CN1007662B - Toner composition for electrofax - Google Patents
Toner composition for electrofaxInfo
- Publication number
- CN1007662B CN1007662B CN 87101835 CN87101835A CN1007662B CN 1007662 B CN1007662 B CN 1007662B CN 87101835 CN87101835 CN 87101835 CN 87101835 A CN87101835 A CN 87101835A CN 1007662 B CN1007662 B CN 1007662B
- Authority
- CN
- China
- Prior art keywords
- toner
- vibrin
- molecular weight
- composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
The invention is characterized that the main component a urethane-modified polyester resin obtained by reacting a polyester resin with an isocyanate compound, in which the mole-equivalent ratio between the hydroxyl group of the polyester resin and the isocyanate group of the isocyanate compound is within a specific range and the glass transition temperature of the obtained resin is within a specific range. This composition has a good fixing property at a low temperature and a good offset resistance at a high temperature, and this composition is especially excellent in the form of a mixture with a polymer having a relatively low molecular weight.
Description
The present invention is relevant with composition having toner particeles for electrophotography.
In electrofax, print speed is an important problem.If machine itself is designed to quick print, can deals with substantially, but, depend merely on it and just can not deal with problems in order to be implemented in print fast under the situation of guaranteeing the print picture.That is to say, must improve the character, the particularly character of toner wherein of used apparent phase material.
But traditional toner may not necessarily satisfy the requirement of high speed print.It the reasons are as follows, when print fast, the heat that the toner-particle on the photographic paper is accepted from the heat fixation cylinder lacks during than low speed, and the speed that photographic paper is captured heat from the heat fixation cylinder increases, its result, heat fixation cylinder surface temperature sharply descends, and makes the fixedly deterioration of toner.Therefore, requirement can be fixed with lower heat, and requires not take place under this fixed temperature and fixed speed inconsistent phenomenon, but is that the tacky resin of main body and toner that carbon black is formed are difficult to realize this goal really with traditional styrene.
As the way that addresses this problem, for example there is on resting barrel coating silicone oil prevent the method that misplaces.Though use this method, when preventing liquid as not adding dislocation at regular intervals, then also inconsistent phenomenon can take place lentamente, finally be absorbed in dislocation fully.Therefore,, must append silicone oil etc. continually, promptly must spend very large labour and carry out so-called maintenance job in order to prevent the reduction of image quality.And the heat ageing product of oil can pollute printer inside, is a big problem in the practicality.
Open in clear 49-101031 number the spy, putting down in writing the method that makes the anti-dislocation property of the crosslinked improvement of a part of tacky resin.This method is the chain reaction that radical reaction causes because of the cross-linking reaction that vinyl monomer forms, and is difficult to control.And, even it can prevent the inconsistent phenomenon under the high temperature to a certain extent, also because of the rising of minimum fixed temperature meanwhile, make the polyvalent carboxylic acid who fixedly becomes described herein under low in calories, malonic acid for example, succinic acid, glutaric acid, hexane diacid, azelaic acid, decanedioic acid, aliphatic dibasic acids such as hexahydro phthalic anhydride, maleic acid, maleic anhydride, fumaroyl, methylene succinic acid, aliphatics unsaturated dibasic acids such as citraconic acid, and phthalate anhydride, phthalic acid, terephthalic acid (TPA), aromatic acid and their lower alkyl esters such as isophthalic acid, wherein, be best with aromatic acid and/or their lower alkyl esters.
Said herein multivalence alcohol, can give an example as ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1,3 butylene glycol, 1,4-butylene glycol, 1, the dibasic alcohol of 6-hexanediol, neopentyl glycol, diglycol, dipropylene glycol, hydrogenation bisphenol-A, bisphenol-A epoxy ethane condiment, bisphenol-A epoxy propane condiment etc., and the trihydroxy alcohol of glycerine, trimethylolpropane, trimethylolethane etc.Wherein, pay with bisphenol-A epoxy propane that to add thing be the best.
Polycondensation method adopts known high-temperature polycondensation method, solution polycondensation method etc. usually, for example, condensation temperature 200-250 ℃, polymerization time 3-20 hour.
The usage rate of polybasic carboxylic acid and polyvalent alcohol, the latter's hydroxyl is generally 0.8-1.4 to the ratio of the former carboxyl.And its number-average molecular weight of molecular weight of this vibrin (A) is 1000-15000.When the number-average molecular weight less than 1000 of (A), the anti-dislocation reduction of the urethane-modified polyester of gained (C), if than 15000 big, vibrin (A) during with polyisocyanate (B) reaction viscosity significantly increase, unfavorable to making.And the reduction of the stationarity of urethane-modified resin (C), also bad.Number-average molecular weight is very excellent in the thermotolerance of the urethane-modified vibrin of scope gained (C) of 6000-10000, in toner was produced, molecular weight reduced hardly when high-temperature fusion is mixing, and anti-dislocation property is good, and veil does not take place in picture, is of extra fine quality.Be lower than 6000 as number-average molecular weight, the molecular weight of urethane-modified resin (C) reduces when melting mixing, and the tendency that veil takes place, reduce anti-dislocation property is arranged.
