JPH08184992A - Electrophotographic toner - Google Patents

Abstract

PURPOSE: To obtain a toner fixable without applying a large amt. of oil or without applying oil at all by using a bonding resin obtd. by subjecting polyol resin to esterification modification with a specified compd. CONSTITUTION: In an electrophotographic toner consisting essentially of a colorant and a bonding resin, a resin obtd. by subjecting polyol resin to esterification modification with a compd. represented by the formula CH3 (CH2 )x COOH (where 35<=x<=250) is used as the bonding resin. The polyol resin is preferably modified by adding the compd. having a high releasing effect by 2-40wt.% of the amt. of the polyol resin. In the case of <2wt.%, the releasing effect of the resultant toner or oilless fixation is not satisfactory. In the case of 45wt.%, the unreacted compd. remains in the resin and deteriorates the preservability of the toner and the transparency of a fixed image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner for fixing an oilless hot roll.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
As disclosed in JP-B No. 43-24748 and Japanese Patent Publication No. 43-24748, it is known by a number of methods. Generally, a photoconductive substance is used, and an electric latent image is formed on a photoreceptor by various means. And then develop the latent image with toner, transfer the toner image to a transfer material such as paper, if necessary, and fix it by heating, pressure or solvent vapor to obtain a copy. is there.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper. The most popular method at present is a pressure heating method using a heating roller.

In the pressure heating method using a heating roller, fixing is performed by passing the toner image surface of the sheet to be fixed under pressure on the surface of the heating roller, the surface of which is formed of a material having releasability for toner. Is to do. In this method, since the surface of the heating roller and the toner image on the sheet to be fixed are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and quick fixing can be performed. Very effective in high speed electrophotographic copying machines. However, in the above method,
Since the heating roller surface and the toner image are in contact with each other in a molten state under pressure, a part of the toner image adheres to and transfers to the fixing roller surface, which retransfers to the next sheet to be fixed, so-called offset phenomenon occurs, It may stain the fixing sheet. It is an essential condition of the heating roller fixing method to prevent the toner from adhering to the surface of the heating fixing roller.

Therefore, in order to prevent the toner from adhering to the surface of the fixing roller, the roller surface is formed of a material having excellent releasability from the toner, such as silicone rubber or fluorine resin, and the surface is prevented from being offset. And silicone oil to prevent fatigue on the roller surface,
It has been practiced to coat the roller surface with a thin film of a highly releasable liquid such as fluorine oil. However,
Although this method is extremely effective in preventing toner offset, it has a problem that the fixing device becomes complicated because an apparatus for supplying the offset preventing liquid is required. Needless to say, this oil coating causes delamination between the layers constituting the fixing roller, resulting in the shortening of the service life of the fixing roller. As the transfer material for fixing the toner image using these fixing devices, various kinds of papers, coated papers, plastic films and the like are generally used. In particular, the need for a transparency film (OHP) that uses an overhead projector for presentation has been attracting attention in recent years. In particular, unlike OHP, OHP has a low oil absorption capacity, so currently available copy OHP.
Inevitably, a sticky feeling due to oil application is unavoidable, and a big problem remains in the quality of the obtained image. In addition, silicone oil etc. evaporates due to heat, polluting the inside of the machine,
There is a high possibility that problems such as the treatment of recovered oil will occur.
Therefore, without using a device for supplying silicone oil,
Instead, from the idea of supplying the offset prevention liquid from the toner at the time of heating, a method of adding releasability such as low molecular weight polyethylene or low molecular weight polypropylene to the toner has been proposed. However, if a large amount of such an additive is added in order to obtain a sufficient effect, filming on the photoconductor or the surface of the toner carrier such as a carrier or a sleeve is contaminated, and the image is deteriorated, which causes a practical problem. Become. Therefore, a small amount of releasing agent is added to the toner to such an extent that the image is not deteriorated, and a small amount of releasing oil is supplied or the offset toner is used in a winding device such as a web or a cleaning pad. A cleaning device is also used together.

