JPS5886558A - Electrostatic image developing toner - Google Patents

Abstract

PURPOSE:To enhance fixability of an electrostatic image developing toner, its resistance to offset and blocking, pulverizability during manufacture, etc., by adding a low mol.wt. polymer and an insoluble and unmeltable high mol.wt. polymer, as main resin components. CONSTITUTION:A monomer, such as styrene or alkyl (meth)acrylate, is (co)polymerized to prepare a low mol.wt. polymer having 3,000-50,000 number average mol.wt. and <=3.5 in ratio of weight average mol.wt./nusmber average mol.wt., and an insoluble and unmeltable high mol.wt. polymer. An intended electrostatic developing toner is obtained by mixing the 10-60wt% low mol.wt. polymer and the 90-40wt% high mol.wt. polymer, when needed, further incorporating a phenol formaldehyde or an epoxy resin with the obtained composition as the main resin components, and besides, adding a suitable pigment or dye as a colorant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new toner for reducing electrostatic charge gIIf in electrophotography, electrostatic printing, electrostatic printing, etc.

The novel toner for electrostatic charge development of the present invention is a fine powder developer used in so-called dry development methods, such as the cascade method, hair push method, magnetic black method, ingress developer method, and/or tau method. Since it can be used in the dry process of the dark cloud method, it is characterized by containing a low molecular weight polymer and an insoluble and infusible high molecular weight polymer as the main resin components.

As is well known, electrostatically charged toners generally include a colorant component consisting of a wood component, a pigment or a dye, and a fixing agent;
jIP is composed of additive components such as a charge control agent,
As the resin component, natural or synthetic resins are used alone or in a suitable mixture.

Toner suitable for the dry development method, whose technology has been rapidly developed in recent years (many different technologies have been proposed regarding its resin components, especially for electrophotographic copying machines aimed at high-speed copying). A heated roller constant adhesion method is adopted, in which the toner image obtained by development on the recording medium (photosensitive drum y) is once transferred to a transfer sheet such as paper, and then the transfer sheet is passed through a fixing roller that performs heat and pressure bonding. Fixation is performed by fusing the toner image onto the sheet.However,
Since the surface of the fixing roll and the toner image come into pressure contact with each other by heating and melting, a portion of the toner forming the image adheres to and is transferred to the fixing roll, and this is transferred again onto the next sheet to be fixed, resulting in a so-called "
"Offset development" occurs, causing all the stains on the sheet to be fixed.There has been a long-awaited demand for a resin acid solution that does not allow toner to adhere to the surface of the fixing roller even during high-speed copying, and yet provides sufficient fixing.

Japanese Patent Publication No. 51-2335ζ describes aoos to 20-weight TE as a toner resin component with excellent so-called "offset resistance" that does not cause such an offset phenomenon.
It has been proposed to use a resin component containing a crosslinking agent of s. In addition, the special public service No. 51 S-sass has a weight average molecular weight of 11
It is disclosed that an electrostatic** developing toner having excellent fixing properties and anti-offset properties can be obtained by using a negative tyrene resin having a number average molecular weight of &S to 4 as the main resin component.

However, in recent years, copying speeds have become increasingly faster than 1k, and there has been a marked trend toward clear and stable copies.Therefore, toners with better fixing properties and anti-offset properties than those of the above-mentioned conventional technologies have become available. As a result of extensive research into toner resin components that can meet these strong demands, the present inventor has finally developed the present invention, which has much better fixing properties and durability than the prior art. We have completed the invention of a toner having offset properties.

The electrostatically charged conventional toner of the present invention has a low molecular weight polymer and an insoluble high molecular weight polymer as main resin components.

Although the present invention is not particularly limited to the molecular weight or molecular electric distribution of the low molecular weight polymer, it is preferable that the number average molecule t(
Hereinafter referred to as MN) is &000-io, ooo and one weight average molecule t (hereinafter referred to as less than t, particularly preferably MN is 翫000~
3 Q,000 and a polymer with Mw/MN of less than 15 is used. If OMN is too low, less than 000, toner blocking (toner coagulation in the developing device) tends to occur, which is not preferable. On the other hand, if it is too high beyond 5 ooot'', the fixing performance will deteriorate, which is undesirable.
/MN of 15 or more is not preferable because the fixing properties deteriorate.1 The term "insoluble and infusible" of an insoluble high molecular weight polymer as used herein refers to both "insoluble" and "infusible". Yes, "insoluble" means AFTM-4or-ox.
(United States of America, Automotive Paint Testing Methods), a press-molded resin test piece is wrapped in a T-5OO mesh wire mesh and heated under reflux in an aquarium for 7 hours.The undissolved resin content is preferably 90 or more per initial weight 961! More than that
-v%＼, on the other hand, "infusible" means that the acetone-insoluble resin component was z
Apply a load of IOK @ at oo℃ and 9 and 1! (Diameter (LIIX
The amount of melting from the I%/m nozzle during the first 1 minute of forging is 1-
means less than

