CN102702485A - Preparation method of modified aralkyl substituted salicylic acid resin polyvalent metal salt - Google Patents
Preparation method of modified aralkyl substituted salicylic acid resin polyvalent metal salt Download PDFInfo
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- CN102702485A CN102702485A CN2012101664392A CN201210166439A CN102702485A CN 102702485 A CN102702485 A CN 102702485A CN 2012101664392 A CN2012101664392 A CN 2012101664392A CN 201210166439 A CN201210166439 A CN 201210166439A CN 102702485 A CN102702485 A CN 102702485A
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- polyvalent metal
- salicylic acid
- substituted salicylic
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Abstract
The invention discloses a preparation method of modified aralkyl substituted salicylic acid resin polyvalent metal salt. Aralkyl substituted salicylic acid obtained by the reaction of salicylic acid or derivatives of the salicylic acid and styrene or derivatives of the styrene by a catalyst reacts with polyvalent metallic compound and activated clay mixture. The reaction temperature is 50-200 DEG C, and the time is 0.5-5 hours. Purification is carried out after the completion of the reaction, and the activated clay modified aralkyl substituted salicylic acid resin polyvalent metal salt is obtained. The preparation method provided by the invention has the advantages of simple process, no waste water and acid generated in the reaction process, high yield and no environmental pollution.
Description
Technical field
The invention belongs to pressure-sensitive, the used organicvisualization reagent of electrothermal sensitive recording paper field, the used zinc salicylate resin color-developing agent of particularly pressure-sensitive noncarbon recording paper field.The present invention relates to a kind of preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt.
Background technology
Noncarbon recording paper is a kind of speciality paper that utilizes the leuco dye be coated on the paper to develop the color with the developer contact reacts, mainly forms by three layers: last paper (CB), and the back side of this layer paper scribbles the microcapsule that are dissolved in the leuco dye in the non-volatile solvent; Middle paper (CF/CB), this layer recto scribbles the coating of developer, and the back side then is being coated with microcapsule; Following paper (CF), this layer paper only scribble the CF coating that contains developer in the front.Its chromophoric principle does, when pressure imposed on paper, the microcapsules rupture that is coated in the paper back side contacted with the positive developer of CF/CB paper and reacts and develop the color.
The developer that is used for CF coating normally can with the acidic substance of leuco dye generation coupling reaction.Mainly contain three major types at present: atlapulgite class developer, resol structure class developer and alkyl salicylate zinc class developer.A lot of to the research of these several types of developers both at home and abroad.
Chinese patent CN1160644 discloses a kind of preparation method of atlapulgite developer; Make raw material through s.t. with wilkinite, basic metal or alkaline earth metal hydroxides neutralizing treatment, the oxide modifying of Ca, Mg, Ba, Sr, Zn, Al is handled; Surfactant-modified processing; The anti UV agent modification is handled, and operations such as inhibitor modification processing are processed developer.Atlapulgite belongs to inorganic solid acid, and specific surface area is big, and adsorptivity preferably and the stronger electronic capability of accepting are arranged.Atlapulgite initial stage chromophoric characteristic is good, color speed is fast, colour density is high, again because of cheap, and handling ease, and nontoxic, security is good, thereby the long term is used.But also there are some shortcomings in the use; As when receiving humidity, sunshine or running into airborne oxynitride, sulfur oxide, cigarette gas etc.; The coloring intensity of developer will reduce, and the colour developing tone fades significantly, and paper is prone to flavescence; And color development image stability to aging is poor, thereby preservation period, usage period are all shorter.
U.S. Pat P46612254 ﹑ European patent EP 0338808A2 etc. discloses the preparation method of a kind of resol structure coloring agent, is that raw material reacts the product that obtains with alkyl-substituted phenols, formaldehyde and metallic compound.The developer of resol structure; Advantage is to have water tolerance and stability to aging preferably; Make the coating good fluidity; Initial stage color development speed is also very fast, the colour developing degree of depth good but its to have unsurmountable shortcoming be paper easy flavescence under the effect of light or oxidizing gas (mainly being NOx gas in the air).
