JPH02308260A - Production of binder resin for toner and toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To enhance a block rate or graft rate and to provide the binder resin for toners having good low-temp. fixability and offset resistance by chemically combining a crystalline polyester and a specific amorphous vinyl polymer by using a carbodiimide deriv. CONSTITUTION:The crystalline polyester and the amorphous vinyl polymer are brought into reaction in the presence of the carbodiimide deriv. to obtain the block copolymer or graft copolymer chemically combined with both. The carbodiimide deriv. used in this invention is expressed by general formula RN= C=NR'. The more specific examples include dicyclohexyl carbodiimide, di-p- toluoyl carbodiimide, etc. Since the above-mentioned amorphous vinyl polymer combines with the crystalline polyester, the polymer has preferably a carboxyl group or hydroxyl group as a functional group. The ratio of a weight average mol.wt. Mw and a number average mol. wt. Mn is required to be >=3.5. The sufficient offset resistance and durabilityh is not obtainable if the ratio Mw/Mn is too small.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a binder resin used in a toner for developing an electrostatic latent image formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to a manufacturing method and toners 1 to 1 for developing electrostatic images containing the binder resin.

[Prior Art] For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image carrier made of a photoconductive photoreceptor, and then this electrostatic latent image is transferred to an electrostatic image carrier made of a resin. It is developed with a toner formed into fine particles by containing a coloring agent in a binder, and the resulting toner image is transferred to a support such as transfer paper and fixed to form a visible image.

In order to obtain a visible image as described above, it is necessary to fix the toner image, and conventionally, a heat roller fixing method that has high thermal efficiency and can perform high-speed fixing has been widely adopted.

However, in recent years, copying machines have become smaller and faster, making it easier to (a) suppress overheating deterioration of the copying machine, (b) prevent thermal deterioration of the photoreceptor, and (c) activate the fuser. (d) shorten the warm-up time required for the heat roller to rise to a temperature that can be fixed after printing, and (d) reduce the temperature drop of the heat roller due to heat absorption by the transfer paper over multiple enabling continuous copying;
(e) Due to demands such as increasing thermal safety,
There is a strong demand for reducing the power consumption of the fixing heater to enable fixing processing at a lower temperature of the heat roller. Therefore, the toner is also required to be able to be fixed well at low temperatures.

Furthermore, toners can exist stably as a powder without agglomerating under the environmental conditions of use or storage;
In other words, it is necessary to have excellent blocking resistance.
Furthermore, in the heat roller fixing method, which is preferable as a fixing method, an offset phenomenon occurs, that is, a part of the toner forming the image is transferred to the surface of the heat roller during fixing, and this is transferred again to the transfer paper that is sent next, and the image is Since the phenomenon of staining the toner is likely to occur, it is necessary to provide the toner with the ability to prevent the occurrence of the offset phenomenon, that is, offset resistance.

For this reason, in the past, for example,
No. 3-27855 discloses crystalline polyester and MW
JP-A-63-27856 discloses a toner containing a block copolymer or a graft copolymer with an amorphous vinyl polymer having an amorphous vinyl polymer of 3.5/Mn≧3.5 and a crystalline polyester having a molecular weight distribution of 2. A block copolymer or a graft copolymer with an amorphous vinyl polymer having two or more peaks is disclosed. Furthermore, JP-A No. 64-35455 discloses an image forming method using a toner containing a block copolymer or a graft copolymer of a crystalline polyester and a non-quality vinyl polymer. No. 35456/1983 discloses a method for producing a toner containing a block copolymer or a graft copolymer of a crystalline polyester and a non-quality vinyl polymer, and which includes an additional heat treatment step.

[Problems to be Solved by the Invention] In the above conventional techniques, in order to obtain a block copolymer or a graft copolymer, specifically o-1-luenesulfonic acid (ester bond), hexamethylene diisocyanate (urethane The crystalline polyester and the amorphous (non-standard) vinyl polymer are chemically bonded using a reaction by heat (bonding) or heat (bonding by amide bond, epoxy group).

However, in the reaction using p-toluenesulfonic acid and heat, the block ratio or graft ratio, which is the bonding ratio between the crystalline polyester and the amorphous vinyl polymer, was low, and the low-temperature fixability was insufficient. This is because unreacted crystalline polyesters aggregate with each other to form large domains, and even if a local viscosity decrease occurs during heating, it does not reduce the viscosity of the toner particles as a whole. Conceivable. Furthermore, since large domains of the crystalline polyester component are formed in each particle, the fluidity of the toner particles is also low.