Preferably 10 to 111% of the low molecular weight polymer and 90% of the insoluble high molecular weight polymer per the total of the low molecular weight polymer and the insoluble and infusible high molecular weight polymer for electrostatic/charge image developing toner of the present invention.
-40 weight-1 Particularly preferably low molecular weight polymer Is-,
Be weight - and insoluble high molecular weight polymer 8s~50 weight -1
Most preferably, it is a resin whose main resin components are a low molecular weight polymer of 23 to 4 s weight and an insoluble high molecular weight polymer of 77 to 4 s of weight. If the low molecular weight polymer is less than 10% by weight, and the insoluble polymer heavy polymer is more than 90i1 (t'jl), the fixing properties will deteriorate, which is undesirable.On the other hand, if the low molecular weight polymer is less than 5afi Many insoluble polymers
If the ts coalescing strength is less than 140% by weight, the offset resistance will deteriorate, which is not preferable.

In this specification, the term "main resin component" refers to all the resin components that account for at least 10% of the electrostatic charge contained in the present toner.

M used in the low molecular weight polymer and insoluble high molecular weight polymer that constitute the main resin components of the toner for electrostatic image development of the present invention.
Examples of the it form include styrenes such as styrene, 6-1Ml-1p-ethylstyrene, p-ethylstyrene, and p-1-butylstyrene, ethylenically unsaturated monomers such as vinylnaphthalenes, ethylene, glopyrene, butylene, and isobutylene. Olefins, vinyl esters such as vinyl chloride, vinyl fluoride, vinyl acetate, vinyl butyrate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, octyl acrylate, ethylhexyl acrylate, chloroethyl acrylate , methyl methacrylate, ethyl methacrylate, methacrylic@*buty/I
/% Ethylene monocarboxylic acid conductors such as isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, etc., vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc. vinyl ethers, ethylenic dicarboxylic acids and their conductors such as dimethyl maleate, diethyl maleate, diptyl maleate, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinylidene halogens such as vinylidene chloride, vinylidene chlorfluoride, etc. and N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone.

Makumoto - Inventive electrostatic charge 11J! It is preferable that the insoluble and infusible high molecular weight polymer constituting the main resin component of the toner for visual images is included as a total component of the crosslinking agent, if necessary. Such crosslinking agents are mainly compounds having two or more polymerizable double bonds, such as aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. ), 1.3 butanediol dimethacrylate,
Examples include diethylene carboxylic acid esters such as aryl methacrylate, N,N divinyl chloride, divinyl ether, divinyl sulfide, and the like.

Divinylbenzene and ethylene glycol dimethacrylate are preferably used.

A preferred example of the low molecular weight polymer and/or insoluble high molecular weight polymer of the present invention is 50 to 100% by weight of styrene.
and (meth)acrylic acid chill ester go-o weight 91t-styrene containing 1r as one unit of seven molecules.
(Meth)acrylic acid ester polymers in alkali, particularly preferred examples are those of styrene 70-90% by weight and butyl acrylate 3Bo-to% polymers having an insoluble and infusible high molecular weight. Most preferably, the polymer contains the crosslinking agent (i) as one unit;
The blending amount is preferably αat to 8 weight per insoluble and infusible high molecular weight polymer.

The main resin component for the toner of the present invention can be produced by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Insoluble and infusible high molecular weight polymers produced by polymerization, suspension polymerization, emulsion polymerization, etc.A method of mixing in a dispersion or solution state and then drying, and a method of drying separately and then polymerizing the toner Polymer? The main resin component of the present invention is obtained by dissolving it in a monomer for an insoluble and infusible high molecular weight polymer, and then performing polymerization to obtain an insoluble and infusible high molecular weight polymer. Since the low molecular weight polymer and the insoluble and infusible polymer are mutually dispersed extremely uniformly, additives such as carbon black can be dispersed extremely efficiently during toner production, resulting in improved toner productivity and Excellent charging characteristics and storage stability.

