JPH036572A - Production of binder for toner and toner for developing electrostatic image - Google Patents

Abstract

PURPOSE:To enhance a block rate or graft rate by polymerizing a vinyl monomer in the presence of crystalline polyester having unsatd. double bonds at the molecule terminal to obtain a specific block copolymer or graft copolymer. CONSTITUTION:The vinyl monomer is polymerized in the presence of the crystalline polyester having the unsatd. double bonds at the molecule terminal to obtain the block copolymer or graft copolymer having >=3.5 value of the ratio Mw/Mn between a number average mol. wt. Mn and weight average mol. wt. Mw. The introduction of the unsatd. double bonds to the molecule terminal of the crystalline polyester is executed by, for example, a method for utilizing the carboxyl group or hydroxyl group at the molecule terminal of the crystalline polyester and chemically bonding these functional groups and the vinyl monomer having a functional group to react therewith. The block rate or graft rate is improved in this way.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a binder used in 1 to 1 to 1 to develop an electrostatic latent image formed in electrophotography, electrostatic printing, ffT electrography, etc. Resin manufacturing method d3 This invention relates to a toner for developing static FFI images containing the binder resin.

[Prior art 1] For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image bearing member made of a photoconductive photoreceptor, and then this electrostatic latent image is transferred to a resin. The image is developed with a toner made of fine particles 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 more compact and equipped with A-copy machines, which require (a) suppression of overheating deterioration of the copying machine, (b) prevention of thermal deterioration of the photoreceptor, and (c) operation of the fixing device. (d) To shorten the warm-up time required for the heat roller to rise to a temperature of t11 degrees at which fixing is possible.
Due to demands such as minimizing the drop in temperature of the heat roller due to heat absorption into the transfer paper, making it possible to perform continuous copying many times, and (e) increasing thermal safety, There is a strong demand for reducing the power consumption of heaters 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.

Moreover, the toner must be able to exist stably as a powder without agglomerating under RII conditions of use or storage, that is, it must have excellent blocking resistance, and the preferred fixing method is the hot roller fixing method. , an offset phenomenon occurs in which part of the toner constituting 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, staining the image. It is necessary to impart the performance of preventing the occurrence of the offset phenomenon, that is, the offset resistance.

For this reason, in the past, for example, Japanese Patent Application Laid-Open No. 63-27855 discloses that crystalline polyester and Mw
A toner containing a block copolymer or a graft copolymer with an amorphous vinyl polymer having /Mn≧3.5 is also disclosed in Japanese Patent Application Laid-Open No. 63-27856. A toner containing a block or graft copolymer with an amorphous vinyl polymer having more than one peak is disclosed. In addition, JP-A No. 64-35455 discloses an image forming method using a toner containing a block copolymer or a graft copolymer of crystalline polyester and a non-quality vinyl polymer. No. 64-35456 discloses a method for producing a toner containing a block copolymer or a graft copolymer of crystalline polynisder and a non-grade vinyl polymer, which includes an additional heat treatment step.

In addition, JP-A No. 62-81644 discloses a copolymer obtained by blending unsaturated monomers at a specific ratio in the presence of a fluorine-containing resin having reactive double bonds and polymerizing the mixture. contains!・Na is disclosed.

[Problems to be Solved by the Invention] In the above-mentioned prior art Φ to ■, in order to obtain a block copolymer or a graft copolymer, specifically p-toluenesulfonic acid (ester bond), hexamethylene diisocyanate ( The crystalline polyester and the amorphous (non-quality) vinyl polymer are chemically bonded using a reaction using heat (urethane bond) or heat (amide bond, epoxy group bond).

However, in the reaction using o-toluenesulfonic acid and heat, the block rate or grafting rate, which is the bonding rate of the crystalline polyester with the amorphous vinyl polymer, was low, resulting in insufficient low-temperature fixability. This is thought to be because unreacted crystalline polyesters aggregate with each other to form large domains, and even though a local viscosity decrease occurs during heating, the viscosity of the entire toner particle does not decrease. . Furthermore, since large domains of the crystalline polyester component are formed in the toner particles, the fluidity of the toner particles is also low. In addition, in the reaction using isocyanate, coupling bonds occur between some H groups at the molecular ends, 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.

In addition, since the above technology (■) uses a fluorine-containing resin,
Depending on the content and type, negative chargeability may be so strong that an 81 degree image may not be produced, and furthermore, there may be drawbacks such as poor pulverization and fixing properties.