Furthermore, in the reaction using isocyanate, a coupling bond occurs between the 10H groups at the end of the molecule, and the reaction proceeds randomly, resulting in a decrease in the blocking rate or grafting rate. Furthermore, when a reaction occurs between crystalline polyesters, they become macromolecules, resulting in a decrease in crushability.

The present invention has been made in view of the above-mentioned conventional problems, and the first object is to manufacture a block copolymer or graft copolymer of a crystalline polyester and an amorphous vinyl polymer to increase the block ratio or graft ratio. to provide law;
The second objective is to provide an i-lunar binder resin that has better low-temperature fixing properties and good offset resistance by increasing the block rate or grafting rate, and the third objective is to provide an i~ Lunar binder resin that has good crushability. The fourth objective is to provide a toner with good fluidity and good agglomeration resistance.The fifth objective is to provide a toner whose properties are not affected by environmental conditions, especially at high temperatures. (a) An object of the present invention is to provide a toner that has constant chargeability, fluidity, and developability even under humid conditions and provides good image quality.

[Means for Solving the Problems] In order to achieve the above object, the method for producing a binder resin for toner of the present invention comprises a crystalline polyester, a functional group that forms a bond with the crystalline polyester, and a number of It is characterized by chemically bonding an amorphous vinyl polymer having a ratio MW/Mn of average molecular weight IMn to average molecular weight MY of 3.5 or more using a carbodiimide derivative. The electrostatic image developing toner of the present invention has a crystalline polyester and a functional group that forms a bond with the crystalline polyester, and has a number average molecular weight f1Mn and a weight average molecular weight MW.
It is characterized by containing a binder resin which is chemically bonded to an amorphous vinyl polymer having a ratio MW/Mrl of 3.5 or more using a carbodiimide derivative.

The present invention will be explained in detail below.

The amorphous vinyl polymer preferably has a carboxyl group or a hydroxyl group as a functional group in order to form a chemical bond with the crystalline polyester.

Examples of polymers having functional groups that provide such amorphous vinyl polymers include acrylic acid, β, β-dimethylacrylic acid, α-ethyl acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, and crotonic acid. , hydroxyethyl methacrylate, acryloyloxyethyl monophthalate, acryloyloxyethyl monosuccinate, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-methylolacrylamide, p-aminostyrene, glycidyl methacrylate, and others. .

A polymer having such a functional group is contained in a monomer composition for obtaining an amorphous vinyl polymer in an amount of 0.1 to 20 mol%.
, preferably in a proportion within the range of 0.5 to 10 mol%.

The vinyl polymer constituting the main portion of the amorphous vinyl polymer is not particularly limited as long as it contains a monomer component having such a functional group, and examples include polystyrene, polymethyl methacrylate, and polymethyl methacrylate. methyl acrylate,
Examples include polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, and others. Among these, styrene polymers, acrylic polymers, and styrene-acrylic polymers are particularly preferred as amorphous vinyl polymers, but examples of monomers that provide these polymers include styrene, 0-methylstyrene, etc. , ■-methylstyrene, p
-Methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, methyl acrylate , ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate,
lauryl methacrylate, stearyl methacrylate,
Mention may be made of cyclohexyl methacrylate, dimethylaminoethyl methacrylate, and others. These monomers can be used alone or in combination.

In this amorphous vinyl polymer, the value of the ratio Mw/Mn between the 7J li average molecular weight MW and the number average molecule ffiMn is 3.
．． It needs to be 5 or more, and 4 to 40 is particularly preferable. When the ratio Mw/Mn is too small, sufficient offset resistance and durability cannot be obtained.

Here, the weight average molecule ffiMW and the number average molecule aM
The value of n can be determined by various methods, and there are slight differences depending on the measurement method, but in the present invention, it is determined by the following measurement method.

Measure the weight average molecule mvw, number average molecule fiMn, and peak molecular weight using gel permutation chromatography (GPC) under the conditions described below.At a temperature of 40°C, the solvent (tetrahydrofuran) was Flowed at a flow rate of 1.2 d/min, concentration 0.20/2
A sample solution of 0 tffi of tetrahydrofuran is injected at 3 mc+ as a sample weight, and 1 llll is determined. sample molecule m
In the measurement, the measurement conditions are selected such that the molecular weight of the sample falls within a range where the logarithm of the molecular weight and the count number of the calibration line prepared using several types of monodispersed polystyrene standard samples are in a straight line. The reliability of the measurement results was determined using the NBS 706 polystyrene standard sample measured under the above measurement conditions (weight average molecule 11Mw = 28.8xlO, number average molecule mmn -13,7x104, Mw
/Mn -2,11) ratio Mw /Mn value is 2.11
Confirm that it is ±0.10.

