JPH03203746A - Electrophotographic toner - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to everything from monochrome copying machines to full-color copying machines for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a toner for dry electrophotography.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297°69
Although many methods are known, as described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., they generally utilize photoconductive substances and perform various methods. forming an electrical latent image on the photoreceptor by means;
The latent image is then developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heat, pressure, solvent vapor, or the like to obtain a copy.

Various methods and devices have been developed for the above-mentioned final step, which is the step of fixing the toner image on a sheet such as paper. The most common method at present is the compression heating method using a heated roller.

The pressure heating method using a heating roller performs fixing by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heating roller whose surface is made of a material that has a preforming property for the toner. . In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be carried out quickly. It is very effective in high-speed electrophotographic copying machines. However, in the above method, since the heated roller surface and the toner image contact each other under pressure in a molten state, a part of the toner image adheres to and rolls on the fixing roller surface, and this is transferred again to the next sheet to be fixed. This causes the so-called offset phenomenon,
It may stain the sheet to be fixed. Preventing toner from adhering to the surface of the heat fixing roller is considered to be one of the essential conditions for the heat roller fixed fixing method.

That is, there is currently a demand for the development of a binder resin for toners that has a wide fixing temperature range and is highly resistant to offset.

Furthermore, many studies and practical applications have been made on two-color copying machines and full-color copying machines. For example, “Journal of Electrophotography Society J.
Vol 22. No.l (1983) and "Journal of Electrophotography Society" Vol. 25. No, 1. P, 52 (1
There are also reports on color reproducibility and gradation reproducibility such as 986).

However, unlike television, photographs, and color printed matter, they cannot be directly compared with the real thing, and people who are more accustomed to seeing processed color images than the real thing are not as happy with the full-color electronic photographs that are currently in practical use. The images are not always satisfactory.

In full-color electrophotography, which requires multiple development steps and the overlapping of several toner layers of different colors on the same support, the following conditions are necessary for the binder resin for color toners: It will be done.

(2) In order to prevent the fixed toner from diffusely reflecting light and hindering color reproduction, it is necessary that the toner particles be in a state of almost complete melting to the point where the shape of the toner particles cannot be discerned.

■ The binder resin must have a transparency that does not interfere with the different toned toner layers below the toner layer.

As described above, for mono-color copying machines, it is desirable to develop toner binder resins with a wide fusing temperature range and high offset resistance. It is required that the fixing surface be flat when it is fixed.

For the purpose of expanding the fixing temperature of vinyl polymers conventionally used as binder resins for toners, Japanese Patent Laid-Open No. 58-
No. 14148, JP-A-8-72948, JP-A-59
-174855-6, JP-A-60-123855,
Special Publication No. 52-3304-5, Special Publication No. 57-52574
Although methods using offset inhibitors are disclosed in Japanese Patent Publication No. 58-8505, etc., they are supplementary.
In particular, when used as a mono-color toner, the transparency of the toner is impaired, and when used as a full-color toner, color mixing properties become poor.

Also, JP-A-56-158340, JP-A-58-H5
No. 58, JP-A-58-203453, JP-A-59-8
No. 8748, JP-A-59-226358, JP-A-60
-45259, JP-A-60-45261, JP-A-6
No. 0-48566 and Japanese Patent Publication No. 60-2411 disclose binder resins for toners having a low molecular weight component and a high molecular weight component. By using these resins, it has become possible to expand the fixing temperature, but due to the presence of high molecular weight components such as gel, when used as a full color toner, the smoothness of the fixing surface when fixed is impaired. , therefore, the color mixing property deteriorates.

That is, it is extremely difficult to simultaneously expand the fixing temperature range and satisfy the toner properties of fluidity, durability, transparency, and smoothness of the fixing surface.

[Problems to be Solved by the Invention] An object of the present invention is to provide a new toner for electrophotography that has improved the above-mentioned problems.

That is, the object of the present invention is to provide a film that has excellent offset resistance, fluidity, and impact resistance, has good fixing properties, and exhibits good charging characteristics that are stable during use, so that clear and fog-free images can be obtained. The purpose of the present invention is to provide a toner for heat fixing.

A further object of the present invention is to provide a heat-fixing toner that, when used as a full-color toner, provides images with excellent smoothness and transparency after fixing, and with good color reproducibility and color mixing. .

