JPS62276566A - Electrostatic image developing toner - Google Patents

Abstract

PURPOSE:To lower the minimum fixing temperature, and to enhance offset resistance by incorporating a crystalline polymer having a melting point of 50-120 deg.C an a nonlinear polymer having a glass transition point of 40-80 deg.C. CONSTITUTION:The toner contains the crystalline polymer, preferably crystalline polyester obtained by polycondensing polyol with polycarboxylic acid, having a melting point of 50-120 deg.C, preferably, 60-110 deg.C, and preferably, lower than the softening point of the nonlinear polymer, and this nonlinear polymer, preferably a nonlinear vinyl type homo- or co-polymer obtained by polymerizing at least one vinyl monomer or >=2 vinyl monomers, having a glass transition point of 40-80 deg.C, preferably, 50-70 deg.C, and a softening point of 100-150 deg.C, preferably, 110-140 deg.C, and nonlinearizable by using >=2 kinds of vinyl monomers.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention [Field of Industrial Application] The present invention provides a method for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to an electrostatic image developing toner constituting a developer, and particularly relates to an electrostatic image developing toner in which a formed toner image is fixed by a heated roller.

[Technology background]

Conventionally, as an electrophotographic method, for example, U.S. Patent No. 2
．． Although various methods are known, including the method disclosed in US Pat. After developing with a two-component developer consisting of a carrier and a carrier, or a one-component developer consisting of a toner containing a magnetic material, and transferring the formed toner image to a sheet such as paper, the visible image is transferred by heating, pressure, etc. A permanent fixing method is used. Although various methods have been adopted for fixing toner images on sheets such as paper, the heat roller fixing method, in which the toner image is fixed using a heat roller, has been widely praised.

The heat roller fixing method is a method in which the sheet carrying the toner image is passed through it while coming into contact with a heated roller, thereby fixing the toner image on the sort.It is a method that reduces heat loss and is safe and energy saving. It is advantageous from

However, in such a hot roller fixing method, when conventional toner is used, the toner in the toner image becomes molten when it comes into contact with the surface of the fixing roller, so a part of the toner image is fused onto the surface of the fixing roller. There is a problem in that a so-called offset phenomenon occurs, in which the toner adheres to and transfers to the next sheet to be fixed, and then transfers again to the next sheet to be fixed, staining the image.

Such an offset phenomenon is likely to occur when a low molecular weight resin is used as a binder resin for a toner, as described in Japanese Patent Publication No. 51-23354.

As a countermeasure to this offset phenomenon, it is possible to use a resin with a high degree of polymerization and therefore a large molecular weight as the binder resin of the toner, but according to the studies of the present inventors, simply using it alone does not necessarily provide good offset resistance. It has been found that in some cases, the fixing temperature simply increases.

Therefore, as described in JP-A-50-134652, by blending a low molecular weight polymer and a high molecular weight polymer to create a resin with an appropriate molecular weight distribution and using this as a binder resin, Attempts have been made to produce a toner that prevents the upper limit of the fixing temperature and has good offset resistance, but in this case, not only is it not possible to sufficiently improve the offset resistance, but when an attempt is made to lower the fixing temperature, There are problems in that the blocking resistance of the toner deteriorates, causing the toner to aggregate in the developing device, and toner filming, in which toner components adhere to carrier particles and the surface of the photoreceptor, to occur.

Furthermore, as described in Japanese Patent Application Laid-Open No. 51-23354, it is possible to use a crosslinked resin as a binder resin for toner, but according to the studies of the present inventors, crosslinked resin is used in cars. It has been found that good results cannot necessarily be obtained only by using a resin that has been modified. In other words, increasing the degree of crosslinking of the binder resin is effective in preventing toner offset, but at the same time the minimum fixing temperature required for fixing increases.On the other hand, if the degree of crosslinking of the binder resin is low, the toner Although the minimum fixing temperature can be maintained low, the offset resistance becomes insufficient, and as a result, the fixing possible temperature range is widened, which is defined as a range above the minimum fixing temperature and below the maximum temperature in which no offset phenomenon occurs. Furthermore, the blocking resistance of the toner deteriorates, making it impossible to obtain a good image.