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 a toner binder resin that has better low-temperature fixing properties and good off-hit resistance by increasing the block rate or grafting rate.・The fourth purpose is to provide a tonneau with good fluidity and good agglomeration resistance.The fifth purpose is to provide a tonneau whose properties are not affected by environmental conditions, especially at high temperatures. An object of the present invention is to provide a toner that has constant chargeability, fluidity, and developability even under high humidity conditions and can provide 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 involves producing a vinyl element in the presence of a crystalline polyester having an unsaturated double bond at the molecular end. polymerize,
Ratio Mw of number average molecule ffiMn and weight average molecular weight Mw
A block copolymer or a graft copolymer having a value of /Mn of 3.5 or more is obtained. The toner for electrostatic image development of the present invention also has a number average molecule ffiMn and a weight average molecule WMv obtained by polymerizing a vinyl monomer in the presence of a crystalline polyester having an unsaturated double bond at the molecular end. It is characterized by containing a block copolymer or graft copolymer having a ratio Mw/Mn of 3.5 or more as a binder resin.

The present invention will be explained in detail below.

Although the crystalline polyester used in the present invention is not particularly limited, polyalkylene polyester is particularly preferred from the viewpoint of low-temperature fixability and fluidity. Specific examples of such polyalkylene polyesters include polyethylene sebacate-1-, polyethylene adipate, polyethylene suberate, polyethylene succinate, polyethylene-p-<carbophenoxy)1-cundecaate,
Polyhexamethylene oxalate, polyhexamethylene sebacate, polyhexastyrene decanedioate, polyoctamethylene dodecanedioate, polynonamethylene avirate, polydecamethylene azelate, polydecamethylene azelate, polydeca methylene off plate,
Polydecamethylene sebacate, polydecamylene succinate, polydecamethylene dodecanedioate, polydecamylene octadecanedioate-1, polytetramethylene sebacate, polytrimethylene dodecanedioate, polytrimethylene octadecane Dioate, boritrimethylene oxalate, polyhexyrimethylene-decamethylene sebacate, polyoxydecamethylene-2-methyl-1,3-probanedodecanedioe-1., and others.

There are various methods for introducing unsaturated double bonds at the molecular ends of such crystalline polyesters. For example, by using the carboxyl group or hydroxyl group at the molecular end of crystalline polynisder, these functional groups can be introduced. It is preferable to chemically bond and introduce a vinyl molecule having a functional group that reacts with the vinyl molecule.

Specifically, after the synthesis of crystalline polyester is completed, a vinyl molecule from a similar company is added to the carboxyl group or water group at the end of the molecule, and an unsaturated double bond is formed at the end of the molecule by ester condensation, amide condensation, epoxy reaction, etc. A crystalline polyester having the following properties is obtained.

In order to efficiently insert an unsaturated double bond at the end of a molecule, it is preferable to refine the crystalline polyester by precipitation purification or column chromatography to remove unreacted raw materials such as glycol and dicarboxylic acid before reacting. .

Monomers having a carboxyl group or a functional group that reacts with water WJM include acrylic acid, β, β-dimethylacrylic acid, α-ethyl acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, Hydroxyethyl methacrylate, acryloyloxyethyl monophthalate, acryloyloxyethyl monosuccinate, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-medyloacrylamide, p-aminostyrene, glycidyl methacrylate, and others may be mentioned. can.

The crystalline polyester has a melting point Tm of 50 to 12
It is preferably within the range of 0°C, particularly 50 to 100°C. If the melting point T of the crystalline polyester used is less than 50°C, the resulting toner will have poor blocking resistance, and if it exceeds 120°C, the melt fluidity of the toner at low temperatures will decrease. The fixing properties deteriorate. In addition, the melting point TI of crystalline polyester is vinyl! tlff
It means the melting point of crystalline polyester in a state where it is not polymerized with the i-form.

The melting point of crystalline polyester can be determined by differential scanning calorimetry (D
SC), it can be measured by, for example, rDsc-20J (manufactured by Seiko Electronics Industries, Ltd.), and the measurement conditions are as follows:
The melting peak value when II+I+ is heated at a constant temperature increase rate (10"C/win) is defined as the melting point.

This crystalline polyester has an average molecular weight of 1
4Mw is 5. Goo ~ 5G, (too, number average molecular weight Mn is preferably 2, Goo ~ 20.Goo. When the molecular weight is within this range, the offset resistance of the toner and the pulverization efficiency in toner production are even better. becomes.