Moreover, any column may be used as the GPC column as long as it satisfies the above conditions. Specifically, for example, TSK-GEL, GMH (manufactured by Toyo Soda Co., Ltd.), etc. can be used. Note that the solvent and measurement temperature are not limited to the above conditions, and may be changed to other conditions as appropriate.

Further, from the viewpoint of further improving low-temperature fixing properties and anti-offset properties, it is preferable that the amorphous vinyl polymer has at least two maximum values in its molecular weight distribution. That is, it has a molecular weight distribution that can be divided into at least two groups, low molecular concave valves and polymer group components, and has at least one maximum value in the molecular weight distribution curve measured by gel permeation chromatography (GPC). Within the range of 2X103 to 2X104, at least 1
It is preferred to have at least two maximum values, such that one maximum value is in the range of 1X105 to 1X106.

Further, the amorphous vinyl polymer has a glass transition point T9
It is preferable that the value of is within the range of 50°C to 100°C, particularly 50°C to 85°C. If this glass transition point T (+ value is less than 50°C, blocking resistance will deteriorate,
If the temperature exceeds 100° C., the toner's solubility at low temperatures decreases, resulting in poor fixing performance. Here, the glass transition point T of the amorphous vinyl polymer (+ means the glass transition point of the amorphous vinyl polymer in a state where it is not bonded to crystalline polynisder).

A crystalline polyester is used as a component that is chemically combined with the above amorphous vinyl polymer to form a block copolymer or a graft copolymer. The crystalline polyester is not particularly limited, but polyalkylene polyester is particularly preferred from the viewpoint of low-temperature fixability and fluidity. Specific examples of such polyalkylene polyesters include polyethylene sebacate, polyethylene adipate, polyethylene adipate, polyethylene succinate, polyethylene-p-(carbophenoxy) undecate, polyhexamethylene sebacate, and polyhexamethylene sebacate. cate, polyhexamethylene decanedioate, polyoctamethylene dodecanedioate]
~, polynonamethylene azelate, polydecamethylene azelate, polydecamethylene azelate, polydecamethylene azelate, polydecamethylene sebacate, polydecamethylene succinate, polydecamethylene dodecanedioate, polydecamethylene Octadecanedioate,
Polytetramethylene sebacate, polytrimethylene dodecanedioate, polytrimethylene octadecanedioate, polydecamethylene azelate, polyhexamethylene-decamethylene-sebacate, polyoxydecamethylene-2-methyl-1,3-propane-dodecane dioates, and others.

The crystalline polyester has a melting point Tl11 of 50 to
The temperature is preferably 120°C, particularly within the range of 50 to 100°C. The melting point of the crystalline polyester used is 50℃
If it is less than 120° C., the resulting toner will have poor blocking resistance, and if it exceeds 120° C., the melt flowability of the toner at low temperatures will decrease, resulting in poor fixing properties. Note that the melting point T11 of the crystalline polyester means the melting point of the crystalline polyester in a state where it is not bonded to an amorphous vinyl polymer.

This crystalline polyester has a weight average molecular f1MW of
tfi 5,000-50,000, number average molecule im
It is preferable that Mn is 2.000 to 20.000. When the molecular weight is within this range, the offset resistance of the toner and the pulverization efficiency in toner production will be even better.

The proportion of the above crystalline polyester to be used is based on the block copolymer with the amorphous vinyl polymer or the copolymer from Graph 1 (where the proportion of the crystalline polyester component is 3
~50fflR1%, preferably 5 to 40% by weight. If this ratio is less than 3% by weight, the resulting toner will have a high minimum constant Il temperature, and if it exceeds 50% by weight, the melt modulus during fixing will be small and the offset resistance will be poor. Deteriorate.

The crystalline polyester and the amorphous vinyl polymer may be compatible or incompatible with each other, but are preferably immiscible from the viewpoint of toner crushability, blocking resistance, and the like. Here, "incompatibility" refers to the fact that the chemical structures of the two are the same or similar, or that the two do not have the property of dispersing in one minute due to the action of functional groups, and the solubility parameter, for example, S by Fedose's method, P, value (R, F, Fedors, Polym, Eno
, Sci.