In addition, in order to prevent the occurrence of offset phenomenon, for example,
The roller surface is made of materials such as silicone rubber and fluororesin that have excellent release properties against toner, and
Furthermore, for the purpose of preventing offset and fatigue of the roller surface, there is a method in which a releasing oil such as silicone oil is applied to the surface of the roller and the roller surface is covered with a thin film.

However, although this method is effective in preventing the offset phenomenon, it requires a device to supply mold release oil, making the fixing device complicated and causing the mold release oil to swell due to heating. This has problems such as giving off an unpleasant odor to the user. This method does not essentially solve the problem of the offset phenomenon. Therefore, it is desired to develop a toner for developing electrostatic images that has characteristics that do not easily cause the offset phenomenon and has a wide fixing temperature range.

Particularly in recent years, due to demands for higher copying speeds and energy savings, there has been a strong desire to develop toners that can be fixed at lower temperatures than conventional ones. In other words, when continuous copying is performed many times in a high-speed copying machine, the heat of the heat roller is absorbed by the image receiving sheet, causing the temperature of the heat roller to drop, resulting in a temperature below the minimum fixing temperature of the toner, resulting in poor fixing. . In addition, due to the need for energy conservation, if the capacity of the heater for heating the heat roller is reduced, the surface temperature of the heat roller cannot rise to the temperature required for fixing the toner (this also results in poor fixing). becomes.

As described above, recently, toners for developing electrostatic images must meet the difficult requirements of lowering the minimum fixing temperature and widening the fixable temperature range while maintaining anti-offset properties.

Furthermore, in order to lower the fixing temperature of the resulting toner, when a binder resin with a low softening point is used, or when a resin whose softening point is lowered by adding a low molecular weight plasticizer is used, Not only does the anti-offset property of the toner deteriorate, but also the glass transition temperature decreases, so if the toner is left in a heated atmosphere inside the copying machine or at a relatively high temperature outside the machine, the toner particles will not bond together. Blocking occurs in which the toner adheres and aggregates into lumps, rendering it useless as a toner. In particular, styrene-acrylic copolymers, which are currently widely used as binder resins for toner,
In the case of toners made of polyester resins, epoxy resins, etc., when the glass transition point temperature is 40° C. or lower, blocking becomes noticeable. Even when a resin whose softening point is simply lowered in this way is used, it is not possible to simultaneously satisfy the three characteristics of offset resistance, low-temperature fixing property, and blocking resistance.

Of course, in addition to fixing properties, offset resistance, and anti-blocking properties, toners also need to be excellent in developability, triboelectric charging properties, transferability, cleaning properties, fluidity, etc. It has been pointed out that conventional toners have at least one or more of the following defects. That is, in many cases, in order to obtain a toner with a low minimum fixing temperature, the softening point is lowered by adding a resin with a low softening point or a plasticizer having a melting point lower than the softening point of the resin. When a binder resin is used as a binder resin, the binder resin has a lowered glass transition point, resulting in poor toner offset resistance and blocking resistance, and poor triboelectric charging properties. Problems such as a decrease in image density and an increase in fog occur, and as a result, it becomes impossible to obtain a good image.

Furthermore, in order to achieve fixing at low temperatures, when a resin made of a plasticizer made of a soft, low-molecular-weight compound with a low melting point such as wax is used as a binder resin, the fluidity of the toner often deteriorates. In an electrophotographic copying machine, it becomes difficult to supply toner, and developability becomes poor (making it impossible to obtain good images).In addition, when performing continuous copying, collisions with carrier particles and contact with the photoreceptor may cause A filming phenomenon occurs in which soft plasticizers and the like adhere to carrier particles and the surface of the photoreceptor, resulting in poor triboelectric charging properties and developability, making it impossible to obtain good images.

