CN100338532C - Method for eliminating image-forming material - Google Patents
Method for eliminating image-forming material Download PDFInfo
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- CN100338532C CN100338532C CNB991029259A CN99102925A CN100338532C CN 100338532 C CN100338532 C CN 100338532C CN B991029259 A CNB991029259 A CN B991029259A CN 99102925 A CN99102925 A CN 99102925A CN 100338532 C CN100338532 C CN 100338532C
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Abstract
A method of decoloring an image formed on a paper sheet by using an image forming material containing a color former, a developer and a decolorizer, comprising the steps of bringing a solvent into contact with the image forming material for decoloring the image, and removing the residual solvent from the paper sheet.
Description
In recent years, because OAization is universal, along with the expansion of various information data amounts, therefore the output quantity of information also and then increases.The output quantity of information is to use to show what output and the hard copy output quantity of printing machine on paper were represented.But, show output, need large-scale circuit substrate in the display part, all having problems aspect Portability and the expense.In addition, hard copy output because information increases, be used the paper as recording medium in a large number, existing problems aspect conservation of resources.And the regeneration of printing machine, duplicating machine printing will be used a large amount of bleaching agents and water, and the expense of regeneration is also very high.Therefore, the someone considers to form the paper printing information that material is made with eliminable image, eliminates the image that forms like this, and remaining blank sheet of paper is recycling, therefore can reduce the use amount of actual paper.
Have the eliminable image of heating to form material in the prior art, for example, the spy open flat 7-81236 number disclosed.This image forms material and contains colour generation compounds such as leuco dye, developer and the organic phosphoric acid compound of elimination effect is arranged.
But, use the image of these compositions to form material, can not thoroughly eliminate, be difficult to be reduced to the blank sheet of paper state.Therefore, eliminable image formation material does not also reach practicability.
Therefore, inventor of the present invention forms material for the novel image that can obtain good elimination state and the image removing method has carried out research constantly, using various compositions to make up various images that modulation obtains in this process forms materials and all can eliminate fast, and can obtain good elimination state, this is not a nothing the matter really.
Purpose of the present invention is the formation component that does not form material according to image, provides and can eliminate image fast, and can obtain the image removing method of good elimination state.
Image removing method of the present invention is characterized in that, uses the image that contains colour generation compound and developer to form the image that material forms in order to eliminate, and makes image form material and contacts the elimination image with the solvent that is dissolved with remover.
Method of the present invention is, makes the solvent that is dissolved with remover form material with image and contact, selects only remover and solvent according to image formation material, eliminates image fast and obtains good elimination effect.
Particularly, the present invention relates to the content of following aspect:
1, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said remover is made of noncrystal phase separation inhibitor of height and low noncrystal phase separation inhibitor.
2, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said image forms in the material and contains high noncrystal phase separation inhibitor, contains low noncrystal phase separation inhibitor in the described solvent.
3, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said image forms and contains low noncrystal phase separation inhibitor in the material, contains high noncrystal phase separation inhibitor in the described solvent.
4, eliminate to use the image that contains colour generation compound and developer to form the method for the image that material forms on paper, comprising:
Above-mentioned image is formed material contact the process of eliminating image with the solvent that is dissolved with remover, wherein said remover contains high noncrystal phase separation inhibitor and low noncrystal phase separation inhibitor; With
Remove the process of remaining solvent from paper.
5, each described method of aspect 1-4, high noncrystal phase separation inhibitor is made of the ring type sugar alcohol, and low noncrystal phase separation inhibitor is made of 5 Yuans that contain hydroxyl above non-aromatic ring compounds or ring type sugar alcohol derivant.
6, each described method of aspect 1-4, low noncrystal phase separation inhibitor is a terpenol.
7, after each described method of aspect 1-4, image form material and solvent contacts, heat.
8, each described method of aspect 1-4, image form in the material and contain bonding agent.
9, aspect 8 described methods, bonding agent is made of the polymer blend of polystyrene or copolymer in cinnamic acrylic ester or polystyrene and polyacrylate resin.
10, aspect 9 described methods, cinnamic ratio accounts for more than the 50wt% in the bonding agent that the polymer blend of copolymer in cinnamic acrylic ester or polystyrene and polyacrylate resin forms.
11, aspect 8 described methods, bonding agent is made of polyester or epoxy resin.
12, each described method of aspect 1-4, image form bonding agent and the alkali compounds that contains polyester or epoxy resin formation in the material.
13, each described method of aspect 1-4, image form and contain polyester or epoxy resin bonding agent that constitutes and the alkali compounds of enclosing microcapsules in the material.
14, each described method of aspect 1-4, image form the bonding agent that material contains polyester or epoxy resin formation, and solvent contains alkali compounds.
15, aspect 4 described methods, image form the bonding agent that contains polyester or epoxy resin formation in the material, contain alkali compounds and remover in the solvent.
16, aspect 4 described methods, image form the bonding agent that contains polyester or epoxy resin formation in the material, and solvent that contains alkali compounds and the solvent that contains remover are contacted with above-mentioned image formation material respectively.
Describe the present invention below in detail.
The image relevant with the present invention forms material and is to use the colour generation compound, and what developer and remover prepared can form the material that image also can be eliminated image.At first, the ultimate constituent that the image of eliminating image is formed material describes.The colour generation compound is the precursor compound that can form the pigment of color development images such as literal or figure, developer be by with the colour generation compound interact (mainly being the exchange of electronics or proton) make the compound of colour generation compound color development.In addition, remover is the compound that shows preferential compatibility in developer and the colour generation compound.In the method for the present invention, remover dissolves in the solvent that the elimination image is used.
The image that forms from these components forms the material compositional system, obtains following two states after the curing.Promptly (1) remover mixes with colour generation compound and the developer with the equilibrium solubility a great deal of only, surpassing the remaining colour generation compound of equilibrium solubility of remover and developer and remover is separated, colour generation compound and developer interact and reach the color development state, (2) amount of remover surpasses the equilibrium solubility of developer or colour generation compound, the interaction of colour generation compound and developer reduces, and forms the colour killing state.
State variation principle between this color development state and the colour killing state is as follows.Here for convenience, the mode that heating is eliminated with regard to image formation material describes.In addition, when being the flow state of fusion, suppose remover optimum solvation developer in the composition system.When room temperature, colour generation compound and developer mutually and the equilibrium state near phase-separated state of remover.At this moment, colour generation compound and developer interact promptly becomes the color development state.From then on state begins, and the composition system is heated to fusing point when above, and developer is by the remover optimum solvation of flow state, and the interaction that loses with the colour generation compound promptly becomes the colour killing state.Will be when the compositional system cooling of molten condition to be forced to solidify, remover will reclaim and amorphization above the developer of equilibrium solubility amount, at room temperature becomes colourless.Non-crystal compositional system becomes nonequilibrium condition relatively, during temperature below glass transition temperature Tg the life-span very long, if Tg is higher than room temperature, can easily not move from non-crystal state to equilibrium state.
Even make image form the method that material contacts with solvent, also basic identical with the method for heating, eliminate according to following principle.Here, image formation material contains bonding agent.The image that is about to be in color development state on the paper forms material and contacts with solvent, because the effect of solvent, bonding agent swelling or be partly dissolved, its result, make developer and remover be in the state that can more freely move, developer mixes with remover, and developer loses the interaction with the colour generation compound, and image forms the material colour killing.Afterwards, except that desolvating, because remover will reclaim and amorphization above the developer of equilibrium solubility amount, the elimination state that image forms material is fixed from paper.This elimination state is highly stable in room temperature.
According to the present invention, also can use the solvent that is dissolved with remover to form material and contact the elimination image with image.At this moment, forming material according to image selects only remover to realize eliminating fast.Advantageous particularly when the method is carried out image elimination processing to a large amount of paper that contain various images formation materials.
In addition, when using solvent to eliminate image, also can improve the quality of the paper of elimination state.The reasons are as follows, because behind the solvent contact elimination image formation material, in case the solvent gasification of bonding agent is arranged, the bonding agent porous materialization, minimizing is reflected because the light scattering effect makes in its surface.In addition, also enlarge, have image formation material and askiatic to form the material portion boundary and become indeterminate along with bonding agent enlarges image formation material.Therefore, no matter be that naked eyes are seen or touched all imperceptible image with hand and form the residual of material.
Below, describe with regard to the particular compound that can be used as image formation material composition of the present invention.
As the spendable colour generation compound of the present invention, the specifiable coloured gold amine that has or not, diaryl phthalein ketone, polyaryl methyl alcohol class, acyl group auramine class, aryl auramine class, the rhodamine B lactams, dihydroindolines, the spiro-pyrans class, glimmering hydro carbons etc. are given the electronics organism.
Concrete colour generation organic matter is specifiable to be had: crystal violet lactone (CVL), the peacock green lactone, 2-anilino--6-(N-cyclohexyl-N-the methylamino)-glimmering hydrocarbon of 3-methyl, the glimmering hydrocarbon of 2-anilino--3-methyl-6-(N-methyl-N-propyl group amino), 3-[4-(4-anilino-phenyl) aminophenyl] amino-6-methyl-glimmering hydrocarbon of 7-chlorine, 2-anilino--6-(N-methyl-N-isopropyl butyl the amino)-glimmering hydrocarbon of 3-methyl, 2-anilino--6-(the dibutylamino)-glimmering hydrocarbon of 3-methyl, the glimmering hydrocarbon of 3-chloro-6-(cyclohexyl amino), the glimmering hydrocarbon of 2-chloro-6-(diethylamino), 7-(N, the N-dibenzyl amino)-3-(N, the N-diethylamino) glimmering hydrocarbon, 3, two (diethylamino) glimmering hydrocarbon-γ of 6--(4 '-nitrobenzene amido) lactams, the glimmering hydrocarbon of 3-diethylamino benzo [a], the amino glimmering hydrocarbon of 3-diethylamino-6-methyl-7-, 3-diethylamino-glimmering the hydrocarbon of 7-xylidine base, 3-(4-diethylamino-2-ethoxyl phenenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalein ketone, 3-(4-diethylamino phenyl)-3-(1-ethyl-2 methyl indole-3-yl) phthalein ketone, 3-diethylamino-glimmering the hydrocarbon of 7-chloroanilino, 3-diethylamino-7, the glimmering hydrocarbon of 8-benzo, 3,3,-two (1-normal-butyl-2 methyl indole-3-yl) phthalein ketone, 3, the glimmering hydrocarbon of 6-dimethyl ethoxy, the amino glimmering hydrocarbon of 3-diethylamino-6-methoxyl-7-, DEPM, ATP, ETAC, 2-(2-the chloroanilino)-glimmering hydrocarbon of 6-dibutylamino, crystal violet methyl alcohol, peacock green methyl alcohol, the colourless auramine of N-(2, the 3-dichlorophenyl), the N-benzoyl auramine, the rhodamine B lactams, N-acetyl auramine, N-phenyl auramine, 2-(benzene imines ethane silicyl sulfenyl)-3,3-dimethyl indoline, N, 3,3-tri-methyl indole and benzo spiro-pyrans, 8 '-methoxyl-N, 3,3-tri-methyl indole and benzo spiro-pyrans, 3-diethylamino-6-methyl-glimmering the hydrocarbon of 7-chlorine, 3-diethylamino-glimmering the hydrocarbon of 7-methoxyl, the 3-diethylamino-glimmering hydrocarbon of 6-benzyloxy, 1,2-benzo-glimmering the hydrocarbon of 6-diethylamino, 3,6-two para-totuidine bases-4, the glimmering hydrocarbon of 5-dimethyl, phenyl hydrazides-gamma-lactam, 3-amino-glimmering hydrocarbon of 5-methyl etc.These compounds can use separately, also can two or more mixing use.Suitably select the colour generation compound can obtain the color development state of multiple color, therefore can correspondence obtain multiple color.