Vinyl monomers used to obtain the copolymer of the present invention include olefins and their It1 forms, dienes and their derivatives, vinyl acetylenes, acrylic acid and methacrylic acid and their derivatives, acrylic esters, and methacrylic acid. Examples include esters, acrylamide and methacrylamide and their derivatives, acrylonitrile and methacrylonitriles, vinylnisderes, vinylkenes and their derivatives, vinyl ethers, styrene and its derivatives. Among these, styrene and its b' derivatives acrylic esters and methacrylic esters are preferred, such as styrene, 0-methylstyrene, fatty methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2, 4-dimethylstyrene, p-n-butylstyrene, p-dodecylstyrene, p-methoxystyrene, p-7enylstyrene, 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-
Examples include butyl methacrylate-1-12-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dimethylaminoethyl methacrylate, and others.

These monomers can be used alone or in combination.

Among the vinyl monomers used, it is more preferable to use 50 to 95 wt% of styrene-based 18 monomers and 5 to 5 wt% of acrylic esters or methacrylic esters. Excellent fixing properties and offset resistance.

The copolymer according to the present invention can be obtained by polymerizing the vinyl monomer in the presence of the crystalline polyester having an unsaturated double bond at the molecular end.

The usage ratio of the above crystalline polyester is such that the ratio of the crystalline polyester component in the block copolymer or graft copolymer with the vinyl monomer is 3 to 50.
% by weight, preferably 5 to 40 ffli1%. If this proportion is 3mff1% without swirling, the obtained toner will have a high minimum fixing temperature, and if it exceeds 50% by weight, the melt elastic modulus during fixing will be small and the offset resistance will be poor.

Any known technique can be used as the polymerization method.

The block rate or graft rate of the obtained co-m polymer refers to the proportion of the crystalline polyester at the time of preparation that actually reacts with the vinyl monomer to form a block copolymer or a graft copolymer. The actual calculation method is as follows:
There are various embodiments, and although not particularly limited, for example, 'H-
A calculation method using NMR can be adopted. The ratio of the signal intensity of the unsaturated double bond bonded to the end of the crystalline polyester molecule to the signal intensity of the methylene group in the main chain can be measured, and the ratio can be calculated from the percentage decrease before and after the block reaction or graft reaction.

Block rate or graft rate is low (both >50%,
It is preferably 75% or more and can be achieved by the method of the present invention.

In the obtained copolymer, it is necessary that the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular ffiMn is 3.5 or more, and 4 to 40 is particularly preferable. Ratio M
When w/Mn is too small, sufficient offset resistance and durability cannot be obtained.

Here, the values of lff1 average molecular weight ffIM W and number average molecular weight Mn can be determined by various methods,
Although there are slight differences due to differences in measurement methods, in the present invention, the values were determined using the following measurement method.

That is, the weight average molecule f was determined by gel permeation chromatography (GPC) under the conditions described below.
f1M! , number average molecular weight Mn, and peak molecular weight are measured. At a temperature of 40°C, the solvent (tetrahydrofuran) was flowed at a flow rate of 1.21 g/min, and the concentration was 0.2 Q/min.
The sample weight is 3111 with a sample solution of 20i1 in tetrahydrofuran! ;Inject and measure. When measuring the molecular weight of a sample, select measurement conditions in which the molecular weight of the sample falls within the range where the logarithm of the molecular weight and the count number of the calibration curve prepared using several types of monodispersed polystyrene standard samples are linear. . The reliability of the measurement results is based on the NBS 706 boristyrene standard sample (weight average molecular ff1Mw -28,8x104) measured under the above measurement conditions.
, number average molecular weight Mn = 13.7x104, Mw
/Mn -2,tl) when the value of Mw /Mn is 2,1
Confirm by checking that it becomes 1±0,10.

Further, as the G l' C column to be used, any column may be employed as long as it satisfies the above conditions. Specifically, for example, TSK-GEL, GMI-
1 (manufactured by Toyo Kaidasha), etc. can be used. Note that the melt Is 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 copolymer according to the present invention has at least two maximum values in one molecule distribution. That is, at least two components, a low molecular weight component and a high molecular weight component,
In a molecular cluster distribution curve that has a molecular weight distribution that can be divided into groups and is measured by gel vermiacetic chromatography (GPC'), at least one local maximum value is within the range of 2X103 to 2X104, and at least Preferably, there are at least two maximum values, with one maximum value being in the range 1X105 to 1X106.

The glass transition point of the obtained copolymer is preferably 40 to 85°C, particularly preferably 40 to 65°C.

Here, the glass transition point Tg is the differential scanning calorimetry method (
DSC), and specifically, for example, rDSC-20J <t? (manufactured by Iko Denshi Kogyo Co., Ltd.) at a heating rate of 10°C/1n, the maximum slope between the extension line of the baseline below the glass transition point and the rising part of the peak to the top of the peak is This refers to the point of intersection with the tangent shown.