In addition, polyisocyanate among the present invention (B), HDI is for example arranged, difficulty is if realistic existing quick print has to fixed temperature is heightened, but raising fixed temperature, exist printer electrical equipment capacity and can not improve and cause the aging variety of issue that waits of photographic paper, so, be difficult to realize quick print with such method.
In addition, open in clear 59-50448 number, disclose the unsaturated polyester nitrogenous in the composition main chain and the toner of vinyl monomer copolymer resins the spy.This resin is also made by radical polymerization, has same problem so open clear 49-101031 number with the spy.
Purpose of the present invention provides a kind of maintenance of may not request, and with print low in calories and quick, and often stable high quality is drawn the composition having toner particeles for electrophotography of phase.
The inventor etc. have carried out research with keen determination in order to finish above-mentioned problem, found that to make the urethane-modified vibrin of isocyanate reaction gained have under the low temperature stationarity good in vibrin, the anti-down dislocation performance of high temperature is also good, particularly in the mixture of polymers of itself and lower molecular weight, can find out the fact that performance is particularly excellent, thereby finish the present invention.Promptly, the present invention is an electrophoto-graphic toner, it is characterized by, the isocyanate compound (B) that makes the 0.05-0.95 molar equivalent and the number-average molecular weight that 1 molar equivalent hydroxyl is arranged are that vibrin (A) reaction of 1000-15000 makes urethane-modified vibrin (C), the glass temperature of this resin (C) is 40-80 ℃, electrofax tinter composition as major component, and the isocyanate compound (B) that makes the 0.05-0.95 molar equivalent is vibrin (A) reaction of 1000-15000 with the number-average molecular weight that 1 molar equivalent hydroxyl is arranged, the urethane-modified vibrin (C) of gained, the glass temperature of this resin (C) is 40-80 ℃, and contain the polymkeric substance that number-average molecular weight is 1000-10000 (D), press (C): (D) weight ratio is 30: 70-95: 5 mix, its glass temperature is 40-80 ℃ a resin compound (E), is the composition having toner particeles for electrophotography of major component with (E).
Be used to implement optimal morphology of the present invention:
Vibrin described in the present invention (A) is the condensed polymer by polyvalent carboxylic acid and multivalence alcohol.The diisocyanate of isophorone diisocyanate, toluene support diisocyanate, methyl diphenylene diisocyanate, xylylene diisocyanate, tetramethylbenzene diformazan diisocyanate etc., following (1)-(5) but shown in 3-6 functional group's polyisocyanate illustration as the back:
Among the figure, R
1Expression is from H-, CH
3-, CH
3CH
2-in optional a kind of base, R
2Table expression is from-(CH
2)
6-,
In optional a kind of or several are basic (but with R in the same form
2Identical also can, inequality also can).
The common amount ranges of isocyanate compound (B) is that the vibrin (A) of 1 molar equivalent hydroxyl is joined the 0.05-0.95 molar equivalent.Quantity not sufficient 0.05 molar equivalent as isocyanate compound (B), the anti-dislocation reduction of toner, as surpassing 0.95 molar equivalent, viscosity significantly improves when making reaction again, cause the gelation of urethane-modified vibrin (C) sometimes, the poor quality.
The OK range of isocyanate compound (B) consumption when using diisocyanate, is the 0.3-0.95 molar equivalent from the requirement of anti-dislocation property, and optimum range is the 0.4-0.9 molar equivalent.When using 3-6 functional group isocyanates, come requirement from resisting dislocation property and being easy to manufacture view, OK range is the 0.05-0.3 molar equivalent, optimum range is the 0.1-0.25 molar equivalent.
The available following method of urethane-modified vibrin (C) is produced.For example, with isocyanate compound (B), 80-150 ℃ next time or divide several to drop into independent vibrin (A), or contain in the solution of vibrin (A), stoichiometric number hour can be made.
Among the present invention, can use urethane-modified vibrin (C) separately, if but be that the polymkeric substance (D) of 1000-10000 is when share with it with number-average molecular weight, then the comminuted of problem place can be improved in the toner manufacture process, and the stationarity under the low temperature also can improve, and is even more ideal.As polymkeric substance (D), can give an example as vibrin or ethylene copolymer.