[Means and effects for solving the problem] In a toner resin made of a polymer synthesized from a vinyl yarn yarn or a mixture of the polymers, a polymerizable functional group having a double bond at the end of the polymer is added. The object of the present invention is achieved by a toner using a resin synthesized using the introduced so-called macromonomer.

The present inventors have understood that the reason for this is as follows.

Conventionally, when a polymerizable crosslinker such as divinylbenzene, which is used for crosslinking in vinyl polymers, is used, the elasticity of the resin increases, which impairs the smoothness of the toner adhesion surface when used for full color applications. It will be done.

Further, JP-A-57-178249-51 discloses a method of crosslinking with a metal compound. In this method, high-temperature offset resistance is certainly improved by crosslinking with a metal compound, but at relatively low temperatures, the toner becomes rigid and may not be sufficiently fixed to the fixing support, or may be difficult to fix for full-color printing. The smoothness of the surface may be impaired.

As a result of intensive research, the inventors of the present invention have invented a toner with excellent viscoelastic properties by using a macromonomer into which a polymerizable functional group having a double bond is introduced at the end of the polymer.

The macromonomer forms a soft segment in the polymer skeleton, and has the effect of increasing only the elasticity without changing the viscosity, unlike the viscoelasticity of conventional vinyl polymers. Therefore, it has become possible to lower the fixing temperature for mono-color toners, and to expand the fixing temperature range for full-color toners without impairing the smoothness of the fixing surface.

Here, the heat fixing method refers to a method of fixing by heating, such as a pressure heating method using a heat roller, a method of fixing by pressing the recording member against the heating member and bringing the recording member into close contact with the heating member via a film. etc.

Examples of vinyl monomers constituting the binder resin used in the present invention include the following.

For example, styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butylstyrene, p-tert-butylstyrene,
p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene% I'-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3.4- dichlorostyrene, m
- Styrene conductors such as nitrostyrene, 0-nitrostyrene, p-nitrostyrene, ethylene and unsaturated diolefins such as ethylene, propylene, butylene, and isobutylene, and unsaturated diolefins such as butadiene and isoprene; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; and methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylate. α-methylene aliphatic monocarboxylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, etc. methyl acrylate Acrylics such as ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate. Acid esters; maleic acid, maleic acid half ester; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone,
Vinyl ketones such as methyl isopropenyl ketone; N
- N-vinyl compounds such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives niacrolein such as acrylonitrile, methacrylonitrile, acrylamide, etc. A species or a mixture of two or more species may be used.

(Margin below) The macromonomer used in the present invention includes:

Any polymer may be used as long as it has a polymerizable double bond at the end of the polymer, but it is generally represented by the following formulas (1) to (X[[).

R.

(IX) CH2-CH(Mll) R20(X)
CH2-CH2-C11-R21(1h2(X[)
CH2-C)1-0-R23(R13) R24(,
X[l) HOOC'CHC-0-Rzs(M+J
R2a+1 ” R1, R3, R5, Re, R11, R'+3; -H
, C+alkyl group of NCs (sec-.

(including branched ones such as RIB, RIB tert-) R2, R4, R7, RIG,
R12, R14; -H, C+-(+o alkyl group (
sec-.

R17, R19, R20, R22, R24, R2 [1t
(including branched ones such as ert-) -OH, C, -C
, alkoxy group H3 R6・R9・RIB・R21,R3,Rzs;
C+ ~ CIO alkyl R+ -Rt-0-, -
0-Rt-, -RIOR3-1M, ~M+4: Any polymerizable polymer may be used.

Those with ether bonding group scolding n; 1-3000 1000 more macros As a specific example of a market, next Structural formula (1) - (59) can be mentioned.

0 C4)1° (55) Macromonomers are usually synthesized by generally known methods. For example, the Society of Polymer Science Microsymposium 81/
3 Proceedings p. 12, Polymer Processing Vol. 35 No. 6 269 (
Examples include methods such as those described in (1986).