Further, the softening point of the copolymer is preferably 85 to 150°C,
Particularly preferred is 85 to 130°C. This softening point was determined using a Koka type flow tester (manufactured by Shimadzu Corporation) at 1C112
A sample of
, a nozzle with a length of 1111Il is extruded, thereby drawing a plunger drop amount-temperature curve (softening flow surface FJ) of the flow tester, and when the height of the S-curve is h, it corresponds to h/2. The softening point was defined as the temperature at which

In the toner of the present invention, a copolymer obtained by the method of the present invention is used as a binder resin.

In such a toner, since the binder contains the copolymer with a high graft rate or block rate, the low-temperature fixability and good wettability during melting due to the crystalline polyester component are improved by 1q. As a result, offset resistance due to the amorphous vinyl polymer component, which itself contributes to low-temperature fixing properties, is enhanced, resulting in good offset resistance and low-temperature fixing properties in the formation of visible images using m-electronic images. A wide fixable humidity range can be obtained, and blocking resistance and fluidity are good, and excellent visible images can be formed many times.

The toner of the present invention needs to contain at least 30% by weight or more, preferably 50 to 100% by weight of the copolymer obtained by the above-described method of the present invention.

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, 1, NO, azoic Blue 3).
), Chrome Yellow (C, 1, No, 14090
), Ur I. Ramarinpuru (C, I.

No. 77103), DuPont Oil Red (C, 1
, No. 26105), Quinoline Yellow (C, 1,
No, 47005), methylene blue chloride (C, 1, No, 52015), phthalocyanine blue (C, 1, NO, 7416G), malachite green ocunarate (C, l No, 42000), lamp black (C, 1, No, 77266), Rose Bengal (C, I.

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 20 parts by weight, per 100 m parts of toner.
10 parts by weight is preferred.

The magnetic material may be a metal or alloy that does not exhibit ferromagnetism, such as iron, cobalt, or nickel, including ferrite or magnetite, or a compound containing these elements, or a material that does not contain a ferromagnetic element but is subjected to appropriate heat treatment. Examples include alloys which exhibit ferromagnetism due to the use of metals, such as alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others. For example, in the case of obtaining a black toner, magnetite, which is black in itself and also exhibits the ability 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 10011 parts of 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 70-neck carbon, etc. can be used. In particular, the softening point (ring and ball method JIS K2531) is 60~
Wax at 150°C is preferred.

M? As the tf 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 inorganic fine particles used in the present invention include -
The secondary particle size is 5 mμ to 2 μl, preferably 5 mμ to 2 μl.
The particles are 500 mμ. Further, the specific surface area measured by the BET method is preferably 20 to 5 GOf10. The proportion mixed into the toner is 0.01 to 5ff! ffi%t'
Ali, good tL, Kuha 0.01~2, Of! It is 1%. Such inorganic fine powders include, for example, fine silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate (condium, zinc oxide, silica sand, clay, mica, wollastonite). , diatomaceous earth, chromium oxide, cerium oxide, red iron,
Examples include antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, and 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, strium silicate, potassium silicate,
It may be any of Kuichu magnesium, zinc silicate, etc., but it is preferably one containing 85% by weight or more of 5i02.

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), Talax 500 (manufactured by Talco), etc. Other examples include silane coupling agents, titanium coupling agents, silicone oils, silicone oils having amines in their side chains, etc. Fine silica powder treated with can be used.

To give an example of a preferred method for manufacturing the toner of the present invention, first, a binder material resin or a toner component such as a colorant is added to it as necessary, for example, EX1.
A toner having a desired particle size can be obtained by melt-kneading with a Ruder, cooling, pulverizing with a jet mill or the like, and classifying the resultant. Or to the extruder:
A toner having a desired particle size can be obtained by spraying or dispersing the melt-kneaded mixture in a molten state using a spray dryer or the like.

The toner of the present invention can be used as a static image formed in, for example, an electrophotographic copying machine. ! The image is developed, and the resulting toner image is electrostatically transferred onto a transfer paper and fixed by an upper heating roller fixing device to obtain a copy image.

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 17x1 second, particularly within 0.5 second.

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

Synthesis of crystalline polyester> (1) Crystalline polyester 1 Sebacin M 1500Q (7.41 mol) and hexamethylene glycol 964Q (816 mol) were combined with a thermometer, a stainless steel stirrer, and a glass nitrogen introduction tube. The reactor was placed in a 5-hole round bottom flask, and the flask was then placed in a mantle heater, and nitrogen gas was introduced through a glass nitrogen inlet tube to maintain an inert atmosphere inside the reactor. The temperature was raised under the condition of 13.
．． Add 20 I)-1-luenesulfonic acid and bring to temperature 15
The reaction was carried out at 0°C.