Can use the vibrin that makes with quadrat method with vibrin (A) about vibrin, used polybasic carboxylic acid and polyvalent alcohol, identical with example in the vibrin (A), also can enumerate here.Best vibrin is the condensation product of bisphenol-A epoxy propane condiment and terephthalic acid (TPA) (dimethyl).Molecular weight is best during as 1000-5000 with number-average molecular weight when using vibrin, and is better during 2000-4000.During number-average molecular weight less than 1000, with its anti-dislocation property reduction of toner of resin compound (E) gained, undesirable, as surpassing 5000, the gained toner is also bad, and its stationarity is poor.
As ethylene-based polymer, with undertaken by vinyl monomer copolymerization gained number-average molecular weight be the multipolymer of 2000-10000 for well, methods such as common available block polymerization, solution polymerization, suspension polymerization, emulsion polymerization are produced.
So-called herein vinyl monomer, can give an example as styrene, aromatic ethylene compounds such as α-Jia Jibenyixi, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, acrylic acid-2-ethyl caproite, the acrylic acid octadecane, the acrylic acid dodecane, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, methacrylic acid-2-Octyl Nitrite, the methacrylic acid octadecane, the methacrylic acid dodecane, acrylic acid, methacrylic acid, 2-Hydroxy ethyl acrylate, (methyl) acrylate of methacrylic acid-2-hydroxy methacrylate etc., vinyl cyanide, vinyl chloride, vinyl acetate, vinyl propionate, methacrylonitrile, acrylic acid amides, methacrylic acid acid amides etc., best vinyl copolymer are the multipolymer of styrene and (methyl) alkyl acrylate.
The molecular weight of above-mentioned vinyl copolymer is advisable with number-average molecular weight 2000-10000, is best with 3000-6000.Bad by the toner qualities of resin compound (E) gained during less than 2000, its anti-dislocation property and the anti-property stopped up all have reduction, but as surpass at 10000 o'clock, the comminuted reduction of resin compound (E), quality is also bad.
Urethane-modified vibrin (C) in the resin compound (E) and the content ratio of polymkeric substance (D), in weight ratio (C): be 30 (D): 70-95: 5, with 40: 60-70: 30 for well.The 30%(weight that adds up to less than both at the content of urethane-modified vibrin (C)) time, poor quality with resin compound (E) gained toner, its anti-dislocation property reduction, and the 5(weight that adds up to less than both at the content of polymkeric substance (D)) during %, the comminuted deterioration of this toner.
In addition, the glass temperature of urethane-modified vibrin (C) and resin compound (E) is 40-80 ℃, with 50-70 ℃ for well.The toner performance of anti-blockage worsened when glass temperature was lower than 40 ℃, the poor quality, if surpass 80 ℃, the fixed performance of toner worsens, and is also bad.
Resin compound (E) for example can following method be produced.With urethane-modified vibrin (C) individually or contain the solution of urethane-modified polyester (C), with polymkeric substance (D) individually or the solution that contains polymkeric substance (D) to scale, in flask, mix, can heat in case of necessity, then, be the foul smell of removing unnecessary solvent, remaining monomer and producing because of heat ageing, available high temperature high vacuum.As solvent, for example can adopt toluene, dimethylbenzene or cyclohexanone etc.
The most general method as the composition having toner particeles for electrophotography of producing the present invention, can give an example as, urethane-modified vibrin (C) or above-mentioned resin compound (E) are ground into the particle of the about 0.5-2mm of particle diameter, add carbon black then, if necessary, also to add acrylic resin, styrene resin, epoxy resin, cis-1 rosin, petroleum resin, colorant, ferrite, magnetic powder such as magnet body, and a spot of electric charge is adjusted agent and cured, after mixing such as He Xier blender, with kneading machine etc. at 100-180 ℃ of following melting mixing, with the gained bulk materials through pulverizing, classification just obtains the particulate that particle diameter is 5-20 μ m.The amount of urethane-modified vibrin (C) or resin compound (E) is generally 50-99wt% in the toner when not adding magnetic, is generally 10-99wt% when adding magnetic.
Toner by the present invention's composition gained, the single component series toner that contains the magnetic powder is arranged, or mix the two component system row toner that uses with carrier, be excellent product, when low in calories and high speed print, can provide stay-in-grade high-quality picture, and, need not extraordinary repair, be suitable for the toner of quick print really.
Below, in explanation the present invention in the manufacturing example of used vibrin (A), urethane-modified vibrin (C) and resin compound (E), illustrate with them and the performance embodiment of electrophotography developer, thereby illustrate in greater detail the present invention.In addition, except that specifying, be parts by weight about umber.
Embodiment 1-9
(the Production Example A1-A9 of vibrin (A))
On 10l4 mouth flask, dress is with reflux cooler, water separation device, nitrogen inlet tube, thermometer and stirring apparatus, and the polybasic carboxylic acid and the polyvalent alcohol of the weight ratio shown in the adding table 1, and as the Dibutyltin oxide of the 0.05wt% of catalyzer, on one side in flask, feed nitrogen, the polycondensation reaction of in bottle, dewatering under 240 ℃ of the temperature.