(a) End cap P n” orP by living polymer ■-X, z-+ X-■-h p n-〇 (b) Initiation of living polymerization by ■-X ■-X=@-
P n"or■-p,'--〇-Pn(C) Conversion of terminal functional group (by chain transfer polymerization, single polycondensation/polyaddition) prl'-y+x-■→Pn-■ (d) Polyaddition■ -A-X→■-(A)n-X ■-A-■+X-B-X-■-(AB).-XX, Y are appropriate functional groups, P, A, B are repeating units ■ is a polymerizable functional group having a double bond, and n' indicates the degree of polymerization.

Particularly preferred polymers for carrying out the present invention include copolymers of styrene and acrylic esters or α-methylene aliphatic monocarboxylic esters.

In addition, as macromonomers, structural formulas (2), (3
).

(4), (10), (11), (28)
, (29), (30), (31), (3
2), (38).

(39), (40), (41), (42)
, (43) , (44) , (46) , (
47).

(48), (49), (50), (52)
, (53), (54), and (55).

In addition, the monomer composition ratio of these monomers is 60 to 95 for styrene.
mar%, esters 1-30 rno1%, macromonomer 0. It is preferable that the content is in the range of 1 to 30 mo1% and the glass transition point is 50 to 70°C.

The toner for electrophotography according to the present invention can be applied to either one-component or two-component toner. Therefore, in order to use the toner of the present invention as a one-component toner, it may contain magnetic powder. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used, and includes powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite. The content of this magnetic powder is preferably 15 to 70% by weight based on the weight of the toner.

Moreover, carbon black, titanium white, and any other pigments and/or dyes can be used as the coloring agent, regardless of whether the toner is a one-component toner or a two-component toner.

For example, when the toner of the present invention is used as a magnetic color toner, for example, C.1, Direct Red 1, C.
,1, Direct Red 4, C,1, Acid Red 1
, C,1, Basic Red 1, C,1, Modern Tread 30, C,1, Direct Blue 1, G,I.

Direct Blue 2, C, 1, Acid Blue 9, C,
1, Acid Blue 15, C, 1, Basic Blue 3
, C,1, Basic Blue 5, C,1, Mordand Blue, C,1, Direct Green 6, C,1, Basic Green 4, C,1, Basic Green 6, etc. Pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow 31 banza yellow G, permanent yellow NCG, tartrazine lake, red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G1 cadmium red, permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B.

Manganese Purple, Fast Violet B1 Methyl Violet Lake, Deep Blue, Cobalt Blue Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indan Stremburu-BC
, chrome green, chromium oxide, pigment green B
, Malachite Green Lake, Final Yellow Green G, etc.

Further, in the case of using an uninvented toner as a two-component full color toner, the following can be mentioned.

Coloring pigments for magenta include C,1, Pigment Red 1.2.3.4.5.6.7.8.9.10.11.1
2゜+3.14.15.1B, 17.18.19.2
1.22.23.30°31.32,37.3B,39
, 40, 41, 48, 49. 50,51゜52.53
, 54, 55, 57.5B, 60, 63. 64. 6
8,81°83.87,88,89,90. 112.
114. 122. 123. 163°202,2
08.207.209, C,1, Pigment Violet 1-19, C,1, Bat Red 1.2. to, 1
3.15.23°29, 35, etc.

Although a pigment may be used alone, it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of image quality of a full-color image.

Magenta dyes include C,1, Solvent Red 1
,3,8,23,24,25,27,30.49.81
,82°83,84.100.109.121,C,1
, Disperse Red 9, C,1, Solvent Violet 8.13.14°21,27, Oil-soluble dyes such as C,1, Disperse Violet 1, C,1, Basic Red 1.2.9.12° 13, 14.15.17.
18.22.23.24.27.29.32゜34,3
5.36.37.38.39.40, C,1, Basic Violet 1.3.7.10.14.15.21.
Examples include basic dyes such as 25.26°27, 28.

Coloring pigments for cyan include C,1, Pigment Blue 2.3.15.16.17, c,r, Bat Blue 6,
C, I Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton having a structure represented by the formula (■).

n=1 to 5 Yellow color pigments include C, 1, Pigment Yellow 1.2.3.4.5.6.7.10.11.12.1
3゜14, 15.16.17.23.65.73.83
, C, L Bat Yellow 1.3.20, etc.

The amount of coloring agent used is 0.00 parts by weight per 100 parts by weight of the binder resin.
The amount is 1 to 60 parts by weight, preferably 0.5 to 50 parts by weight.