However, considering recent demands for size reduction, weight reduction, and high reliability, it is necessary to remove even these auxiliary devices, which is preferable. Therefore, if there is no further performance improvement such as toner fixing, offset, etc.
It is difficult to realize it without further improvement of the binder resin, release agent, etc. of the toner.

Further, especially in the full color field,
When OHP is used as the transfer material, the transparency and haze of the image after fixing are slightly lowered by including the release agent due to causes such as high crystallization of the release agent and a difference in refractive index with the resin. There will be a problem.

It is known to include a wax as a releasing agent in the toner. For example, Japanese Patent Publication No. 52-3304
Japanese Patent Publication No. 52-3305, Japanese Patent Publication No. 57-5.
The technology is disclosed in Japanese Patent Publication No. 2574.

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27.
3554, JP 61-94062, JP 61-138259, JP 60-25236.
1, JP-A-60-252360, JP-A-6
A technique for containing waxes is disclosed in, for example, 0-217366.

Waxes are used for improving the offset resistance of the toner at low temperature and high temperature, and for improving the fixing property at low temperature, but on the other hand, it deteriorates the blocking resistance and makes a copy machine. When exposed to heat due to the temperature rise of the toner, the developability deteriorates, and when the toner is left for a long period of time, the wax migrates on the toner surface to deteriorate the developability.

No conventional toner satisfies all of these aspects, and some problems have occurred. For example, high-temperature offset and developability are excellent, but low-temperature fixability is not good enough, or low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability decreases due to temperature rise inside the machine. There is an adverse effect such as the fact that the offset resistance at both low temperature and high temperature cannot be achieved at the same time.
The transparency was extremely bad.

With respect to the transparency of OHP, in particular, in order to reduce the crystallization of the wax itself, it is proposed to add a crystallization nucleating agent or the like to the wax (JP-A-4-149559 and JP-A-4-107467). , A proposal to use a wax having a low crystallinity (Japanese Patent Application No. 3-09110).
No. 8 and Japanese Patent Application No. 3-242397) and a material having a good compatibility with the binder and a lower melt viscosity than the binder is added to the binder, so that the surface smoothness of the toner layer after fixing is good. The proposal to make is Japanese Patent Application No. 3-21
As disclosed in Japanese Patent No. 2652, this also poses a problem of migration of a substance having a low melt viscosity.

Further, Japanese Patent Laid-Open No. 1-267561 proposes a method of reacting an epoxy resin with a monovalent carboxylic acid. However, the releasing effect of the monovalent carboxylic acid itself used is small, so that an oil is used. Offset occurs except for the fixing roller for coating.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic toner which can be fixed without applying a large amount of oil or without applying oil at all.

[0015]

The present invention relates to an electrophotographic toner containing a colorant and a binder resin as main components, and a polyol resin of CH ₃ (CH ₂ ) as the binder resin.
An electrophotographic toner comprising a binder resin esterified with _x COOH (x = 35 to 250).

The inventor of the present invention has so far studied a toner having a high releasing effect and requiring no application of silicone oil to the fixing roller. However, even if a releasing agent having a high releasing effect is added to the binder resin, the releasing agent is released. CH ₃ (CH ₂ ) has a particularly high release effect, considering the compatibility of the release agent with the binder resin, dispersibility, transparency, wax migration, etc., and considering modifying the release agent into a resin. _The present invention has been accomplished as a result of earnest studies of the (I) compound represented by _x COOH (x = 35 to 250) by paying attention to a polyol resin having many reaction active points. Originally, the (I) compound has high crystallinity and deteriorates the transparency of the toner. However, by modifying the polyol resin with high reactivity with the (I) compound, the problem of the molecular assembly of the (I) compound (crystallinity) The present inventors have found that the release effect of one molecule of the compound (I) can be given to the resin by eliminating the above.

