JPS5868752A - Powder toner - Google Patents

Abstract

PURPOSE:To fix a powder toner for electrophotography with a heat roll without using anti-offset liquid and without allowing sticking of the toner on the heat roll by using a specific polymer of a vinyl monomer and a modified epoxy resin as a binder. CONSTITUTION:In a powder toner for electrophotography, a vinyl polymer prepd. by causing a vinyl monomer and a modified spoxy resin having average >=1.1 unsatd. groups copolymerizable with said vinyl monomer (preferably 0.1-30wt% the resin of about 350-5,000mol.wts. in the entire vinyl monomer) to react is used, then the mol.wts. of the polymer increase and the distributions of the mol.wts. spread, whereby offsetting phenomena to heat rollers is obviated even without using anti-offset liquid, and the formation of electrophotographs at a higher speed with good fixability is made possible.

Description

[Detailed description of the invention]

*The invention relates to a toner for developing a-images in electrophotography, electrostatic recording, static printing, etc. The electrostatic latent image forming methods are roughly divided into liquid development method, cascade method, two-bristle brush method, magnetic brush method, impression method, and powder cloud method. 1- Dispersion of colorant such as carbon black into natural or synthetic resin using electrostatic induction method, jumping method, etc. 1.
- There is a dry developing method that uses a 71 powder developer called a toner.1 The present invention is used in the latter dry developing method.
This is related to filter toner. For more information, see Heat (Pressure)
Roller fixability? The present invention relates to a disguise toner that is quickly and firmly fixed to a medium in the apparatus used. Conventionally, the powder toner used for static latent development has different thermal properties depending on the fixing method and the thermal properties of the resin. For ax close-up copying, etc., it has become common practice to use a contact heated roller fixing method with good thermal efficiency. In this fixing method, the powder toner becomes sticky due to heating. A so-called "offset phenomenon" occurs in which a portion of the heat roller sticks to the surface and bites. Conventionally, measures to prevent this offset have been devised to prevent this offset. For example, the surface of the roller is made of a material that is highly resistant to toner, such as a multilayer resin. Further offset protection such as silicone oil is added to the surface.
1-Liquid supply 1, 1 sheet shallow 1 thin 1 "J-
Is it possible to coat the surface of La? (Waretaifu). This method is clearly effective in preventing toner offset 1 and 4), (method 4), but offset IX,
If the body is heated for a long time, odor will be generated, and a liquid supply to prevent vomit offset will be required. The mechanism of the 1υ copier is duplicator, 1.if, and stable binding is 1.
j-) Because of '-I+, ;75 I;3:7 degrees are "finished", so i" (there is a drawback that photo-mounting +?9 is busy at high level). However, Jl Ka et al. Off =) - Throat prevention liquid'
Body supply 1