The spendable developer of the present invention, specifiable have phenol, phenol slaine, carboxylic metallic salt, benzo benzophenone, sulfonic acid, sulfonate, phosphoric acid, phosphate metal salt, phosphate ester acid, phosphate ester acid slaine, phosphorous acid, acid compounds such as phosphorous acid slaine.These compounds can use separately, or two or more mixing is used.
The spendable remover of the present invention preferably has good colourless property when non-crystal state.At non-crystal state is water white remover, after the color of eliminating ink, paper is reduced near original blank sheet of paper state.Because require such character, so the remover preferred molecular weight is big, and weight crystal to melt enthalpy change Δ H little, the little compound of maximum crystalline growth speed MCV.H is little if the enthalpy change Δ is melted in the crystallization of remover, and it is few that required heat energy is melted in crystallization, also is preferred from the angle of saving energy therefore.And the fusing point of preferred remover is more than 50 ℃.In addition, preferably high with developer compatibility remover for example preferably contains the compound of alcoholic extract hydroxyl group.As preferred remover, the compound of following (a)-(c) is arranged.
(a) sterol compound.The concrete example of specifiable sterol compound has cholesterol, stigmasterol, pregnenolone, anadrol, estradiol, benzoic ether, the table androstene, ス テ ノ ロ Application, cupreol, the pregnenolone acetate, beta-cholestanol, 5,16-pregnen diethylene-3 β-alcohol-20-ketone, 5 α-pregnene-3 β-alcohol-20-ketone, 5-pregnene-3 β, 17-glycol-20-ketone 21 acetates, 5-pregnene-3 β, 17-glycol-20-ketone 17 acetates, 5-pregnene-3 β, 21-glycol-20-ketone 21 acetates, 5-pregnene-3 β, 17-glycol diacetin, the American aloe aglycon, cautious paddy aglycon, エ ス ミ ラ グ ニ Application, sisal hemp sapogenin, Chinese yam soap aglycon and their derivant.These removers can use separately, also can two or more mixing use.In these removers, the anadrol that has of elimination state is stablized in suitable obtaining, sisal hemp sapogenin, American aloe aglycon, cautious paddy aglycon, Chinese yam soap aglycon, エ ス ミ ラ グ ニ Application etc.
And when using these removers, when being heated to non-crystal state composition system above the vitrifacation transition temperature, the rate of propagation of developer is increased sharply, and shifts to equilibrium state, and the motion that is separated of developer and remover is quickened.Therefore, compositional system is heated the back when slowly being cooled to room temperature in the temperature between crystallized temperature and the fusing point,, reach stable phase-separated state and promptly show as the color development state more near equilibrium state.Therefore, use the compositional system of (a) remover, color development state and colour killing state are reversible on the principle.This just means, and is as described below, and (a) remover is called " reversibility remover ".In fact, but can utilize this reversible variation motion regenerative recording medium.Just, image of the present invention forms material, and purpose is to eliminate after forming for image again, except special purposes, reversibility is not had the requirement of essence.
(b) cholic acid, lithocholic acid, stosterone and cortisone, and their derivant.Concrete example has, cholic acid, Methyl cholate, sodium taurocholate, lithocholic acid, Methyl lithocholate, lithocholic acid sodium, hyodeoxycholic acid, hyodeoxycholic acid methyl esters, stosterone, Methyltestosterone, 11 Alpha-hydroxy Methyltestosterones, hydrocortisone, cholesterol methyl carbonic, α-cholestanol.Wherein, the compound that especially preferably contains two above hydroxyls.
(b) remover is compared with the remover of (a), during fusion and the compatibility of developer strong, so compatibility is very high.And (b) the noncrystal property of remover is very high, is difficult to be separated after system solidifies even form.In this sense, claim that below the remover of (b) is " a compatibility remover ".Therefore, use the compositional system of (b) remover can obtain more stable colour killing effect.
(c) contain 5 Yuans above non-aromatic ring shape compounds of more than one hydroxyl.And preferably this compounds fusing point is more than 50 ℃.Concrete example is specifiable 1 yuan of alcohol of alicyclic ring (for example, the ring lauryl alcohol), and 2 yuan of alcohol of alicyclic ring (for example, 1,4-cyclohexanediol, 1, the 2-cyclohexanediol, 1,2-cyclododecane glycol), ring type sugar alcohol (for example, glucose, sucrose), the ring type sugar alcohol derivant (for example, 1,2:5,6-diisopropyl fork-D-mannitol).
Though remover (c) can use separately, use effective especially with the remover of (a).Promptly the remover of (c) and remover compatibility (a) are strong, solidify the back and are difficult to be separated.In this sense, claim that below the remover of (c) is " the inhibition remover is separated " or " phase separation inhibitor ".Use the remover of (c) can obtain more stable colour killing state.
Above-mentioned phase separation inhibitor also can be divided into 2 classes.I.e. (C1) fusing point and glass transition point height, normal temperature easily form non-crystal compound (below, be called high non-crystal phase separation inhibitor) and (C2) fusing point and glass transition point are lower, be difficult for forming noncrystal at normal temperature, but can form micro-crystallization, and during flow state and the high compound of the compatibility of developer (below, be called low non-crystal phase separation inhibitor).As remover, high non-crystal phase separation inhibitor and low non-crystal phase separation inhibitor and time spent, can keep the colour killing state that image forms material highly stablely.
Suitable high noncrystal phase separation inhibitor is the ring type sugar alcohol.Concrete example has D-glucose, D-mannose, D-galactose, D-fructose, the L-sorbose, L-rhamnose, L-fucose, D-ribodesose, the alpha-D-glucose pentacetate, acetyl glucosamine, diacetyl-D-glucose, D-glucuronic acid, the D-galacturonic acid, D-aminoglucose, D-fructosamine, the acid of D-heterosugar, vitamin C, the acid of エ Le ト Le PVC Application, trehalose, sucrose, maltose, セ コ ヒ オ-ス, gentiobiose, lactose, melibiose, gossypose, gentianose, melezitose, stachyose, methyl α-Bi Nanputanggan, salicin, amygdalin, euxanthic acid etc.Can use in them one or more.
Suitable low noncrystal phase separation inhibitor is 5 Yuans above non-aromatic ring type compounds that contain hydroxyl or the ring type sugar alcohol derivant beyond the ring type sugar alcohol, and representative is terpenol.Concrete example has, and 1 yuan of alcohol of alicyclic ring for example encircles 12 (alkane) alcohol, six hydrogen salicylic acids, menthol, isomenthol, neomenthol, neoisomenthol, Sheep's-parsley alcohol in the Meng, α-phosphinylidyne menthol, piperitenol, α-terpilenol, β-terpilenol, γ-terpilenol, 1-Foxlene-4-alcohol, isopulegol, dihydrocarveol, carveol; The alicyclic ring polyvalent alcohol, for example, 1,4-cyclohexanediol, 1,2-cyclohexanediol, a phloroglucite, quercitol, inositol, 1,2-cyclododecane glycol, chinic acid, 1,4-terpinum, 1,8-terpinum, pinol ヒ De ラ ト, betulin; Many cyclol derivants, borneol for example, isoborneol, adamantanol, norborneol, fenchol, camphor, isosorbite; The cyclitol derivant, for example 1,2:5,6-diisopropyl fork-D-mannitol.In addition, when sterically hindered big molecular material that the compound reaction of using above-mentioned cyclic alcohol and other to contain ring texture obtains, can make image form the temperature stability raising of material at the colour killing state.For example, isosorbite and cyclohexyl dicarboxylic acid's reaction obtain ester, are suitable low noncrystal phase separation inhibitors.Can use wherein one or more.
The optimum ratio of colour generation compound, developer and remover in the image formation material of the present invention is as follows: the proportioning of developer is that 1 weight portion colour generation compound uses 0.1-10 weight portion, more preferably 1-2 weight portion developer.During developer less than 0.1 weight portion, rely on the color development of the interactional image formation of colour generation compound and developer material insufficient.When developer surpasses 10 weight portions, be difficult to fully reduce interaction between the two.The proportioning of remover is that 1 weight portion colour generation compound uses the 1-200 weight portion, preferred 10-100 weight portion remover.When remover is less than 1 weight portion, be difficult to cause that image forms the color development state of material and the conversion between the colour killing state.Remover is during more than 200 weight portions, and the color development state that image forms material is incomplete.
Image of the present invention forms material and can use at various states.For example, can be used as the China ink of thermal printer, the China ink of ink-jet printer, duplicating machine (PPC), laser printer, the toner of facsimile recorder etc.; Serigraphy or type printing China ink; The ink that ball pen or pen etc. are Writing utensil equipped.As the China ink of thermal printer, can be with the colour generation compound, developer, the cancellation agent, mixing such as wax are coated on the plastic sheeting and are used.As the China ink of ink-jet printer, can be with the colour generation compound, developer, removers etc. are dispersed in the solvent and use.As toner, can will contain the colour generation compound, developer, remover, the composition of bonding agent etc. is pulverized modulation and is used.Here, representational bonding agent has polystyrene, styrene-propene acid copolymer, polyester, epoxy resin etc.And, no matter which purposes all will add remover as required.
The image that contains bonding agent forms material, preferably adjusts its amount in image formation material according to the mean molecular weight of bonding agent.This be because, when using solvent to eliminate image, the mean molecular weight of bonding agent is big more, the compatibility of solvent and bonding agent is low more.