[Purpose of the invention]

An object of the present invention is to provide a toner for electrostatic image development that has a low minimum fixing temperature, good anti-offset properties, and good anti-blocking properties.

Another object of the present invention is to provide a toner for electrostatic image development that has excellent fluidity, does not cause filming on carrier particles or the surface of a photoreceptor, and has excellent durability.

Still another object of the present invention is to provide a toner for electrostatic image development which has a high image yield and can provide clear images with little fog.

[Structure of the invention]

The object of the present invention is achieved by a toner for electrostatic image development characterized by containing a crystalline polymer having a melting point of 50 to 120°C and a nonlinear polymer having a glass transition point of 40 to 80°C. .

The crystalline polymer used in the present invention has a melting point of 5
0 to 120°C, more preferably a melting point of 6
Preferably, the temperature is 0 to 110°C and the melting point is lower than the softening point of the nonlinear polymer.

If the crystalline polymer satisfies these conditions, the crystalline polymer will melt at a lower temperature than the non-linear polymer will soften, and as a result, the entire toner can be softened at a lower temperature. , the minimum fixing temperature of toner can be lowered.

When the melting point of the crystalline polymer is higher than 120°C,
Since the melting point is not much different from the softening point of the non-linear polymer or, on the contrary, becomes higher, the minimum fixing temperature cannot be lowered too much.

When the melting point of the crystalline polymer is less than 50° C., the minimum fixing temperature can be lowered, but blocking resistance deteriorates.

Further, the crystalline polymer is preferably hard with a penetration hardness of 5.0 or less at a temperature of 25°C, and if a soft crystalline polymer with a penetration hardness of more than 5.0 is used, the The toner produced forms a film on the carrier particles and the surface of the photoreceptor, and the fluidity deteriorates and the developability deteriorates, making it impossible to obtain a good image.

Further, the crystalline polymer has a weight average molecular weight M- of 2.0 as measured by gel permeation chromatography.
000 or more, preferably 3,000 to 20,000, number average molecular weight Mn is 1,000 or more, preferably 1,0
It is suitable that it is 00-15,000. When the weight average molecular weight Mn is less than 2,000, or when the number average molecular weight Mn is less than 1,000, the toner has poor blocking resistance. Also, the weight average molecule is 11M
If w exceeds 20,000 OOQ, or if the number average molecular weight Mn exceeds 15,000, the viscosity of the toner when melted becomes high, making it impossible to obtain good fixing properties.

Note that the values of weight average molecular weight tMm and number average molecular weight Mn can be determined by various methods, but there are slight differences depending on the measurement method, so in the present invention,
It is determined by the following measurement method.

That is, the weight average molecular weight of 1
11 Mw and number average molecular weight Mn are measured.

At a temperature of 40°C, a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2-min/min, and a sample solution of 3 mg of tetrahydrofuran sample solution with a concentration of 0-2 g/20117 is injected and measured. Measurement conditions are selected in which the molecular weight of the sample falls within a range in which the logarithm of the molecular weight and the count number of a calibration curve created using several types of monodisperse polystyrene standard samples form a straight line.

The reliability of the measurement results is determined by the N
The BS 706 polystyrene standard sample has a weight average molecular weight Mw = 28.8 x 10" number average molecular weight Mn =
This can be confirmed by calculating 13.7 x 10'.

Moreover, any column may be used as the GPC column as long as it satisfies the above conditions. Specifically, for example, TSK-GEL.

GMHb (manufactured by Toyo Soda Co., Ltd.), etc. can be used.

The content ratio of such crystalline polymer to the entire binder resin is preferably 0.5 to 511%, more preferably 5 to 40% by weight. If this content exceeds 50% by weight, the toner Good images cannot be obtained because the anti-offset properties or fluidity of the film deteriorates. Conversely, if the proportion is less than 0.5% by weight, the minimum fixing temperature will be high.

The crystalline polymer is preferably present in the toner particles as particles dispersed in a matrix in the non-linear polymer, and to ensure that such a state is achieved, the crystalline polymer and the non-linear polymer are It is desirable that these are incompatible with each other. If these resins are compatible with each other, the glass transition point of the toner will be lowered as a result, and the blocking resistance of the toner will be lowered.