In the present invention, the compound (I) is preferably modified in an amount of 2 to 40% by weight based on the polyol resin.
If it is less than 2% by weight, the releasing effect of the toner on the oilless fixing is insufficient, and if it exceeds 40% by weight, the unreacted (I) compound remains in the resin, and the storability of the toner and the transparency of the fixed image are improved. And so on.

The compound (I) used in the present invention is synthesized as follows.

After ethylene is polymerized using a Ziegler catalyst, it is oxidized to form an alkoxide of a catalyst metal and polyethylene. After that, hydrolysis is performed to synthesize a long-chain alkyl alcohol, and the long-chain alkyl alcohol is further oxidized to obtain a long-chain alkylcarboxylic acid that is a compound (I).

X showing the length of the alkyl chain of the compound (I)
Is 35 to 250, preferably 35 to 200. When x is 34 or less, a sufficient releasing effect cannot be obtained, and offset tends to occur in oilless thermal roll fixing. In addition, the storage stability of the toner tends to decrease. When x exceeds 251 the OHP transparency of the color toner decreases, and
It is difficult to uniformly modify the polyol resin.

As the polyol resin used in the present invention, a polycondensation product of bisphenol A and epichlorohydrin is desirable. As such a polyol resin, an epoxy resin can be mentioned. Asahi epoxy resin 330R, 331R, 331B, is a representative of commercially available products. 331C, 331
D, 331L, 331K, 337, 354, X229
8, X2302 (all manufactured by Asahi Kasei Co., Ltd.), ADEKA RESIN EP-4100, EP-4900, EP-434
0, EP-4100TX, EP-4200, EP-43
00, EP-4400, EP-4500A, EP-45
20, EP-5100-75X, EP-5100-75
T, EP-4340-90X, EP-4340-90
T, EP-6027, EP-6030, EP-400
4, EP-5100, EP-5400, EP-570
0, EP-5900, EP-4080 (all manufactured by Asahi Denka Co., Ltd.), Sumiepoxy ELA-115, ELA-1
17, ELA-118, ELA-127, ELA-12
8, ELA-134, ESA-011, ESA-01
2, ESA-014, ESA017, ESA019 (all manufactured by Sumitomo Chemical Co., Ltd.), D.I. E. FIG. R. -317,
D. E. FIG. R. -330, D.I. E. FIG. R. -331, D.
E. FIG. R. -332, D. E. FIG. R. -337, D.I. E. FIG.
R. -383, D.I. E. FIG. R. -324, D.I. E. FIG. R. −
361, D. E. FIG. R. -343 (all manufactured by Dow Chemical Japan Co., Ltd.) and the like.

Further, these epoxy resins and the bisphenol derivative represented by the formula (2)

[0023]

Embedded image Examples thereof include a polyol resin obtained by a polyaddition reaction with

The electrophotographic toner of the present invention may optionally contain a charge control agent in order to further stabilize its chargeability. The charge control agent is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

Charge control agents known in the art today include the following:

For example, organic metal complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and aromatic dicarboxylic acid-based metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples thereof include esters and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co and Ni. Like metals, or these metals and Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Examples thereof include alloys with metals such as d, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

Conventionally, as a magnetic material, ferrosoferric oxide (F) has been used.
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe)
₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuF)
e ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above magnetic materials are used alone or in combination of two or more kinds. Particularly suitable magnetic materials for the purposes of the present invention are fine powders of ferric tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
The magnetic characteristics under the application of 10 K oersted are about 20 μm to 20 oersted coercive force and 50 to 200 eersted saturation magnetization at about μm.
Those having a mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

For 100 parts by weight of the binder resin, 1 magnetic material is used.
It is recommended to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

Carbon black, titanium white, and any other pigments and / or dyes can be used as the colorant regardless of whether it is a single component or a two component. For example, when the toner of the present invention is used as a magnetic color toner, the dye may be C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G. , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indren Sren Blue BC,
Chrome Green, Chrome Oxide, Pigment Green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of magenta color pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0,11,12,13,14,15,16,17,1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1, 52, 53, 54, 55, 57, 58, 60, 6
3,64,68,81,83,87,88,89,9
0,112,114,122,123,163,20
2,206,207,209, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment in combination. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3,8,23,24,25,27,30,49,81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6,37,38,39,40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
Basic dyes such as 26, 27 and 28 can be mentioned.