The toner for developing electrostatic images according to the present invention has the above-mentioned resin as the main resin component, but other polymers may be mixed as necessary in addition to the main resin component. I can do it. Other polymers used in this VC mixture include phenol formaldehyde resins, epoxy resins, urethane resins, cellulose resins, 4-reaether resins, xylene resins, etc. be.

A suitable pigment or dye is blended as a coloring agent in the electrostatic charge image developing toner according to the present invention.

Examples of such pigments or dyes include carbon black, roux oil blue, de:LdIIin 4th Lure 2)"
There are mixtures of dyes such as , 7taden blue, nigrosine blue, nigrosine dye, tart 1 to phosphorus blue, quinoline yellow, pine kaitodine oxalate, -zbengali, etc., and the amount necessary for coloring the toner is blended. Ru.

Furthermore, the electrostatic charge developing toner of the present invention must be 1Ivc.
Depending on the release agent tI! An example of such a compound that may be blended in is Cd of sterophosphoric acid.

Ba, Ni%Co, St, Cm, Mg, C
a salt, oleic acid OZ s, ms, F#, CO, 0%,
Pb, M (1 salt, Zv+ of nordatenic acid, Co, C1 &
, MQ, 81. Ca salt, 2% of linol food, CO, Ca
salt, 2% of ricinoleic acid, also dcd salt, P of caprylic acid
B salts, caproic acid P& salts, etc., higher fatty acid salts, natural and synthetic craffins and fatty acid esters, partially saponified products thereof, alkylene bis fatty acid amides, etc., and one type of these compounds. Alternatively, two or more kinds may be suitably combined vertically and blended into the toner of the present invention.

1! In addition, other types of toner additives such as a charge control agent and a plasticizer can be added to the electrostatic charge one-quadrant toner according to the present invention, if necessary.

Thus, the electrostatic charge developing toner Fi according to the present invention has excellent fixing properties in high-speed electronic copying by containing a low molecular weight polymer and an insoluble and infusible polymer as main resin components. Although there are products that have excellent anti-offset properties and even better anti-blocking properties, the present invention surprisingly also has the completely unexpected effect of having excellent pulverizability during toner production. It turns out. Toner is made into a final product by cooling a molten mixture and then finely pulverizing it with a jet mill, etc. Conventionally, the yield of a product with a desired particle size distribution was about 10 -
However, according to the present invention, final products with a particle size distribution of 10 to 15 tones can be obtained in yields as high as about 70 mm.

The present invention will be explained in more detail below.

Example 1 In the polymerization machine of sOL, styrene 6.4 to 4, acrylic acid butylene #L @ Kg・8 Mercatoethanol 13 ott
Preparation, inside lK! While blowing air at zL/WLin from the %O blowing pipe, the inside of the polymerization machine was heated to 90°C and a polymerization reaction was carried out for 10 hours.

Next, styrene i, aV4, butyl acrylate 400
f, divinylbenzene 16 F, benzene peroxide 1
G? A mixed solution of 60 t of benzoyl peroxide was added to the above reaction product, and 20 t of an aqueous solution of deionized water in which 10 f of Hitomi polyvinyl alcohol (Gohsenol KA (-17) was completely dissolved) was added, and the inside of the polymerization machine was heated to 80°C with stirring. The polymerization reaction was completed by holding for 12 hours.The resulting slurry was subjected to the usual post-treatments of dehydration, washing and drying to form bead-shaped trees #1LIIclItll.

When the obtained resin was extracted with THFt using a Soxhlet extractor, the extraction weight became constant in 40 hours, and the insoluble component (insoluble and infusible high molecular weight polymer) was si weight 100%, and the soluble component (low molecular weight 1 polymer) was 45%. AfNFis, a low molecular weight monopolymer, has a 006°Mw/J/7y of 21, and the insoluble and infusible high molecular weight polymer is AFTM-40'1-
In the test No. 02, the insoluble content was determined to be SS*, and the amount of melting was aS- in the Koka type flow tester test.