When the amount of water distilled by the esterification reaction reached 2501 g, the reaction was stopped and the reactant was taken out. This crude crystalline polyester (1.0) (g) was placed in a 51 beaker, approximately 2.5 KQ of xylene was added to bring the total volume to 42, and the mixture was stirred well to form a homogeneous solution. The solution was added dropwise at about 1 ff [with stirring into 202 methanol using the same method. After being left for about 1 hour, it was filtered and washed twice with about 12 methanol. After that, it was left standing in warm air at 30 ° C. for a day and night. The purified crystalline polyester had an acid value of 2.811 (JK OH/Q) and a hydroxyl value of 10.61 (JK OH/Q, Mw -13
,000 and Mn -5,900. This purified product 1
．． 0K (J) and 1.0Q of p-toluenesulfonic acid were placed in the above-mentioned round bottom flask No. 51, and the temperature was raised to 150°C. Then, 13.6 g of acrylic acid was added dropwise from the dropping funnel, and the temperature was raised to 150°C for about 30 minutes. After confirming that no water was distilled out due to the esterification reaction, the reactant was taken out.The reactant was cooled to room temperature to form a crystalline polyester made of polyhexamethylene sepacate having an unsaturated double bond at the end of the molecule. I got 1.

(2) Crystalline polyester 2 Purified crystalline polyester in the same manner as crystalline polyester 1 using 1500 g (7.41 mol) of Sepacin R, ethylene glycol SOEG (8.16 mol), and p-toluenesulfonic acid io, og. Polyester was obtained. Acid value is 4.5
1aKOf-1/a, water M haze value is 13.6111!7
KO+-I10, Mw-11,200, Mn =
It was 5,400. 1.0KQ of this purified product was placed in the above-mentioned 5-hole round bottom flask, and the temperature was raised to 150°C. Then, glycidyl methacrylates 4S and 8Q were added dropwise from the dropping funnel, and after reacting at 150° C. for about 30 minutes, the reactants were taken out.

This was cooled to room temperature to obtain a crystalline polyester 2 made of polyethylene sebacate having an unsaturated double bond at the molecular end.

(3) Crystalline Polyester 3 Purified in the same manner as Crystalline Polyester 1 using Adipine M 10100O (6.85 mol), decamethylene glycol 1311 g (7.53 mol), and p-toluenesulfonic acid 11.6Q. Polyester was obtained. Acid value is 4.61<IK OH/Q, hydroxyl value is 12.0m
gKOH/CI, Mw −13,100, Mn −
(i, 560) Next, crystalline polyester 3 was obtained in the same manner as crystalline polyester 2 except that glycidyl methacrylate 42.OQ was used.

Synthesis of copolymer> (1) Copolymer A (present invention) 100 m of toluene was placed in a separable flask with a volume of 15 ffi.
Put 1 part of ff, 7.5 mIn parts of styrene, n
-2.5 parts by weight of butyl acrylate and 0.02 ffl of benzoyl peroxide! After adding the fi part and replacing the gas phase in the flask with nitrogen gas, the temperature was raised to 80°C and maintained at this temperature for 15 hours to carry out the first stage polymerization. after that,
The inside of the flask was cooled to a temperature of 40°C, and 1 part of crystalline polyester 1 15mff, 65 parts by weight of styrene, 10 parts by weight of n-butyl methacrylate, and 3 parts by weight of benzoyl peroxide were added thereto. After stirring was continued for 2 hours at ℃, the temperature was raised again and maintained at that temperature for 8 hours to carry out the second stage polymerization.

Thereafter, 1 to toluene was distilled off using an aspirator and a vacuum pump to obtain a graph 1 to copolymer At.

This graft copolymer A had a 1Iffi average molecular weight Mw of 105.000, a ratio Mw/Mn of 18.0, and a softening point Tsp of 110°C. Incidentally, this copolymer A had one peak in its molecular weight distribution.

(2) Copolymer B (invention) Table-1 A mixture having the composition shown in Coating-1 above was mixed with toluene 10
The mixture was added to a separable flask with a capacity of 511 containing part 011 ffi, and the gas phase in the flask was evacuated with nitrogen gas.
Polymerization was carried out for a certain period of time. Thereafter, by distilling off toluene using a 7 subilator and a vacuum pump,
Copolymer B was obtained. This copolymerization holiday ffi! Average molecular weight/Mw/Mn is 6.9, softening point TSD is 10
The temperature was 5°C.