U.S. Pat P5382560 ﹑ Japanese Patent JP853536 ﹑ Japanese Patent JP6227117 etc. discloses the preparation method of a kind of zinc salicylate structure coloring agent.The developer of zinc salicylate structure has that cryogenic displaying color speed is fast, and tone is bright-coloured, and better ageing-resistant performance once was called best developer by the Japanese.But the chromogenic reagent degree of depth and the expection of zinc salicylate structure have certain gap.
Continuous development along with society; People are also increasingly high to the requirement of developer: promptly hope in the production process environment not to be polluted, hope that again the developer product has good chromophoric characteristic (normal temperature, low temperature, anti-water and ageing-resistant) and use properties (stability of dispersion liquid, coating flexibility).
Summary of the invention
Main purpose of the present invention provides a kind of preparation method of atlapulgite modification aralkyl substituted salicylic acid resin polyvalent metal salt, and this method technology is simple, does not produce wastewater and waste acid in the process, belongs to the green chemical industry synthesis technique; It is fast that it has under the coldcondition color development speed, and final color development density is high, the bright-coloured performance of colour developing tone.
Advantages such as another object of the present invention provides a kind of resin color-developing agent, and its existing cryogenic displaying color speed is fast, and lovely luster has colour developing concentration dark again, and the writing photooxidation aging property is good, and the coating photoaging is inhibited from yellowing.Accomplished the present invention on this basis.
The 3rd purpose of the present invention is to disclose a kind of new developer resin combination.Its composition is mainly the aralkyl substituted salicylic acid resin polyvalent metal salt of atlapulgite modification, and it has overcome the defective of type developer in the past as developer for non-carbon copying paper.
The 4th purpose of the present invention is to disclose a kind of new developer resin emulsion.Its composition is mainly novel developer resin combination of the present invention.
In order to reach above-mentioned purpose of design, the technical scheme that the present invention adopts is following:
A kind of preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt; Aralkyl substituted salicylic acid that Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof generate under the effect of catalyzer and polyvalent metal compounds and atlapulgite mixture react; Temperature of reaction is 50～200 ℃; 0.5～15 hour time, after accomplishing, reaction, obtains atlapulgite modification aralkyl substituted salicylic acid resin polyvalent metal salt through refining.
Said Whitfield's ointment or derivatives thereof is meant Whitfield's ointment, alkyl substituted salicylic acid and their ester class, halo Whitfield's ointment etc.Whitfield's ointment for example, wintergreen oil, the 3-cresotinic acid, 5-ethyl Whitfield's ointment, 3-ethyl salicylic ether, 5-nonyl Whitfield's ointment, 5-ethyl wintergreen oil, the 3-chloro-salicylic acid, the 5-bromination salicylic acid ... Or the like.
Said vinylbenzene or derivatives thereof is meant vinylbenzene, ring-alkylated styrenes, alpha-alkyl phenylethylene.Vinylbenzene for example, the 3-vinyl toluene, the 4-propylstyrene, alpha-methyl styrene, α-ethyl styrene ... Or the like.
Said catalyzer is selected from one or several in inorganic acids, organic sulfonic acid class, the polyvalent metal compounds class.The catalyst consumption in fact influence to reaction is very big, and when catalytic amount was very few, reaction was difficult to carry out fully, and the temperature of perhaps reacting required is too high and cause that by product too much and the local ageing phenomenon; Too high usage quantity will increase catalyzer residual in system, thereby the use properties of final product is worked the mischief, and is too high like viscosity, be difficult to disperse and serious foaming tendency, also reduced combined coefficient and yield simultaneously.Catalyst consumption for the Whitfield's ointment or derivatives thereof be benchmark weight percent 0.01%～50%, preferred 0.01%～25%.