Furthermore, although the toner in the present invention is not limited to being negatively chargeable or positively chargeable, when producing a negatively chargeable toner,
In particular, it is preferable to add a charge control agent for the purpose of stabilizing the negative charge characteristics. As a negative charge control agent, for example, a metal complex of alkyl-substituted salicylic acid (for example, Z-tert
-organometallic complexes such as chromium or zinc complexes of butylsalicylic acid).

In the case of a positive IF toner, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinylpyridine, or the like may be used as a charge control agent exhibiting positive IF charge. In the case of producing color toners, aminocarboxylic acid esters such as dimethylaminomethyl methacrylate which exhibit positive chargeability are used in an amount of 0.1 to 40 man%, preferably 1 to 30 moff.
% of the binder resin may be used, or a colorless or light-colored positive charge control agent that does not affect the color tone of the toner may be used. As a positive charge control agent, for example, structural formula (A
), quaternary ammonium salts represented by (B), and the like.

Structural formula (A) Ra, R,, Rc, Rd, alkyl group having 1 to 10 carbons Structural formula (B) R,, alkyl group having 1 to 5 carbons R,, -H, -H , -Cool, or an alkyl group having 1 to 5 carbon atoms Among quaternary ammonium salts represented by structural formulas (A) and (B), structural formula (A)-1, -2, structural formula (B)- It is preferable to use the positive charge control agent represented by 1 because it exhibits good charging properties with little environmental dependence.

Structural formula (A)-1 Phenyl group R'; alkyl group Re having 1 to 5 carbon atoms, -H, -OH, -COOH, or having 1 to 5 carbon atoms;
Alkyl group of 5 Structural formula (A)-2 Structural formula (B)-1 Also, as a resin component of the binder resin in the positively chargeable toner,
When using an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate that exhibits positive charge characteristics, a positive charge control agent or a negative charge control agent is used as necessary.

In the case of a negatively chargeable toner, the amount of the negative charge control agent used is preferably 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

When an aminocarboxylic acid ester such as dimethylaminomethyl methacrylate, which exhibits positive charging characteristics, is not used as a resin component in a positively chargeable toner, the amount of the positive charge control agent is 0.00 parts by weight per 100 parts by weight of the binder resin. It is desirable to use 1-15 parts by weight, preferably 0.5-10 parts by weight. In addition, when using aminocarboxylic acid esters, a positive charge control agent and/or a negative charge control agent may be added to 100 parts by weight of the binder resin as necessary in order to provide good chargeability with less environmental dependence. 0 to 10 parts by weight, preferably 0 to 8 parts by weight
It is desirable to use parts by weight.

Further, in the toner of the present invention, a fluidity improver may be added for the purpose of improving the fluidity of the toner.

As the fluidity improver used in the present invention, any fluidity improver can be used as long as it can increase the fluidity by comparing before and after addition by adding it to the colorant-containing resin particles.

For example, fluororesin powder, such as vinylidene fluoride powder, polytetrafluoroethylene fine powder, fatty acid metal salts, such as zinc stearate, calcium stearate, lead stearate, etc.; or metal oxides, such as zinc oxide powder; or finely powdered silica, i.e. wet process silica,
There are dry-processed silica, and treated silica that is surface-treated with silane coupling agents, titanium coupling agents, silicone oil, etc.

A preferred flow improver is a fine powder produced by vapor phase oxidation of a silicon halide compound, so-called dry process silica or fumed silica, which is produced by conventionally known techniques. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

5 i(:R4+ 2 t12 + 02→SiO2+
4 NCR Also, in this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halide compounds, such as aluminum chloride or titanium chloride, together with the silicon halide compound,
These are also included.

The average primary particle size of the particles is preferably within the range of 0.001 to 2μ, particularly preferably 0.00μ.
It is preferable to use silica fine powder within the range of 2 to 0.2 microns.

Commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds used in the present invention include those commercially available under the following trade names, for example.