Reach 1 at acid number and cool off when following, promptly get the vibrin (A) of character shown in the table 1.
(the Production Example C1-C9 of urethane-modified vibrin (C))
The vibrin (A) of weight ratio shown in the dress table 1 adds 10l4 mouth flask with dimethylbenzene, flask is equipped with reflux cooler, nitrogen inlet tube, thermometer and stirring apparatus, after the dissolving, feeding nitrogen stream, when temperature is 120 ℃ in the bottle, press weight ratio shown in the table 1, isocyanate compound is divided into four parts, per hour divide 4 times and add flask, under uniform temp, make it to react 1 hour then.Then on flask, load onto solvent separation unit, slowly the interior temperature of bottle raises, under normal pressure, heat up in a steamer removal xylene, refill reliever, in bottle, heat up in a steamer volatile component fully under 190 ℃ of temperature, the interior pressure 10mmHg, just must have the urethane-modified vibrin (C) of character shown in the table 1.
(toner Production Example 1-9)
After with the hammer grinding machine urethane-modified vibrin (C) the C1-C9 coarse crushing of such gained being become the particle of particle diameter 0.5-2mm, by resin (C) weight is 100 parts, carbon black MA-100(Mitsubishi is changed into industry (strain) system) 5 parts of weight, as 2 parts of " Si Pailonghei TRH " (hodogaya chemical (strain) system) weight of charged adjustment agent, polypropylene-based cured, 2 parts of " Viscor 550P " (Sanyo change into industry (strain) system), bisamide is cured " the cured EBS of Ah not " (reining in the Ang Amashe system) 3 parts, in the He Xier mixer after the dispersing and mixing, under 1600 ℃, in biaxial mixing machine PCM30(pond shellfish ironworker (strain) system) go up melting mixing and promptly get block method for producing toner and toner.
With said composition hammer mill coarse crushing, use jet mill (the Japanese Niu Maqike system IDSZ of society type) fine powder broken then, then with gas flow sizing machine (the Japanese Niu Maqike system DS-Z of society type) classification, obtain accounting for 3wt% below the mean grain size 10 μ m(5 μ m, account for 2wt% more than the 20 μ m) toner-particle.With this toner-particle weight is 100 parts, add to mix hydrophobic silica micro mist R-972(Japan Chinese mugwort Ah family Xi Er society system inward) 0.4 part, just must test and use toner 1-9.
With this toner weight is 4 parts, makes it and ferrite carrier F-150(Japan iron powder (strain) system) 96 parts mix, be the two component system photographic developer.
With commercially available magnetic brush type printer (Toshiba's (strain) row Duola difficult to understand she 8411), make hot bowl temperature change the fixed performance as a result that institute's print of doing tests and be shown in table 1.
Picture characteristic when table 1 also has seal to 50,000 with fixing after the situation of the anti-vinyl chloride plasticizer of toner animal migration.
In addition, this toner was comminuted when the thermal stability of this resin and fine powder were broken in the mixing operation when method for producing toner and toner is made, and also was shown in table 1 with the performance of anti-blockage of gained toner.
As understand from the result of table 1 like that owing to adopt the obtained toner of the present invention, can provide good picture in the necessary abundant wide temperature range of print fast.
In addition, the anti-obstruction of this toner, thermotolerance and anti-vinyl chloride plasticizer migration performance are also fine, comminuted might as well, unlikely formation problem aspect practical.
Embodiment 10-21
With the same method shown in the embodiment 1-9, produce vibrin (A) A10-A21 and urethane-modified vibrin (C) C10-C21, the character of these resins is shown in table 2.
, with the urethane-modified vibrin of gained (C) C10-C21, produce toner 10-21 with the same method shown in the embodiment 1-9 herein, its performance test the results are shown in table 2.
As from table 2 finding, no matter be any toner, its anti-property stopped up, anti-vinyl chloride plasticizer animal migration are all good.Comminuted also good, can protect the practical no problem of going up.But thermotolerance, anti-dislocation property with by screen degree different with the molecular weight of used vibrin (A), performance changes to some extent, reduce as molecular weight, then thermotolerance worsens, it is the anti-dislocation mis-behave of toner as a result, may be simultaneously to worsen owing to carbon black, charged adjustment agent disperse bad causing by the screen degree.
From the result of table 1 and table 2 as seen, use is during by the urethane-modified resin (C) of vibrin (A) gained of molecular weight more than 6000, in the operation of mixing of toner manufacturing, heat ageing takes place in this resin hardly, do not call together and cause molecular weight and reduce, so can keep its anti-performance and image quality of misplacing good.