The inorganic acids catalyzer comprises atlapulgite, molecular sieve, heteropolyacid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.Organic sulfonic acid class catalyzer is the metal-salt of methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid, right-toluenesulphonic acids, right-EBSA, alkyl benzene sulphonate(ABS), perfluoro alkyl sulfonic acid etc. or organic sulfonic acid, and wherein the metal-salt of organic sulfonic acid is meant the calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin of organic sulfonic acid, plumbous salt.Polyvalent metal compounds class catalyzer is meant the polyvalent metal compounds of calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, lead, can be organic cpds, also can be mineral compound.Organic cpds can be calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, plumbous stearate, acetate, benzoate etc.; For example like calcium stearate, lithium stearate, Zinic stearas, zinc acetate, lime acetate, Zinc dibenzoate, phenylformic acid iron ... Or the like. mineral compound can be calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, plumbous vitriol, nitrate salt, muriate, oxide compound, oxyhydroxide etc., for example like calcium sulfate, zinc sulfate, single nickel salt, manganous sulfate, lithium chloride, aluminum chloride, nickelous chloride, zinc chloride, tin chloride, Natural manganese dioxide, aluminum oxide, zinc oxide, red stone, nickel oxide, manganese oxide ... Or the like.The catalyzer of reaction process can be selected a kind of or two or more mixing as catalyzer among the present invention from aforementioned any one type of catalyzer, also never selects two kinds or two or more mixing in the similar catalyst as catalyzer.
Set forth stage by stage in the face of the building-up process of modification aralkyl substituted salicylic acid resin polyvalent metal salt down.
Fs: Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof react under the effect of catalyzer.
The mol ratio of Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof is generally 1:1～10, and too high ratio causes the cohesion of product surface skining phenomenon and dispersion liquid particle easily, and usually, the ideal ratio is 1:1.5～4.5.
Under these conditions, Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof react in 40～200 ℃ range of reaction temperature.Higher temperature condition helps styrene derivatives and the Whitfield's ointment or derivatives thereof carries out substitution reaction, when higher substitution degree helps contacting with leuco dye of final product coupling reaction can take place promptly.But too high temperature can cause the autohemagglutination of styrene derivatives and the increase of side reaction, has influenced final effect on the contrary.
Subordinate phase: aforementioned Whitfield's ointment or derivatives thereof and the resultant of vinylbenzene or derivatives thereof reaction and the reaction between polyvalent metal compounds and the atlapulgite mixture.
The definition of the polyvalent metal compounds in the definition of polyvalent metal compounds and the catalysts is identical.The dosage of polyvalent metal compounds is a benchmark with the Whitfield's ointment or derivatives thereof, and the mol ratio of polyvalent metal compounds and Whitfield's ointment or derivatives thereof is 0.1～2:1.The weight ratio of atlapulgite and polyvalent metal compounds is 0.01～10:1, preferred 0.05～5:1.The adding mode of polyvalent metal compounds and atlapulgite mixture can directly add also and can add indirectly.The adding mode of polyvalent metal compounds and atlapulgite preferably adds with the form of dispersion liquids such as solution or suspension liquid; Do like this and can improve polyvalent metal compounds and the degree of scatter of atlapulgite in system, solved the coagulation problems of product " conglomeration " and developer dispersion effectively.Dispersion medium can be an organic solvent, also can be water, also can be two kinds mixture.Organic solvent comprises acetate, ether, MTBE, Ethyl Tertisry Butyl Ether, ETHYLE ACETATE, butanone, ethanol, Virahol, primary isoamyl alcohol, toluene, YLENE, toluylic acid, N, dinethylformamide, DMSO 99.8MIN., normal heptane etc.
Need in polyvalent metal compounds and the atlapulgite dispersion liquid process for preparation to add tensio-active agent, tensio-active agent not only can improve the degree of scatter of polyvalent metal compounds and atlapulgite greatly, can also the emulsification of finished product be contributed.The amount of tensio-active agent is benchmark with the polyvalent metal compounds, and the weight ratio of tensio-active agent and polyvalent metal compounds is 0～0.2:1 (not comprising end points 0).The scope of the concentration of polyvalent metal compounds and atlapulgite slurries (solid content) is more than or equal to 5% and less than 100%.Tensio-active agent can be that aniorfic surfactant can be nonionogenic tenside or polymeric surface active agent also, mainly comprises: alkyl carboxylate, alkyl sulfuric ester salt, alkyl ethoxylated sulfuric acid, alkyl phenol ether sulfuric acid, sulfonated alkylbenzene, sulfosuccinate ester salt, long-chain fat amine salt, polyxyethylated alkylphenol, polyoxyethylene polyols fatty ester, Sorbic Acid fatty ester, Z 150PH, ZX-I, CMC 99.5 or its sodium salt, Natvosol, polyoxyethylene, alginates etc.