When using polystyrene, be preferably as follows according to mean molecular weight and adjust its content in image formation material as bonding agent.
Mean molecular weight 1,000-200,000 o'clock, 30-90wt%.
Mean molecular weight 200,000-600,000 o'clock, 30-80wt%.
Mean molecular weight 600,000-1000,000 o'clock, 30-70wt%.
The acrylic monomers that forms the styrene-propene acid copolymer can be the normal-butyl methacrylate, the isobutyl methacrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, methyl propenoic acid glycidyl base ester, dimethyl amino ethyl methacrylate, diethylamino ethyl-methyl acrylate, diethylamino propyl group acrylate, 2-ethylhexyl acrylate, butylacrylic acid ester-N-(ethoxymethyl) acrylamide, glycolmethacrylate, 4-hexafluoro butyl methyl acrylate etc.Can use a kind of or such acrylate monomer more than 2 kinds.In addition, except the monomer of styrene and acrylic compounds, also can with copolymerization such as butadiene, maleate, chlorbutadiene, preferably below this ingredients constitute 10wt%.Cinnamic ratio is more than 50wt% in the preferred adhesive.When using the styrene-propene acid copolymer, be preferably as follows according to mean molecular weight and adjust its content in image formation material as bonding agent.
Mean molecular weight 1,000-200,000 o'clock, 30-95wt%.
Mean molecular weight 200,000-400,000 o'clock, 30-85wt%.
Mean molecular weight 400,000-1000,000 o'clock, 30-75wt%.
The polymer blend of polystyrene and acryl resin also can be used as bonding agent.Can use acryl resins a kind of or more than 2 kinds.And, also can use the butadiene that contains below 10%, maleate, the multipolymer of chlorbutadiene etc.Preferred polystyrene accounts for the above bonding agent of 50wt%.The polymer blend that uses polystyrene and acryl resin is during as bonding agent, is preferably as follows to adjust it according to mean molecular weight and form content in the material at image.
Mean molecular weight 1,000-200,000 o'clock, 30-95wt%.
Mean molecular weight 200,000-400,000 o'clock, 30-85wt%.
Mean molecular weight 400,000-1000,000 o'clock, 30-75wt%.
Carboxylic acid and polyvalent alcohol as polyester raw material are had no particular limits.Carboxylic acid can be a terephthalic acid (TPA), fumaric acid, maleic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, Brazilian diacid, phthalic acid, citraconic acid, glutaconic acid, middle health diacid, itaconic acid, teraconic acid, phthalic acid, isophthalic acid, benzene-1,2,3-tricarboxylic acid, inclined to one side benzene tetracarboxylic acid, trimesic acid, プ レ-ニ ト acid, trimellitic acid etc.Can use in them one or more.Polyvalent alcohol can be a bisphenol-A, hydrogenation bisphenol-A, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexanediol, heptandiol, ethohexadiol, new penta triol, pentaerythrite, cyclohexanediol, the ring pentanediol, pinacol, glycerine, etherificate diphenol, catechol, resorcinol, Pyrogallol, benzenetriol, phloroglucin, phenetetrol etc.Can use wherein one or more.And can use the blending of polymers of two or more polyester.When using polyester, be preferably as follows and adjust it according to mean molecular weight and form content in the material at image as the bonding agent of toner.
Mean molecular weight 1,000-5,000 o'clock, 30-95wt%.
Mean molecular weight 5,000-10,000 o'clock, 30-90wt%.
Mean molecular weight 10,000-20,000 o'clock, 30-87wt%.
Mean molecular weight 20,000-100,000 o'clock, 30-85wt%.
Mean molecular weight 100,000-1000,000,30-80wt%.
When using polyester as the bonding agent of heat copying China ink, although can use paraffin as the wax composition, the content of preferred polyester is 2-50wt%.
Epoxy resin can use epichlorokydrin and the compound that contains the polyhydric phenol hydroxyl synthetic as raw material.Polyhydric phenols can be bisphenol-A, hydrogenation bisphenol-A, bisphenol S, etherificate diphenol, catechol, resorcinol, Pyrogallol, benzenetriol, phloroglucin, phenetetrol etc.Can use wherein one or more.And also can contain phenolics below the 15wt% for epoxy resin, and urea resin, the melanocyte resin, alkyd resin, acryl resin, polyester, polyamide, polyurethane etc. form admixture.
When using epoxy resin, be preferably as follows and adjust it according to mean molecular weight and form content in the material at image as the bonding agent of toner.
Mean molecular weight 1,000-5,000 o'clock, 30-95wt%.
Mean molecular weight 5,000-10,000 o'clock, 30-90wt%.
Mean molecular weight 10,000-20,000 o'clock, 30-87wt%.
Mean molecular weight 20,000-100,000 o'clock, 30-85wt%.
Mean molecular weight 100,000-1000,000 o'clock, 30-80wt%.
When using epoxy resin as the bonding agent of heat copying China ink, although can use paraffin as the wax composition, the content of preferred polyester is 2-50wt%.
The spendable solvent of the present invention (A) preferably has the solvent that helps between developer and remover to form hydrogen bond, and (B) preferably with the compatibility height of bonding agent, easily infiltrate through the solvent that image forms material internal.Can use the solvent that has above-mentioned (A) character separately.Also can the solvent more than 2 kinds use, have above-mentioned two character.
Have above-mentioned (A) and (B) solvent of two aspect character is specifiable that ether, ketone, ester etc. are arranged.Concrete example has, saturated ethers, for example, ether, ethyl propyl ether, ethyl isopropyl ether, isopentyl methyl ether, butyl ethyl ether, dipropyl ether, Di Iso Propyl Ether, ethyl isoamyl ether, dibutyl ethers, diamyl ether, diisoamyl ether, hexyl ether; Unsaturated ethers, ethyl vinyl ether for example, allyl ethyl ether, diallyl ether, EPE; The ether of dibasic alcohol, 2-methoxyethanol for example, 2-ethoxy ethanol, 2-fourth oxyethanol, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, 1,2-two fourth oxidative ethanes; Cyclic ethers, oxetanes for example, tetrahydrofuran, oxinane, dioxolane, dioxan, trioxane; Saturated ketone, acetone for example, methyl ethyl ketone, methyl propyl ketone, metacetone, isopropyl methyl ketone, butyl methyl ketone, ethyl propyl ketone, isobutyl methyl ketone, pinacoline, methyl amyl ketone, n-Butyl ethyl ketone, dipropyl ketone, diisopropyl ketone, hexyl methyl ketone, the isohesyl methyl ketone, heptyl methyl ketone, dibutyl ketone; Beta-unsaturated ketone, for example, ethylidene acetone, allylacetone, isopropylidene acetone; Cyclic ketone, cyclopentanone for example, cyclohexanone, cycloheptanone, cyclooctanone; Ester, ethyl formate for example, propyl formate, butyl formate, formic acid isobutyl, amyl formate, isoamyl formate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isoamyl acetate, acetate second month in a season-amyl group ester, the acetate hexyl ester, allyl acetate, 2-methoxyethyl acetic acid esters, 2-ethoxyethyl acetic acid esters, 1,2-diacetoxyl ethane, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, amyl propionate, isoamyl propionate, propionic acid second month in a season-amyl group ester, 2-methoxycarbonyl propyl acetic acid esters, the 2-ethoxy propyl acetate(EPA), methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyl butyrate, amyl butyrate, isoamyl butyrate, butyric acid second month in a season-amyl group ester, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyric acid pentyl ester, isoamyl isobutyrate, isobutyric acid second month in a season-amyl group ester, methyl valerate, ethyl valerate, propyl valerate, isopropyl isovalerate, butyl valerate, methyl caproate, ethyl hexanoate, propyl hexanoate, isopropyl hexanoate etc.Solvent beyond above-mentioned has methylene chloride, gamma-butyrolacton, beta-propiolactone, N-crassitude, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) etc.These can use separately, also can mix use more than 2 kinds.When solvent is used, can set mixing ratio arbitrarily.
Character with above-mentioned (A), but have with the low solvent of bonding agent compatibility, water for example, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, amylalcohol, 2-amylalcohol, 3-amylalcohol, isoamylol, 1-hexanol, 2-hexanol, the 3-hexanol, cyclopentanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, glycerine etc.
The character that does not have above-mentioned (A), but have with the high solvent of the compatibility of bonding agent, toluene for example, ethylbenzene, propyl benzene, isopropyl benzene; butylbenzene, isobutylbenzene, the second month in a season-butyl benzene, amylbenzene, diethylbenzene, 1; 3,5 trimethylbenzenes, dimethylbenzene, cresols, diethylstilbestrol, dimethoxy benzene; dimethoxy toluene, benzylalcohol, tolyl alcohol, cumic alcohol, acetophenone, propionyl benzene; hexane, pentane, heptane, octane, cyclohexane; cyclopentane, cycloheptane, cyclooctane, petroleum fraction (sherwood oil, volatile oil) etc.
Above-mentioned first group of solvent can use separately.Though second group of solvent also can use separately, also can use with first group of solvent.At this moment, these solvents also can with the solvent with elimination ability with any than mixing use.When second group of solvent and the 3rd group of solvent are used, in order fully to eliminate, mixing ratio is had no particular limits, but preferred the 3rd group of solvent accounts for 20-80wt%.The 3rd group solvent also can use with first group solvent.At this moment, preferred third party's solvent accounts for below the 90wt%.The solvent that also can mix in addition, first to the 3rd group of use.At this moment, preferred the 3rd group solvent accounts for below the 80wt%.In order to make image form material colour killing effectively, also can preheat solvent.At this moment, the temperature of preferred solvent is in 40-150 ℃ of scope.
When using polyester or epoxy resin,, can not eliminate image well owing to the unreacted carboxylic acid residual in the bonding agent or the influence of phenol as bonding agent, and the stability decreases of the state of elimination.
According to the present invention,, can use alkali compounds for fear of the influence that unreacted carboxylic acid or phenol are eliminated image.And, if use alkali compounds, even, also can avoid the influence that image is eliminated at 8 o'clock in the situation of pH less than the image that on paper, formed.Alkali compounds is had no particular limits, and can be that mineral compound also can be an organic compound.
Suitable mineral compound has, lime chloride, potassium hydroxide, calcium hydroxide, NaOH, baryta hydrate, magnesium hydroxide, hartshorn salt, sal tartari, lime carbonate, sodium carbonate, magnesium carbonate, ammonium bicarbonate, saleratus, sodium bicarbonate, alkali borate, tripotassium phosphate, dipotassium hydrogen phosphate, calcium phosphate, tertiary sodium phosphate, sodium hydrogen phosphate.