[Yukiai Kiyu, 71 sudden r1-ra return song is activated by toner and off-set: l l-! j1. Since W, has these drawbacks, bC' is still off despite its generation method.
Please supply the liquid to stop Sol-+ε1 #i)
t(,+ha's current IQ. On the other hand, -t,: Self-off hit phenomenon "knee <M' i
In order to improve the properties of toner, for example, polyolefins, waxes, high grade fats, or their metal bases, I
A method has also been proposed in which it is added as a lubricant to the process of forming a rubber or roughening process. The basic concept of these offseno) prevention, t)-t't,
) When the lubricant is on the heat roller (C), the lubricant 14 comes out at the heat roller interface εC on the surface of the lubricant, and the lubricant is used to prevent offset η. F1 Pro.However, such a toner suffers from a lubricant coming out at the interface between the toner surface and the heat roller.
High speed i = photo! Mainly unusable, 31F, and when added in large quantities, the l-ner turns into a demon, has poor flow control, poor stability, and is electrified by friction. load! , system 'l;'j ''l cowjg which toner is familiar with the characteristics;) (influenced. 1, as a binder for powder toner, vinyl column +i
It is known that Evokin 7+ & Y can be used alone or as a blend of the two. These alone and blends are used as komonogaki and kinder.
This toner is generally used in the oven foot storm method, and when it is intended to be used in the hot roller fixed shield method, the toner is
− An offset phenomenon occurs. Also, vinyl! 1'L
The method of using a Jli polymer having two or more polymerizable double bonds in the I11 body as a crosslinking agent is known, but since this 1v crosslinking agent has a relatively short chain, A1) is also used as a Jli polymer. However, if the quality of the polymer (main product It has the drawback that it is unstable and has a short tC.The purpose of the present invention is to prevent the heat roller table 1tii & this issue), to prevent liquid from being supplied, and to prevent the offset phenomenon of IY4 toner when used. Gyusuge-f V
C Efficient and good fixation of the butt roller? VCrh can also provide powder toner. moreover. In addition, the purpose of the storage room is to provide a long-life powder toner.In addition, the purpose of one pile is that the polymerization is stable, Moreover, it is necessary to use a powder RCl-ner with good dispersibility. As a result of the above-mentioned purpose and as a result of intensive research, the present inventors have found that an average of 5 to 11 non-Showa bonds in the molecule are copolymerizable with the vinyl-based mono-Vi and the vinyl-based mono-14. The present inventors have discovered that a powder toner made of a polymer obtained by polymerizing a modified epoxy resin having at least 100 epoxy resins in the presence of a polymerization initiator can achieve the above object, and have completed the present invention. The polymer is a crosslinked product of vinyl polymer and modified Evoquin resin, so it has the advantages of vinyl polymer alone, epoxy/polymer alone, or a blend.It also has the disadvantage of solving the offset phenomenon. This is because it is cross-linked with loosely modified semi-epoxy resin.It provides a powder toner that is difficult to be pulverized by carrier collision even after repeated copying for a single time, and the molecular weight of one polymer is low. By increasing the molecular weight distribution and broadening the molecular weight distribution, the offset phenomenon to the heated roller does not occur even without the use of anti-offset agents such as silicone oil, and it has good stability, making it possible to create higher-speed electrophotographs, etc. The vinyl-based tl'i-l-111ζ-C used in the present invention can be made from one material. Styrene, vinyltoluene, 2-methylstyrene
t 7' Styrene type 'P' L of tyrstyrene nato
T-form, methyl acrylate, ethyl acrylate. Isopropyl acrylate + 11-butyl acrylate l” + 2-ethylhexyl acrylate-1-, methyl methacrylate, ethyl methacrylate-1. Propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate-1,,2-ethylhexyl methacrylate Any acrylic acid 17< is methacrylic acid algyl ester, acrylic acid, methacrylic rit
, ``1 ton! 11.r Which monobasic acid, fumaric acid, itacon 1χ, the di-salt of Mullein Falls ni 'j-
Bamboo shoots, so 11 anhydrides (which ethylenic i:, saturated carboxylic acid mono! iJ 11: + N-methy-acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide. N-butoxymethyl N-substituted (such as methacrylamide)
