrial Applicability The present invention relates to a toner for developing a negatively chargeable and positively chargeable electrostatic image for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. The toner is an excellent toner having high image density, resolution and printing durability, and does not cause fogging or scattering.

──────────────────────────────────────────────────続 き Continued on the front page Examiner Yoshio Kanno (56) References JP-A-63-226665 (JP, A) JP-A-63-186253 (JP, A) JP-A-61-172155 (JP, A) JP-A 1-238673 (JP, A) JP-A 1-267560 (JP, A) JP-A 3-28858 (JP, A) JP-A 4-146450 (JP, A) JP-A 4-195166 ( JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (4)

(57) [Claims] 1. Negatively chargeable particles comprising primary particles and colorant particles of a polymer having an acidic polar group, and secondary particles containing a quaternary ammonium salt represented by the following general formula: Toner for developing electrostatic images. In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group having 1 to ₃ carbon atoms, and R ₄ represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, and derivatives thereof. A ⁻ represents an anion, and represents a molybdate anion, a tungstate anion, or a heteropolyacid anion containing molybdenum or a tungsten atom. 2. The toner for developing a negatively chargeable electrostatic image according to claim 1, wherein said toner is a developer containing a carrier. 3. A positive charge, comprising primary particles and colorant particles of a polymer having a basic polar group and secondary particles containing a quaternary ammonium salt represented by the following general formula: Toner for developing an electrostatic image. In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group having 1 to ₃ carbon atoms, and R ₄ represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, and derivatives thereof. A ⁻ represents an anion, and represents a molybdate anion, a tungstate anion, or a heteropolyacid anion containing molybdenum or a tungsten atom. 4. The toner for developing a positively chargeable electrostatic image according to claim 3, wherein said toner is a developer containing a carrier.