Here, "incompatibility" means that in a temperature range lower than the glass transition temperature of the non-linear polymer, at least a portion of the crystalline polymer forms crystalline particles and exhibits a cloudy state.

As a result of the crystalline polymer being held as dispersed particles by the network structure of the non-linear polymer, the crystalline polymer is firmly held in the toner particles, and the toner particles are transferred to carrier particles and photoreceptors. It is believed that the release of the crystalline polymer is suppressed even when it comes into contact with the surface, so that filming does not occur and the fluidity of the toner is improved, resulting in the formation of clear visible images. It will be done.

In the present invention, the term "crystalline polymer" refers to a polymer in which at least a portion thereof has a crystal structure, and a homopolymer or a copolymer in which at least one component is crystalline, that is, a partially crystalline polymer. including. Such a crystalline polymer exhibits a sharp and distinct melting point, and exhibits clouding due to crystallized portions at temperatures below the melting point. The crystallinity of the polymer may be determined, for example, by ASTM D-12
It can be measured by the method of No. 48-65.

Furthermore, the melting point Tl11 of the crystalline polymer and the glass transition point Tg of the nonlinear polymer resin were determined as follows.

According to differential scanning calorimetry (DSC), the temperature of the sample was
The melting peak value when g is heated at a constant temperature increase rate (10° C./m1n) is defined as the melting point Tl11.

Glass transition point Tg> According to differential scanning calorimetry ([1SC), the Lon of the sample
g is heated at a constant temperature increase rate (10° C./5 in), and the glass transition point Tg is obtained from the intersection of the baseline and the slope of the endothermic peak.

The penetration degree in the present invention is JIS K 2235-19.
Measured according to 80. Specifically, the diameter is approximately 1mm+
This value is the penetration depth expressed in units of 0.111 m when a needle having a conical tip with an apex angle of 9 degrees is penetrated into a sample under a constant load. The test conditions were a sample temperature of 25
℃, the load was 100 g, and the penetration time was 5 seconds.

As the crystalline polymer in the present invention, a crystalline polyester resin is preferable. Specific examples include polyethylene sebacate, polyethylene adipate, polyethylene adipate, polyethylene succinate, polyethylene-p-<carbophenoquine) undecaate, polyethylene-p-(carbophenoxy)butyrate, polyethylene-p-phenylene diacetate, Hexamethylene carbonate, polyhexamethylene-p-<carbophenoxy)undecaate, polyhexamethylene oxalate, polyhexamethylene sebacate, polyhexamethylene decanedioate, polyoctamethylene dodecanedioate, polynonamethylene Azelate, polynonamethylene terephthalate, polydecamethylene adipate, polydecamethylene azelate, polydecamethylene oxalate, polydecamethylene sebacate, polydecamethylene succinate, polydecamethylene dodecanedioate, polydecamethylene octadecanedioate ate, polytetramethylene sebacate, polytetramethylene-p-phenylene diacetate, polytrimethylene dodecanedioate, polytrimethylene octadecanedioate, polytrimethylene oxalate, poly-p-xylene adipate, poly-p- xylene sebacate, poly-4,4
'-isopropylidene phenylene malonate, poly-4
, 4'-isopropylidene phenylene malonate, polyhexamethylene-decamethylene sebacate, polydecamethylene-sebacate-terephthalate, polydecamethylene-2-methyl-1,3-propanediol-dodecanedioate, and others. Can be done.

The above-mentioned crystalline polyester resin is obtained by a polycondensation reaction between alcohol and a carboxylic acid compound,
Examples of the alcohol include ethylene glycol, diethylene glycol, 1,3-propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,
Octamethylene glycol, nonamethylene glycol,
Decamethylene glycol, 4.4''-isopropylidene biphenol, p-xylylene glycol, neopentyl glycol, cyclohexane dimetatool, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, and others can be mentioned. .