meth) acrylic monomers, hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyglobyl acrylate V-to, hydroxyethyl methacrylate 2-hydroxypropyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, etc. Can be mentioned. The modified epoxy resin used in the present invention, which has an average of 1.1 or more unsaturated groups in the molecule that can be copolymerized with the vinyl monomer, has a molecular weight of about 350 to 5,000 IW, and 1
For example, there are oil modified epoxy resins, acrylic acid modified epoxy resins, etc., in which the oil is used alone as a mixture, and the total vinyl monomer content ranges from 0005 to 0005.
Use 50% by weight, preferably 0.1-30% by weight. If the molecular weight of the modified epoxy resin is less than 350, the advantages of the modified epoxy resin as a powder toner cannot be imparted to the monopolymer obtained. Got it,
If the molecular weight of the modified epoxy 131 resin is too high, it may interfere with the polymerization operation during filtration. In addition, the modified Ebogishi resin is 0.0% based on the total vinyl monomer. When O05xi is lower than 1, the modified epoxy fj+'fl. The effect as a cross-linking component is small, 5[]it%.
If the polymer is mixed, the obtained polymer will be difficult to melt, so the object of the present invention will not be achieved.In the reaction related to the non-invention, a polymerization initiator is used. Polymerization initiator G1 is mainly a compound that generates tL leaving groups.
-ru. In the case of the emulsion polymerization method, hydrophilic initiators such as ammonium persulfate, peroxide, l'i, potassium, and water peroxide can be used. Ji3 polymerization used in suspension polymerization and melt polymerization is used for ZOJ1 agents, and peroxides such as oil-soluble penzoyl peroxide and dicumyl peroxide, and azole such as azobisisobutyronitrile, etc. Compounds, etc. are used + 1 is vinyl monobj and modified epoxy 9111i11;) 0*
Ml +=”l Vc vs. 1., Te0. O+ −1(
l i4-, ; part 1 + 1 (for -J h, Z >. 001 heavy part? If it is less than that, the polymerization process will be incomplete + 10 i, ii part - 2) is l
jOne thing - Initiator separation increases, there is a lot of scraping, and it has a negative impact on the polymerization product ■
! give. 1. Use an initiator as described above, and add methyl alcohol if necessary. A chain transfer agent such as ethyl alcohol + C2 carbon chloride is used. Various conventional methods can be applied to produce the toner, but one example is the binder and carbon black used in the VC of the present invention. ],) A layer coloring agent such as Russianine Blue is melted and mixed, and then ground to 1190. s ~ 50 microns (
μ) approximately ON diameter. ) When reacting with vinyl-based heavy electric and modified epoxy resin, pre-mix Y such as A, 11, etc. and make it % f @
6゜ 1 piece, vinyl type; 1 piece? - and a tinting agent may be added to the toner by bathing, drying or dispersing, or by hot spray drying. In addition, instead of two-layer colored paper, 02 and other 1 (magnetic powder wood, A regular 01 to 5μ, even if mixed, 5 [resistance, furthermore, load Σ control @ agent, fixed heron auxiliary h1]), lubricant It can also be used in combination with other 1G + fatty binder - 1. It can also be used in combination with other 1G + fatty binders - 10 - 10 - 10 - 10 - 10 - 10 - 10 - can be used in combination. Possible. In some cases, low molecules such as divinylbenzene't and c, and tK crosslinking agents may be used in combination. How many months does it take to use the dry M law method?It can be applied to various methods as a developing method.Hereinafter, it will be explained using the example IT-1.In the example, "parts" refers to parts by weight. Example 1 141 Stirring pigeon, temperature control, 1 drop of condenser [J-]. Into a flask equipped with 8 gases/G, 74 parts of Evogishi]vI fat (Epicote 828./manufactured by El Chemical Co.) was added and 1 drop was added. Into a funnel, charge 28 parts of acrylic, 01 part of i-rietheramine, and 05 parts of hydro-non, and blow in an empty Ct. By continuing to heat the knife until the value reaches around 3, epoxy acrylate (modified epoxy 4a fat has a molecular weight of approximately 500
) got 7. Next, one epoxy acrylate 154'
5 (J,, 2 parts of penzoyl peroxide is mixed with styrene (
st) 607fll, methyl methacrylate (MMA)
) 30 parts, butyl methacrylate l/-) (BMA) 60
Polyvinyl alcohol (
GH-20, Japan Go, Nozomi Kagakusha) 0.2% water bath 'f'
t: Add 350 parts, stir to disperse, and react at 85°C for about 8 hours while blowing nitrogen gas to form a burl-shaped polymer (softening temperature 74°Cr TMA method).101
child. 90 parts of the above polymer, 55 parts of metal-containing gL dye, 5 parts of carbon black, heated, mixed with nerol for 2 to 4 hours, and then ground to produce a toner having an average particle size of about 12 μm, which was used as a sample. On the other hand, in place of the above-mentioned torago salary, 828゜24 parts't