After mixing the above gIlilOO part and la part of carbon black (Diamond Black EIH), they were thoroughly kneaded for a total of 0 minutes using heated rolls at 140°C. After cooling, it is coarsely crushed into a powder of approximately 300μ, and the air pressure S-
The powder was finely pulverized with a /-1 supply amount reef-/H device to obtain a fine powder with an average particle size of 15 μm, which was used as a toner.

A commercially available copying machine (Fuji Xerox SS
Copying tests are carried out using an O@ type copier), and one-time fusing is possible from 1mB'C, and even at IoC, there is no contamination due to toner offset to the roller. Even after copying, clear images with no stains were obtained.

Implementation 1J'l Snow I (I to polymerization machine was charged with 40 tons of styrene, 1.0 Kl of butyl acrylate, and 80 tons of 2-mercaptoethanol, and the polymerization machine was heated while blowing air at 217 m1 from a blowing pipe with an inner diameter of 2~. The interior was heated to 90°C and the polymerization reaction was carried out for 10 hours.Next, a mixed solution of 10F styrene, 1.0111F butyl acrylate, 20F divinylbenzene, and 70F benzoyl peroxide was added to the reaction product. After adding 20 kg of an aqueous solution of deionized water in which 10 ft of Go-Sevenol KH-7 had been dissolved, the polymerization reaction was completed by keeping at 80°C for 12 hours with stirring.The rest of the procedure was the same as in Example 1.
The obtained 11 fats had an insoluble component (insoluble and infusible high molecular weight polymer) of 7611* and a soluble component (low molecular weight 1 polymer) of 24% by weight.
The MNFifLls00MW/KN of the low molecular weight polymer was xi, the 4FTM test value of the insoluble and infusible high molecular weight polymer was 1, and the high pressure flow tester IR was α4.

When this product was made into toner using the same method as in Example 1,
Jet mill processing capacity FiLsKtt/Hr (average 1
3μ), and fixing in the copying test is possible from 180℃,! ! Even when heated to 6111°C, no offset phenomenon occurred, and clear, clean images were obtained even after making several copies.

! The polymerization reaction was carried out for 10 hours by heating the inside of the polymerization machine to 10° C. while blowing air at 147 m (s) from the blowing pipe.

Next, styrene 24 (, butyl acrylate 600F,
-/vinylbenzene 17 F, benzoyl perdecena 6
After adding the mixture of sf fIIfIL to the above reaction product,
Add 8 ml of an aqueous solution of dissolved deionized water to the inside of the polymerization machine while stirring.
1 to t! The polymerization reaction was completed after a certain period of time.

The rest of the procedure was the same as in Example 1, and the resulting resin was 62 times the weight of the insoluble component (insoluble and infusible high molecular weight polymer) - 1 weight of the soluble component (low molecular weight polymer) - 88 weight of the soluble component (low molecular weight polymer) - 1 weight of the low molecular weight polymer. of a body%
$18.200 Mvy/M7V was λ3, and the AI'TM trial value of the insoluble and infusible molecular ψ polymer was 97- for the insoluble content, and the test value on the Koka type flow tester was 0.11-.

When this product was made into a toner in the same manner as in Example 1,
Gen) processing capacity d3Kg/H (average 11sμ
), and fixing in copying tests is possible from 125°C, and no offset phenomenon occurs even at 250'C!
! You can get 0.000 copies of clean, clear images.

Example 4 Polymerization of styrene 5.6 i4. Butyl acrylate Z4Kt, 2-mercaptoethanol 260rYr
The inside of the polymerization machine was heated to 10°C and the polymerization reaction was carried out for 10 hours while blowing air at 2t/s (%) from a blowing pipe with an inner diameter of 2~.Subsequently, styrene L 4 IQ, butyl acrylate 6 G Of, divinylbenzene a l F
, a mixed solution of benzoyl peroxide 60f t'' = 10 times the amount after adding to the above reaction product, Go-7Nol KH-1'l
10ft! Dissolve and add deionized water or water** tohtm,
1 at SO℃ under stirring! The polymerization reaction was completed after a period of time.

The same operation as in G7441 was carried out, and the resulting resin insoluble component (insoluble and infusible high molecular weight polymer) had a BS weight of 100%, and the soluble component (low molecular weight polymer) 4I! Weight: low molecular weight polymer auras, oeoMw/Myuz 8,
In addition, the AFTM test value of the insoluble and infusible high molecular weight polymer was 19 - in the Koka type flow tester test value after 6 hours.This material was made into a toner using the same method as in Example 1. Jet mill 0 processing capacity t'! 4? /Hde(average tR
X), and the retention in the copying test is 1! ! This became possible from 0°C, and even at 250°C, no offset phenomenon occurred and clear images with little stain were obtained even after 20,000 copies were made.