Suitable organic compound has, 1-3 level amine or 4 grades of ammonium salts.With 4 grades of corresponding ions of ammonium hydroxyl ion, halide ion, alkoxy ion are arranged.
The non-aromatic organic basic compound has, and has the aliphatic hydrocarbyl of 1-50 carbon atom or has the alicyclic hydrocarbon radical of 1-50 carbon atom.These alkyl are selected from vinyl by one at least, ethynylene, ethinyl, hydroxyl; hydroxycarbonyl group, thiocarbonyl, two thiocarbonyls, sulfenyl; sulfinyl, sulfonyl, carbonyl, hydrazo; azo group, the nitrogen base that changes, cyano group, diazoamino support; imino group, urea bond, thio urea key; amido link, urethane bond, the substituting group of carbonyldioxy replaces.
The aromatic series organic basic compound is specifiable the phenyl ring of containing, cyclohexyl biphenyl, and naphthalene nucleus, benzo cyclohexanone ring, anthracene nucleus, 9,10-dihydro phenanthrene ring, the indenes ring, indane ring, penta takes ring, ring difficult to understand, heptalene ring, the compound of aromatic rings such as glimmering hydrocarbon ring.These aromatic rings can be had the aliphatic group of 1-50 carbon atom or be had the alicyclic hydrocarbon radical replacement of 1-50 carbon atom.These alkyl can be replaced by above-mentioned substituting group again.
Specifiable cyclic amine has, aziridine, azetidine, pyrrolin, pyrrolidine, isodrin, pyridine, piperidines, hydrogenated pyridine, quinoline, isoquinoline, tetrahydroquinoline, tetrahydroisoquinoline, bifurcation pyridine, phenanthridines, phenanthroline, pyrazoles, benzopyrazoles, pyridazine, pyrimidine, pyrazine, imidazoles, histamine, decahydroquinoline, pyrazoline, imidazoline, imidazolidine, piperazine, quinoline once, phthalazines, quinazoline, キ ノ サ リ Application, dihydro phenol piperazine, triazole, benzotriazole, triazine, tetrazolium, pentamethylenetetrazole, tetrazine, purine, the pyridine of talking endlessly, carboline, naphthyridines, indolizine, quinolizine, quinoline rather encircles, oxazole, oxazolidine, benzoxazoles, isoxazole, the adjacent first lactams of benzene, oxazines, oxazoline, thiazole, thiazolidine, benzothiazole, benzothiazole quinoline, isothiazole, thiazine, oxadiazoles, furazan, oxadiazines, thiadiazoles, diazosulfide, thiadiazine, dithiazine, morpholine, hexamethylene tetramine, diazabicyclo etc.
Spendable organic basic compound has amidine except above-mentioned, guanidine, aminoguanidine, urea, thio urea, semicarbazides, thiosemicarbazide, carbohydrazide.
According to the present invention, but the alkali compounds former state is mixed with other composition that image forms material.Mix with other composition of image formation material again after also alkali compounds can being enclosed microcapsules.At this moment, when eliminating image image being formed material heats.
As the material of microcapsule shell, should be chosen in when image formed the material heating and eliminate image can be destroyed and discharge the material of alkali compounds.The fail temperature of preferred microcapsules is 120-200 ℃.Suitable material has polyethersulfone, polyetherketone, epoxy resin, tygon, polypropylene, polyphenylene ether, polyphenylene sulfides, polyalkylene oxides, polystyrene, poly-phenolic ether, nylon, polyamide, polyurethane, gelatin, polymethylacrylic acid, polyimide, the melanocyte resin, polyester, polyacrylic acid, polyvinyl alcohol (PVA), polyacrylonitrile, polymethacrylonitrile, polysiloxane, polythiaether, polyvinyl acetate base ester, NC Nitroncellulose, methylcellulose, acetylcellulose, ethyl cellulose, gum arabic, polyvinyl pyrrolidone, polycarbonate, polysulfones, polyisocyanate, polypyrrole, shitosan, collagen, polyaminoacid etc.These can use separately, also can mix use.In addition, also can use their interpolymer.
According to the present invention, for containing colour generation compound, developer, remover and polyester or epoxy resin form the image that material forms as the image of bonding agent, when eliminating this image, also can allow image form material and alkali compounds contact after, heat the method for elimination image again.
According to the present invention, for with containing the colour generation compound, developer, remover and polyester or epoxy resin form the image that material forms as the image of bonding agent, when eliminating this image, also can allow image form material and contact with the solution that is dissolved with remover and alkali compounds.And, also can distinguish modulation eliminating agent solution and alkaline compound solution, make image form material and contact respectively with remover or alkali compounds.
When image formation material is contacted with solvent, both solution can be sprayed onto on the paper, also paper can be immersed solution.In addition, also can form material and contact the back heating with the solution that is dissolved with remover and alkali compounds at image.
The used solvent of modulation alkaline compound solution is had no particular limits.Concrete example has water, methyl alcohol, ethanol, isopropyl alcohol, acetone, methylene chloride, ethyl acetate, ethyl lactate, ethyl butyrate, n-pentyl butytate, ether, tetrahydrofuran, glycol dimethyl ether, ethylene glycol diethyl ether, the cellosolve acetic acid esters, gamma-butyrolacton, beta-propiolactone, N-Methyl pyrrolidone (n-メ チ Le ピ ロ リ ジ ノ Application), N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), methyl ethyl ketone, methyl isopropyl Ketone, toluene, dimethylbenzene, hexane, pentane, heptane, petroleum fraction (sherwood oil, volatile oil).The preferred 1-40wt% of the concentration of alkaline compound solution.
Make image formation material contact and remove the image cancellation element of the function of desolvating with solvent in order to use solvent to eliminate image, can to use to have from paper.
Make on the paper image of color development form device that material contact with solvent and can use paper to immerse the roller of solution in the container, on paper, spray the fog nozzle of solvent, the nozzle of a solvent on paper, the gravure roller of donor solvent etc. on paper.Can use hot blast, infrared lamp, thermo roll, hot pressing, thermal print head (TPH), temperature-sensitive rod etc. from the paper device that desolventizes that gets on.In addition, if solvent for use gasifies easily, also can use air dry.In addition, device of the present invention preferably has the back of use solvent recovery unit.The object lesson of the device of use solvent elimination image is shown in Fig. 1-5.
The bottom of the image cancellation element of Fig. 1 is provided with solvent container 101 and to the solvent tank 103 of these container 101 donor solvents 102.To have under the image principal direction simultaneously page by page by in input roller 104 input medias, by the conveying of transportation roller.When paper is delivered between dipping roller 105 and the roller 106 relative with it, solvent 102 dippings that are equipped with in the container 101, image is eliminated.Afterwards, paper betransported roller and carries, and the heated-air drying that the radiator of the aftermentioned electronic cooler on dependence device top is emitted is along with the heating of thermo roll 107 is stretching with wrinkle.Like this will except that the paper that desolvates by output roller 108 output units, in hutch, collect.
Be provided with solvent recovery unit in this device.This retracting device, by the recover that adsorbent 110 and electronic cooler 111 are housed and ebullator 114 as main parts.Used solvent comes out to 109 storages of recovery solvent container from solvent container 101.The solvent of gasification in reclaiming solvent container 109,111 coolings are adsorbed agent 110 absorptions through electronic cooler (for example brightness antimony device).The temperature of electronic cooler 111 is set at solvent vapour and presses below the 100ppmm.The solvent that adsorbent 110 absorbs is drawn back by ebullator 114, and suction strainer 113 absorbs.Leading portion at ebullator 114 is provided with filtrator 113, can prevent the infringement of solvent to pump.In order to prevent that the moisture in the atmosphere from sneaking into, also dehumidifier can be set.From the hot blast that the radiator 112 of electronic cooler 111 is emitted, the paper after can utilizing it to immersion solvent as mentioned above carries out drying.
The image cancellation element of Fig. 2 forms the contact device of material and solvent as the image on the paper except using gravure roller 121, and other device with Fig. 1 is identical.121 rotations of gravure roller are flooded paper in the solvent 102 of solvent container 101 after, adjust the quantity of solvent of its surface attachment through braid 123.The paper of input media between gravure roller 121 and the roller relative with it by the time, by gravure roller 121 donor solvent on paper, image is eliminated.
The image cancellation element of Fig. 3 except using pump 131 and fog nozzle 132 contact device as formation material of the image on the paper and solvent, uses outside the lamp well heater 133 when removing solvent, and other device with Fig. 1 is identical.Paper in the input media sprays 102 extractions of the solvent in the solvent container 101 by pump 131 through nozzle 132, eliminate image.Afterwards, along with the paper of carrying by heated-air drying, simultaneously with 133 heating of lamp well heater except that desolvating.
The solvent that is to use shown in Fig. 4 (A)-(C) is eliminated the device of image in batches.(A) be planimetric map, outboard profile in the time of (B) and (C).In the bottom of this device, be provided with solvent tank 201, solvent 202 wherein is housed.Be provided with solvent impregnated groove 203 on the top of this device.Between solvent tank 201 and flux bath 203, be provided with the liquor charging pipeline 205 that is connected with chemical pumping 204.In the bottom of solvent impregnated groove 203, be provided with the supine electronic cooler of heat release (for example brightness antimony device) 206.Give electronic cooler 206 power supplies from power supply 207.
Use this device, carry out the elimination of image as follows.The lid of solvent impregnated groove 203 is opened, placed about about 100 pages paper therein.By chemical pumping 204 solvent 202 is supplied to solvent impregnated groove 203 by solvent tank 201, paper floods in solvent and eliminates image.Afterwards, by chemical pumping 204 solvent from solvent tank 201 to solvent impregnated groove 203 is discharged.Simultaneously, utilize the heat that electronic cooler 206 is put that solvent is removed from paper.In addition, the solvent that has gasified can reclaim by electronic cooler 206 coolings.
Shown in Figure 5 is pipeline system integrated mill equipment.This installs the following elimination of carrying out image.Bundled paper 301 is delivered in the solvent processing groove 303 with solvent 304 dippings and elimination image by travelling belt 302.One-tenth pack of paper 301 in the solvent processing groove 303 is by travelling belt 305 outputs and deliver to disposable drying bed.At disposable drying bed, the hot blast of supplying with by well heater 306 and fan blower 307 carries out drying, and the very fast drying of paper also is delivered to the redrying field.In the redrying field, when carrying, passes through by paper infrared heater 309 bone dries on travelling belt.Dried paper is housed in the storage vault 310.