st/MMA/2EliA = 113/15/22
150 parts of a polymer of 150 parts V was blended with 1. Except for this, a toner with an average size of 12 μm was prepared by exactly the same procedure. Two types of developers were prepared by mixing 95 parts of carrier iron powder with an average size of about 150 μm each, and used for the development of these. Coated with Polymer silica (manufactured by Devon)
As a result of repeated desaturation using test duplication performed by contact at 70°C (190°C), the comparative sample was found to have offset prevention + I = /, and a nuclear seal on the surface of the silicone oil roller made in 1. However, an offset phenomenon occurs from the beginning. On the other hand, we carried out 6'll trials (1) fixing without silicone oil (7 ronon tape peeling trial), offset phenomenon (
Visual judgment of the surface of the heat roller) showed good results. Further, the obtained image was good with no background stains. Example 2 Epoxy J B'Ft (Epicor) 1004. Chez 13
- 300 parts (manufactured by Le Chemical Co., Ltd.), 20 parts of maleic anhydride and 213 parts of Butylseron Lube were heated and reacted at 130° C. for 4 hours to give an acid value of 14. The resulting reaction solution was stripped to remove most of the butyl cellosolve, and the same modified epoxy (partially 1,700 molecule) resin was obtained. This 4i1 Ba ¥1.
Except for using 5 parts, the above-mentioned poor combination 50 parts S powder ・15 Part Nigrosine dye 5 parts The above composition was prepared using a pressure kneader (opened at 2 o'clock, after grinding, cooled and crushed) to obtain toner having an average particle size of about 15 .mu.m. Use this toner as a flow improver. Fine powder 7 lica'f! : Dry mix 0.3% and make one final toner. A monopolymer crosslinked with 15 parts of divinylbenzene was used in place of the modified epoxy resin as the ratio ζ19, and a toner having an average diameter of about 15μ was obtained with the same composition except for one. This toner comparison 14- Samples were evaluated for dispersion Iff, uniformity, thickness, and the results are shown in Table 1. Melting, Firno, compared to [Hll,? Dihinylbenzene, which is a cross-linking agent, does not disperse the coloring agent sufficiently in the case of narrow cross-linking intervals.On the other hand, in the present invention (Example), the thermal melting of the heptad polymer 1.1: is also more difficult to stomach than in the comparative example. It seems that the elbow coloring agent is sufficiently dispersed (1).For the reasons mentioned above, as shown in Table 1, 'J!: The application has good fixing properties, high electrostatic stitching, and good two-stroke 'rR. The results are as follows.Instead of the modified epoxy pattern resin used in Example 1. Showa Kobunshi (epoxy acrylic manufactured by ◇) sP 40
Polymer 7 with a softening temperature of 66°C was obtained by using 15 parts of 10 (Uy value 3 or less) and reacting with iC in the same manner as above. 95 parts of the above polymer 5 parts of carbon black After kneading for 5 hours in the above set HZ heating kneader, about
Powder l-naan with an average particle diameter of 171 was produced and was successful. Add 10 parts of toner to 90 parts of 100μ carrier powder.
) Add 1 dressing and 1 piece. Performed using this developer (
'I 1 and the same method as the fixed 1st offseno l-
I checked the temperature range for about 1 noon, and it was 1300C~20.
It has been found that both fixing and offset are good at a roller surface temperature of 0°C. Example 4 In a stirred graded stainless steel reactor, 250 parts of styrene, 50 parts of butyl acrylate, 0.01 part of modified Ebony/Taka obtained in Example 1], 3 parts of lauryl mercaptan, Add 10 parts of azobisin butyronitrile, heat at 85°C for 3 hours, then heat to 130°C for 7 hours. Shifko. (Softened 1st and temperature 62°C) Ail: Polymerization 1: 95 parts Carbon black: 5 parts: 1: 5” Carry out using a lby ladle. Same as 3 (2,
Powder toner 1 (prepared and tested, this 1)
The constant lubricity and offset due to the body tonneau are both good.
) ivy. For patent use, 4 people Toyo Ink Manufacturing Co., Ltd. 171

Claims (1)

[Scope of Claims] 1. A vinyl monomer and a modified epoxy resin having an average of 11 or more per 71 molecules of unsaturated groups copolymerizable with the monomer. 2. A vinyl polymer t used as a binder. A powder toner characterized by: 2. The powder toner according to claim 4, g1, wherein the modified epoxy resin has a molecular weight of 350 to 5,000. 3 Modified epoxy resin is added to 0.0% of the monomer
The powder toner according to claim 1 or 2, which uses 05-50 Juryu Ame.