14, (2) 147 (1974) ) (7) The difference is 0.5yo') large.

Melting point TIIJ' of crystalline polynisder according to the present invention
3 and the glass transition point T of the amorphous vinyl composite body are measured as follows.

Measurement of melting point Tffi of crystalline polyester Differential scanning heat M
According to the measurement method (DSC), for example f'Dsc-20J
(manufactured by Seiko Electronics Co., Ltd.), and the measurement conditions were a sample of approximately 10 months at a constant R knitting speed (10°C/10°C).
The melting peak value when heated at is defined as the melting point.

Determination of the glass transition point 1- of amorphous vinyl polymers according to differential scanning calorimetry (DSC), e.g. rDsc-20
J (manufactured by Seiko Electronics Co., Ltd.), and specifically, a sample temperature of 10+++a can be measured at a constant heating rate (10
℃/n+in), and the glass transition point is determined by one point from the intersection of the baseline and the slope of the endothermic peak.

In the present invention, the crystalline polyester and the amorphous vinyl polymer are reacted in the presence of 149 carbodiimide, and a block copolymer or graft copolymer in which the two are chemically bonded is formed into a 196° carbodiimide used in the present invention. The derivative is represented by the following general formula [IJ, and the general formula [IJ RN-C-NR' (R and R' are each a hydrocarbon group.) Specific examples include dicyclohexylcarbodiimide, di-p- Examples include dollar oil carbodiimide.

The carbodiimide derivatives are preferably used in proportions equivalent to the functional groups present in each polymer used. If too little m is used, the blocking rate or grafting rate will not be high.

In order to increase the blocking rate or grafting rate, it is preferable that one polymer has a hydroxyl group and the other polymer has a carboxyl group as terminal functional groups.

There are various ways to actually calculate the grafting rate or block rate of the obtained copolymer, and there are no particular limitations.
A calculation method using NMRGX-400 (manufactured by Japan 1iltl) can be adopted.

For example, in the following binding polyalkylene polyester having a hydroxyl group at the end of the molecule [IJ, the signal of the proton (b) of the methylene group bonded to the oxygen atom is 3.6 to 3
．． 7 ppm, while the signal of the proton (a) of the methylene group bonded to the hydroxyl group at the end of the molecule is 4.0 to 4.0 ppm. l
ppm, the ratio of (number of molecular terminal water ji!1 groups (a)/?i! number of methylene groups bonded to elementary atoms (b)) of the crystalline polyester can be determined from these intensity ratios. Similarly, the ratio of the crystalline polyester in the graft copolymer or block copolymer (the number of hydroxyl groups at the end of the molecule, the number of methylene groups bonded to 7M elementary atoms) is determined, and the graft ratio or Block rate can be calculated.

[II] In the toner of the present invention, a binder resin in which the above crystalline polyester and amorphous vinyl polymer are chemically bonded using a carbodiimide derivative is used.

In such a toner, since the binder contains the copolymer with a high grafting rate or block rate, it is possible to obtain low-temperature fixability and good wettability during melting due to the crystalline polyester component. , the amorphous vinyl polymer component, which itself contributes to low-temperature fixing properties, exhibits anti-offset magnetism, resulting in good and wide-ranging offset resistance and low-temperature fixing properties in the formation of visible images using electrostatic images. A fixable temperature range can be obtained, blocking resistance and fluidity are good, and excellent visible images can be formed many times.

The toner of the present invention needs to contain the copolymer of the crystalline polyester and the amorphous vinyl polymer in an amount of at least 30% by weight or more, preferably in a range of 50 to 100% by weight.

The toner of the present invention contains a colorant in a binder made of the above-mentioned specific copolymer, but may also contain a magnetic material and a property improver in the resin, if necessary. good.

Examples of the coloring agent include carbon black, nigrosine dye (C, 1, No. 50415B), aniline blue (C, 1, NO, 50405), and calco oil blue (C.l No. azOic Blue 3).
), Chrome Yellow (C.[, NO.14090)
, Kuru 1 to Lamarin Blue (C.I.

No. 77103), DuPont Oil Red (C,
1. No. 26105), quinoline yellow (C
．． 1. No. 47005), methylene blue chloride (C.[, No. 52015), phthalocyanine blue (C. 1. NO. 74160>, malachite green oxale-1- (C.l. No. 42000)
>, Lamp black (C.1.140.7726G>
, Rose Bengal (, C. [.