Embodiment
Below, describe with regard to embodiments of the invention.
In the following embodiments, the paper of image elimination uses the neutralized paper (pH=9.4) of the Neusidler manufacturing of using according to European standard.The reflection density of this paper is 0.07.
Embodiment 1
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, remover cholesterol 10 weight portions and D-glucose 10 weight portions, mean molecular weight is 45,000 polystyrene adhesive 77 weight portions, mix, stir with charged inhibitor LR-147 (Japanese カ-リ Star ト company makes) 1 weight portion with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
With the image cancellation element that the solvent shown in the table 1 is packed into shown in Figure 2, after image was eliminated when the paper that forms image was contacted 30 seconds with solvent, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 1.As shown in table 1, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of organic solvent can both eliminate image well.
Table 1
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.08 |
| Ethyl propyl ether | 0.08 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.08 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.08 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.09 |
In addition, the paper of eliminating image after 300 hours, there is not image reproduction 60 ℃ of placements.Afterwards, on the paper of eliminating image, duplicate other image, eliminate 9 times repeatedly again.Image that duplicates for the 10th time and the 1st time image have equal quality.Further, duplicate and eliminate 50 times repeatedly, its result, though some damage of the physical state of paper, the quality of duplicating image is fine with the quality of the state of elimination.
Embodiment 2
Except the polystyrene that adds molecular weight 45,000 according to the ratio shown in the table 2 as outside the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of laser printer, on paper, print image.
The ethylene glycol diethyl ether of packing in the image cancellation element of Fig. 1 flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 2.When using polystyrene content as the toner of 20-25wt%, when flooding in solvent, image forms material and flows out, and leaves a trace on the paper surface, does not therefore measure reflection density.When using the toner of polystyrene content more than 30wt%, it is identical with the reflection density that begins most to eliminate behind the image reflection density of paper, can eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 2
| Polystyrene accounts for the weight % of toner total amount | Reflection density |
| 20 | - |
| 25 | - |
| 30 | 0.07 |
| 40 | 0.07 |
| 50 | 0.07 |
| 60 | 0.07 |
| 70 | 0.07 |
| 80 | 0.07 |
| 90 | 0.07 |
Embodiment 3
Except the polystyrene that adds different molecular weight according to the ratio shown in the table 3 as the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of facsimile recorder, on paper, duplicate image.
The ethylene glycol diethyl ether of in the image cancellation element of Fig. 3, packing into, the spraying solvent is 30 seconds on the paper that forms image, after image is eliminated, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 3.As shown in table 3, when using the big polystyrene of molecular weight, preferably use low content.
Table 3
| The mean molecular weight of polystyrene | Polystyrene accounts for the weight % of toner total amount | Reflection density |
| 45,000 | 40 | 0.07 |
| 45,000 | 85 | 0.09 |
| 45,000 | 90 | 0.18 |
| 220,000 | 40 | 0.07 |
| 220,000 | 75 | 0.07 |
| 220,000 | 85 | 0.12 |
| 630,000 | 40 | 0.07 |
| 630,000 | 70 | 0.09 |
| 630,000 | 80 | 0.25 |
| 630,000 | 90 | 0.52 |
Embodiment 4
Except add mean molecular weight be 130,000 the positive butyl ester multipolymer of styrene/methacrylic acid (content of n-BMA is 10wt%) 77 weight portions as outside the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of duplicating machine, on paper, duplicate image.
The organic solvent shown in the table 4 of packing in container flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 4.As shown in table 4, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of organic solvent can both eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 4
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.07 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.08 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.08 |
Embodiment 5
Except add according to the ratio shown in the table 5 mean molecular weight be 130,000 the positive butyl ester multipolymer of styrene/methacrylic acid (content of n-BMA is 10wt%) as outside the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of laser printer, on paper, print image.
The ethylene glycol diethyl ether of packing in container flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 5.When using binder content as the toner of 15-20wt%, when flooding in solvent, image forms material and flows out, and leaves a trace on the paper surface, does not therefore measure reflection density.When using the toner of binder content more than 30wt%, it is identical with the reflection density that begins most to eliminate behind the image reflection density of paper, can eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 5
| The weight % of binder constitutes toner total amount | Reflection density |
| 15 | - |
| 20 | - |
| 30 | 0.07 |
| 55 | 0.07 |
| 65 | 0.07 |
| 75 | 0.07 |
| 85 | 0.07 |
| 95 | 0.07 |
| 98 | 0.12 |
Embodiment 6
Except the positive butyl ester multipolymer of styrene/methacrylic acid (content of n-BMA is 10wt%) that adds different molecular weight according to the ratio shown in the table 6 as the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of facsimile recorder, on paper, duplicate image.
The ethylene glycol diethyl ether of packing in the image cancellation element of Fig. 1 flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 6.As shown in table 6, when using the big bonding agent of molecular weight, preferably use low content.
Table 6
| The mean molecular weight of bonding agent | The weight % of binder constitutes toner total amount | Reflection density |
| 130,000 | 40 | 0.07 |
| 130,000 | 85 | 0.09 |
| 130,000 | 98 | 0.12 |
| 352,000 | 40 | 0.07 |
| 352,000 | 80 | 0.07 |
| 352,000 | 90 | 0.21 |
| 850,000 | 40 | 0.07 |
| 850,000 | 70 | 0.07 |
| 850,000 | 80 | 0.25 |
| 850,000 | 90 | 0.52 |
Embodiment 7
Except add according to the ratio shown in the table 7 mean molecular weight be 130,000 n-BMA content different the positive butyl ester multipolymer of styrene/methacrylic acid as outside the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of duplicating machine, on paper, duplicate image.
The ethylene glycol diethyl ether of packing in the image cancellation element of Fig. 1 flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 7.As shown in table 7, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 7
| The methacrylic acid n-butyl accounts for cinnamic weight % | The weight % of binder constitutes toner total amount | Reflection density |
| 5 | 85 | 0.07 |
| 10 | 85 | 0.07 |
| 15 | 85 | 0.07 |
| 20 | 85 | 0.07 |
| 25 | 85 | 0.07 |
| 30 | 90 | 0.07 |
| 35 | 90 | 0.07 |
| 40 | 90 | 0.08 |
| 45 | 80 | 0.08 |
| 50 | 80 | 0.08 |
Embodiment 8
Except adding mean molecular weight is 130,000, the acrylate monomer content shown in the table 8 be styrene-propene acid copolymer 77 weight portions of 10 weight % as outside the bonding agent, other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of duplicating machine, on paper, duplicate image.
The ethylene glycol diethyl ether of in the image cancellation element of Fig. 3, packing into, the solvent of on the paper that forms image, spraying, after image is eliminated, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 8.As shown in table 8, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 8
| Acrylate monomer | Reflection density |
| The methacrylic acid n-butyl | 0.07 |
| The methacrylic acid isobutyl | 0.07 |
| Ethyl acrylate | 0.07 |
| The methacrylic acid n-butyl | 0.07 |
| Methyl propenoic acid glycidyl base ester | 0.07 |
| Diethylamino propyl group acrylate | 0.07 |
| The 2-ethylhexyl acrylate | 0.07 |
| Glycolmethacrylate | 0.07 |
| Methyl methacrylate | 0.08 |
| Dimethyl amino ethyl methacrylate | 0.08 |
Embodiment 9
Except adding shown in the table 9, mean molecular weight is 130,000, and blending polymkeric substance (polyacrylic acid ester content 10 weight %) 77 weight portions that polystyrene and polyacrylate are formed are as outside the bonding agent, and other is according to the identical method modulation toner of embodiment 1.The gained toner is put into the toner tube of duplicating machine, on paper, duplicate image.
The ethylene glycol diethyl ether of packing in container floods the paper that forms image in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 9.As shown in table 9, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.Stability and embodiment 1 that gained is eliminated state come to the same thing.
Table 9
| Polyacrylate | Reflection density |
| The polymethylacrylic acid n-butyl | 0.08 |
| The polymethylacrylic acid isobutyl | 0.08 |
| Polyethyl acrylate | 0.09 |
| The polyacrylic acid n-butyl | 0.09 |
| The polymethylacrylic acid glycidyl esters | 0.10 |
| Poly-diethylamino propyl group acrylate | 0.10 |
| Poly-2-ethylhexyl acrylate | 0.09 |
| Polyethylene glycol methacrylate-styrene polymer | 0.11 |
| Polymethylmethacrylate | 0.13 |
| Poly dimethyl amino-ethyl methacrylate | 0.10 |
Embodiment 10
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, remover cholesterol 10 weight portions and D-glucose 10 weight portions, mean molecular weight is 11,500 fumaric acid/etherificate diphenols polyester binder 72 weight portions, alkali compounds 5 weight portions shown in charged inhibitor 1 weight portion and the table 10 mix, and stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of laser printer of gained toner, on paper, duplicate image.
The paper that forms image is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 10.As shown in table 10, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.
Table 10
| Alkali compounds | Reflection density |
| Lime chloride | 0.08 |
| Ammonium hydroxide | 0.08 |
| Tetramethylammonium hydroxide | 0.08 |
| Lime carbonate | 0.08 |
| Hartshorn salt | 0.08 |
| NaOH | 0.08 |
| Potassium hydroxide | 0.08 |
| Triethylamine | 0.08 |
| Dibutylamine | 0.08 |
| Butylamine | 0.08 |
| Cyclohexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.08 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
In addition, the paper of eliminating image after 300 hours, there is not image reproduction 60 ℃ of placements.Afterwards, on the paper of eliminating image, duplicate other image, eliminate again 9 times repeatedly.Image that duplicates for the 10th time and the 1st time image have equal quality.Further, duplicate and eliminate 50 times repeatedly, its result, though some damage of the physical state of paper, the quality of duplicating image is fine with the quality of the state of elimination.
Embodiment 11
In the 40mL aqueous solution that is dissolved with the 4g gelatin (37 ℃), add the listed alkali compounds 4g of table 11, and add the solution 45mL (37 ℃) that is dissolved with 11g sodium sulphate, bring out cohesion.After this dispersion liquid was cooled to 30 ℃ of placements, logical decant was isolated microcapsules.Add the formaldehyde of equivalent and stirred 5 minutes in 1mL gained microcapsules, then, the ethanol that adds 2 times of amounts of formaldehyde stirred after 5 minutes, leached microcapsules.It is dry that the gained microcapsules are cleaned the back with cold water.The microcapsules of alkali compounds are enclosed in preparation in this way.