Aralkyl substituted salicylic acid resin (oligopolymer) is 50～200 ℃ with polyvalent metal salt and atlapulgite dispersion liquid in temperature; React under the condition of 0.5～15 hour time; Reaction finishes the raw material that the back is removed byproduct of reaction through rectification under vacuum and do not participated in reaction, obtains aralkyl substituted salicylic acid resin polyvalent metal salt.
Modification aralkyl substituted salicylic acid resin polyvalent metal salt can also be used to produce the developer resin combination; This reagent composition is normally in the presence of polyvalent metal compounds, and the product of condensation reaction takes place under the effect of aldehyde for modification aralkyl substituted salicylic acid resin polyvalent metal salt, alkylphenol, Whitfield's ointment.This reagent composition can directly be used to produce developer.
Modification aralkyl substituted salicylic acid resin polyvalent metal salt can directly be used to produce developer, also can be used to produce developer with other reagent compositions.Under the latter event, modification aralkyl substituted salicylic acid resin polyvalent metal salt and other reagent composition weight percents are generally 1:0.1～2.
The polyvalent metal salt of said modification aralkyl substituted salicylic acid resin obtains the developer emulsion through dispersion and emulsion under influence of surfactant.
A kind of developer product emulsion comprises the developer resin combination.
The preparing method's of modification aralkyl substituted salicylic acid resin polyvalent metal salt of the present invention beneficial effect is: technology is simple, and reaction process does not produce wastewater and waste acid, and yield is high, and environment is not produced pollution.
Embodiment
Do further detailed description in the face of optimum implementation of the present invention down.
Embodiment 1
In the there-necked flask that is equipped with whisking appliance, reflux exchanger, TM, add 146 gram Whitfield's ointments, 5.3 gram nickelous chlorides, 4.23 gram methylsulphonic acids; 106 gram vinylbenzene, warming while stirring to 125 ℃ dripped 220 gram vinylbenzene in 2 hours; Be warming up to 180 ℃ after adding, reacted 3 hours.Then temperature of reaction system is reduced to 95 ℃, add preparation slurries 201.5 grams (zinc hydroxide 45 grams, atlapulgite 5 grams, Virahol 15 grams; Water 135 grams, Z 150PH 0.3 gram, ZX-I 1.2 grams); Reaction is 5 hours under this temperature of reaction, carries out rectification under vacuum then, steams unreacted reactant.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin zinc salt 525 grams at last.
Embodiment 2
According to carrying out, just replace the methylsulphonic acid among the embodiment 1 with atlapulgite with embodiment 1 identical method.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin zinc salt 523 grams at last.
Embodiment 3
According to carrying out, just replace the nickelous chloride among the embodiment 1 with lithium chloride with embodiment 1 identical method.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin zinc salt 526 grams at last.
Embodiment 4
According to carrying out, just replace the zinc hydroxide among the embodiment 1 with zinc oxide with embodiment 1 identical method.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin zinc salt 521 grams at last.
Embodiment 5
According to carrying out, just change into dropping 108 gram vinylbenzene in 2 hours to the 220 gram vinylbenzene that in 2 hours, drip among the embodiment 1 with embodiment 1 identical method.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin zinc salt 413 grams at last.
Embodiment 6
According to carrying out, just replace the zinc hydroxide among the embodiment 1 with quicklime with embodiment 1 identical method.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin calcium salt 520 grams at last.