No. 45435), mixtures thereof, and the like can be used. The amount of colorant used is usually 0.1 to 20 parts by weight, particularly 0.5 to 1 part by weight, per 1 part of toner 100i.
0 parts by weight is preferred.

The magnetic material may be a ferromagnetic metal or alloy such as magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Alloys that become ferromagnetic when subjected to
Mention may be made of a type of alloy called Heusler alloy containing manganese and copper, such as copper-aluminum, manganese-copper-tin, or chromium dioxide, among others. For example, when obtaining a black toner, magnetite, which is black in itself and also functions as a coloring agent, can be particularly preferably used.

Further, when obtaining a color toner, it is preferable to use a material with little darkness, such as metal iron. Some of these magnetic materials also function as a coloring agent, and in that case, they may also serve as a coloring agent. These magnetic substances are uniformly dispersed in the resin in the form of fine powder having an average particle size of 0.1 to 1 μm, for example. And its content is
In the case of magnetic toner, 20 per part of 100 weight toner
-70 parts by weight, preferably 40-70 parts by weight.

The property improver includes a fixability improver, a charge control agent,
There are others.

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, polyamide waxes, polyhydric alcohol esters, Silicon varnish, aliphatic fluorocarbon, etc. can be used. In particular, the softening point (ring and ball method J i S K2531) is 6.
0 to 15 (1°C wax is preferred.

As the charge control agent, conventionally known ones can be used, and examples thereof include nigrosine dyes, metal-containing dyes, and the like.

Further, the toner of the present invention is preferably mixed with inorganic fine particles such as a fluidity improver.

The S trowel fine particles used in the present invention include -
The secondary particle size is 5i1μ to 2μm, preferably 5mμ
The particles are ~500 μm. Further, the specific surface area measured by the BET method is preferably 20 to 500t2/ ().The proportion mixed in the toner is 0.01 to 51% by weight, preferably 0.001 to 2.0% by weight. Examples of such inorganic fine powders include fine silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate,
Zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Among them, fine silica powder is particularly preferred.

The silica fine powder referred to herein is a fine powder having a 5i-0-3i bond, and includes both those manufactured by a dry method and a wet method. In addition to anhydrous silicon dioxide, aluminum silicate, sodium silicate, potassium silicate,
Any of magnesium silicate, zinc silicate, etc. may be used, but those containing 851ffi% or more of 5iC)+ are preferable.

Specific examples of these fine silica powders include various commercially available silicas, but those having hydrophobic groups on the surface are preferred;
For example, AERO8IL R-972, R-974, R
-805, R-812 (manufactured by Aerosil), and Tarax 500 (manufactured by Talco). In addition, silica fine powder treated with a silane coupling agent, a titanium coupling agent, silicone oil, silicone oil having an amine in its side chain, etc. can be used.

To give an example of a preferred method for producing the toner of the present invention, first, a binder material resin or a toner component such as a colorant is added thereto as necessary is melt-kneaded using, for example, an extruder, and after cooling, a jet A toner having a desired particle size can be obtained by pulverizing the toner using a mill or the like and classifying the powder. Alternatively, 1 q of toner having a desired particle size can be obtained by spraying or dispersing the toner in a molten state using a spray dryer or the like in a liquid after melting and kneading it using an extruder.

The toner of the present invention is used to develop an electrostatic image formed in, for example, an electronic copying machine, and the obtained toner image is electrostatically transferred onto a transfer paper and fixed by an upper heating roller fixing device to form a copy. Elephant is obtained.

The toner of the present invention is particularly preferably used when fixing is performed at a high speed such that the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.

[Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these Examples.

Production of crystalline polyester> (1) Crystalline polyester 1 1500 g (7.41 mol) of sebacic acid and 1 (8.16 mol) of hexamethylene glycol 964 were mixed using a thermometer, a stainless steel scale stirrer, and a glass The reactor was placed in a round-bottomed flask with a capacity of fM51 equipped with a nitrogen inlet tube made of glass and a sinking condenser, and then the flask was placed in a mantle heater, and nitrogen gas was introduced through the nitrogen inlet tube made of glass to create an inert atmosphere inside the reactor. The temperature was raised while the temperature was maintained, and 13.20 p-toluenesulfonic acid was added to react at a temperature of 150°C.