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, remover cholesterol 10 weight portions and D-glucose 10 weight portions, mean molecular weight is 11,500 maleic acid/propandiols polyester binder 67 weight portions, charged inhibitor 1 weight portion and microcapsules 10 weight portions fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
The paper that forms image is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 11.As shown in table 11, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 10 come to the same thing.
Table 11
| Alkali compounds | Reflection density |
| Triethylamine | 0.08 |
| Dibutylamine | 0.08 |
| Butylamine | 0.08 |
| Cyclohexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.08 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 12
Except use mean molecular weight be maleic acid/etherificate diphenols polyester 72 weight portions of 11,500 as bonding agent, butylamine 5 weight portions are as outside the alkali compounds, use the method identical with embodiment 10 to modulate toner.The gained toner is put into the toner tube of duplicating machine, on paper, duplicate image.
The organic solvent shown in the table 12 of packing in the image cancellation element of Fig. 2 flooded the paper that forms image 30 seconds in solvent, after image is eliminated, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 12.As shown in table 12, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of organic solvent can both eliminate image well.Stability and embodiment 10 that gained is eliminated state come to the same thing.
Table 12
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.08 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.09 |
Embodiment 13
With colour generation compound ODB-2 (the Yamamoto system of changing into) 1 weight portion, developer 2,4,4 '-trihydroxybenzophenone, 1 weight portion, remover 1,2:5,6-diisopropyl fork-D-mannitol 10 weight portions and D-fructose 10 weight portions, molecular weight are Pyromellitic Acid/glycols polyester binder 3 weight portions of 2,500, mix with paraffin 15 weight portions, fully stir with kneader.Use the heat seeling coating machine that it is coated on the PET sheet of thick 4.5 μ m in potpourri, the about 2 μ m of coating thickness make the heat copying sheet.The heat copying sheet overlapped on the paper in thermal printer, solidify, print image.
On the one hand, prepare to contain the solution of the alkali compounds shown in the table 13 of 3wt%.Solvent can use in the table 13 listed, and the difference according to alkali compounds makes water, ethanol or acetone.
The paper that forms image was flooded 1 minute in the solution that contains the alkali compounds shown in the table 13, dry then, afterwards,, eliminate image with 200 ℃ warm winds 30 seconds.Measure the reflection density of paper behind the elimination image, the results are shown in table 13.As shown in table 13, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter which kind of situation can both be eliminated image well.Elimination state stability is identical with embodiment 10.
Table 13
| Alkali compounds (solvent) | Reflection density |
| Lime chloride (water) | 0.07 |
| Ammonium hydroxide (water) | 0.08 |
| Tetramethylammonium hydroxide (water) | 0.08 |
| Lime carbonate (water) | 0.07 |
| Hartshorn salt (water) | 0.08 |
| NaOH (water) | 0.08 |
| Potassium hydroxide (water) | 0.08 |
| Triethylamine (water) | 0.07 |
| Dibutylamine (ethanol) | 0.08 |
| Butylamine (ethanol) | 0.08 |
| Cyclohexylamine (ethanol) | 0.08 |
| Dicyclohexyl amine (ethanol) | 0.08 |
| Pyridine (acetone) | 0.07 |
| Pyrazine (acetone) | 0.08 |
| Piperazine (acetone) | 0.08 |
Embodiment 14
Except bisphenol A epoxide resin 72 weight portions that use mean molecular weight 5,500 as outside the bonding agent, other is identical with embodiment 10, modulates the toner that contains the alkali compounds shown in the table 14.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
The paper that forms image is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 14.As shown in table 14, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 10 come to the same thing.
Table 14
| Alkali compounds | Reflection density |
| Lime chloride | 0.08 |
| Ammonium hydroxide | 0.08 |
| Tetramethylammonium hydroxide | 0.09 |
| Lime carbonate | 0.08 |
| Hartshorn salt | 0.09 |
| NaOH | 0.08 |
| Potassium hydroxide | 0.08 |
| Triethylamine | 0.08 |
| Dibutylamine | 0.08 |
| Butylamine | 0.09 |
| Cyclohexylamine | 0.09 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.08 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 15
Identical with embodiment 11, the microcapsules of alkali compounds shown in the table 15 are enclosed in modulation.In addition, except bisphenol A epoxide resin 67 weight portions that use mean molecular weight 5,500 as outside the bonding agent, identical with embodiment 11, modulation contains the toner of microcapsules.With pack into the toner tube of laser printer of gained toner, on paper, duplicate image.
The paper that forms image is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 15.As shown in Table 15, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 10 come to the same thing.
Table 15
| Alkali compounds | Reflection density |
| Triethylamine | 0.08 |
| Dibutylamine | 0.08 |
| Butylamine | 0.08 |
| Cyclohexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.08 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 16
Except bisphenol-A based epoxy resin 72 weight portions that use mean molecular weight 5,500 as bonding agent, outside alkali compounds cyclohexylamine 10 weight portions, other and embodiment 10 identical modulation toners.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
Image cancellation element with the organic solvent shown in the table 16 is packed into shown in Figure 2 contacts 30 seconds with the paper that forms image with solvent, behind the elimination image, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 16.Shown in table 16, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of organic solvent can both eliminate image well.The stability of elimination state and embodiment 10 come to the same thing.
Table 16
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.08 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.08 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.07 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.08 |
Embodiment 17
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight are 45,000 polystyrene 70 weight portions, mix with charged inhibitor LR-147 (Japanese カ-リ Star ト corporate system) 1 weight portion, fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 5wt% and D-glucose 5wt% are dissolved in preparation elimination solution in the organic solvent shown in the table 17 as remover.Gained is eliminated the image cancellation element that solution that image uses is packed into shown in Figure 2, the paper that forms image is contacted 30 seconds with solvent, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 17.Shown in table 17, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, anyway can both eliminate image well.
Table 17
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.07 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.07 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.08 |
Then, the paper of eliminating image was placed 300 hours at 60 ℃, image does not reproduce.Afterwards, on the paper of eliminating image, duplicate other image, and then eliminate 9 times so repeatedly.Image that duplicates for the 10th time and the 1st time image have equal quality.Further, duplicate and eliminate 50 times repeatedly, its result, though some damage of the physical state of paper, the quality of duplicating image is fine with the quality of the state of elimination.
Embodiment 18
Except the polystyrene that adds molecular weight 45,000 according to the ratio shown in the table 18 as outside the bonding agent, other and embodiment 17 identical modulation toners.With pack into the toner tube of laser printer of gained toner, on paper, print image.
On the one hand, cholesterol 3wt% and D-glucose 3wt% are dissolved in preparation elimination solution in the ethylene glycol diethyl ether as remover.Gained is eliminated the image cancellation element that solution that image uses is packed into shown in Figure 1, the paper that forms image was flooded in solution 30 seconds, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 18.Shown in table 18, when using polystyrene content as the toner of 20-25wt%, when flooding in solvent, image forms material and flows out, and leaves a trace on the paper surface, does not therefore measure reflection density.When using the toner of polystyrene content more than 30wt%, it is identical with the reflection density that begins most to eliminate behind the image reflection density of paper, can eliminate image well.Stability and embodiment 17 that gained is eliminated state come to the same thing.
Table 18
| Polystyrene accounts for the weight % of toner total amount | Reflection density |
| 20 | - |
| 25 | - |
| 30 | 0.07 |
| 40 | 0.07 |
| 50 | 0.07 |
| 60 | 0.07 |
| 70 | 0.07 |
| 80 | 0.07 |
| 90 | 0.07 |
Embodiment 19
Except according to the ratio shown in the table 19, add the different polystyrene of molecular weight as beyond the bonding agent, other and embodiment 17 identical modulation toners.With pack into the toner tube of facsimile recorder of gained toner, on paper, duplicate image.
On the one hand, cholesterol 3wt% and D-glucose 3wt% are dissolved in preparation elimination solution in the ethylene glycol diethyl ether as remover.Gained is eliminated the image cancellation element that solution that image uses is packed into shown in Figure 3, to the paper spray solution that forms image, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 19.Shown in table 19, when using the big polystyrene of molecular weight, preferred low content.
Table 19
| The mean molecular weight of polystyrene | Polystyrene accounts for the weight % of toner total amount | Reflection density |
| 45,000 | 40 | 0.07 |
| 45,000 | 85 | 0.07 |
| 45,000 | 90 | 0.08 |
| 220,000 | 40 | 0.07 |
| 220,000 | 75 | 0.07 |
| 220,000 | 85 | 0.08 |
| 630,000 | 40 | 0.07 |
| 630,000 | 70 | 0.07 |
| 630,000 | 80 | 0.08 |
| 630,000 | 90 | 0.42 |
Embodiment 20
Except adding mean molecular weight is that 130,000 the positive butyl ester multipolymer of styrene/methacrylic acid (n-BMA content 10wt%) 70 weight portions are as outside the bonding agent, according to the identical methods modulation toner of embodiment 17.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 5wt% and D-glucose 5wt% are dissolved in the solution that the modulation eliminating image is used in the organic solvent shown in the table 20 as remover.With this solution container of packing into, the paper that forms image was flooded in solution 30 seconds, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 20.Shown in table 20, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter which kind of situation can both be eliminated image well.The stability of elimination state and embodiment 17 come to the same thing.
Table 20
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.07 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.07 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.07 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.08 |
Embodiment 21
Except add mean molecular weight according to the ratio shown in the table 21 is that 130,000 the positive butyl ester multipolymer of styrene/methacrylic acid (n-BMA content 10wt%) is as outside the bonding agent, according to the identical methods modulation toner of embodiment 17.With pack into the toner tube of laser printer of gained toner, on paper, print image.
On the one hand, cholesterol 3wt% and D-glucose 3wt% are dissolved in the solution that the modulation eliminating image is used in the ethylene glycol diethyl ether as remover.With this solution container of packing into, the paper that forms image was flooded in solution 30 seconds, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 21.Shown in table 21, when using binder content as the toner of 15-20wt%, when flooding in solvent, image forms material and flows out, and leaves a trace on the paper surface, does not therefore measure reflection density.When using the toner of binder content more than 30wt%, it is identical with the reflection density that begins most to eliminate behind the image reflection density of paper, can eliminate image well.Stability and embodiment 17 that gained is eliminated state come to the same thing.
Table 21
| The weight % of binder constitutes toner total amount | Reflection density |
| 15 | - |
| 20 | - |
| 30 | 0.07 |
| 55 | 0.07 |
| 65 | 0.07 |
| 75 | 0.07 |
| 85 | 0.07 |
| 95 | 0.07 |
| 98 | 0.10 |
Embodiment 22
Except according to the ratio shown in the table 22, add the different positive butyl ester multipolymer of styrene/methacrylic acid (n-BMA content 10wt%) of mean molecular weight as beyond the bonding agent, other and embodiment 17 identical modulation toners.With pack into the toner tube of facsimile recorder of gained toner, on paper, duplicate image.