Aerosil (AERO5IL) 13
0 (Japan Aerosil Co., Ltd.) 200 00 80 T600 M[lX170 MoX 80 COW 84 Ca-0-5iL (CABOT Co., Ltd.) -5 S-7 5-75 S-5 H-5 Vtacker)! DK N 20 (
WACKER-C:) IEMIE 6M88) 15 20E 30 40 (Francil) Furthermore, it is more preferable to use treated silica fine powder obtained by hydrophobizing the silica fine powder produced by gas phase oxidation of the silicon halogen compound. . Among the treated silica fine powders, it is particularly preferred that the silica fine powders be treated so that the degree of hydrophobicity as measured by a methanol titration test is in the range of 30 to 80.

Hydrophobicity can be imparted by reacting with fine silica powder or chemically treating with an organosilicon compound that physically adsorbs it.

In a preferred method, fine silica powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate , vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyljethoxysilane,
Hexamethyldisiloxane, l,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and St having 2 to 12 siloxane units per molecule, one for each terminally located unit. There are dimethylpolysiloxanes containing hydroxyl groups bonded to . These may be used alone or in a mixture of two or more.

The particle size of the treated silica fine powder is 0.003-0.
It is preferable to use one in the range of 1μ.

Commercially available products include Taranox-500 (Talco Co., Ltd.)
and Aerosil R-972 (Japan Aerosil Co., Ltd.).

Furthermore, positively chargeable silica fine particles may be used for the positively chargeable toner in order to not only improve its fluidity but also to obtain good chargeability with little environmental dependence.

In order to obtain such positively charged silica fine particles, it is preferable to treat them with a coupling agent or silicone oil containing an amino group. An example of such a treatment agent is 82NCII. CH2CH2Si (OCH3) 3H
2NCIhCthCl(2si (OC2H5) 3C
1 (3 1bNclhcH2cH2si (QC)I:+) 2
C1(3 H2NCH2ClbNHCH2CH2CH2Si (O
CH3) 2HJCONIICH2CH2CH2Si
(OC2H5)3H2NCII2Ct12NHCH2C
LCLSi (OCH3) 3) 12NC82ClhN
)lcH2cH2NHcH2c)I2CI(2si (
QC) 13) 5H3C20COCthCH2NHCH
2C:H2CH2S1 (OC+(3) 3HsC20
COCH2CH2NHCH2CH2NHCH2CH2C
H2Si (DC)13)383GOGOCI(zC1
hNHCLC82N)IC)hC)I2CH2Si (
OCH3) 3SC2 \ N-C)H2C)H2C)I2Si (OCH3) 3
/ II s C2 HOC) 12CH2 \ N-C) I2CH2CH2S1 (OCH8) s/ HOC82CI(2 ()12CO) 3SiC) H2C) 12c) I2-N
)IC)12(82GO) 3sic)I2CLCH2
-NHCL (85C20) 351c) I2c) I2c
)! 2\H / (H8C20)3SiCH2CH2CH2JCN)IC
H2C82C1(zsi (OC2Ha)382N(C
H2Cl(2N)I) 2cH2cfhc)12si
(OCH3) 311sc-NHCONHC+HaSi
There are aminosilane coupling agents such as (OCH3)3.

As the silicone oil, amino-modified silicone oil having a partial structure having an amino group in the side chain of the following formula is generally used.

(Here, R3 represents hydrogen, an alkyl group, an aryl group, or an alkoxy group, R2 represents an alkylene group, or a phenylene group, and R, R4 represents hydrogen, an alkyl group, or an aryl group. However, the above alkyl group , an aryl group, an alkylene group, and a phenylene group may contain an amine, or may have a substituent such as a halogen within a range that does not impair chargeability. m and n represent positive integers. .

) Examples of such silicone oils having amino groups include the following.

F8417 (made by Toray Silicone), F393 (made by Shin-Etsu Chemical), F857 (made by Shin-Etsu Chemical), F860 (made by Shin-Etsu Chemical), F861 (made by Shin-Etsu Chemical), F884 (made by Shin-Etsu Chemical), KF885 (manufactured by Shin-Etsu Chemical) F369 (manufactured by Shin-Etsu Chemical) F3113 (manufactured by Shin-Etsu Chemical) X-22-3680 (manufactured by Shin-Etsu Chemical -38
0IC (Shin-Etsu Chemical Co., Ltd. X-22-3810B (Shin-Etsu Chemical Co., Ltd.) 120
0 3500 60 360 70 830 250 7600 3500 2000 750 1900 1700 3800 90 4400 20 320 20 320 ) 90 8800 ) 2300 3800 ) 3500 3800 ) 1300 1700 The amine equivalent is the equivalent per amine (g/
eqiv), which is the molecular weight divided by the number of amines per molecule.