Water distilled from esterification reaction 250111
When the temperature reached 2, the reaction was stopped and the reactant was taken out.

This was cooled to room temperature to obtain a crystalline polyester 1 made of polyhexamethylene sebacate having a hydroxyl group at the end of the molecule. The melting point of this crystalline polyester 1 is 64
(measured with a differential scanning calorimeter rDSC-20J (manufactured by Seiko Electronic Industries)). weight average molecule ω
Mw = 12,300.

(2) Crystalline polyester 2 Same as crystalline polyester 1, melting point Tl11=70
A polyethylene sebacate with Mw = 11,000 was obtained.

(3) Crystalline polyester 3 Same as crystalline polyester 1, melting point I = 74°C,
Polydecamethylene adipate with MSV = 13,100 was obtained.

Production of amorphous vinyl polymer (1) Amorphous vinyl polymer 1 Put 100 parts by weight of toluene into a separable flask with a volume of ω11, and add 7.5 parts by weight of styrene and 2.5 parts by weight of butyl acrylate. 1 part by weight and 0.1 part by weight of benzoyl peroxide, and after replacing the gas phase in the flask with nitrogen gas, the temperature was raised to 80°C once and the temperature was maintained at 1°C.
The first stage polymerization was carried out for 5 hours.

Thereafter, the inside of the flask was cooled to a concentration of 40°C, and therein were added 85 parts by weight of styrene, 10 parts by weight of butyl methacrylate, 5 Lffi parts of acrylic acid, and 4 parts of benzoyl peroxide.
After adding the polymerization part and continuing stirring at a temperature of 40°C for 2 hours, the temperature was raised again to 80°C and maintained at that temperature for 8 hours to carry out second stage polymerization.

Next, in the flask, zinc oxide, which is a polyvalent metal corrosion compound, is added.
, sg and stirred while keeping at reflux temperature.
The reaction was carried out over a period of time.

Thereafter, toluene was distilled off using an aspirator and a vacuum pump, and the mixture was dried to produce an amorphous vinyl polymer 1 in which zinc oxide reacted with the carboxyl groups of the vinyl polymer to form ionic crosslinks. Note that this amorphous vinyl polymer 1 has a carboxyl group as a functional group for bonding with the crystalline polyester.

The weight average molecular weight MW of this amorphous vinyl polymer 1 is 93
．． 200, the value of the ratio Mw/Mn is 18.4, the glass transition point T (+ is 60°C, the softening point Tsp is 128°C).

(2) Amorphous vinyl polymer 2 Styrene 851 parts n-butyl methacrylate 10 parts acryloyloxyethyl monosuccinate 5 parts by weight Benzoyl peroxide 4 parts The llffi mixture having the above composition was added with 100 parts by weight of toluene. In addition, after replacing the gas phase in this flask with nitrogen gas, the temperature was increased to 80°C.
The temperature was raised to .degree. C. and maintained at this temperature for 15 hours to carry out polymerization.

Thereafter, toluene was distilled off using an aspirator and a vacuum pump to obtain amorphous vinyl polymer 2, which is a styrene-acrylic resin having carboxyl groups. The weight average molecule [IM
W is 71,000. The value of the ratio MW/Mn was 7.5, the glass transition point T (J was 67°C, and the softening point TSD was 123°C).

(3) Amorphous vinyl polymer 3 In the production of amorphous vinyl polymer 1, the monomer charges for the first stage polymerization were 151 parts of styrene, 5 parts of butyl acrylate, and 0.04 parts of benzoyl peroxide.
Amorphous vinyl polymer 3 was obtained in the same manner except that part i was changed.

This amorphous vinyl polymer 3 has two peaks in the molecular m distribution determined by GPC, the peak molecular weight on the high molecular m side is 363.000, and the peak molecular weight on the low molecular m side is 7.000.
It is 590. In addition, the weight average molecular weight Mw is 165.0
00, ratio Mw/M mouth value is 25.9, glass transition point T
o is 62°C, and the softening point TSρ is 130°C.

(4) Amorphous Vinyl Polymer 4 Amorphous vinyl polymer 4 was obtained in the same manner except that 1 part of hydroxyethyl methacrylate 5 was used in place of 151ffi parts of acrylic l in Amorphous vinyl polymer 3. This amorphous vinyl polymer 4 has a hydroxyl group as a functional group for bonding with the crystalline polyester, and has two peaks in the molecular m distribution determined by GPC, with the peak molecule 1 on the high molecular weight side being 395. 000, and the peak molecular weight on the low molecular m side is 9,430. Also, the weight average molecular weight M
W is 174,500. The value of the ratio MW/Mrl is 23.1
, the glass transition point Tg is 63°C, and the softening point TSρ is t28.
The temperature is 5°C.