On the one hand, cholesterol 3wt% and D-glucose 3wt% are dissolved in modulation eliminating solution in the ethylene glycol diethyl ether as remover.Gained is eliminated the image cancellation element that solution that image uses is packed into shown in Figure 1, the paper that forms image was soaked in solvent 30 seconds, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 22.Shown in table 22, when using the big bonding agent of molecular weight, preferred low content.
Table 22
| The mean molecular weight of bonding agent | The weight % of binder constitutes toner total amount | Reflection density |
| 130,000 | 40 | 0.07 |
| 130,000 | 85 | 0.07 |
| 130,000 | 98 | 0.12 |
| 352,000 | 40 | 0.07 |
| 352,000 | 80 | 0.07 |
| 352,000 | 90 | 0.15 |
| 850,000 | 40 | 0.07 |
| 850,000 | 70 | 0.07 |
| 850,000 | 80 | 0.14 |
| 850,000 | 90 | 0.42 |
Embodiment 23
Except add mean molecular weight according to the ratio shown in the table 23 is that the different positive butyl ester multipolymer of styrene/methacrylic acid of 130,000 n-BMA content is as outside the bonding agent, according to the identical methods modulation toner of embodiment 17.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 5wt% and D-glucose 5wt% are dissolved in the solution that the modulation eliminating image is used in the ethylene glycol diethyl ether as remover.In packing this solution into the image cancellation element shown in Figure 1, the paper that forms image was flooded in solution 30 seconds, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 23.Shown in table 23, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.The stability of elimination state and embodiment 17 come to the same thing.
Table 23
| The methacrylic acid n-butyl accounts for cinnamic weight % | The weight % of binder constitutes toner total amount | Reflection density |
| 5 | 85 | 0.07 |
| 10 | 85 | 0.07 |
| 15 | 85 | 0.07 |
| 20 | 85 | 0.07 |
| 25 | 85 | 0.07 |
| 30 | 90 | 0.07 |
| 35 | 90 | 0.07 |
| 40 | 90 | 0.07 |
| 45 | 80 | 0.08 |
| 50 | 80 | 0.08 |
Embodiment 24
Except adding mean molecular weight is 130,000, and the acrylate monomer content shown in the table 24 is that styrene-propene acid copolymer 70 weight portions of 10wt% are as outside the bonding agent, according to the identical methods modulation toner of embodiment 17.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the ethylene glycol diethyl ether as remover.In packing this solution into the image cancellation element shown in Figure 3, on the paper that forms image, use this solution spray, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 24.Shown in table 24, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.The stability of elimination state and embodiment 17 come to the same thing.
Table 24
| Acrylate monomer | Reflection density |
| The methacrylic acid n-butyl | 0.07 |
| The methacrylic acid isobutyl | 0.07 |
| Ethyl acrylate | 0.07 |
| The methacrylic acid n-butyl | 0.07 |
| Methyl propenoic acid glycidyl base ester | 0.07 |
| Diethylamino propyl group acrylate | 0.07 |
| The 2-ethylhexyl acrylate | 0.07 |
| Glycolmethacrylate | 0.07 |
| Methyl methacrylate | 0.07 |
| Dimethyl amino ethyl methacrylate | 0.08 |
Embodiment 25
Except adding mean molecular weight is that blending polymkeric substance (content of polyacrylate is 10wt%) 70 weight portions of 130,000 polystyrene and polyacrylate are as outside the bonding agent, according to the identical methods modulation toner of embodiment 17.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the ethylene glycol diethyl ether as remover.This solution is packed in the container, the paper that forms image is flooded in this solution, eliminate image after, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 25.As shown in Table 25, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use the toner that contains which kind of bonding agent can both eliminate image well.The stability of elimination state and embodiment 17 come to the same thing.
Table 25
| Polyacrylate | Reflection density |
| The polymethylacrylic acid n-butyl | 0.07 |
| The polymethylacrylic acid isobutyl | 0.07 |
| Polyethyl acrylate | 0.08 |
| The polyacrylic acid n-butyl | 0.09 |
| The polymethylacrylic acid glycidyl esters | 0.09 |
| Poly-diethylamino propyl group acrylate | 0.09 |
| Poly-2-ethylhexyl acrylate | 0.09 |
| Polyethylene glycol methacrylate-styrene polymer | 0.10 |
| Polymethylmethacrylate | 0.11 |
| Poly dimethyl amino-ethyl methacrylate | 0.09 |
Embodiment 26
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight is 11,500 fumaric acid/etherificate diphenols polyester binder 72 weight portions, alkali compounds 5 weight portions shown in charged inhibitor 1 weight portion and the table 26 mix, and fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of laser printer of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the toluene as remover.With this solution container of packing into, the paper that forms image was soaked in solution 30 seconds, eliminate image after, drying.Paper is contacted 30 seconds with the roller that is heated to 200 ℃, measure the reflection density of paper behind the elimination image, the results are shown in table 26.Shown in table 26, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.
Table 26
| Alkali compounds | Reflection density |
| Lime chloride | 0.07 |
| Ammonium hydroxide | 0.07 |
| Tetramethylammonium hydroxide | 0.07 |
| Lime carbonate | 0.08 |
| Hartshorn salt | 0.08 |
| NaOH | 0.08 |
| Potassium hydroxide | 0.08 |
| Triethylamine | 0.07 |
| Dibutylamine | 0.08 |
| Butylamine | 0.08 |
| Cyclohexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.08 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Then, the paper of eliminating image was placed 300 hours at 60 ℃, image does not reproduce.Afterwards, on the paper of eliminating image, duplicate other image, and then eliminate 9 times so repeatedly.Image that duplicates for the 10th time and the 1st time image have equal quality.Further, duplicate and eliminate 50 times repeatedly, its result, though some damage of the physical state of paper, the quality of duplicating image is fine with the quality of the state of elimination.
Embodiment 27
In the 40mL aqueous solution that is dissolved with the 4g gelatin (37 ℃), add the listed alkali compounds 4g of table 27, and add the solution 45mL (37 ℃) that is dissolved with 11g sodium sulphate, bring out cohesion.After this dispersion liquid is cooled to 30 ℃ of placements, isolate microcapsules by decant.Add the formaldehyde of equivalent and stirred 5 minutes in 1mL gained microcapsules, then, the ethanol that adds 2 times of amounts of formaldehyde stirred after 5 minutes, leached microcapsules.It is dry that the gained microcapsules are cleaned the back with cold water.The microcapsules of alkali compounds are enclosed in preparation in this way.
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight are maleic acid/propandiols polyester binder 67 weight portions of 11,500, charged inhibitor 1 weight portion and microcapsules 10 weight portions mix, and fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the toluene as remover.With this solution container of packing into, the paper that forms image was soaked in solution 30 seconds, eliminate image after, drying.Then, paper is contacted 30 seconds with the hot-rolling that is heated to 200 ℃ and eliminate image.Measure the reflection density of paper behind the elimination image, the results are shown in table 27.Shown in table 27, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 26 come to the same thing.
Table 27
| Alkali compounds | Reflection density |
| Triethylamine | 0.07 |
| Dibutylamine | 0.08 |
| Butylamine | 0.08 |
| Cyclohexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.07 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 28
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight are fumaric acid/etherificate diphenols polyester binder 72 weight portions of 11,500, charged inhibitor 1 weight portion and lime chloride 5 weight portions mix, and fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of laser printer of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the organic solvent shown in the table 28 as remover.Image cancellation element with this solution is packed into shown in Figure 2 contacts 30 seconds with the paper that forms image with solution, behind the elimination image, and drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 28.Shown in table 28, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of solution can both eliminate image well.The stability of elimination state and embodiment 26 come to the same thing.
Table 28
| Organic solvent | Reflection density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| Methyl ethyl ketone | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Ethyl lactate | 0.07 |
| Gamma-butyrolacton | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.07 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| Methyl ethyl ketone/hexane (mixing ratio: 1: 1) | 0.08 |
Embodiment 29
With colour generation compound ODB-2 (the Yamamoto system of changing into) 1 weight portion, developer 2,4,4 '-trihydroxybenzophenone, 1 weight portion, molecular weight are Pyromellitic Acid/glycols polyester binder 3 weight portions of 2,500, mix with paraffin 15 weight portions, fully stir with kneader.Use the heat seeling coating machine that it is coated on the PET sheet of thick 4.5 μ m in potpourri, the about 2 μ m of coating thickness make the heat copying sheet.The heat copying sheet overlapped on the paper in thermal printer, solidify, print image.
On the one hand, prepare to contain the solution of the alkali compounds shown in the table 29 of 3wt%.Solvent can use in the table 29 listed, and the difference according to alkali compounds makes water, ethanol or acetone.In addition, with 1 of 3wt%, 2:5,6-diisopropyl fork-D-mannitol and D-fructose 3wt% are dissolved in the solution that the modulation eliminating image is used in the toluene.
Alkaline compound solution and elimination image are respectively charged into 2 containers with solution.The paper that forms image was flooded in alkaline compound solution 1 minute, dry then.Afterwards, eliminating image, eliminate image with flooding 30 seconds in the solution.Then, with 200 ℃ warm wind 30 seconds.Measure the reflection density of paper behind the elimination image, the results are shown in table 29.Shown in table 29, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter which kind of feelings can both be eliminated image well.Elimination state stability is identical with embodiment 26.
Table 29
| Alkali compounds (solvent) | Reflection density |
| Lime chloride (water) | 0.07 |
| Ammonium hydroxide (water) | 0.08 |
| Tetramethylammonium hydroxide (water) | 0.07 |
| Lime carbonate (water) | 0.07 |
| Hartshorn salt (water) | 0.07 |
| NaOH (water) | 0.07 |
| Potassium hydroxide (water) | 0.08 |
| Triethylamine (water) | 0.07 |
| Dibutylamine (ethanol) | 0.08 |
| Butylamine (ethanol) | 0.08 |
| Cyclohexylamine (ethanol) | 0.07 |
| Dicyclohexyl amine (ethanol) | 0.08 |
| Pyridine (acetone) | 0.07 |
| Pyrazine (acetone) | 0.08 |
| Piperazine (acetone) | 0.08 |
Embodiment 30
The heat copying sheet of embodiment 29 preparation overlapped on the paper in thermal printer, solidify, print image.