Embodiment 7
In the there-necked flask that is equipped with whisking appliance, reflux exchanger, TM, add 146 gram Whitfield's ointments, 9.5 gram nickelous chlorides, 106 gram vinylbenzene; Warming while stirring to 145 ℃; In 2 hours, drip 108 gram vinylbenzene, be warming up to 180 ℃ after adding, reacted 3 hours.Then temperature of reaction system is reduced to 125 ℃, add aluminum oxide slurries 206 grams (aluminum oxide 25 grams, atlapulgite 20 grams; YLENE 10 grams, water 150 grams, Z 150PH 0.1 gram; Sulfosuccinate ester salt 1.1 grams); Reaction is 5 hours under this temperature of reaction, carries out rectification under vacuum then, steams byproduct of reaction. obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin aluminium salt 409 grams at last.
Embodiment 8
According to carrying out, just replace 25 gram aluminum oxide among the embodiment 9 with 50 gram magnesium chlorides with embodiment 7 identical methods.Obtain arborescens atlapulgite modification aralkyl substituted salicylic acid resin magnesium salts 421 grams at last.
Embodiment 9
Under certain temperature and pressure, the polyvalent metal salt of the arborescens atlapulgite modification aralkyl substituted salicylic acid resin of embodiment 1 preparation is passed through dispersion and emulsion obtain the developer emulsion of median size under the effect of tween 20 and PVA less than 1.5 μ m.
Embodiment 10
Under certain temperature and pressure; The polyvalent metal salt of the arborescens atlapulgite modification aralkyl substituted salicylic acid resin of 90 gram embodiment 1 preparations is restrained zinc oxide with 14 gram tert.-butyl phenols, 3.5 gram Whitfield's ointments, 0.8; The intensification fusion; Under the formaldehyde effect, carry out polycondensation, obtain the developer resin combination.
Embodiment 11
Under certain temperature and pressure, the developer resin combination that embodiment 10 is prepared obtains the developer emulsion of median size less than 1.5 μ m through dispersion and emulsion under sodium lauryl sulphate and PVA effect.
Embodiment 12
Under certain temperature and pressure; Getting embodiment 10 prepared developer resin combinations 40 restrains; Mixes with the polyvalent metal salt of the aralkyl substituted hydroxy-benzoic acid resin of 50 gram the present invention preparations, under the effect of tween 20 and sodium lauryl sulphate, pass through dispersion and emulsion and obtain the developer emulsion of median size less than 1.5 μ m.
The developer emulsion is pressed the CF slurry that the CF formulated becomes, and hardened coating is weighed after drying on the scraps of paper, calculates glue spread.In the environment of certain temperature, humidity condition, after the third gear tetrad on the EPSEN-III type type-writer is printed, survey its colour developing value with Beijing Kang Guang SC-80C color color difference meter.The colour developing data are as shown in the table.
Colour developing data (25 ℃ of temperature, humidity RH45%)
Annotate: 1, reference substance-1, reference substance-2 are existing market developer commodity commonly used;
2, the CF prescription:
80 milliliters in china clay 20 gram lime carbonate 20 gram amylans (12%) 92 gram styrene-butadiene latex 6 gram developer emulsions 15 gram dispersion agents 1 gram water
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and is convenient to these those skilled in the art and can understands and use the present invention, can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, and needn't pass through performing creative labour.Therefore, those skilled in the art should be within protection scope of the present invention to the simple modifications that the present invention makes according to announcement of the present invention.
Claims (10)
1. the preparation method of a modification aralkyl substituted salicylic acid resin polyvalent metal salt; It is characterized in that: aralkyl substituted salicylic acid that Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof generate under the effect of catalyzer and polyvalent metal compounds and atlapulgite mixture react; Temperature of reaction is 50～200 ℃; 0.5～15 hour time, after accomplishing, reaction, obtains atlapulgite modification aralkyl substituted salicylic acid resin polyvalent metal salt through refining.
2. the preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt according to claim 1 is characterized in that: said Whitfield's ointment or derivatives thereof is meant Whitfield's ointment, alkyl substituted salicylic acid and their ester class, halo Whitfield's ointment.
3. the preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt according to claim 1, it is characterized in that: said vinylbenzene or derivatives thereof is meant vinylbenzene, ring-alkylated styrenes, alpha-alkyl phenylethylene.