In addition, carboxylic acid compounds include malonic acid, succinic acid,
Glutaric acid, adipic acid, pimelic acid, superric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid Mention may be made of the acids, terephthalic acid, cyclohexanedicarboxylic acid, anhydrides and lower alkyl esters of these acids, and others.

The non-linear polymer used in the present invention has the function of strongly retaining the crystalline polymer in the toner particles, and also imparting releasability to the fixing roller when melted during fixing. Such a non-linear polymer has a glass transition point Tg of 40 to 80°C,
Preferably, it is necessary that the temperature is 50 to 70°C, and when the glass transition point Tg of the nonlinear polymer used is less than 40°C, the toner tends to be blocked and tends to have low offset resistance. Further, when the glass transition point Tg exceeds 80° C., the minimum fixing temperature of the toner becomes high.

The non-linear polymer has a softening point Tsp of 100 to 150°C,
Preferably, one having a temperature of 110 to 140°C is suitable. When the softening point is less than 100° C., the toner tends to block (and tend to have low offset resistance), and when the softening point exceeds 140° C., the minimum fixing temperature of the toner becomes high.

In the present invention, the softening point Tsp is determined using a flow tester (manufactured by Shimadzu Corporation) under the measurement conditions of a load of 20 kg/C11
”% Nozzle diameter III 11 Nozzle length 11,
Flow tester plunger drop amount vs. temperature curve obtained when preheating at 40°C for 10 minutes, heating rate at 6°C/n+in, and measuring and recording sample amount lea' (weight expressed as intrinsic specific gravity x 1 cmff) (Softening flow curve)
When the height of the S-curve at is h, the temperature is h/2.

Furthermore, the non-linear polymer used is preferably harder than the crystalline polymer and has a penetration hardness of 1.0 or less. By using a hard non-linear polymer resin, the resulting toner has good fluidity and the toner has good triboelectric charging properties. Further, the gel content in this non-linear polymer resin is preferably 50% by weight or less.

In the present invention, a nonlinear vinyl polymer is preferably used as the nonlinear polymer. Such non-linear vinyl polymers are homopolymers or copolymers obtained by polymerizing monomers having one or more types of vinyl groups, and are used to obtain non-linear vinyl polymers. For this purpose, a monomer having two or more vinyl groups may be used.

In the present invention, it is preferable to use a copolymer of a styrene monomer and an acrylic ester and/or a methacrylic ester as the nonlinear vinyl polymer. Examples of styrenic monomers for obtaining such copolymers include styrene, O-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methkinstyrene, p-phenylstyrene, p-chlorostyrene, 3.4
-Dichlorostyrene and the like can be mentioned.

Specific examples of acrylic esters or methacrylic esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, and lauryl acrylate. , acrylic acid 2-
Ethylhexyl, stearyl acrylate, acrylic acid 2
-Chlorethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate,
Examples include phenyl methacrylate, dimethylamine ethyl methacrylate, and diethylaminoethyl methacrylate.

Furthermore, monomers having two or more vinyl groups for nonlinearization include, for example, divinylbenzene, divinylnaphthalene, derivatives thereof, other aromatic divinyl compounds; ethylene glycol diacrylate, ethylene glycol dimethacrylate, and divinyl divinyl compounds; Examples include methylolpropane triacrylate, other acrylic esters or methacrylic esters having two or more double bonds, and others. The usage amount of such monomers having two or more vinyl groups is 0.0 based on the total monomers.
It is 1 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight.

The toner of the present invention may contain other resins, such as linear styrene.
Although resins such as acrylic resins, polyesters, polyamides, polyurethanes, polyureas, epoxy resins, and phenol-formalin resins may be contained, the proportion thereof is preferably in the range of 50% by weight or less of the resin.

In the present invention, toner components such as a colorant, a charge control agent, a fixability improver, magnetic particles, and other property improvers may be dispersed and contained in the toner particles.