Incidentally, this copolymerization holiday had one peak in its molecular weight distribution.

(3) Copolymer C (present invention) In the synthesis of copolymer A, copolymers were produced in the same manner except that the charging ratios in the first stage polymerization and second stage polymerization were changed to the compositions shown in Table 2. I got a C.

Table 2 l of this copolymer C! The weight average molecule 11Mw is 16B,G
oo, ratio MY/Mn is 24.5, softening point Tsp is 11
The temperature was 5°C. In addition, this copolymer C had two peaks in its molecular distribution.

(4) Copolymer D (present invention) In the synthesis of copolymer A, copolymers were produced in the same manner except that the charging ratios in the first stage polymerization and second stage polymerization were changed to the compositions shown in Table 3. I got it.

Table-3 Mw of this copolymer - 175,000, Mw
/Mn-22.5, Tsp-105°C, and two peaks were present in the molecular weight distribution.

(5) Copolymer E (present invention) Copolymer E'4r was obtained in the same manner as Copolymer A using the charging composition shown in Table 4.

Table-4 Mw of this copolymer E = 142,000, Mw
/Mn-24,5,T,sp-100℃teari,molecule i
1! There were two peaks in the distribution.

(6) Copolymer F (for comparison) Styrene 85! I! ffi part n-butyl methacrylate 10 parts by weight acryloyloxyethyl monosuccinate 5 parts m benzoyl peroxide 4 parts by weight The monomer mixture having the above composition was added to a separable flask with a volume of ff1iz containing 100 mm part of toluene, After replacing the gas phase in this flask with nitrogen gas, the temperature was 80°C.
The temperature was raised to 1, and polymerization was carried out by keeping this temperature for 15 hours. Thereafter, toluene was distilled off using an aspirator and a vacuum pump to obtain an amorphous vinyl polymer having carboxyl groups. mm of this amorphous vinyl polymer
The average molecular weight Mw was 71,000, the value of the ratio Mw /MTI was 1.5, the glass transition point Tg was 67°C, and the softening point Tsp was 123°C.

This amorphous polymer 85 layered cylinder part and crystalline polyester 1
Crude crystalline polyester 15 obtained by 1q in the synthesis of
ffiffi part and xylene 100ff! ffi part were placed in a separable flask with a capacity of 51 cm, and nitrogen gas was introduced to maintain the inside of the reactor in an inert atmosphere, and the temperature was raised. The amorphous polymer and crystalline polynisdel are completely dissolved,
When it becomes a homogeneous solution, p-toluenesulfone i! ! o
, os was added and then refluxed at 150° C. for 1 hour. After xylene was distilled off using an aspirator and a vacuum pump, the reaction product was taken out and cooled to room temperature to obtain copolymer F. This copolymer F had an average molecular weight Mw of 67.000, a ratio Mw/Mn of 7.1, and a softening point Tsp of 108°C. Incidentally, this copolymer F had one peak in its molecular weight distribution.

(7) Copolymer G (for comparison) In the synthesis of copolymer A, the charging ratios in the first stage polymerization and second stage polymerization were changed to those shown in Table 5, and an amorphous polymer having carboxyl groups was used. I got it.

Table 5 The weight average molecule ff1Mw of this amorphous polymer is 165.
000, ratio Mw/Mn is 25.9, glass transition point TC
I was 62°C, and the softening point Tsp was 130°C. In addition,
This amorphous polymer has two peaks in its molecular weight distribution.
There was one.

85fiffi parts of this amorphous polymer, 15i1ffi parts of the crude crystalline polyester obtained in the synthesis of crystalline polyester 1, and 10011! of xylene! Copolymer G was obtained in the same manner as Copolymer F using the ffi part and p-toluenesulfone M O,05 ffi part. This copolymer G has a weight average molecular weight Mw of 160,000. Ratio M
The value of w/Mn was 24.3, and the softening point Tsp was 115°C. Incidentally, this copolymer G had two peaks in its molecular weight distribution.

(8) Copolymer H (for comparison) In the synthesis of copolymer A, ff'! Amorphous polymers having hydroxyl groups were obtained by changing the charging ratios in the first-stage polymerization and second-stage polymerization to those shown in Table 6.

The flfi1 average molecular weight of the amorphous polymer shown in the table is 174.50.
0, the value of the ratio Mw /Mn is 23,1, the glass transition point To
was 63°C, and the softening point TSII was 128.5°C. Note that this amorphous polymer had two peaks in its molecular weight distribution.