Example 5 Styrene R, O6, butyl acrylate and benzoyl peroxide 300? were placed in a 60t polymerization machine. ? After mixing and dissolving Gohsenol KH-17Soft-, an aqueous solution of deionized water go4 was added to the polymerization machine under stirring.
80'C [Heat to conduct polymerization reaction for 11 hours.
5. A soluble resin with MW/KN of 'AB was obtained.

The above m fat 4, 11, styrene 41, butyl acrylate 1. ? ! V4, ethylene glycol dimethacrylate) 1
After dissolving it in a mixed solution of 60 f of benzoyl peroxide, add 10 ft of Gohsenol KH-1 aqueous solution of 20 ft of dissolved Yue ion water and charge it into the polymerization machine of rtrot. ″cm16L1
A polymerization reaction was carried out at 15 hours, and the resulting resin was composed of an insoluble component (insoluble and infusible high molecular weight polymer) - 57 layers, 1 soluble acid component (low molecular weight polymer), and a 48 layer M71/is. can be,
The 477M test value of the insoluble and infusible polymer having a molecular weight of 1 was 98% insoluble content, and the Koka type flow tester value was F1a5-.

This product was made into toner using the same method as in Example 1, and the processing capacity of the jet mill was F1!5h/H (average 14 tones).
Therefore, fixing in the copying test is possible from 116°C Ke
e) The 4-offset phenomenon did not occur at gso''cVc! Even 000 copies φ were obtained without stains.

Example 6 Styrene aO2, butyl acrylate 10-1, and benzoyl peroxide were mixed and dissolved in a SOTV polymerization machine, and then 20-20% of an aqueous solution of deionized water in which GOHSENOL KH-1v109 was dissolved was added and polymerized with stirring. Inside the aircraft t-
Heat to 85℃! ! Perform a time polymerization reaction.
) E8.000Mw/MN-1) Xz3 soluble resin (
A) (polymer of low molecules) was obtained.

Styrene & O14, acrylic, acid pull LOKg, divinylbenzene 15Of, benzoyl peroxide 100fYt were mixed and dissolved in a separate vcsot polymerization machine, and then an aqueous solution ROKgf of deionized water in which 10t of Gohsenol KH-1'1 had been dissolved was added and stirred. Inside the lower polymerization machine? lIO'CK
After heating and polymerization reaction for 12 hours, the insoluble content was 98%° according to the AFTM test value, and α5 ~ according to the Koka flow tester test value.
Resin 1)' of an insoluble and infusible high molecular weight polymer was obtained.

The above resin (A) aollB, resin (Z?311 (1 part)
VK, which was mixed with carbon black (dia black 5y) and coarsely crushed using a Nara-type crusher, was thoroughly kneaded for 100 minutes with a mtaot hot roll, and when the same fine crushing operation as in Example 1 was performed, the jet building was obtained. The processing capacity of m El
1H (average 13μ), copying test 1'C$P is possible to fix from 125℃, and offset phenomenon occurs even in lazy Io'c. Even after copying, clear images with less stains can be obtained. It was done.

Implementation tube Te 10j! Styrene & 414. Butyl acrylate t・-1-mercaptoethanol 130f1 After mixing and dissolving 1 azobisisovaleronitrile 1
The inside of the polymerization machine was heated to 90°C, and the polymerization reaction was carried out for 1 hour.Styrene 1.6-, butyl acrylate 4-
After adding a mixed solution of 0 Of, divinylbenzene 16F, and benzoyl oxide 80F to the above reaction product, an aqueous solution 10W4 of deionized water dissolved in Go-7Nol KH-I and the like was added to the polymerization machine. 80℃ with internal stirring
So 1! Keep time to complete the polymerization.

*11m is insoluble component (low molecular weight polymer) 25 parts by weight, 7 parts by weight of soluble component (insoluble infusible high molecular weight polymer) - AF of an insoluble and infusible high molecular weight polymer
TM test value d98L advanced flow tester test value is α4
It was m.