Examples of colorants include carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride,
Phthalocyanine blue, malachite green offsalate, lamp black, rose bengal, mixtures thereof, and the like can be used. The amount of this colorant used is
The amount is preferably 1 to 20 parts by weight per 100 parts by weight of the binder resin. If this amount is too small, the coloring density and hiding power may be insufficient, while if it is too large, the tone of the image will become dark and the toner may become charged. In some cases, unfavorable effects may appear on properties or physical properties during heat fixing.

As the magnetic material, known materials can be used, such as ferromagnetic metals such as cobalt, iron, and nickel, aluminum, cobalt, steel, lead, magnesium, nickel, tin, zinc, antimony, beryllium, and bismuth. , alloys of metals such as cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, etc., and mixtures thereof, metal oxides such as aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide, magnesium oxide, etc. A metal compound containing the like can be used.

It is preferable that these magnetic substances are uniformly dispersed in the binder resin in the form of fine particles having an average particle size of 0.1 to 1 nm. When the finally obtained toner is used as a one-component developer, the content of the magnetic material is 20 parts by weight per 100 parts by weight of the toner.
-70 parts by weight is preferred, more preferably 40-70 parts by weight.
Parts by weight.

Examples of fixability improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, liquid or solid paraffin waxes, amide waxes, polyhydric alcohol esters, Silicon varnish, aliphatic fluorocarbon, etc. can be used. In particular, the softening point according to the ring and ball method is 70 to 150℃, especially 110 to 150℃.
150°C polyolefins are preferred.

As the charge control agent, conventionally known ones can be used.

To give an example of a preferred method for producing the toner of the present invention, first, the material resin of the binder resin or a toner component such as a colorant added thereto as necessary is melt-kneaded using an extruder, and then cooled. After that, it is finely pulverized using a jet mill or the like, and then classified to obtain a toner having a desired particle size. Alternatively, a toner having a desired particle size can be obtained by melting and kneading the toner using an extruder and then spraying it in a molten state using a spray dryer or dispersing it in a liquid.

〔effect〕

As described above, in the electrostatic image developing toner of the present invention,
A crystalline polymer with a low melting point is strongly held in a nonlinear polymer with an appropriate glass transition point, and therefore,
Due to the low softening point of the crystalline polymer, the minimum fixing temperature of the toner can be lowered, and the release properties of the non-linear polymer are fully developed, making it difficult for offset phenomena to occur, and furthermore, toner profking can be reduced. As a result, good visible images can be formed even during high-speed continuous copying.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Note that the numbers in the examples are parts by weight unless otherwise specified.

Spun 8 Polymer 1'! f [Production of crystalline polymer A] Dimethyl sebacate 230.0 g (1.0 mole
) and hexamethylene glycol 147.2g (1,
1 mole), -2.0 g of lead oxide, and g-tert-
2.0 g of butylhydroquinone was placed in a 4-neck round bottom flask with a capacity of 11 equipped with a thermometer, a stirrer, a glass nitrogen inlet tube, and a flowing down condenser, and then the flask was placed on an oil bath and nitrogen Nitrogen gas was introduced through the introduction tube to maintain an inert atmosphere inside the reaction vessel, and the reaction vessel was heated to react at a temperature of 160° C., and distilled methanol was removed. When methanol is no longer distilled out, the temperature is increased to 200°C.
The temperature was raised to 0.05 ffimHg, and the pressure was gradually reduced to 0.05 ffimHg. The progress of the reaction was followed by monitoring the melting point of the product, and when the melting point reached 65° C., the reaction was stopped and cooled to room temperature.

In the manner described above, a cloudy crystalline polymer was obtained. This will be referred to as crystalline polymer A. The melting point Tm of this crystalline polymer A is 65" C1 needle size is 4.01 weight average molecular weight 1
Mw was 6,500, and number average molecule i1Mn was 3,400.