This amorphous polymer 85 layered cylinder part and crystalline polyester 2
A copolymerization holiday was obtained in the same manner as for copolymer F, except that 15 parts of the crude crystalline polyester obtained in the synthesis of FFI, 1 part of 100 parts of xylene, and 2 parts of hexamethylene diisocyanate were used. Ta.

The weight average molecule ff1Mw of this copolymerization holiday is 171.0
00, the value of the ratio MY/Mn was 23.1, and the softening point Tsp was 118°C. Incidentally, this copolymer To1 had two peaks in its molecular distribution.

(9) Copolymer ■ (for comparison) Volume ff15j! Toluene 100 in a separable flask
! uffi part, and therein are placed 15 parts by weight of crystalline polyester 1, 65 parts by weight of styrene, 2OfIfi parts of n-butyl acrylate, and 0.2 parts of benzoyl peroxide!
After adding the uffi part and exchanging the gas phase in the flask by 1F with nitrogen gas, the temperature was raised to 80°C and the temperature was increased to 1F.
Polymerization was carried out for 5 hours. Thereafter, toluene was distilled off using an aspirator and a vacuum pump to obtain copolymer (1). Copolymer ■ has a weight average molecular weight MI = 490,0
00. The ratio Mw/Mn is 3.2, and the softening point Tsp is 1.
The temperature was 35°C. Note that this copolymer (1) had one peak in its molecular weight distribution.

(10) Copolymer J (for comparison) A xylene solution of a fluorine-containing copolymer with water 11 (Lumiflon LF210, hydroxyl group (iIli108, number average molecule fil M n = 25.000, solid content 50%)
, made by Asahi Glass) 100mm? JS was placed in a separable flask with a volume of 15Q, and after replacing the gas phase in the flask with nitrogen gas, the temperature was raised to 50°C. Then, a mixed solution of 0.611 parts of maleic anhydride and 0.6 mm part of xylene was added dropwise from the dropping funnel, and the mixture was heated at 50°C for 1 hour.
The reaction was carried out at 20°C for 2 hours. After taking out a portion of the reactant and brominating the unsaturated 2m bonds, it was confirmed by titration that the copolymer was a fluorine-containing copolymer having 0.013 mol of double bonds per 100 g of the copolymer. 50 parts of xylene was further added to this copolymer solution, and the temperature was raised to 100°C. After replacing the gas phase in the flask with nitrogen gas, 30 parts by weight of styrene and n-butyl methacrylate-1-2014! A mixture of 1.5 parts by weight of azobisisobutyronitrile and 1.5 parts by weight of azobisisobutyronitrile was added dropwise from the dropping funnel over a period of 2 hours, and the mixture was further reacted at the same temperature for 4 hours. After that, xylene is distilled off using an aspirator and a vacuum pump to take out the reactant.
Copolymer J was obtained by cooling to room temperature. Copolymer J L [
1ffi average molecule ff1Mw -43, Goo, 1t
The value of Mw/Mn was 3.75 and the softening point was 135°C. Incidentally, this copolymer J had one peak in its molecular weight distribution.

Examples 1 to 5 Table 7 Regarding copolymers A to E, the respective substances were placed in a V-type mixer in the proportions shown in Table 7 and mixed for 20 minutes, followed by melt mixing using a twin-screw extruder. After cooling, it was coarsely ground using a Wiley mill to obtain a 2 mm mesh pass product. Further, the mixture was 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 silica was added to 1 part of 100 ffl fi of the colored fine particles.
．． 8 parts by weight and 0.05 mff 1 part of Stearin M zinc were mixed in a V-type mixer to obtain five types of toners of the present invention.

These are called toners 1 to 5.

Comparative Examples 1 to 4 and 6 Comparative toners 1 to 4 and 6 were prepared in the same manner as Examples 1 to 5 except that copolymers F to ① and J were used.

Comparative Example 5 15ff1m part of crystalline polynisdel 1 and copolymer G
Comparative toner 5 was obtained in the same manner as in Example except that 85 g/at part of the mixture of the amorphous polymer obtained in the synthesis of Example 1 was used.

The following evaluations were performed on the above Toners 1 to 5 and Comparative Toners 1 to 6, and the results are shown in Table 8.

Evaluation> (1) Measurement of graft ratio The graft ratio was determined using 'H-NMR. For Copolymers A-E and Hafi Coalescence (2), the ratio of the signal intensity of the unsaturated double bond of the crystalline polyester to the signal intensity of the main chain methylene group was measured and calculated from the degree of decrease before and after the grafting reaction.