Other coloring pigments include cyan pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton having the structure represented by the chemical formula 3 or the like.

[0035]

Embedded image

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat yellow 1,3,20
Etc.

The colorant is used in an amount of 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin.
0 parts by weight.

Further, in the present invention, one or more releasing agents may be contained in the toner, if desired.

As the negatively chargeable fluidizing agent used in the present invention, any agent can be used as long as the fluidity can be increased by adding it to the colorant-containing resin particles as compared with before and after addition. It is possible. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine powder silica such as dry process silica, and silane coupling agents thereof, Examples include titanium coupling agents and treated silica that has been surface-treated with silicone oil.

For example, the dry-process silica is a fine powder produced by vapor-phase oxidation of a silicon halogen compound, which is so-called dry-process silica or fumed silica, which is manufactured by a conventionally known technique. Is. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is also possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with the silicon halogen compound. Also includes. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, silica fine powder in the range of 0.002 to 0.2 μm is used. .

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

AEROSIL (Japan Aerosil Co.) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 V15 (WACKER) -CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by vapor-phase oxidation of the silicon halogen compound to a hydrophobic treatment. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by the methanol titration test is in the range of 30 to 80 are particularly preferable.

As a method of hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on the silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl. Dimethylchlorosilane, brommethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, there is dimethylpolysiloxane having siloxane units and each terminal unit having a hydroxyl group bonded to Si. These are used alone or as a mixture of two or more.

As the fluidizing agent used in the present invention, one obtained by treating the above-mentioned dry process silica with a coupling agent having an amino group as described below or a silicone oil is necessary for achieving the object of the present invention. You may use according to it.

[0049]

Embedded image

[0050]

[Chemical 4]

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

[0052]

Embedded image

(Here, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group. However, the above alkyl group,
The aryl group, alkylene group and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property. m and n represent positive integers. )

Examples of such silicone oil having an amino group are as follows.

Viscosity at 25 ° C. Amine equivalent Product name (cPs) SF8417 (manufactured by Toray Silicone Co., Ltd.) 1200 3500 KF393 (manufactured by Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (manufactured by Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (manufactured by Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-2680 (manufactured by Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (manufactured by Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-2810B (manufactured by Shin-Etsu Chemical Co., Ltd.) Shin-Etsu Gakusha, Ltd.) 1300 1700

The amine equivalent is the equivalent per amine (g / eqiv), and is the value obtained by dividing the molecular weight by the number of amines per molecule.

[0057] fluidizing agent used in the present invention has a specific surface area by nitrogen adsorption measured by BET method is 30 m ² / g or more, preferably not less than 50 m ² / g give good results. Fluidizing agent 0.01 per 100 parts by weight of toner
-8 parts by weight, preferably 0.1-4 parts by weight.

To prepare the electrophotographic toner of the present invention, a binder resin, a colorant and / or a magnetic material, a charge control agent or other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill, Using a heat kneader such as a kneader or an extruder to melt, knead and knead the meat to make the resins compatible with each other, and to cool and solidify the melt-kneaded product to pulverize the solidified product, and classify the pulverized product. Can be obtained.

Further, the fluidizing agent and the toner are thoroughly mixed with a mixer such as a Henschel mixer to obtain the electrostatic image developing developer of the present invention having the additive on the surface of the toner particles.

Transparency and gloss (glossiness) in the present invention
The measuring method of is described below.

1) Transparency The transmittance and haze value (haze) for each toner amount per unit area of the obtained fixed image were measured to obtain an image density of 1.5.
The transparency was evaluated using the numerical value in. The method of measuring the transmittance and haze will be described below.