[Production of crystalline polymer B]

Dimethyl succinate 146.0g (1,OIIIole
), ethylene glycol 149.0g (2.4m
ole), 3.0 g of calcium acetate dihydrate, and 0.1 g of antimony dioxide were reacted by a method similar to the method for producing crystalline polymer A described above. That is,
Keep the inside of the reaction vessel in an inert atmosphere and heat it to a temperature of 160℃.
The reaction was carried out at ℃, the methanol distilled out was removed, and when no more methanol was distilled out, the temperature was gradually raised to 200 ℃, the ethylene glycol distilled out was removed, and the amount of distillation was reduced to a small amount. When the pressure becomes 0. O5
The reaction was completed by gradually reducing the pressure to mmHg, and then cooled to room temperature to obtain a cloudy crystalline polymer. This will be referred to as crystalline polymer B.

This crystalline polymer B has a melting point Tm of 95°C and a penetration degree of 1
．． 0, the weight average molecular weight M- was 8000, and the number average molecular weight n was 3300.

[Manufacture of crystalline polymer C]

Dimethyl adipate 174.0g (1.0mole)
and decamethylene glycol 191.7g (1.1m
A crystalline polymer was obtained by reacting in the same manner as in the production of crystalline polymer A using oleic acid, 2.0 g of lead oxide, and 2.0 g of di-tert-butylhydroquinone. This will be referred to as crystalline polymer C.

This crystalline polymer C has a melting point Tm of 78°C and a penetration degree of 2.
．． 0, the weight average molecular weight 11Mw was 8300, and the number average molecular weight -n was 3400.

[Manufacture of crystalline polymer D]

Dimethyl adipate 174.0g (1.0mole)
and ethylene glycol 149. Og (2.4 mol
e), 3.0 g of calcium acetate dihydrate, and 0.1 g of antimony dioxide were reacted in the same manner as in the production of crystalline polymer B to obtain a crystalline polymer. This will be referred to as crystalline polymer D.

This crystalline polymer D has a melting point Tm of 47°C and a penetration degree of 6
．． 0, weight average molecular weight is 4600. Number average molecule I division n
was 2100.

[Production of crystalline polymer E]

Dimethyl terephthalate 194.0 g (1.0 mol
e) and 114.5 g of pentamethylene glycol (
1,1 mole), -2.0 g of lead oxide, and ter
Using 2.0 g of t-butylhydroquinone, a reaction was carried out in the same manner as in the production of crystalline polymer A to obtain a crystalline polymer. This will be referred to as crystalline polymer E.

This crystalline polymer E has a melting point Tm of 134°C, a penetration rate of 1.0, a weight average molecular weight of 6800, and a number average molecular weight of -
n was 2,700.

Production of non-linear vinyl polymer [Production of non-linear vinyl polymer A] Styrene 83.5 parts n-butyl acrylate 15 parts divinylhenzene 1.5 parts benzoyl peroxide
5. Into a four-part flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 600 d of water containing 2% by weight tricalcium phosphate and 0.2% by weight sodium dodenruhenzenesulfonate was charged, and nitrogen was introduced into the flask. After creating a nitrogen gas atmosphere inside the reaction vessel via the introduction tube, 200 g of the above composition was added.
was added under stirring at room temperature to suspend the mixture, and then the temperature was raised to 80°C and reacted for about 8 hours. After the reaction is complete, the system is cooled, hydrochloric acid is added, and filtration and washing are repeated.
A non-linear vinyl polymer was obtained by removing tricalcium phosphate and sodium dodecylbenzenesulfonate and drying. This is referred to as nonlinear vinyl polymer A.

The softening point Tsp of this nonlinear vinyl polymer A is 131
℃, the glass transition point Tg was 65°C, and the penetration was 1.0 or less.

[Production of non-linear vinyl polymer B]

Styrene 73.5 parts n-butyl acrylate 25 parts Divinylbenzene 1.5 parts Benzoyl peroxide
5 parts A nonlinear vinyl polymer was obtained in the same manner as in Nonlinear Vinyl Polymer A except that the above composition was used.

This is referred to as nonlinear vinyl polymer B.

The softening point Tsp of this non-linear vinyl polymer B is 97°C,
The glass transition point Tg was 39°C.