It is preferable to use silica fine particles treated with these amino group-containing coupling agents or silicone oils after further hydrophobic treatment with the above-mentioned organosilicon compound.

When the toner of the present invention is used as a two-component toner, the carrier used during development also plays an important role in order to fully exhibit its effects.

As the carrier used in the present invention, for example, surface-oxidized or unoxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, alloys or oxides thereof, and ferrites can be used. Moreover, there are no special restrictions on the manufacturing method.

Further, a system in which the surface of the carrier is coated with a resin or the like is particularly preferred in the above-mentioned J/B development method. The method involves dissolving or suspending a coating material such as a resin in a solvent and applying it to the carrier. Any conventionally known method can be applied, such as a method of simply mixing powder.

Substances that adhere to the carrier surface vary depending on the toner material, but include, for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, and g-tert-
It is appropriate to use metal complexes of butylsalicylic acid, styrene resins, acrylic resins, polyamides, polyvinyl butyral, nigrosine, aminoacrylate resins, basic dyes and their lakes, fine silica powder, fine alumina powder, etc., singly or in combination. However, it is not necessarily limited to this.

The amount of the above compound to be treated may be appropriately determined so that the carrier satisfies the above conditions, but generally the total amount is 0.1 to 30% by weight (preferably 0.5 to 30% by weight) based on the carrier of the present invention.
20% by weight) is desirable.

The average particle size of these carriers is preferably 10 to 100 microns, preferably 20 to 70 microns.

A particularly preferred embodiment is a ternary ferrite of Cu-Zn-Fe, whose surface is coated with a combination of resins such as fluororesin and styrene resin, such as polyvinylidene fluoride and styrene-methyl methacrylate resin; Fluoroethylene and styrene-methyl methacrylate resin, fluorine-based copolymer and styrene-based copolymer;
etc. 90:10~2080, preferably 70:30~
A mixture with a ratio of 30 to 0, 0.01 to 5
% by weight, preferably 0.1-1% by weight,
Examples include coated ferrite carriers having the above average particle size and containing 70% by weight or more of carrier particles of 250 mesh pass and 400 mesh pass. Examples of the fluorine-based copolymer include vinylidene fluoride-tetrafluoroethylene copolymer (10:90-90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80-20:80). 80:20) and styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60:5-30:10-50).

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties for the toner of the present invention, and has the effect of improving electrophotographic properties.

When preparing a two-component developer by mixing with the toner of the present invention, the mixing ratio is 2 as the toner concentration in the developer.
．． Good results are usually obtained from 0% to 15% by weight, preferably from 4% to 13% by weight. If the toner concentration is less than 2.0%, the image density will be low and it will not be practical.
% or more increases fogging and in-machine scattering, shortening the useful life of the developer.

The measurement method according to the present invention will be described below.

Measurement of glass transition temperature Tg In the present invention, measurement is performed using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by PerkinElmer).

The sample to be measured is accurately weighed in an amount of 5 to 20 mg, preferably 10 mg.

This was placed in an aluminum pan, an empty aluminum pan was used as a reference, and the measurement temperature range was 30°C to 200°C at a heating rate of 10°C/min at room temperature.

Take measurements.

In this temperature raising process, a main endothermic peak in the temperature range of 40 to 100°C is obtained.

The intersection of the line between the baselines before and after the endothermic peak appears and the differential thermal curve is defined as the glass transition temperature Tg in the present invention. (Fig. 1) Measurement of Molecular Weight In the present invention, the molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40°C, and THF was added to the column at this temperature as a solvent.
(Tetrahydrofuran) is flowed at a flow rate of 1 mi+ per minute, and 50 to 200 μp of T)IF sample solution of resin adjusted to a sample concentration of 0.05 to 0.6% by weight is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve, for example, Pressure Chemical Co., Ltd.
Chemical Co.) or Toyo Tsudani Gyo Co., Ltd. with a molecular weight of 6 x 102°2, I x 1034
X 10' 1.75 X 10' 5. IX
10'1, I XIO', 3.9X10', 8.
It is appropriate to use 6X1 (1', 2X106゜4.48X 106) and at least 10 standard polystyrene samples.
refractive index) detector.