This material was made into a toner using the same method as in Example 1, and the jet mill had a crushing capacity of H4Kg/H, which was possible from a constant wh of 12G°C in the copying test. No offset phenomenon was observed even at 00° C., and clear images with little staining were obtained even when making copies of approximately 00 sheets per page.

Example 8 Add 5 oots of butyl acrylate to a 1 ton flask.

The polymerization reaction was carried out for 10 hours by heating the flask to an internal temperature of 90 DEG C. while blowing air through a blow tube with an internal diameter of α5 to 40 ft of naoglycolic acid using a 7-meter blade.

In another KIOt polymerization machine, % styrene 6KIF, butyl methacrylate 111, lauryl methacrylate 2-,
Divinylbenzene! Of, benzoyl peroxide 400
After mixing and dissolving 500 f of the above reaction product f'i, add an aqueous solution of deionized water goK4 dissolved in the polymerization machine and stir the inside of the polymerization machine for 80 minutes.
C. and kept for 12 hours to complete the polymerization reaction.

After that, the same operation as in Example IF11 was carried out, and the resulting resin was obtained by separating the insoluble component (insoluble non-uniform high molecular weight polymer) by 91s weight, and the soluble component (low molecular weight polymer) by 5 weight - 1 low molecular weight polymer. MN is 80G, My/MN is Lma,
In addition, the AFTM test for insoluble and nonuniform high molecular weight polymers is 9
3 seconds, the test value of Koka type flow tester was 1 m.

This product was made into a toner in the same manner as in Example 1, and then
The crushing capacity of the jet mill is Fi15 Kg/Hr (average 18μ), and the fixation in the copying test is 141
This became possible from S'C, and no offset phenomenon appeared even at 250°C. Furthermore, clear images with little staining were obtained even when copying approximately 00 sheets onto snow.

Example 9 s o ttv Togoki, styrene 6.4 to 9, butyl acrylate 1.611,! -Mercagtoethanol 520
ft-Preparation, 2% inner diameter blowing tube F) 217mm
Heat the entire interior of the polymerization machine to 90℃ while blowing air with
The polymerization reaction was carried out for o hours. Next, styrene Lllb, butyl acrylate 400 F, divinylbenzene 16 F
After adding a mixed solution of 60 tons of benzoyl peroxide to the above reaction product, 1 orll of an aqueous solution of deionized water dissolved in 16 ft of Go7ol KH-x was added, and the inside of the polymerization machine was heated at 80°C with stirring. ! The polymerization reaction was completed for a certain period of time. The rest is the same operation as in Example 1jll, and the resulting insoluble component of the resin (insoluble insoluble high molecular weight polymer) frame, 551
1! and 48 layers of soluble component (low molecular weight polymer),
WN of low molecular weight polymer is ta 00 Mw/AfN
It was Fl 3L R. Further, the AFTM cage test value of the insoluble and infusible high molecular weight polymer was s, and the Koka type flow tester test value was a8-.

Make toner using the same method as 9 [11] and 7
However, the crushing capacity of Jet Gill is @Kg/Hr (average 14 Jl), and fixing in copying tests is possible from 110°C, and no offset phenomenon was discovered until goo'c, and it was Even when copying images, clear images with few stains can be obtained.

Example 1 Styrene 7:00 and butyl acrylate were added to the O-OL polymerizer! −
Stearyl methacrylate 1? J benzoyl peroxide 1GO
f @ Preparation, after mixing and dissolving, Go-Sevenol KH-1
'l An aqueous solution of deionized water dissolved in 10f1 go
Add al and heat to t-80℃ inside the polymerization machine while stirring for 12
The soluble resin kl was subjected to a time polymerization reaction.

The above resin 4: styrene tab, butyl acrylate L
2 KIF, ethylene glycol dimethacrylate 12
After dissolving 0f mixed solution vc, go-sevenol KH-1
Aqueous solution of deionized water containing 10F 20-
was added and the inside of the polymerization machine was heated to 80° C. while stirring to complete the polymerization reaction. After that, the same post-treatment operation as in Example 1 was carried out, and the insoluble component (insoluble and infusible high molecular weight polymer) of the obtained resin was s6 weight -, and the soluble component (low molecular weight polymer) was 44 weight -5 is 'L4 and is the ultimate. The vAFTM test value of the insoluble and infusible high molecular weight polymer was 9B-, and the Koka flow tester test value was A6.