For copolymer F-H, the ratio of the signal intensity of the main chain methylene group and the signal intensity of the terminal methylene group of the crystalline polyester was measured, and calculated from the degree of decrease before and after the grafting reaction.

For copolymer J, the unsaturated 2m bonds were brominated and titrated to obtain a window, and the ratio was calculated from the percentage decrease before and after the grafting reaction.

(2) Supersonic jet mill for crushable 2mm mesh pass products! F'JM
-100J (manufactured by Japan Pneumatic Kogyo TTM), the amount of feed required to obtain an average particle size of 10 μm during pulverization was measured and used as an index of pulverizability. If the discharge air pressure is 6.0KO/Cf and the supply m15a/1n or more is "○", if 5~15C1/1ain is [ΔJ, 5a
/sin was defined as rXJ.

(3) Evaluation of fluidity Taking advantage of the fact that powders with high fluidity have a low degree of compaction,
Each of the above toners has a diameter of 28111111 and a volume of 1001.
The toner was loosely filled from above into 12 containers and the weight was measured to determine the static bulk density of the toner. The evaluation is that the static bulk density is 0.40
g/v (1 or more is rOJ, 0-40 (less than 1/lR is "
×”.

(4) Evaluation of cohesiveness 2g of each toner was placed in a sample tube and tapped 500 times with a tap densityer, then the temperature was 60°C and the relative humidity was 3.
The mixture was left in a 4% atmosphere for 2 hours, and then separated using a 48-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 ferrite core material with an average particle size of 80 μm was coated with 2% by weight of a fluorinated alkyl methacrylate polymer consisting of repeating units shown by the following formula. and its content (toner concentration) is 5
A two-component developer in weight percent was prepared.

It is equipped with a latent image carrier made of an organic photoconductive semiconductor, a developing device for two-component developer, and a heating roller fixing device, and has been modified so that the set temperature of the heating roller can be variably adjusted. U-BOX 1550 MRJ (manufactured by Konica ■)
With the modified machine, the linear speed of the heating roller was increased to 1391111/
seconds, and while keeping the temperature of the pressure roller lower than the set temperature of the heating roller, set the temperature of the heating roller to 100 seconds.
A photocopying test was conducted in which a fixed toner image was formed using each of the above developers while changing the temperature stepwise within the range of ~240°C, and a constant load was applied to the edge of the resulting fixed toner image using a rubbing tester. After rubbing 7fi 4 times, measure the residual rate of the image at the edge with a microdensitometer,
The lowest set temperature (minimum fixing temperature) exhibiting a residual rate of 80% or more was determined. Note that the heating roller fixing device has a surface layer of P.
Diameter 3Q+++m made of FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer)
It has a heating roller of The nip width was 4.3 ml and was not equipped with a mechanism for applying a release agent such as silicone oil.

(6) Evaluation of hot offset resistance A fixed toner image was formed in the same manner as 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, a recording material of The set temperature (offset generation temperature) was determined.

(7) Image quality under high temperature and high humidity environmental conditions (temperature ff!, 33°C, relative humidity 80%) Electrophotographic copying equipped with the above organic latent image carrier, a developing device for two-component developer, and a heated roller fixing device Machine “U-B ix 1
Using a modified machine of 550 MRJ (manufactured by Konica), set the temperature of the upper roller to the lowest fixing temperature, and apply each of the above developers under high temperature and high humidity environmental conditions (@3 degrees Celsius, relative humidity 80%). A photocopy test was conducted in which a copy image was formed using each, and the image quality of the resulting image was visually evaluated.

From the results in Table 8, according to the production method of the present invention, a copolymer with a high graft ratio can be obtained. Also, from the results in Table 8,
The toner of the present invention containing the copolymer according to the present invention as a binder has good low-temperature fixing properties and offset resistance,
It can be seen that it has excellent crushability, fluidity, and agglomeration resistance, and furthermore, good image quality can be obtained even under high temperature and humid conditions.

Claims (2)

[Claims] (1) A vinyl monomer is polymerized in the presence of a crystalline polyester having an unsaturated double bond at the molecular end, and the value of the ratio Mw/Mn of number average molecular weight Mn to weight average molecular weight Mw is 3.
A method for producing a binder resin for toner, characterized by obtaining a block copolymer or a graft copolymer having a molecular weight of 5 or more. (2) The value of the ratio Mw/Mn between the number average molecular weight Mn and the weight average molecular weight Mw obtained by polymerizing a vinyl monomer in the presence of a crystalline polyester having an unsaturated double bond at the molecular end is 3 A toner for electrostatic image development, characterized in that it contains a block copolymer or a graft copolymer having a molecular weight of .5 or more as a binder resin.