<Synthesis of copolymer> (1) Copolymer A (invention) 225 g (15 parts by weight) of crystalline polyester 1, 1275 g (WfA part for 85) of amorphous vinyl polymer 1, and 1.5 g of xylene! 2. were placed in a separable flask with a capacity of ff15ffi, and nitrogen gas was introduced to maintain the inside of the reactor in an inert atmosphere, and the temperature was raised. When the crystalline polyester and amorphous vinyl polymer are completely dissolved in xylene to form a homogeneous solution, a 10% ffi% solution of N,N'-dicyclohexylcarbodiimide in xylene 80
(Drop the + from the dropping funnel, then 1 at a temperature of 150℃.
Refluxed for an hour. After xylene was distilled off using an asbilator and a vacuum pump, the reaction product was taken out and cooled to room temperature to obtain copolymer A.

(2) Copolymer B (Invention) Copolymer B was synthesized in the same manner as Copolymer A using 12750 (85 tAWi parts) of Amorphous Vinyl Polymer 2.

(3) Copolymer C (present invention) Copolymer C was synthesized in the same manner as Copolymer A using 1275 g (85 parts by weight) of Amorphous Vinyl Polymer 3.

(4) Copolymer D (invention) Using 225!7 (15 parts by weight) of crystalline polyester 2 and 1275 g (85@ [1 part)] of amorphous vinyl polymer 1, copolymer A and A copolymer was synthesized in the same manner.

(5) Copolymer E (present invention) Crystalline polyester 3-375! It (25 layers ffi
part) and 1125 of amorphous vinyl polymer 3! It (75
Copolymerize in the same manner as Copolymer A, except that 140 g of di-p-doloylcarbodiimide 10W (%) xylene solution was used instead of the N,N'-dicyclohexylcarbodiimide solution. Combined E was synthesized.

(6) Copolymer F (comparative example) p-toluenesulfone instead of the xylene solution of N,N'-dicyclohexylcarbodiimide of copolymer B! l! Copolymer F was synthesized in the same manner except that 0.05111 parts were used.

(7) Copolymer G (comparative example) Same procedure except that p-toluenesulfonic acid O,OS was used instead of the xylene solution of N,N'-dicyclohexylcarbodiimide in copolymer C. Copolymer G was synthesized.

(8) Copolymer H (comparative example) 225 g (15 weight parts) of crystalline polyester 2 and 1275 g (+ (85 fflff) of amorphous vinyl polymer 4)
Copolymer H was synthesized in the same manner as Copolymer A using 2 parts of N,N'-dicyclohexylcarbodiimidosocyanate.

Examples 1 to 5 Regarding copolymers A to E, each substance was placed in a V-type a-type container in the proportions shown in the table above, mixed for 20 minutes, and dissolved using a twin-screw extruder. ! The mixture was kneaded, cooled, and coarsely ground using a Wiley mill to obtain a 2 mm mesh pass product. The mixture was further finely pulverized using a supersonic jet mill, and then fine powder with a particle size of 5 μm or less was removed using an air classifier to obtain colored fine particles with an average particle size of 11 μm.

0.8 parts by weight of silica and 0.05 parts by weight of zinc stearate were mixed with 100 parts by weight of the colored fine particles using a V-type mixer to obtain five types of toners of the present invention.

These are designated as toner 1 to toner 5.

Comparative Examples 1-3 Copolymers F, G. Comparative toners 1 to 3 were obtained in the same manner as in Examples 1 to 5 except that H was used in each case.

The following evaluations were performed on each of the above Toners 1 to 5 and Comparative Toners 1 to 3, and the results are shown in Table 1.

<Evaluation> (1) Measurement of graft ratio 'Measure the ratio of the main chain methylene signal intensity and terminal methylene signal intensity of the crystalline polyester by H-NMR,
The grafting rate of the graft copolymer was calculated from the degree of decrease before and after the grafting reaction using formula (I).