When this material was made into toner using the same method as the actual ipH, the crushing capacity of the jet mill was 4 Kt/H and 6? , the fixing f in the copying test became possible from 1140℃ and lO・
Offsera F development was not found up to ℃. O to tala
Even when copying about 00 sheets, good-looking images with little staining were obtained.

Example 11! Toluene SK#, acetic acid, butyl SB, and hydroquinone 1ft were charged into a polymerization machine and the inside of the polymerization machine was heated to 10°C. To this mixture, a warm solution of 8 g of styrene, 4 g of butyl acrylate, and 150 g of benzoyl peroxide was sequentially added under stirring for 3 hours, and the polymerization reaction was continued for an arbitrary period of time. It is reprecipitated into the water and separated as flaky resin, of which 4Kfk
After dissolving in a mixed solution of styrene 48, butyl acrylate 1.2Kf, divinylbenzene 16f, and benzoyl peroxide 60t, Gohsenol KH-1'l 10f
An aqueous solution of deionized water dissolved in! 0 was added to the polymerization machine and heated to 80°C inside the polymerization machine while stirring. A time polymerization reaction was performed. The obtained tree Ill is unsatisfactory
The component (insoluble and infusible high molecular weight polymer) was 57 times, the soluble component (low molecular weight polymer) was 43,811 times, and the MpJ of the low molecular weight polymer was as, ooo&W/MN was 48. In addition, AFTM test value F195 of insoluble and infusible high molecular weight polymer
The gG test value on the Koka type flow tester was 16-, which was a perfect score.

When this material was made into a toner in the same manner as in Example 1, the crushing capacity of the jet mill was L Is KI/Hf, and fixing in the copying test was possible from 140°C.
Even if the offset current gIIrt is not found, it is dangerous.
Also, even when copying about 600 copies to a 1-inch paper, clear images with little staining were obtained.

Comparison cylinder 1 sate polymerization machine with 6 kg of styrene L and bunal acrylate L
4 Immediate snow - 110ft of mercaptoethanol, inside I
From the l1%O blowing pipe, air was sent at 1147 m (s).
The inside of the polymerization machine was heated to 00°C from 1000 to 000°C, and the polymerization reaction was carried out for 16 hours.

Next, styrene 14 EF, butyl acrylate SO
After adding a warm solution of ethylene glycol dimethacrylate 11, ethylene glycol dimethacrylate 11, tetrachloride, benzoyl peroxide 6sf to the above reaction product,
H-1110ft-Dissolved deionized water O aqueous solution
- was added and the interior of the polymerization machine was kept stirring for 110'cK:1ffi to complete the polymerization reaction.

The rest of the procedure is the same as in Example IP1t, and the resulting resin contains an insoluble component (insoluble and infusible high molecular weight polymer) stitt*
, the soluble component (low molecular weight polymer) was 39 weight Mpp*S, but the AFTM test value of the insoluble and infusible high molecular weight polymer was 8 s- for the insoluble content, and the Koka type flow tester test value was 5 m
This was outside the definition of infusible according to the present invention.

When this material was made into toner in the same manner as in Example 1, the processing capacity of the jet mill was ijt s Kg/H (average 1
0 μ), and fixation in copying tests was possible from 145°C, and at 180°C, image stains due to the off-drying phenomenon were observed, and it was discovered that the images became smudged when the number of copies was changed to a, ooo. .

Comparative Example 2 Polymerization of sOt II! Styrene ao4. Butyl acrylate i@-1 1g00f of benzoyl peroxide was added, mixed and dissolved for 4t, then Gohsenol KH-1'r101@ToS
Add 20 bt of an aqueous solution of deionized water and heat to 85°C inside the polymerization machine with stirring, and at 12 o'clock the i3 soluble resin (
A) (Low molecular weight polymer) t-toku also different? C3oAO polymerization machine with styrene ILOKf, 7-butyl-9-alpharate noodles, 150 tons of divinylbenzene, and turtle lauryl mercaptan! ! Of, 106 to bency peroxide
After mixing and dissolving fl, Go-Sevenol KH-1?
An aqueous solution of 10 tk of deionized water dissolved in 10 E[i
-Add and heat to t-80t inside the polymerization machine while stirring and 1! A polymerization reaction was carried out for a period of time to obtain a resin (B) (insoluble and infusible high molecular weight polymer) with an AFTH test value of 6-1 in the case of a flow tester with an unaccumulated fraction of 0-1.