On the one hand, with pyridine 3wt% as alkali compounds, 1,2:5, the solution that 6-diisopropyl fork-D-mannitol 3wt% and D-fructose 3wt% use as modulation eliminating image in the remover dissolving toluene.With this solution container of packing into, the paper that forms image was flooded in solution 30 seconds, eliminate image after, paper is dried with 200 warm wind.The reflection density of paper is 0.08 behind the elimination image.The stability of elimination state is identical with embodiment 26.
Embodiment 31
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight are fumaric acid/etherificate diphenols polyester binder 72 weight portions of 11,500, mix with charged inhibitor 1 weight portion, fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, with pyridine 3wt% as alkali compounds, 1,2:5,6-diisopropyl fork-D-mannitol 3wt% and D-fructose 3wt% are dissolved in the solution that the modulation eliminating image is used in the ethylene glycol diethyl ether as remover.With this solution container of packing into, the paper that forms image was flooded in solution 30 seconds, eliminate image after, drying.The reflection density of paper is 0.08 behind the elimination image.The stability of elimination state is identical with embodiment 26.
Embodiment 32
Except bisphenol A epoxide resin 72 weight portions that use mean molecular weight 5,500 as beyond the bonding agent, other is identical with embodiment 26, modulates the toner that contains the alkali compounds shown in the table 30.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the toluene as remover.This solution is packed in the container, the paper that forms image was soaked in solution 30 seconds, eliminate image after, drying.Paper is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 30.Shown in table 30, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 26 come to the same thing.
Table 30
| Alkali compounds | Reflection density |
| Lime chloride | 0.07 |
| Ammonium hydroxide | 0.07 |
| Tetramethylammonium hydroxide | 0.08 |
| Lime carbonate | 0.08 |
| Hartshorn salt | 0.09 |
| NaOH | 0.08 |
| Potassium hydroxide | 0.08 |
| Triethylamine | 0.08 |
| Dibutylamine | 0.08 |
| Butylamine | 0.09 |
| Cyclohexylamine | 0.09 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.07 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 33
Identical with embodiment 27, the microcapsules of the alkali compounds shown in the modulation Feng Youbiao 31.In addition, except bisphenol A epoxide resin 67 weight portions that use mean molecular weight 5,500 as beyond the bonding agent, identical with embodiment 27, modulation contains the toner of microcapsules.The gained toner is packed in the toner tube of laser printer, on paper, duplicate image.
On the one hand, cholesterol 7wt% and D-glucose 7wt% are dissolved in the solution that the modulation eliminating image is used in the toluene as remover.This solution is packed in the container, the paper that forms image was soaked in solution 30 seconds, eliminate image after, drying.Paper is contacted 30 seconds eliminate image with the hot-rolling that is heated to 200 ℃.Measure the reflection density of paper behind the elimination image, the results are shown in table 31.Shown in table 31, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of alkali compounds can both eliminate image well.The stability of elimination state and embodiment 26 come to the same thing.
Table 31
| Alkali compounds | Reflection density |
| Triethylamine | 0.07 |
| Dibutylamine | 0.07 |
| Butylamine | 0.08 |
| Cyclo-hexylamine | 0.08 |
| Dicyclohexyl amine | 0.08 |
| Pyridine | 0.07 |
| Pyrazine | 0.08 |
| Piperazine | 0.08 |
Embodiment 34
With colour generation compound crystal violet lactone (CVL) 1 weight portion, developer n-propyl gallate 1 weight portion, mean molecular weight is 5,500 bisphenol A epoxide resin is as bonding agent 72 weight portions, charged inhibitor 1 weight portion and pyridine 5 weight portions mix as alkali compounds, fully stir with kneader.Potpourri is ground into the powder that mean grain size is 10 μ m with comminutor.In this powder 100wt%, add hydrophobic silica 1wt% and be modulated into toner.With pack into the toner tube of duplicating machine of gained toner, on paper, duplicate image.
On the one hand, cholesterol 5wt% and D-glucose 5wt% are dissolved in the solution that the modulation eliminating image is used in the organic solvent shown in the table 32 as remover.This is eliminated in the image cancellation element that solution that image uses packs into shown in Figure 1, the paper that forms image is contacted 30 seconds with solution, behind the elimination image, drying.Measure the reflection density of paper behind the elimination image, the results are shown in table 32.Shown in table 32, the reflection density of paper is identical with the reflection density that begins most behind the elimination image, no matter use which kind of solution can both eliminate image well.The stability of elimination state and embodiment 26 come to the same thing.
Table 32
| Organic solvent | Reaction density |
| Diethylene glycol diethyl ether | 0.07 |
| Isoamyl butyrate | 0.07 |
| MEK | 0.07 |
| Tetrahydrofuran | 0.07 |
| Ethyl propyl ether | 0.07 |
| Dioxolanes | 0.08 |
| Cyclohexanone | 0.07 |
| Lactic acid-ethyl ester | 0.07 |
| Gamma butyrolactone | 0.08 |
| Methanol/toluene (mixing ratio: 1: 1) | 0.07 |
| Ethanol/dimethylbenzene (mixing ratio: 1: 2) | 0.07 |
| Cyclohexanol/toluene (mixing ratio: 1: 3) | 0.07 |
| Isopropyl alcohol/ethyl acetate (mixing ratio: 1: 2) | 0.07 |
| Iso-propanol/toluene (mixing ratio: 1: 1) | 0.08 |
| MEK/hexane (mixing ratio: 1: 1) | 0.08 |
Claims (16)
1, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said remover is made of noncrystal phase separation inhibitor of height and low noncrystal phase separation inhibitor.
2, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said image forms in the material and contains high noncrystal phase separation inhibitor, contains low noncrystal phase separation inhibitor in the described solvent.
3, eliminate to use the image that contains colour generation compound, developer and remover to form the method for the image that material forms on paper, comprising:
By make above-mentioned image form material contact with solvent the elimination image process and
The process of removing remaining solvent from paper,
Wherein said image forms and contains low noncrystal phase separation inhibitor in the material, contains high noncrystal phase separation inhibitor in the described solvent.
4, eliminate to use the image that contains colour generation compound and developer to form the method for the image that material forms on paper, comprising:
Above-mentioned image is formed material contact the process of eliminating image with the solvent that is dissolved with remover, wherein said remover contains high noncrystal phase separation inhibitor and low noncrystal phase separation inhibitor; With
Remove the process of remaining solvent from paper.
5, each described method of claim 1-4, high noncrystal phase separation inhibitor is made of the ring type sugar alcohol, and low noncrystal phase separation inhibitor is made of 5 Yuans that contain hydroxyl above non-aromatic ring compounds or ring type sugar alcohol derivant.
6, each described method of claim 1-4, low noncrystal phase separation inhibitor is a terpenol.
7, after each described method of claim 1-4, image form material and solvent contacts, heat.
8, each described method of claim 1-4, image form in the material and contain bonding agent.
9, the described method of claim 8, bonding agent is made of the polymer blend of polystyrene or copolymer in cinnamic acrylic ester or polystyrene and polyacrylate resin.
10, the described method of claim 9, cinnamic ratio accounts for more than the 50wt% in the bonding agent that the polymer blend of copolymer in cinnamic acrylic ester or polystyrene and polyacrylate resin forms.
11, the described method of claim 8, bonding agent is made of polyester or epoxy resin.
12, each described method of claim 1-4, image form bonding agent and the alkali compounds that contains polyester or epoxy resin formation in the material.
13, each described method of claim 1-4, image form and contain polyester or epoxy resin bonding agent that constitutes and the alkali compounds of enclosing microcapsules in the material.
14, each described method of claim 1-4, image form the bonding agent that material contains polyester or epoxy resin formation, and solvent contains alkali compounds.
15, the described method of claim 4, image form the bonding agent that contains polyester or epoxy resin formation in the material, contain alkali compounds and remover in the solvent.
16, the described method of claim 4, image form the bonding agent that contains polyester or epoxy resin formation in the material, and solvent that contains alkali compounds and the solvent that contains remover are contacted with above-mentioned image formation material respectively.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11681/98 | 1998-01-23 | ||
| JP11682/98 | 1998-01-23 | ||
| JP1168198A JP3315360B2 (en) | 1998-01-23 | 1998-01-23 | Erasable image forming material erasing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243274A CN1243274A (en) | 2000-02-02 |
| CN100338532C true CN100338532C (en) | 2007-09-19 |
Family
ID=11784757
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991029259A Expired - Fee Related CN100338532C (en) | 1998-01-23 | 1999-01-23 | Method for eliminating image-forming material |
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|---|---|
| JP (1) | JP3315360B2 (en) |
| CN (1) | CN100338532C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001350380A (en) * | 2000-06-09 | 2001-12-21 | Minolta Co Ltd | Sheet regenerating device |
| EP1542093A3 (en) | 2003-12-08 | 2007-12-05 | Kabushiki Kaisha Toshiba | Image-erasing apparatus and image-erasing method |
| WO2007078006A1 (en) * | 2006-01-06 | 2007-07-12 | Mitsubishi Chemical Corporation | Electrophotographic photosensitive member, image forming device using same, and electrophotographic photosensitive member cartridge |
| US7659359B1 (en) * | 2008-11-18 | 2010-02-09 | Sabic Innovative Plastics Ip B.V. | Stabilization of isosorbide-based polycarbonate |
| EP3151066B1 (en) * | 2009-11-23 | 2019-09-11 | Toshiba TEC Kabushiki Kaisha | Electrophotographic toner |
| US8647799B2 (en) * | 2010-01-04 | 2014-02-11 | Toshiba Tec Kabushiki Kaisha | Erasable toner and method for producing the same |
| EP2341394B1 (en) * | 2010-01-04 | 2016-08-31 | Toshiba TEC Kabushiki Kaisha | Toner |
| EP2354855A1 (en) * | 2010-01-28 | 2011-08-10 | Toshiba TEC Kabushiki Kaisha | Developing agent and method of manufacturing the same |
| US8603722B2 (en) * | 2010-04-27 | 2013-12-10 | Toshiba Tec Kabushiki Kaisha | Toner producing method and toner |
| CN109278449A (en) * | 2018-09-30 | 2019-01-29 | 胡玉英 | A kind of waste and old paper recycle device |
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| JPS5830765A (en) * | 1981-08-17 | 1983-02-23 | Tomoegawa Paper Co Ltd | Electrophotographic developer |
| DE3247804A1 (en) * | 1981-12-25 | 1983-07-14 | Pentel K.K., Tokyo | Ink and eraser therefor |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP3315360B2 (en) | 2002-08-19 |
| CN1243274A (en) | 2000-02-02 |
| JPH11212410A (en) | 1999-08-06 |
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