4. the preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt according to claim 1, it is characterized in that: the mol ratio of said Whitfield's ointment or derivatives thereof and vinylbenzene or derivatives thereof is 1:1～10.
5. the preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt according to claim 1 is characterized in that: said catalyzer is one or several in inorganic acids, organic sulfonic acid class, the polyvalent metal compounds class; Catalyst consumption for the Whitfield's ointment or derivatives thereof be benchmark weight percent 0.01%～50%; Said inorganic acids catalyzer comprises atlapulgite, molecular sieve, heteropolyacid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid; Said organic sulfonic acid class catalyzer is the metal-salt of methylsulphonic acid, ethylsulfonic acid, Phenylsulfonic acid, right-toluenesulphonic acids, right-EBSA, alkyl benzene sulphonate(ABS), perfluoro alkyl sulfonic acid etc. or organic sulfonic acid, and wherein the metal-salt of organic sulfonic acid is meant the calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin of organic sulfonic acid, plumbous salt; Said polyvalent metal compounds class catalyzer is meant the polyvalent metal compounds of calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, lead.
6. the preparation method of modification aralkyl substituted salicylic acid resin polyvalent metal salt according to claim 1 is characterized in that: said polyvalent metal compounds is meant the organic or inorganic compound of the polyvalent metal of calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, lead; Wherein, organic cpds is stearate, acetate, the benzoate of calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, lead; Mineral compound is vitriol, nitrate salt, muriate, oxide compound, the oxyhydroxide of calcium, magnesium, lithium, aluminium, iron, manganese, nickel, zinc, tin, lead; The dosage of said polyvalent metal compounds is a benchmark with the Whitfield's ointment or derivatives thereof, and the mol ratio of polyvalent metal compounds and Whitfield's ointment or derivatives thereof is 0.1～2:1; The weight ratio of said atlapulgite and polyvalent metal compounds is 0.01～10:1.
7. the method according to any described modification aralkyl substituted salicylic acid resin polyvalent metal salt production developer emulsion of claim 1 ~ 6 is characterized in that: the polyvalent metal salt of modification aralkyl substituted salicylic acid resin is obtained the developer emulsion through dispersion and emulsion under influence of surfactant.
8. the method for manufacture of a developer resin combination; It is characterized in that: in the presence of polyvalent metal compounds; Condensation reaction takes place in modification aralkyl substituted salicylic acid resin polyvalent metal salt, alkylphenol, Whitfield's ointment by any said method preparation of claim 1 ~ 6 under the effect of aldehyde, obtain the developer resin combination.
9. a developer resin combination is characterized in that: comprise the product that condensation reaction is taken place under the effect of aldehyde by modification aralkyl substituted salicylic acid resin polyvalent metal salt, alkylphenol, the Whitfield's ointment of any said method preparation of claim 1 ~ 6.
10. a developer product emulsion is characterized in that: comprise the described developer resin combination of claim 10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382560A (en) * | 1991-12-18 | 1995-01-17 | Sanyo Chemical Industries, Ltd. | Color developers and sheets thereof |
| EP1072623A2 (en) * | 1999-07-21 | 2001-01-31 | Daedong Company, Ltd. | Polyvalent metal salts of salicyclic acid resin and process for the preparation thereof |
| CN101377066A (en) * | 2008-06-27 | 2009-03-04 | 东莞市天盛特种纸制品有限公司 | Coating formula of non-carbon carbon paper color development face for aqueous ink jet printing bar code symbol |
-
2012
- 2012-05-25 CN CN201210166439.2A patent/CN102702485B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382560A (en) * | 1991-12-18 | 1995-01-17 | Sanyo Chemical Industries, Ltd. | Color developers and sheets thereof |
| EP1072623A2 (en) * | 1999-07-21 | 2001-01-31 | Daedong Company, Ltd. | Polyvalent metal salts of salicyclic acid resin and process for the preparation thereof |
| CN101377066A (en) * | 2008-06-27 | 2009-03-04 | 东莞市天盛特种纸制品有限公司 | Coating formula of non-carbon carbon paper color development face for aqueous ink jet printing bar code symbol |
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