After mixing the above resins (Acts part, resin 17 TIS part, cardan black (dia black, ¥H) 10! Grinding capacity FiL !I
Kg/H de (average 15μ), fixation in copying tests was possible from 145°C, and image staining due to offset phenomenon was observed at 190°C, and it was discovered that the image was significantly smeared after copying about aooo sheets. .

Comparison Example 3 (Special Publick Publication No. 511331 $ Reef Example 1
Supplementary test) Styrene 7KF, methacrylic acid dibutyl aKf, ethylene glycol dimethacrylate L'-) 1
18P, s-Lauryl Melt 1ton - 19゜7 After mixing and dissolving 100t of zobisisobutyronitrile, dissolve Gohsenol KH-111()f and add an aqueous solution of deionized water go4t- to clean the inside of the polymerization machine. 86'C under stirring
The mixture was kept for 11 hours to carry out a polymerization reaction. After that, the same post-processing operation as in execution N1 was performed, and Soxhlet extraction was performed with the obtained resin @ THF. The Koka type flow tester test value for SO- is Ims, and the MN of the soluble component is g5. ooooo.

Mw/My is i3 and 9.

When this 4ot was made into toner using the same method as the actual fil, the crushing capacity of the jet building was 2Kg/H [average 1
7s) and the fusing rate in the copying test (at 160°C) was high.
2! Although the offset phenomenon was not discovered until O'C, %
When copying, the image was noticeably smudged to the extent of OOO&.

Comparison 4 (Tokukai Showa! No. 15-6895 implementation $
Supplementary test) Pour 20 - of toluene into the i o to polymerization machine and 110
After heating to °C, t-butyl pivalate peroxide 4G O
f, benzoyl peroxide 400 ft mixed solution of styrene solution lα8Kft? It was added into the polymerization machine in 4 hours.

After further polymerization reaction Yh1 was continued for 2 hours at the same temperature, the obtained specific polymer solution f by cooling to 5G'C was re-precipitated in 100 t of methanol, and the flaky soluble resin (A1 min. MNhasoo%Mvv/MN is 4.
It was 5.

Separately, when using a styrene solution instead of the above styrene solution, 1.8 Kp of butyl methacrylate and t-butyl peroxide
Using a mixed solution of butyl 4G Of and benzoyl peroxide 4GOf, the polymerization and post-treatment operations were carried out in exactly the same manner as above, and My was &200M)y/MN was 4.
A soluble resin (B) of No. 3 was obtained.

Mixture of the above tree 11 (A) io part and resin (B) go part @
Insoluble components obtained by Soxhlet extraction using t-THF were not separated, and the mixture was
When subjected to the M test, the result was 2-, and when subjected to the Koka type flow test, it was 115W.

When this was also made into a toner using the same method as in Example 1, the jet mill had a crushing capacity of F'12 KI/Hr, and it became possible to fix the image at a fixing temperature of 145°C in the copying test, but an offset effect was observed at 1°C. 4000&0 copy, the painting was very dirty.

Claims (1)

[Claims] L: An electrostatic charge developing toner containing a low molecular weight polymer and an insoluble and infusible high molecular weight polymer as main resin components. i The total weight of the low molecular weight polymer and the insoluble high molecular weight polymer is 10 to 60% by weight of the low molecular weight polymer and 90 to 40% by weight of the insoluble high molecular weight polymer. A toner according to claim 1. 3L The number average molecular weight of the wrinkled low molecular weight polymer is 000~
The toner according to claim 1, wherein the toner has a weight average molecular weight/number average molecular weight of less than &s. Claim I!! No. 1-41 wherein the 4 lk low molecular weight polymer and/or the insoluble and infusible high molecular weight polymer is a styrene-(meth-J acrylic A-acid alkyl ester comonomer)
．． The toner according to any of item B. 4 In the styrene-(meth)acrylic acid alkyl ester copolymer, styrene is 50 to 100 weight-1 (
meth)C acrylic acid ester ester is 0 to 50 times heavier.
The toner according to any one of claims 1 to 10. 2. The toner according to claim 1, wherein the tg ester copolymer contains divinylbenzene as a crosslinking agent. ? , #(methane acrylic acid alkyl ester is abutyl acrylate).