In addition, in order to accurately measure the molecular weight region of 103 to 2 x 10', it is recommended to use a combination of commercially available polystyrene gel columns, such as Waters (
μm Stella gel (styrage) manufactured by
l) 500.103.10', 105 combination,
F- on Showa Denko's shodex
80M, a combination of KF-801, 1103, 804, 805, and A-802.

803, 804.805 combination, or Toyo Soda T
SKgel G100OH, G2000H, G2500
H, G3000H.

G4000H9G5000H, G3000H, G700
A combination of OH, GM)I is preferred.

[Example] The present invention will be explained in detail below with reference to Examples.

In addition, all parts indicate parts by weight.

was added dropwise over 4 hours while refluxing cumene, and the reaction was further carried out at 150°C for 3 hours to complete solution polymerization, and then cumene was removed.

The Mn of the graft polymer obtained here is 2900, M
w was 6800 and Tg was 61°C.

The graft polymer obtained here is referred to as Resin A. Hereinafter, as shown in Table 1, resins B to E were synthesized by changing the type and amount of macromonomer, styrene/n-butyl acrylate ratio, amount of initiator, etc.

(Left below) Example 1 was melt-kneaded in a roll mill, cooled, coarsely pulverized, finely pulverized into 1 classification, and further treated with hexamethyldisilazane as a fluidity improver, silica fine powder was added to 100 parts by weight of the classified product. A toner was prepared by externally adding 0.5 parts by weight and 0.2 parts by weight of aluminum oxide fine powder.

As a carrier, styrene-acrylic 2-ethylhexyl-methyl methacrylate (copolymerization weight ratio 50:2
Cu-Z coated with 0:05% by weight of 30)
n-Fe-based ferrite carrier (average particle size 47 μm.

A developer was prepared using a 250 mesh bath (400 mesh bath, 85% by weight) so that the toner concentration was 6.0% by weight.

Using these developer and toner, an unfixed image was obtained which was developed and transferred using a Canon full color copying machine CLC-500, and a fixing test was performed using an external fixing device.

As a result, the fixing temperature range in which colors can be mixed is 140 to 200.
It was at ℃.

An image reproduction test was conducted using CLC-500 using these developers and toners.

As a result, even after printing 15,000 sheets in monochrome mode, there was no offset to the fixing roll, and a full-color image that faithfully reproduced the original color chart without fogging was obtained. Furthermore, the toner transportability within the copying machine was good and stable image density was obtained.

Even when the 011P film was used, the toner permeability was very favorable.

Examples 2 to 5 and Comparative Example 1 The same procedure as Example 1 was carried out except that the resin was changed to B-H, and the results shown in Table 2 were obtained.

(Left below) Example 6 The materials in Table 3 were melt-kneaded in a roll mill, cooled, coarsely pulverized, then finely pulverized into 1 classification. Furthermore, 100 parts by weight of the classified product was subjected to dry positively charged hydrophobization treatment as a fluidity improver. A one-component magnetic toner was prepared by externally adding 0.6 parts by weight of permeability.

An unfixed image was obtained using this toner using a Canon copier NP-4835, and a fixing test was performed using an external fixing device. As a result, the fixable range was 145 to 210°C.

Furthermore, an image reproduction test was conducted using this toner and a copying machine. As a result, even after printing 10,000 sheets, there was no offset to the fixing roll, and a good image without fogging or scattering was obtained.

Layer Sides 7 to 10 and Comparative Example 2 The same procedure as in Example 6 was performed except that the resin was changed to BE, and the results shown in Table 3 were obtained.

[Effects of the Invention] As described above, according to the present invention, it is possible to stably supply high-quality copy images for a long period of time without offset in both monochrome and full color.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the glass transition temperature Tg in the present invention.

Claims (1)

[Claims] (1) A polymer synthesized from a vinyl monomer or a resin for toner made of a mixture of the polymers, which is synthesized using a macromonomer into which a polymerizable functional group having a double bond is introduced at the end of the polymer. An electrophotographic toner characterized by using.