Embodiment 22-25
With with the identical manufacture method of the vibrin (A) shown in the embodiment 1-9, with the polyvalent alcohol and the polybasic carboxylic acid of parts by weight shown in the table 3, produce vibrin (A) A22-A25, the character of gained vibrin (A) A22-A25 is shown in table 3.
Secondly, with vibrin (A) A22-A25 and isocyanates, with with the same method of urethane-modified vibrin (C) manufacture method shown in the embodiment 1-9, produce urethane-modified vibrin (C) C22-C25, the character of gained resin C is shown in table 3.
With urethane-modified vibrin (C) C22-C25, to produce toner 22-25 with method same shown in the embodiment 1-9, table 3 illustrates the result to its performance test of doing.
As by known to the table 3, no matter be which kind of toner, but its fixed temperature scope is all very wide, is suitable for quick print, and the performance of its anti-property stopped up, anti-vinyl chloride plasticizer is also fine.
In addition, it is comminuted also good, can be no problem in practicality.Aspect thermotolerance, toner-22,23 is aging serious, compares with toner-24,25, and its anti-dislocation performance is also poor, also has picture by screen.Toner-24,25 has excellent thermotolerance and picture characteristic.
Table 3
Embodiment 22 23 24 25
A22 A23 A24 A25
KB300K (parts by weight) 626 297 454 358
Vibrin (A) diglycol (parts by weight) 193 92 140 110
Isophthalic acid (parts by weight) 465 249 398 332
Dehydrating amount (parts by weight) 101 54 86 72
Acid number＜1＜1＜1＜1
Hydroxyl value 93 47 30 19
Mn 2000 4000 6300 9700
Mw 4400 9200 15100 24000
C22 C23 C24 C25
Vibrin (A) (parts by weight) 1,000 1,000 1,000 1000
Urethanes dimethylbenzene (parts by weight) 1,000 1,000 1,000 1000
Modified polyester resin isocyanates (18) (parts by weight) 101 47 26 8.3
NCO/OH 0.25 0.23 0.2 0.1
Mn 4200 5600 8000 11000
The property Mw 135,000 138,000 145,000 130000 of resin (C)
Matter Mw/Mn 32 25 18 12
Tg（℃） 60.5 61 59.7 59.7
The anti-property stopped up ◎ ◎ ◎ ◎
Comminuted ◎ ◎ 00
The performance thermotolerance of toner * △ ◎ ◎
Fixed temperature 135 142 145 160
Dislocation initial temperature 230 250 250＜250＜
Picture concentration is dense
By screen * △ ◎ ◎
Anti-vinyl chloride plasticizer animal migration ◎ ◎ ◎ ◎
Embodiment 26-36
(the Production Example D1-D5 of polymkeric substance (D))
With with the same method of manufacture method of the vibrin (A) shown in the embodiment 1-9, by Dibutyltin oxide synthetic polymer (D) D1-D4 of polyvalent alcohol, polybasic carboxylic acid and the 0.05wt% of parts by weight shown in the table 4, table 4 illustrates the character of resulting polymers (D).
In addition, in above-mentioned manufacture method, without dehydration, and carry out condensation with separating methanol reaction, without Dibutyltin oxide, and with the positive metatitanic acid n-butyl of 0.05wt% as ester exchange catalyst, other is all the same as same method synthetic polymer (D) D5, the character of resulting polymers (D) is shown in table 4.
(the Production Example E1-E11 of resin compound (E))
Press the parts by weight shown in the table 5, with urethane-modified vibrin (C) C1 synthetic among the embodiment 1,7,24, C7, polymkeric substance shown in C24 and the table 4 (D) D1-D5 adds in the 10l releasable flask with the dimethylbenzene of parts by weight 100, and temperature is after 120 ℃ dissolving mixes down in bottle, to heat up in a steamer removal xylene with the same method shown in the embodiment 1-9, with 190 ℃, the high temperature of 10mmHg is handled then, gets resin compound (E) E1-E11.
The character of gained resin compound (E) E1-E11 is shown in table 5 herein.
(toner Production Example 26-36)
With resin compound (E) E1-E11, produce toner 26-36 by identical method shown in the embodiment 1-9.
Table 5 shows the result with toner 26-36 testing.
Toner 26, though practical no problem, the anti-property stopped up dislikes not enough slightly, and other is then fine as fixed performance, picture characteristic, and thermotolerance is also very excellent.In addition, compare with embodiment 1-25 gained toner, toner 26-36's is comminuted good, toner is easy to manufacture, and yield height, in addition, but low fixed temperature and enough fixed temperature scopes are widely arranged, the very good properties of using as print is fast arranged.