[Production of non-linear vinyl polymer C]

Styrene 93.5 parts n-butyl acrylate 5 parts Divinylbenzene 1.5 parts Benzoyl peroxide
5 parts A nonlinear vinyl polymer was obtained in the same manner as in Nonlinear Vinyl Polymer A except that the above composition was used. This is referred to as nonlinear vinyl polymer C.

The softening point Tsp of this nonlinear vinyl polymer C is 153°C
, the glass transition point Tg was 81°C.

[Production of non-linear vinyl polymer]

Styrene 68.0 parts Methyl methacrylate 10 parts N-butyl acrylate 20 parts Divinylbenzene 0.3 parts A non-linear vinyl polymer was obtained in the same manner as Non-linear vinyl polymer A except that the above composition was used. Ta. This is called a non-linear vinyl polymer.

The softening point Tsp of this non-linear vinyl polymer is 123°C.
, the glass transition point Tg was 57°C.

The composition shown in Table 1 was heated and kneaded using an extruder, cooled, and then coarsely ground, further finely ground using a supersonic jet mill, and then classified using a wind classifier to remove colored particles. Obtained. 100 parts by weight of the colored particles and silica fine powder rR
-972J (manufactured by Nippon Aerosil Co., Ltd.)) and 0.6 parts by weight were mixed in a ■ type mixer to obtain Toners 1 to 4 of the present invention and Comparative Toners 1 to 7.

In Table 1, the carbon blank "Mogul LJ (manufactured by Cabot)" was used as the "colorant". The fixability improvers "PP-^" and rPP-BJ were respectively polypropylene "Viscol 660PJ (softening point 135°C)". ,
rPE-AJ indicates polyethylene wax "Mitsui Hiwax 400PJ (softening point 132°C, manufactured by Mitsui Petrochemicals)." .The softening point of the fixing property improver is determined by the ring and ball method JIS.
This is a value measured by K2531.

The fluidity of each of the toners obtained in the above manner was visually determined, and blocking (agglomeration) was observed after being left in an environment at a temperature of 55°C and a relative humidity of 60% for one day.
We investigated whether or not this occurred.

Furthermore, a developer was prepared by mixing 4 parts of each of the above toners with 96 parts of a spherical iron powder carrier coated with a styrene-methyl methacrylate copolymer (composition ratio 3 near), and using this developer, Set the fuser line speed to 70mm/se
Electrophotocopy machine "υ-Bix 1600J" set to c
(manufactured by Konishi Roku Photo Industry Co., Ltd.), an image formation test was conducted in which copied images were formed 30,000 times in succession, and the resulting copied images were evaluated for fogging and image quality at the beginning and end of the test. The presence or absence of filming on the photoreceptor of an electrophotographic copying machine was investigated.

Further, an unfixed image is formed by the electrophotographic copying machine,
The lowest fixing temperature and the lowest temperature at which an offset phenomenon occurs (offcent occurrence temperature) were determined for each toner by fixing the toner at different fixing temperatures using a separately prepared fixing tester. Specifically, the minimum fixing temperature is the minimum temperature at which stains do not occur when the formed copy image is rubbed with a wiper, and the offset generation temperature is the minimum temperature at which no stains occur when the formed copy image is rubbed with a wiper. The lowest temperature at which staining occurs was determined.

The above results are shown in Table 2.

As is clear from the results in this table, the toner of the present invention has
Low minimum fixing temperature (good offset resistance, good blocking resistance, excellent fluidity, filming resistance and durability, high image 1 degree,
A clear visible image with less capri can be formed.

Claims (1)

[Scope of Claims] 1) A toner for electrostatic image development, comprising a crystalline polymer having a melting point of 50 to 120°C and a nonlinear polymer having a glass transition point of 40 to 80°C. 2) The toner for electrostatic image development according to claim 1, wherein the toner image formed is fixed by a heat roller. 3) The toner for electrostatic image development according to claim 1, wherein the non-linear polymer is a non-linear vinyl polymer.