(I) (2) Evaluation of grindability Measure the amount of feed required to obtain an average particle size of 10μ during pulverization using a jet mill rPJM-100 J (Japan Pneumatic Kogyo ¥A) This was used as an index of crushability. Discharge air pressure 6.0Ko/(supplied in vl f
f115o/mtn or higher is "0", 5-150/Ii
n was [ΔJ, less than 5 g/win was marked as "×".

(3) Evaluation of fluidity Taking advantage of the fact that powder with high fluidity has a low degree of compaction,
Each of the above-mentioned toners was loosely filled from above into a container having a diameter of 28 mff1 and a volume of 1001 g, and its vertical surface was measured to determine the static bulk density of the toner. The evaluation is that the static bulk density is 0.40 (1/
n or more was rated as "○", and less than 0.40 g/lN was rated as "x".

(4) Evaluation of cohesiveness 2g of each toner was placed in a sample tube, tapped 500 times with a tap densityer, left for 2 hours in an atmosphere with a temperature of 6'O'C, and a relative humidity of 34%.
The mixture was separated using an 8-mesh sieve, and the proportion of aggregates remaining on the sieve was measured.

(5) Evaluation of low-temperature fixability Each toner was mixed with a coachite carrier in which a fluorinated alkyl methacrylate aggregate was coated on a ferrite core material with an average particle size of 80 μm to a concentration of 2% by weight. A two-component developer having a concentration of 5% by weight was adjusted to vA.

An electrophotographic copying machine rU-Bix 1550 equipped with a latent image carrier made of an organic photoelectric semiconductor, a developing device for a two-component developer, and a heating roller fixing device, and modified so that the set temperature of the heating roller can be variably adjusted. Using a modified MRJ (manufactured by Konica U) machine, the linear speed of the heating roller was set to 139a+m/sec, and the temperature of the heating roller was set to 100 to 240°C while keeping the temperature of the pressure roller lower than the temperature of the heating roller.
A live-action test was performed using each of the above-mentioned phenomenon agents to form fixed toner images while changing the temperature stepwise within the range of °C. After scrubbing with Part M, the residual rate of the image at the edge was measured using a microdensitometer, and the lowest set temperature (minimum fixing temperature) at which the residual rate was 80% or more was determined. The heating roller fixing device includes a heating roller having a diameter of 3C+m and whose surface layer is made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer);
Silicone rubber whose surface layer is coated with PFA K
E-1300RT VJ (manufactured by Shin-Etsu Chemical Co., Ltd.) with a pressure roller, and the linear pressure is 0.8KO/c.
a+, the nip width is 4.311I11, and it is not equipped with a coating system for applying a mold release agent such as silicone oil.

(6) Evaluation of hot offset resistance A fixed toner image was formed in the same manner as in the evaluation of low temperature fixability above, except that the pressure roller was kept at a temperature close to the set temperature of the heating roller. Under similar conditions, the recording material was sent to the heating roller fixing device and visually observed whether or not toner stains were generated on the recording material at each set temperature of the heating roller. The set temperature (offset allowable temperature) was determined.

(7) High temperature and high humidity environmental conditions (temperature 33℃, relative humidity 80℃)
%) image quality above 81 Electrophotographic copying machine "U-3ix 1" equipped with a latent image carrier, a developing device for two-component developer, and a heated roller fixing device.
550 MRJ (manufactured by Koni 11) modified 3iWIk-Yori, under high temperature and high humidity environment conditions (temperature 33℃, relative humidity 80%)
), a photocopying test was conducted in which a copy image was formed using each of the above-mentioned developers, and the image quality of the obtained image was visually evaluated.

From the results in Table 1, it is clear that by containing a copolymer with a high graft ratio as a binder resin, low-temperature fixing properties are good, offset resistance is good, and grindability, fluidity and i.e.
It is clear that 54 has good aggregation properties and that good image quality can be obtained even under high temperature and high humidity conditions.

Claims (2)

[Claims] (1) Amorphous vinyl having a crystalline polyester and a functional group that forms a bond with the crystalline polyester and having a ratio Mw/Mn of number average molecular weight Mn to weight average molecular weight Mw of 3.5 or more. A method for producing a binder resin for toner, which comprises chemically bonding a binder resin to a polymer using a carbodiimide derivative. (2) Amorphous vinyl having a crystalline polyester and a functional group that forms a bond with the crystalline polyester and having a ratio Mw/Mn of number average molecular weight Mn to weight average molecular weight Mw of 3.5 or more. A toner for electrostatic image development, comprising a binder resin chemically bonded to a polymer using a carbodiimide derivative.