(resin compound (E) Production Example E12-E23)
With urethane-modified vibrin (C) C10-21 synthetic among the embodiment 10-21, with the polymkeric substance shown in the table 4 (D) D5, by the parts by weight that are shown in table 6, and add in the 10l releasable flask with the dimethylbenzene of 100 parts by weight, temperature is heated up in a steamer removal xylene with the same method shown in the embodiment 1-9 after 120 ℃ dissolving mixes down in the bottle, then, with 190 ℃, the pyroprocessing of 10mmHg gets resin compound (E) E12-E23.
The character of gained resin compound (E) E12-E23 is shown in table 6 herein.
(toner Production Example 37-38)
With resin compound (E) E12-E23, produce toner 37-48 with the same method shown in the embodiment 1-9.
Table 6 shows the result with toner 37-48 testing.
With regard to its anti-property stopped up, comminuted and anti-vinyl chloride plasticizer animal migration, no matter which kind of toner has all shown excellent performance, but the thermotolerance of toner 37-40 and 42-46 is not quite enough, and picture is random, and its anti-dislocation property reduction.
In contrast, contain vibrin (A) A14, A22 and urethane-modified vibrin (C) C14, the C22 of A23 manufacturing and the toner 41,47 and 48 of C23 of useful number-average molecular weight more than 6000, thermotolerance is good, possible fixed range is also wide, picture is also fine, has the performance of the excellence that is suitable for quick print.
Embodiment 48-58
(polymkeric substance (D) Production Example D6-D10)
On 10l4 mouth flask, load onto reflux cooler, nitrogen inlet tube, thermometer and monomer dripping device, press parts by weight shown in the table 7 and add dimethylbenzene, be warming up to till the refluxing xylene.
When refluxing xylene (temperature is 140 ℃ in the bottle), one introduces nitrogen in flask, simultaneously, splash into monomer and polymerization initiator from the monomer dripping device by parts by weight shown in the table 7, drips continuously 4 hours.
After dripping off, 140 ℃ kept 2 hours in the bottle, and non-volatile value is cooling off afterwards more than 99% of theoretical value in confirming solution, and with the dimethylbenzene dilution of parts by weight shown in the table 7, making reacts completely stops.
The polymkeric substance (D) that removes volatile matter such as removal xylene from the xylene solution of polymkeric substance (D) with high temperature decompression of gained herein, its character is shown in table 7.
(resin compound (E) Production Example E23-33)
With embodiment 1,7 and the urethane-modified vibrin of 24 gained (C) C1, C7 and C24, with the polymkeric substance with character shown in the table 7 (D) D6-D10, add in the 10l releasable flask by the parts by weight that are converted into solid state component weight shown in the table 8, after temperature is dissolved down for 120 ℃ and is mixed in the bottle, heat up in a steamer removal xylene with the same method shown in the embodiment 1-9, with the high temperature reduced pressure treatment, promptly get resin compound (E) E23-E33 then.
Table 8 illustrates the character of gained resin compound (E) E23-E33 herein.
(toner Production Example 48-58)
With the same method shown in the embodiment 1-9, E23-E33 produces toner 48-55 with resin compound (E).
Table 8 shows the result with toner 48-58 testing.By known to the table 8, no matter be which kind of toner, all have the necessary enough wide fixed temperature scope of quick print, picture characteristic, the anti-property stopped up, thermotolerance with comminuted aspect all have the performance of excellence.
Table 7
Polymkeric substance (D) D6 D7 D8 D9 D10
Polymer solvent dimethylbenzene (parts by weight) 150 150 100 80 60
Styrene (parts by weight) 40 40 40 40 40
Vinyl monomer methyl methacrylate (parts by weight) 57 45 33 22 33
Ethyl propylene acid esters (parts by weight) 3 15 27-27
Second-ethylhexyl ester first (parts by weight)---33-
The base acrylates
Methacrylic acid (parts by weight)---5-
The polymerization initiator tert-butyl is crossed caprylate 8.0 5.0 2.5 2.0 1.0
（
-ブテルバ-オリトエ-ト）
(parts by weight)
Diluting solvent dimethylbenzene (parts by weight) 50 50 100 120 140
Polymerization temperature (℃) 140 140 140 140 140
Interpolymer character Mn 2,200 3,100 4,300 6,200 9500
Mw 4900 7400 10000 15000 23000
Mw/Mn 2.4 2.4 2.4 2.4 2.4
Tg（℃） 57.8 60.4 58.0 59.0 61.5
Embodiment 59
Resin compound (E) E10 that is produced with embodiment 35, need not " Si Pailong " the black TRH of charged adjustment agent and be EX(hodogaya chemical (strain) system C, I solvent black 7 with nigrosine), parts by weight are 2, make positively charged toner 59 with other method identical with embodiment 35.
With commercially available printer SF-900(Sharp (strain) system), make its resting barrel temperature variation, the preparing condition of photographic developers such as carrier is carried out the evaluation identical with embodiment, its result is shown below.