The transmittance was measured by Shimadzu's own spectrophotometer UV.
2200 (manufactured by Shimadzu Corporation) is used, and the transmittance of the OHP film alone is set to 100%. Magenta toner: 650 nm Cyan toner: 500 nm Yellow toner: 600 nm Transmittance at the maximum absorption wavelength To measure.

The haze is measured by the haze meter ND.
It was measured using A-300A (manufactured by Nippon Coloring Industry Co., Ltd.).

2) Gloss (Glossiness) Measuring Method Using a VG-10 type gloss meter (manufactured by Nippon Denshoku Co., Ltd.), each solid image used for chromaticity measurement is measured as a sample.

For the measurement, first, 6 V was measured by a constant voltage device.
Set to. Next, the projection angle and the reception angle are each 6
Set to 0 °.

Using the zero point adjustment and the standard plate, after the standard setting, the sample image is placed on the sample table, and the white paper is 3
Perform overlay measurement on a sheet and read the value shown in the marking section in%. At this time, the S / S / 10 switch SW is set to S, and the angle / sensitivity switch SW is set to 45-60.

A sample having an image density of 1.5 ± 0.1 is used.

[0068]

EXAMPLES The present invention will be described below with reference to examples. All parts are parts by weight.

(Resin Production Example 1) Polyol resin (Asahi Epoxy Resin 330R, manufactured by Asahi Kasei Kogyo Co., Ltd.) 100 parts Bisphenol derivative represented by the formula (2) 50 parts (R = propylene group, x + y = 2.1) Toluene 50 parts Is heated to 80 ° C. under N ₂ atmosphere, 0.1 N potassium hydroxide aqueous solution is added, the temperature is raised to 190 ° C., and toluene is distilled off under reduced pressure. CH ₃ (CH ₂ ) ₆₀ COOH
Was added and reacted for 10 hours. Tg = 61 ° C., Tm
= 103 degreeC resin (A) was obtained.

(Resin Production Example 2) C in Resin Production Example 1
T 3 was synthesized in the same manner as in Resin Production Example 1 except that H ₃ (CH ₂ ) ₆₀ COOH was replaced with CH ₃ (CH ₂ ) ₃₆ COOH.
A resin (B) having g = 65 ° C. and Tm = 108 ° C. was obtained.

(Resin Production Example 3) C in Resin Production Example 1
H ₃ (CH ₂ ) ₆₀ COOH to CH ₃ (CH ₂ ) ₂₄₈ COOH
Was synthesized in the same manner as in Resin Production Example 1 except that
Resin (C) having g = 68 ° C. and Tm = 112 ° C. was obtained.

(Resin Production Example 4) Polyol resin (EP-4340, manufactured by Asahi Denka Kogyo Co., Ltd.) 100 parts Bisphenol derivative represented by the formula (2) 30 parts (R = ethylene group, x + y = 2.2) Toluene 50 parts Was heated to 90 ° C. under N ₂ atmosphere, 0.1N sodium hydroxide aqueous solution was added, the temperature was raised to 185 ° C., toluene was distilled off under reduced pressure, and then CH ₃ (CH ₂ ) ₁₂₀ C
Add 10 parts of OOH and react for 10 hours, Tg = 58
Resin (D) having a temperature of Tm = 99 ° C was obtained.

(Resin Production Example 5) C in Resin Production Example 4
H ₃ (CH ₂ ) ₁₂₀ COOH is converted to CH ₃ (CH ₂ ) ₂₀₀ COOH
All were synthesized in the same manner as in Resin Production Example 4 except that
Resin (E) having g = 63 ° C. and Tm = 107 ° C. was obtained.

Resin Production Example 6 C in Resin Production Example 4
H ₃ (CH ₂ ) ₁₂₀ COOH to CH ₃ (CH ₂ ) ₄₅ COOH
All were synthesized in the same manner as in Resin Production Example 4 except that
A resin (F) having g = 57 ° C. and Tm = 94 ° C. was obtained.