Table 9
Embodiment 59
Resin compound (E) № E10
The anti-property stopped up ◎
Comminuted ◎
Thermotolerance ◎
The lower limit fixed temperature (℃) 136
The dislocation initial temperature (℃) 250＜
Picture concentration is dense
By screen ◎
Anti-vinyl chloride plasticizer animal migration ◎
By known to the table 9, with resin compound (E) but positively charged toner that E10 produced 59 and electronegative property toner 35 have the low lower limit fixed temperature that is suitable for quick print and wide fixed temperature scope equally, its anti-property stopped up, comminuted, thermotolerance and anti-vinyl chloride plasticizer animal migration be excellence also, can provide the second best in quality picture.
The note meaning is as follows in the table:
1) biphenol A-(2.2)-epoxypropane condiment (chemical industry (strain) system is pressed in Mitsui east)
2) JIS(Japanese Industrial Standards) K5400 method
3) pyridine-acetic anhydride method
4) being standard with single decentralized standard polystyrene, is eluant with the tetrahydrofuran, with index meter as detecting device, the number-average molecular weight of asking for by gel permeation chromatography (GPC).
5) with 4) the identical method weight average molecular weight of trying to achieve.
6) with 4) the identical method molecular weight distribution of trying to achieve.
7) diphenyl methane-4.4-diisocyanate.
8) the isocyanic acid alkali molar equivalent of isocyanates (B) is to the ratio of the hydroxyl molar equivalent obtained by the hydroxyl value of vibrin (A).
9) glass temperature of obtaining by differential scanning calorimeter (DSC).
10) toner that will produce is placed after 24 hours in the environment of 50 ℃ of temperature, humidity 60%, estimates its powder cohesion degree, judges by following mark.
◎: there is not cohesion fully,
Zero: little have cohesion, but vibration container is just loose gently,
△: even firmly vibration container also has not loose condensation product,
*: lump fully.
11) be that the yield of the particle of 5-20 μ m is done following judgement to broken, the classified gained particle diameter of micro mist.
◎: yield is more than 90%,
Zero: yield 80%-less than 90%,
△: yield 70%-less than 80%,
*: yield less than 70%.
12) through twin shaft muller (PCM-30, pond shellfish ironworker (strain) system) the mix toner of gained of fusion under the temperature of mixing 160C, 2 minutes the condition of mean residence time, be dissolved in the acetone, make resin (C) or (E) outside indissolvable component separate with centrifugal settling after, the urethane-modified resin (C) or the molecular weight (E) of gained are measured with GPC.
The reduction degree of resin after will mixing (C) or weight average molecular weight (E) with mix before compare, judge as follows:
◎: the reduction of weight average molecular weight is less than 5%,
Zero: weight average molecular weight be reduced to 5% to less than 10%,
△: weight average molecular weight be reduced to 10% to less than 20%,
*: being reduced to more than 20% of weight average molecular weight.
13) with learning the formula friction fastness test-run a machine (the smart device of (strain) Daiei science is made made) that shakes, with 125g/cm
2Loading, behind toner that the base plate black of 2cm * 2cm is partly drawn go up mutually and the sand rubber friction 50 times, the weight survival rate of its toner layer surpasses 80% necessary minimum heat fixation cylinder surface temperature.
14) the fusion toner invests on the heat fixation cylinder, is fixed in the minimum heat fixation cylinder surface temperature that so-called inconsistent phenomenon takes place beginning on the photographic paper once more.
15) picture that adds after 50,000 of the prints is gone up the black level at range estimation base plate black position mutually.
16) picture that adds after 50,000 of the prints is gone up mutually, and range estimation is attached to the white white ground contamination degree that causes because of toner on the ground of background.
◎: pollution-free,
Zero: little pollution is arranged less,
△: suitable pollution is arranged,
*: seriously polluted,
17) commercially available polyvinyl chloride film (phthalandione two octanes that contain 50wt%, chemistry (strain) system is pressed in Mitsui east) is overlapped on the base plate black position of 5cm * 5cm, loads 20g/cm
2, 50 ℃, leave standstill 24 hours after, stripping film under room temperature, range estimation this moment toner to the transition state of vinyl chloride film, judge as follows:
◎: can't see the migration of dyestuff and toner fully,
Zero: dye migration only,
△: the migration of part toner,
*: most of toner migration.
18) Sumitomo Bayer (strain) system triphenylmethane tri isocyanate (being converted into solid-state amount).
Claims (6)
1, a kind of electrofax tinter combination, said composition comprises the urethane-modified vibrin (C) that obtains with isocyanate compound (B) reaction of hydroxyl 0.05～0.95 molar equivalent of every mole of vibrin (A) by making that to have number-average molecular weight be 1000～15000 vibrin (A), the glass temperature of said resin (C) is 40～80 ℃, with number-average molecular weight be 1000～10000 polymkeric substance (D), (C)/(D) weight ratio is 30/70～95/5, and the glass temperature of this resin combination is 40～80 ℃.