(Resin Production Example 7) C in Resin Production Example 4
H ₃ (CH ₂ ) ₁₂₀ COOH to CH ₃ (CH ₂ ) ₂₅ COOH
Resin (G) having Tg = 53 ° C. and Tm = 90 ° C., synthesized in the same manner as in Resin Production Example 4 except that (Montanic acid) was used.
I got

(Resin Production Example 8) C in Resin Production Example 4
H ₃ (CH ₂ ) ₁₂₀ COOH to CH ₃ (CH ₂ ) ₁₅ COOH
A resin (H) having Tg = 67 ° C. and Tm = 125 ° C. was obtained in the same manner as in Resin Production Example 4 except that (stearic acid) was used.

Resin Production Example 9 C in Resin Production Example 4
H ₃ (CH ₂ ) ₁₂₀ COOH to CH ₃ (CH ₂ ) ₂₇₃ COOH
All were synthesized in the same manner as in Resin Production Example 4 except that
Resin (I) having g = 60 ° C. and Tm = 110 ° C. was obtained.

Example 1 Resin The resin (A) used in Production Example 1 was premixed with a Henschel mixer according to the following formulation, and then 100 ° C. to 130 ° C.
The kneaded product melt-kneaded by a twin-screw kneading extruder at 0 ° C. is cooled, then roughly crushed by a cutter mill, finely crushed by a jet stream, and further classified by an air classifier to obtain a weight average diameter D ₄ =
8.0 μm colored fine particles were obtained, and to 100 parts of the colored fine particles, 1.0 part of titanium oxide fine particles surface-treated with a silane coupling agent (BET 100 m ^{2 /} g) was externally added with a Henschel mixer to obtain a toner. .

A Cu-Zn-ferrite carrier whose surface was coated with a silicone resin (average diameter 50 μm)
m) with a toner / carrier weight ratio of 5% to form a developer.

<Magenta Toner> Resin A 100 parts C.I. I. Pigment Red 122 4 parts Di-tert-butyl-chromic salicylate complex 4 parts <Yellow toner> Resin A 100 parts C.I. I. Pigment Yellow 17 5 parts Di-tert-butyl-chromic salicylate complex 4 parts <Cyan toner> Resin A 100 parts Copper phthalocyanine pigment 4 parts Di-tert-butyl-salicylic acid chromium complex 4 parts <Black toner> Resin A 100 parts Carbon black (Toker Black 4400) 5 parts Di-tert-butyl-salicylic acid chromium complex 4 parts These 4 color toners and developers were subjected to an image production test with a Canon color copying machine CLC800 with the oil coating system and the fixing roller web removed. It was The image output test is a full-color double-sided image, and 50 sheets are continuously copied for 2000.
After repeating this process, the stain resistance of the fixing roll, the glossiness (gloss) of the 10,000-sided double-sided image, and the transparency were examined to check the offset resistance, and the results are shown in Table 1.

Even on the 10000th sheet on both sides, a very good image equivalent to the initial image was obtained.

Table 1 also shows the evaluation of the appearance of the toner (toner blocking resistance) when the toner was left at 50 ° C. for 7 days.

Examples 2 to 6 As shown in Table 1, the resins B to F were evaluated in the same manner as in Example 1. Similar to Example 1, good results were obtained.

Comparative Examples 1 to 3 As shown in Table 1, the resins G to I were evaluated in the same manner as in Example 1. Comparative Examples 1 and 2 do not have sufficient offset resistance for the oilless fixing system. Comparative Example 3 has poor transparency and also has insufficient blocking resistance.

[0085]

[Table 1]

[0086]

According to the present invention, it has been possible to find an electrophotographic toner that is remarkably improved in releasability from a fixing roller and can be applied to a fixing system in which fixing oil is not applied. Moreover, it has excellent transparency and good blocking resistance, and is very suitable for a compact full-color image forming system.

Claims (1)

[Claims] 1. An electrophotographic toner comprising a colorant and a binder resin as main components, wherein a polyol resin is esterified and modified with CH ₃ (CH ₂ ) _X COOH (X = 35 to 250) as the binder resin. A toner for electrophotography, characterized by using a binder resin as described above.