2, a kind of composition as claimed in claim 1, polymkeric substance wherein (D) are 1000～5000 vibrin for a kind of number-average molecular weight.
3, a kind of composition as claimed in claim 2, vibrin wherein are a kind of epoxypropane condiment of bisphenol-A and the concentrate of aromatic acid and/or its lower alkyl esters.
4, a kind of composition as claimed in claim 1, composition wherein (D) are 2000～10000 vinyl copolymer for a kind of number-average molecular weight.
5, a kind of composition as claimed in claim 4, vinyl copolymer wherein is the multipolymer of styrene and aliphatics esters of unsaturated carboxylic acids.
6, a kind of composition as claimed in claim 4, isocyanate compound wherein (B) comprise the polyisocyanate compounds of 3～6 functional groups of hydroxyl 0.05～0.3 molar equivalent of every mole vibrin (A).
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53690/86 | 1986-03-13 | ||
| JP5369086 | 1986-03-13 | ||
| JP59570/86 | 1986-03-19 | ||
| JP59571/86 | 1986-03-19 | ||
| JP5957086 | 1986-03-19 | ||
| JP5957186 | 1986-03-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106089 Division CN1032009C (en) | 1986-03-13 | 1989-07-24 | Composition having toner particeles for electrophotography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101835A CN87101835A (en) | 1987-12-02 |
| CN1007662B true CN1007662B (en) | 1990-04-18 |
Family
ID=27295039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101835 Expired CN1007662B (en) | 1986-03-13 | 1987-03-12 | Toner composition for electrofax |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007662B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102621840B (en) * | 2012-03-28 | 2015-03-25 | 南京新天兴影像科技有限公司 | Develop toner for non-contact photographic fixing of engineering drawing copier |
| US9785074B2 (en) | 2014-02-04 | 2017-10-10 | Ricoh Company, Ltd. | Polyester resin for toner, toner, developer, and image formation device |
| CN104950612A (en) * | 2015-07-22 | 2015-09-30 | 武汉宝特龙科技股份有限公司 | Powdered ink for high speed printer and preparation method of powdered ink |
| CN107942627A (en) * | 2017-11-23 | 2018-04-20 | 天津市栢力迪新材料科技有限公司 | Toner adhering resin composition and its manufacture method |
-
1987
- 1987-03-12 CN CN 87101835 patent/CN1007662B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87101835A (en) | 1987-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1157635C (en) | Toner or developing electrostatic images | |
| CN1734357A (en) | Full color toner, image forming method, fixing device, developer, process cartridge, and image forming apparatus | |
| CN1521570A (en) | Toner and toner binder | |
| CN1908822A (en) | Toner, image forming method and process cartridge | |
| CN1075724A (en) | Novel polymeric amide and by the goods of its acquisition | |
| CN1017437B (en) | Continuous production of high impact polystyrene | |
| CN1808291A (en) | Magenta color toner, toner cartridge, and process cartridge and image forming apparatus using the magenta color toner | |
| CN101034265A (en) | Process for producing toner for electrophotography | |
| CN1105688A (en) | Aromatic polycarbodiimide crosslinkers | |
| CN1955850A (en) | Method of producing toner for developing electrostatic charge image, toner for developing electrostatic charge image, developer for electrostatic charge image and method for forming image | |
| CN1394298A (en) | Toner composition and method for production thereof | |
| CN1321917A (en) | Toner for electrostatic photography and image forming method using said toner | |
| CN1675592A (en) | Binder resin for toner and toners | |
| CN1166989C (en) | Dry toners | |
| CN1275102C (en) | Toner binder used for electrophotography, and toner for electrophotography | |
| CN1776534A (en) | Process for preparing toner for electrophotography | |
| CN1432568A (en) | Pigment dispersant, pigment dispersant composition, toner and its prepn process | |
| CN1416539A (en) | Toner binder and process for producing same | |
| CN100335977C (en) | Resin for toner binder and toner composition | |
| CN1975589A (en) | Toner manufacturing method | |
| CN1111019A (en) | Resin composition for electrophotographic toner | |
| CN1007662B (en) | Toner composition for electrofax | |
| CN1408079A (en) | Toner for electrostatically charged image development | |
| CN1467575A (en) | Binder resin for toner and toner | |
| CN1894635A (en) | Polyester resin for toner, toner composition and resin particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: MITSUI TOATSU CHEMICALS, LTD. TO: MITSUI CHEMICALS, INC. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: Mitsui Chemical Industry Co., Ltd. Patentee before: Mitsui Toatsu Chem. Inc. |
|
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |