CN1007814B - Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of copolymers, and color-developing sheets employ in agents - Google Patents
Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of copolymers, and color-developing sheets employ in agentsInfo
- Publication number
- CN1007814B CN1007814B CN87100709A CN87100709A CN1007814B CN 1007814 B CN1007814 B CN 1007814B CN 87100709 A CN87100709 A CN 87100709A CN 87100709 A CN87100709 A CN 87100709A CN 1007814 B CN1007814 B CN 1007814B
- Authority
- CN
- China
- Prior art keywords
- mole
- iii
- resin
- structural unit
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Images
Landscapes
- Color Printing (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Disclosed herein are novel linear copolymers having weight average molecular weight of 500-30,000 and comprising structural units represented by the following formulae (I), (II), (III) and (IV), wherein R1, R2 and R3 mean individually an alkyl group having 4 or fewer carbon atoms and R4 denotes an alkyl, cycloalkyl, aralkyl or phenyl group, and multivalent metal salts thereof in each of which the multivalent metal forms the multivalent metal salt between carboxyl groups within the same molecule of the copolymer or between different molecules of the copolymer.
Description
The present invention relates to the salicyclic acid resin and the polyvalent metal salt thereof of a class novelty, as developer effective constituent, that be applicable to pressure-sensitive carbon paper, and use colour developing paper this developer, that be applicable to pressure-sensitive carbon paper with multivalent metal modified resin.
The pressure-sensitive copy paper also claims noncarbon recording paper.By pressure machinery or ballistic, for example a stroke write or the printing of type-writer can both make them produce a kind of color.Therefore, just can obtain many parts of autotypes at one time.This class pressure-sensitive copy paper, the title that has " transfer printing type transfer paper ", the title that has " transfer paper of controlling oneself " etc.Their chromophoric mechanism depends on to the leuco dye parent of electronics separately and accepts color development reaction between the developer of electronics.With the transfer printing type pressure-sensitive carbon paper as an example, and narrate with reference to Fig. 1, Fig. 1 is the cross section view of a signal, and it has represented the structure of the pressure-sensitive carbon paper that exemplifies.
It is that several microns are to tens microcapsule 4 more than the micron that the back side of CB-paper 1 and CF/CB-paper 2 scribbles diameter, microcapsule are that a kind of colourless pressure sensitive dye parent is dissolved in the nonvolatile oil, use polymeric membrane then, for example gelatin film is bundled into capsule with dissolving solution well and obtains.On the other hand, the front of CF/CB-paper 2 and CF-paper 3 is coated with the coating ingredients that one deck contains developer 5, and it has such specific character, and promptly when it contacted with the pressure sensitive dye parent, developer 5 reacted with dye matrix, makes dye matrix produce color thus.For duplicating, they are pressed CB-paper, (CF/CB-paper), (CF/CB-paper) and the order of CF-paper stack, on one side and make one side of scribbling dye matrix and scribble developer and be close to.Use whether CF/CB paper is arbitrarily.When exerting pressure with ballpoint pen 6 or type-writer, 4 of the micro-capsules at pressurized place break.The result is that the solution that contains the pressure sensitive dye parent is transferred on the developer 5, has obtained a thus or many parts of manifolding records.
As nucleophobic developer, once recommended (1) inorganic solid acid, for example acidic white earth and attapulgite are published in U.S. Patent number 2712507; (2) substituted phenol and bis-phenol are published in Japanese patent publication 9309/1965; (3) para-orientation phenol-yuban is published in Japanese patent publication 20144/1967; (4) metal-salt of aromatic carboxylic acid is published in Japanese patent publication 10856/1974 and 1327/1977; Deng.Wherein there are some in fact to utilize.
Think satisfied colour developing paper, what its aspect of performance should propose is, be exposed to ray in the storage process neutralization, for example seldom flavescence under the sunlight, and the coloured writing fastness that produces is fine, so they are under the influence of radiation, water or softening agent, and color can not disappear or be not easy to fade, so be not only harsh product, and extremely excellent colour developing ability all arranged after long storage.
Developer of having recommended so far and the colour developing paper that scribbles these developers commonly used all have merits and demerits at aspect of performance.For example, though inorganic solid acid price is cheap, but when storing, understand gas and moisture in the absorbed air.Therefore, make paper surface flavescence, chromophoric characteristic is reduced.The color development ability of substituted phenol is not enough and coloured writing color depth that produce is very low.Usually the contraposition phenylphenol phenolic novolac that is used as the phenol-yuban of para-orientation has extremely excellent color development ability, but its coated paper meeting flavescence, and the coloured writing that generates is exposed in daylight or the storage process obviously fade (influenced by airborne nitrogen oxide).In addition, the metal-salt of aromatic carboxylic acid is all fine at aspects such as color development ability, anti-flavescence and light fastnesses, but the ability of water tolerance and plasticizer-resistant can't be thought satisfaction.
First purpose of the present invention provides a kind of linear copolymers of novelty, and it all is fabulous in the performance of aspects such as flexibility, oxidation-resistance, formability and plasticity-.And can generate metal-chelating resin and polyvalent metal salt, the developer of using as pressure-sensitive carbon paper is fabulous.
Second purpose of the present invention provides the good developer that a kind of pressure-sensitive carbon paper is used, and it is a kind of metal-modified product, comprises the polyvalent metal salt of above-mentioned multipolymer or contains the molten mixture of above-mentioned multipolymer polyvalent metal salt.
The 3rd purpose of the present invention provides a kind ofly to be utilized the good colour developing paper of above-mentioned developer and is applicable to pressure-sensitive carbon paper.
The present inventor has carried out a large amount of test works, so that realize above-mentioned multiple purpose.Finally finished the present invention.
Therefore, a kind of linear copolymers provided by the invention, comprise the 5-60%(mole) structural unit (I), the 30-50%(mole) structural unit (II), the 0-60%(mole) structural unit (III) and 0-60%(mole) structural unit (IV), and its heavy about molecular weight is 500-30,000, above-mentioned structural unit (I), (III), (IV) is by structural unit (II) and structural unit (I), different one is connected in (III) or (IV), and said structure unit (I), (II), (III) and (IV) is separately with following formula I, (II), (III) and (IV) represented:
R in the formula
1, R
2And R
3Be expressed as 4 or the alkyl of carbon atom still less separately, R
4Expression alkyl, cycloalkyl, aralkyl or phenyl, or their polyvalent metal salt, wherein polyvalent metal has formed the polyvalent metal-salt between multipolymer is with the carboxyl of a part or between the carboxyl of the differing molecular of multipolymer; Contain the multivalent metal modified resin as effective ingredient in the developer, it comprises above-mentioned a kind of polyvalent metal salt or contains the molten mixture of polyvalent metal salt, and is applicable to pressure-sensitive carbon paper; With a kind of colour developing paper that scribbles above-mentioned developer, and developer almost is to be coated on equably on the one side at least of colour developing paper.Described colour developing paper is applicable to pressure-sensitive carbon paper.
Multipolymer and their polyvalent metal salt are the macromolecular compound and its esters of a class novelty, and production had not also been arranged so far.Therefore, developer of the present invention also is novel developer.
Compare with the colour developing paper that utilizes inorganic solid acid or contraposition phenyl phenol phenolic novolac to make, utilize its colour developing ability of the prepared colour developing paper of the novel developer of the present invention with it quite or better, and the coloured writing fastness that produces is good, is not subject to the influence of water, softening agent or light and fades.
Another advantage of the present invention is improved by the problem of sun exposure flavescence, and particularly preventing has had tangible improvement because of the influence flavescence of nitrogen oxide in the air, and the processing of colour developing paper and store very conveniently, and price is also low.
Above-mentioned purpose of the present invention and other purposes, characteristic and advantage illustrate in together with accompanying drawing at following description of the invention and additional claims, wherein:
Fig. 1 is the cross section view of a signal, and it represents the structure of pressure-sensitive paper; With
Fig. 2 is the infrared spectrogram of synthetic salicyclic acid resin among the synthetic embodiment 1 of a resin.
Employed salicyclic acid resin (copolymer) is the resin of the class novelty of not producing so far in the invention process.
α, α '-dialkoxy dimethylbenzene are the basic raw materials that production cocondensation gold in resin belongs to modified resin, and this metal-modified resin is in the present invention as developer, and α, α '-dialkoxy dimethylbenzene react with corresponding phenolic compounds and obtain phenol resin. Phenol resin further with alkali compounds, for example, hexamethylene-tetramine reaction is in order that make the phenol resin sclerosis. That is to say that phenol resin is used as the composition (Japanese patent publication 15111/1972) of so-called thermmohardening polymer.
Yet, use phenolic acid, alkyl phenol, phenylphenol, p-Aminophenol, 1,2,3,-thrihydroxy-benzene or fluoro glycinol in the composition of these thermmohardening polymer. As if they and salicylism reaction also are entirely ignorant of, also do not study in this respect, because infer easily, as phenolic compounds and α, when α '-dialkoxy dimethylbenzene reacts in the presence of acidic catalyst, owing to dealcoholization generates alcohol. Yet contain the phenolic compounds of organic carboxyl, namely as the salicylic situation of a kind of composition of the present invention because the alcohol reaction that salicylic acid generates when existing with acid catalyst forms salicylate and its resin blend thing, therefore, be difficult to obtain desirable product.
Yet the present inventor has been surprised to find that, as salicylic acid and α, α '-dialkoxy dimethylbenzene, if the phenol one that needs to have trialkyl benzene and/or contraposition to replace reacts, when reaction temperature surpasses 110 ℃ in the presence of acid catalyst, resemble paying reaction and basically can not take place the corresponding esterification, be used for implementing salicyclic acid resin of the present invention and just can obtain.
When the reaction temperature among the present invention surpassed 110 ℃, reaction was carried out very fast, did not have esterification to take place, and if α, the carbon atom number of each alkyl is 4 or still less in α '-dialkoxy dimethylbenzene, then just is easy to obtain the measured resin of matter. At the alkyl with 4 carbon atoms, namely among the butyl, the tert-butyl group tends to cause long response time.
Can access for cocondensation resin of the invention process α preferably, α '-dialkoxy dimethylbenzene can be α, α '-dimethoxy-ortho position-dimethylbenzene, α, α '-dimethoxy-position-dimethylbenzene, α, α '-dimethoxy-contraposition-dimethylbenzene, α, α '-diethoxy-ortho position-dimethylbenzene, α, α '-diethoxy-position-dimethylbenzene, α, α '-diethoxy-contraposition-dimethylbenzene, α, α '-two positive propoxies-ortho position-dimethylbenzene, α, α '-two positive propoxy-position-dimethylbenzene, α, α '-two positive propoxies-contraposition-dimethylbenzene, α, α '-diisopropoxy-ortho position-dimethylbenzene, α, α '-diisopropoxy-position-dimethylbenzene, α, α '-diisopropoxy-contraposition-dimethylbenzene, α, α '-two n-butoxies-ortho position-dimethylbenzene, α, α '-two n-butoxy-position-dimethylbenzene, α, α '-two n-butoxies-contraposition-dimethylbenzene, α, α '-two is butoxy-ortho position-dimethylbenzene in addition, α, α '-two is butoxy-position-dimethylbenzene in addition, α, α '-two is butoxy-contraposition-dimethylbenzene in addition, α, α '-two isobutoxies-ortho position-dimethylbenzene, α, α '-two isobutoxy-position-dimethylbenzene, α, α '-two isobutoxies-contraposition-dimethylbenzene. Yet the present invention not necessarily is limited to these α that enumerate, α '-dialkoxy dimethylbenzene.
Be used for enforcement of the present invention obtaining the trialkyl benzene of cocondensation resin, three alkyl are respectively that 4 or the alkyl of carbon atom are still less arranged. Be used for the present invention preferably trialkyl benzene comprise 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2, the 4-trimethylbenzene, 2,3-dimethyl ethyl benzene, 2,6-dimethyl ethyl benzene, 3,4-dimethyl ethyl benzene, 3,5-dimethyl ethyl benzene, 2,5-dimethyl ethyl benzene, 2,4-dimethyl ethyl benzene, 1,2,3-triethylbenzene, 1,2,4-triethylbenzene, 1,3, the 5-triethylbenzene, 2,3-dimethyl cumene, 2,3-diethyl cumene, 2, the 3-dimethyl-just-propylbenzene, 3, the 5-dimethyl-just-propylbenzene, 3,5-dimethyl cumene, 2,6-dimethyl-cumene, 2,6-diethyl-cumene, 3,5-diethyl cumene, 3,4-dimethyl cumene, 3,4-diethyl-just-propylbenzene, 2,5-dimethyl-cumene, 2,5-diethyl cumene, 2,4-dimethyl cumene, 2,4-diethyl cumene, 3,5-dimethyl cumene, 3,5-two Isopropyl toluene, 1,2,3-triisopropylbenzene, 1,2,4-triisopropylbenzene, 1,3,5-triisopropylbenzene, 1,2,4-three n-propylbenzene, 1,3,5-three n-propylbenzene, 2, the 3-dimethyl-just-butyl benzene, 3,4-dimethyl isobutyl benzene, 3, the 4-diethyl-just-butyl benzene, 2,3-di-n-butyl toluene, 3,5-di-n-butyl toluene, 1,2,4-three n-butylbenzenes, 1,3,5-three n-butylbenzenes, 2-ethyl-4-normal-butyl toluene, 2-ethyl-3-isopropyl toluene etc. Yet the present invention not necessarily is limited to these trialkyl benzene of enumerating. In the butyl that 4 carbon atoms are arranged, the tert-butyl group is difficult to carry out the cocondensation reaction. Therefore do not wish to use the tert-butyl group.
In these trialkyl benzene, 1,3,5-trimethylbenzene is known to be dual functional (Kogyo Kagaku Zasshi 65(4) 626-629(1962)). Other trialkyl benzene it is believed that it also is dual functional.
In the condensation reaction of trialkyl benzene, if alkyl in ortho position and contraposition, then alkyl is hyperconjugation. For example, in 1,2,4-trialkyl benzene, think that condensation reaction carries out in the position of 3-and 5-. Yet in 1,2,3-trialkyl benzene, think that condensation reaction carries out at 4-and 6-position.
The phenol example that uses in the embodiment of this invention to provide the contraposition of cocondensation resin to replace has pair alkyl phenol, and alkyl wherein has 1-12 carbon atom, right-cycloalkyl phenol, right-aralkyl phenol and right-phenylphenol. To can be paracresol, paraethyl phenol, australol in the alkyl phenol, to sec-butyl phenol, p-t-butyl phenol, to tert-octyl phenol, nonylphenol etc. To in the cycloalkyl phenol being right-cyclopenta phenol and p-cyclohexylphenol. Right-benzylphenol, right-alpha-methyl benzyl phenol, right-alpha, alpha-dimethylbenzyl phenol and analog can be as right-aralkyl phenol.
These contraposition substituted phenols can use separately also can mix use.
Condensation reaction is to carry out at the ortho position of hydroxyl in the contraposition substituted phenol.
At salicylic acid and α, the dimethylbenzene condensation of α ' dialkoxy or salicylic acid, α, when α ' dialkoxy dimethylbenzene, trialkyl benzene and/or contraposition substituted phenol cocondensation were produced salicyclic acid resin, the various raw material of use can be in following ratio.
α, α ' dialkoxy dimethylbenzene available amount is the 0.1-1.0 mole, preferably uses the 0.3-0.8 mole, is with every mole of Whitfield's ointment or every mole of the phenol total amount of Whitfield's ointment, trialkyl benzene and/or para-orientation when mix using.
Trialkyl benzene available amount is every mole of Whitfield's ointment 0.1-20 mole, 0.5-10 mole preferably, but whether the use of trialkyl benzene is arbitrarily.
Will use para-orientation phenol, then its consumption is every mole of Whitfield's ointment 0.1-15 mole, preferably the 0.5-10 mole.
Para-orientation phenol or 1,3, the α of trialkyl benzene that the 5-Three methyl Benzene is such and Whitfield's ointment and its condensation, the purpose that α '-dialkoxy dimethylbenzene uses together, be to make to be applied to CF-paper 1 and CF/CB-paper 2(is shown in Fig. 2) in the microcapsule at the back side fixed oil be applied to CF/CB-paper 2 and CF-paper 3(also is shown in Fig. 2) positive developer, be polyvalent metal modified salicylic acid resin, the warm property when pressurization improves.Because contain the developer of the multivalent metal modified resin of the multipolymer that generates by 3-4 structural unit, leuco dye parent as easy as rolling off a log and that be dissolved in the fixed oil reacts when pressurization, and this just makes it have the instantaneous advantage that just forms the sharp outline writing of pressurizeing.
When producing salicyclic acid resin of the present invention, temperature of reaction must be above 110 ℃.Any temperature that is lower than 110 ℃ all can cause extremely slow speed of response, and produces the reaction of paying as esterification probably.Preferably about about 130-240 ℃ of temperature range is to shorten the reaction times as far as possible.Reaction times can be from 1 hour to 20 hours in the scope.The available acid catalyst is mineral acid or organic acid, can use mineral acid especially, and for example hydrochloric acid, phosphoric acid or sulfuric acid also have formic acid.In addition, Fu Ruidi-Ke comes the Ford catalyzer, for example zinc chloride, tin chloride or iron(ic) chloride, or use organic sulfonic acid, for example methylsulfonic acid or tosic acid, can be separately with or the usefulness that is mixed.These catalyst consumption approximately are Whitfield's ointment and α, the α '-dialkoxy dimethylbenzene and the 0.01-5%(weight of the gross weight of trialkyl benzene and/or para-orientation phenol arbitrarily).
The resin that uses in the invention process, general production method are with starting material for example Whitfield's ointment and catalyzer, once add by desired amount, and heating is reacted under preset temperature then.The alcohol that generates in the reaction process is separated from reactive system.Residual a small amount of alcohol in the reactive system if desired, can lead to nitrogen and remove from reactive system.
After reaction was finished, it was tolerant to emit institute from reactor, after cooling, their are ground or does similar processing to obtain desired resin.If the Whitfield's ointment of remained unreacted in the resin can be removed with the Warm Wash resin, or use organic solvent, for example benzene,toluene,xylene, chlorobenzene, methyl iso-butyl ketone (MIBK) or pimelinketone are washed resin, wash to remove residual Whitfield's ointment with warm water then again.
The weight-average molecular weight of resin of the present invention (MW) in 000 scope, better is 500-10, in 000 scope at 500-30.
Each structural unit, for example Whitfield's ointment, dialkoxy dimethylbenzene, trialkyl benzene and para-orientation phenol each partly the ratio in resin be respectively the 5-60%(mole), the 30-50%(mole), the 0-60%(mole) and the 0-60%(mole).
By Whitfield's ointment and α, α '-dialkoxy-right-dimethylbenzene is made the resin of raw material generation and is represented with following general expression (V):
N represents the polymerization degree and represents the integer of 1-100 in the formula.In each Whitfield's ointment group at two ends-CH
2-the position of substitution can be any one in the position between two of carboxyl.
By Whitfield's ointment, α, the salicyclic acid resin that α '-dialkoxy dimethylbenzene and trialkyl benzene are done the raw material generation is a kind of cocondensation resin, and its structural unit that contains is represented with following general formula VI and (VII)
R in the formula
1, R
2And R
3Represent 4 or the alkyl of carbon atom still less separately, and its weight-average molecular weight is 500-30,000.The ratio of structural unit (VI) and (VII) changes according to amount of used Whitfield's ointment and trialkyl benzene etc.
When using para-orientation phenol, the resin that obtains is a kind of cocondensation resin, and it comprises the structural unit with following general expression (VIII) expression:
R in the formula
4Represent alkyl, cycloalkyl, aralkyl or a phenyl, together with adding structural unit (VII) under said structure unit (VI) and some situation, then weight-average molecular weight is 500-30,000.
As mentioned above, salicyclic acid resin of the present invention comprises dual functional structural unit and is line style, and is considered to not exist any reticulated structure.
Narration by the front knows that used " polyvalent metal modified salicylic acid resin " this noun is meant the polyvalent metal salt of above-mentioned salicyclic acid resin or refers to contain the molten mixture of polyvalent metal salt here.
Several currently known methodss can be used for producing the polyvalent metal salt of Whitfield's ointment cocondensation resin.For example, an alkali metal salt that they can be by the cocondensation resin and water miscible polyvalent metal salt in water or two kinds of salt react in can both the dissolved organic solvent and obtain.
In other words, the polyvalent metal salt of multipolymer can obtain with sedimentary form, as long as multipolymer is dispersed in the aqueous solution, alcoholic solution or the alcohol-water solution of the oxyhydroxide of alkali metal containing or carbonate or alkoxide, the amount of alkali-metal oxyhydroxide, carbonate or alkoxide is equivalent to the amount of carboxyl in the multipolymer at least, multipolymer is 0-100 ℃ of dissolving, (can also can be the aqueous solution same as before with water miscible polyvalent metal salt then, the form of alcoholic solution or alcohol solution) adds in the copolymer solution, 0-100 ℃ of reaction.The consumption of water-soluble polyvalent metal salt preferably is about 0.5-1 gram equivalent (by carboxyl-content in the multipolymer).
The molten mixture that contains the polyvalent metal salt of salicyclic acid resin also can prepare, method is that the polyvalent metal salt of this resin with organic carboxyl acid (for example formic acid, acetate, propionic acid, valeric acid, caproic acid, stearic acid or phenylformic acid) mixed, heating makes it to react, and then reaction mixture is cooled off.In some cases, can also add alkaline matter again, for example volatile salt, bicarbonate of ammonia, ammonium acetate or ammonium benzoate.And then once with the mixture heating up that obtains, melting and reaction.Also carbonate, oxide compound or the oxyhydroxide of this resin with polyvalent metal might be used, they heat and fusion with alkaline matter, alkaline matter has organic carboxylic acid ammonium, for example ammonium formiate, ammonium acetate, caproic acid ammonium, ammonium stearate or ammonium benzoate, utilize it, it is reacted together.Reaction mixture cooling subsequently obtains molten mixture.
When heating and molten metal and resin when next life, pan belonged to modified resin, common melt temperature is at 100-180 ℃.Reaction times is generally within 1 hour to several hours, but the reaction times is depended on resin composition, melt temperature and and the value volume and range of product of polyvalent metal salt.About the usage quantity of polyvalent metal, when require using the organic carboxylate, carbonate, oxide compound of polyvalent metal or oxyhydroxide, metal content is the 1%(weight of total resin weight) to about 20%(weight).
Used alkaline substance quality does not have particular restriction.General usage quantity is the 1-15%(weight of total resin weight).When using alkaline matter, preferably in advance with it with re-use after polyvalent metal salt mixes.
Used typical metal in polyvalent metal modified salicylic acid resin of the present invention comprises and removes basic metal, for example the metal beyond lithium, sodium and the potassium.Polyvalent metal comprises magnesium, aluminium, copper, calcium, zinc, tin, barium, cobalt and nickel preferably.Wherein zinc is effective especially.Each polyvalent metal can form polyvalent metal salt with the same a part or the carboxyl in the differing molecular of salicyclic acid resin.
Developer of the present invention can with one or more known developers, inorganic solid acid atlapulgite for example just, organic polymer, for example the metal-salt of resol and aromatic carboxylic acid mixes and uses, and does not have any problem or inconvenience.
Developer of the present invention also can mix use with oxide compound, oxyhydroxide and the carbonate of at least a polyvalent metal.Alternative polyvalent metal comprises zinc, magnesium, aluminium, lead, titanium, calcium, cobalt, nickel, manganese and barium.
The present invention who is applicable to pressure-sensitive carbon paper paper that develops the color, its manufacture method, can utilize following any: (1) is coated in the water base coating component of using the developer aqeous suspension on the base material resemble the rolled paper; (2) when production rolls coil paper, developer is sneaked in the rolls coil paper; (3) organic solution of developer or the suspension in organic solvent are applied on the base material.
During the preparation coating formula, add kaolin or similar carclazyte, lime carbonate, starch, synthetic or natural rubber latex etc. to obtain having suitable viscosity and the good coating formula of coating applicability.The ratio of the developer 10-70% of total solids content preferably in coating formula.If the ratio of developer less than 10%, just can not demonstrate enough color development abilities.Surpass 70% anyly degenerate than the regular meeting paper surface property that causes developing the color.The application rate of coating formula is 0.5 gram/rice
2Or higher, 1-10 gram/rice preferably
2(in dry weight).
In being applicable to the colour developing paper of the present invention of pressure-sensitive carbon paper, can use more a spot of developer and coating formula.In addition, the concentration of coating formula, viscosity etc. can change in quite wide scope, so the coat operations of startup and shutdown is all very convenient.This all is a very big advantage not only from the performance perspective of pressure-sensitive carbon paper, and from manufacturing step.
The present invention provides the salicyclic acid resin of this novelty and their polyvalent metal salt, and developer comprises the multivalent metal modified resin of salicyclic acid resin and is applicable to the developer of pressure-sensitive carbon paper and contains developer and be applicable to the colour developing paper of pressure-sensitive carbon paper.
Colour developing paper of the present invention can not be subjected to light and airborne gas basically, and for example nitrogen oxide influences and flavescence.All very stable and colour density does not reduce the coloured writing that produces basically to light, softening agent or the like.They all have good water tolerance.So the present invention can expand the use range of pressure-sensitive carbon paper to the occasion that requires long term storage stability, and common colour developing paper is inapplicable.Therefore, the present invention has great practical significance.
The present invention will further be described in detail by following embodiment.
Below method be the reliable method that is used for measuring the colour developing paper performance of pressure-sensitive carbon paper.
1, the colour density of color development speed and formation
(is that 65% air-conditioned room carries out 20 ℃ and relative humidity): the CB-commodity paper that uses (1) a kind of Fa Lanse respectively, wherein contain crystal violet lactone (CVL) as main pressure sensitive dye parent (trade name " NW-40T " is produced by Jujo system paper company), (2) a kind of CB-commodity paper of the look that turns black wherein contains 3-diethylamino-6-methyl-7-phenyl amino firefly hydrocarbon (ODB) as main pressure sensitive dye parent (trade name " KW-40T " is produced by Jujo system paper company).A kind of sample colour developing paper (CF-paper) that scribbles water base plinth coating formula is superimposed together with them, its coating is contacted.The pressure-sensitive carbon paper of folding like this produces color with the type-writer typewriting.
Reflectivity " ∑-80 colour-difference meter " (trade name ∑-80 colour-difference meter of sample colour developing paper; Tokyo electricity look Co., Ltd. produces Tokyo Denshoku Kogyo K.K, and the mensuration of later tests is also used same colour-difference meter) measure secondary, measured in back 24 hours in typewriting back 1 minute and 30 seconds and typewriting.Result's Y value representation.
Y is a numerical value that obtains according to the double-view field display packing, and this method is by CIE(International Commission on Illumination) definite.It is by (the Y value in the determination test is also the used same definition in the back) expression that establishes an equation down:
Y＝K∫
780 380P（λ） Y（λ）τ（λ）dλ
K＝100/∫
780 380P（λ） Y（λ）dλ
P(λ in the formula): the power of standard light source distributes
Y(λ): the color matching functions in double-view field
τ (λ): the spectral response curve of each sample.
About P(λ) and Y(λ), can be with reference to the JIS Z8722(Z8722 of Japanese Industrial Standards).
2, produce the light fastness of coloured writing:
Each that mode by above-mentioned test method 1 has been produced color is opened sample colour developing paper, exposes 2 hours (with 4 hours) in the fugitometer (being made by Suga trier company) of carbon arc lamp.After the exposure, use " ∑-80 colour-difference meter " to measure its reflectivity, result's Y value representation.
The Y value is littler, and littler with the difference of the preceding Y value of test, and then light fading is less, and performance is more excellent.
3, anti-softening agent:
Dop microencapsulation coating paper makes by generating many microcapsule, contains DOP dioctyl phthalate (Dop) in the capsule as core substance, and capsular mean size is 5.0 microns, and capsule wall is a melamino-formaldehyde resin, adds the tackiness agent of amount of starch class again.With the coating formula that makes like this, utilize the coating machine of air doctor blade to be coated on the high-quality rolled paper, the weight that makes it dry coating reaches 5 gram/rice
2, the dry then rolled paper that coats like this.The colour developing paper that produces coloured writing in Dop microcapsule coat paper and the above-mentioned test method 1 stacks mutually with coat side.Be allowed to condition at subsequently under the line pressure of 100 kilograms per centimeter and prolong roller, cause Dop to infiltrate through colored surface equably by supercalender.
The reflectivity of colour developing paper is measured in after the test 1 hour with " ∑-80 colour-difference meter ".End value Y value representation.The Y value heals little and littler with the difference of the preceding Y value of test, and then the performance of coloured writing plasticizer-resistant of Sheng Chenging better.
4, generate the water resistance of coloured writing:
Open sample colour developing paper by painted each of test method 1 and soaked in water 2 hours, the colour density of estimating coloured writing changes.
5, the flavescence of colour developing paper:
(5-1) because NO
xFlavescence:
NO according to Japanese Industrial Standards' JIS L-1055(coloured material and dyestuff
xThe test method of gas fastness), each sample colour developing paper is stored in NO
xIn the encloses container of atmosphere 1 hour, NO
xGas is by NaNO
2(Sodium Nitrite) and H
3PO
4(phosphoric acid) reaction generates.Study its flavescence degree.
It's 1 hour after finishing, pasts test, with the reflectivity of " ∑-80 colour-difference meter " mensuration colour developing paper, measurement result WB value representation.The WB value is bigger, it with test before the WB value difference not little, then at NO
xA little less than the performance of flavescence heals in the atmosphere.
(5-2) because the light flavescence:
Each opens the illumination 4 hours in the fugitometer of carbon arc lamp of sample colour developing paper, (fugitometer is made by Suga trier company).After the test, with the reflectivity of " ∑-80 colour-difference meter " working sample colour developing paper.Measurement result is represented with the WB value.The WB value is bigger, it with test before the WB value difference not little, the flavescence performance when then exposing is littler.
Various salicyclic acid resin of the present invention and their metal-modified resin are obtained by synthetic example 1-42 of resin and the synthetic example 1-50 of metal-modified resin respectively.Be described in detail below:
Resin synthesizes example 1:
In glass reactor, add the Whitfield's ointment of 27.6 grams (0.2 mole), the α of 23.2 grams (0.14 mole), α '-dimethoxy-right-dimethylbenzene and 0.1 gram are made the tosic acid of catalyzer, add the back 170-180 ℃ of following condensation 3 hours.In condensation course, steam 8 gram methyl alcohol altogether.Under above-mentioned uniform temp, immediately reaction mixture to be poured in the shallow enamel tray, reaction mixture is stayed in the dish.So resinoid reaction product is solidified, and has obtained 40 like this and has restrained the transparent resin of reddish-brown slightly.The resin that obtains like this, its weight-average molecular weight is 5,200.Its softening temperature is pressed JIS K-2548 and is measured with ring and ball softening point determinator.Recording softening temperature is 140 ℃.
Infrared analysis result (measuring with KBr compressing tablet form) is shown in Fig. 2
Resin synthesizes example 2:
In glass reactor, the Whitfield's ointment of 27.6 grams (0.2 mole) of packing into, the α of 10 grams (0.06 mole), α '-diethoxy-right-dimethylbenzene and 0.75 gram are as the Zinc Chloride Anhydrous of catalyzer, then 160-170 ℃ of following condensation 4 hours.Internal temperature is chilled to 100 ℃ again, the methyl iso-butyl ketone (MIBK) that adds 70 milliliters is subsequently made solution.The warm water that then adds 500 milliliters in the solution, the mixture of gained stirred 20 minutes down at 95-100 ℃.Remove water layer.Separate with Warm Wash and with water layer, more than the repeatable operation secondary, so that unreacted Whitfield's ointment is removed.Solvent steams and cools off condenses, obtains the pale red brown transparent resin of 18.4 grams, and the resin weight-average molecular weight that obtains like this is 820, and its softening temperature is 84 ℃
Resin synthesizes example 3-5
The same manner with synthetic resins example 1 obtains salicyclic acid resin, be α, the kind of the kind of α '-dialkoxy-right-dimethylbenzene, it and salicylic mol ratio, catalyst system therefor and consumption and condensation reaction condition have all been done change respectively, are shown in table 1.
Resin synthesizes example 6
In reactor, pack into 13.8 the gram (0.1 mole) Whitfield's ointments, 36.1 the gram (0.3 mole) 1,3, the α of 5-Three methyl Benzene and 33.2 grams (0.2 mole), α '-dimethoxy-right-dimethylbenzene then adds 0.2 tosic acid that restrains and the 0.2 gram Zinc Chloride Anhydrous as catalyzer again.Then, the reactant heating was also stirred, 150 ℃-160 ℃ reactions 4 hours.Reaction process steams methyl alcohol 13.3 grams altogether.After reaction is finished, add 200 milliliters of toluene with the solubilizing reaction mixture.Add 400 milliliters of warm water then in the solution.Under the backflow situation, reaction mixture stirred after 30 minutes, with lower floor, be that water layer is removed.With the extraction of 400 milliliters of warm water with separate unreacted monomer, repeat more than the secondary then solvent distillation, just toluene distillation under reduced pressure.Then molten resin is poured out and cooled off, obtain pale red brown transparent resin.The resin that obtains like this, its weight-average molecular weight is 2,400.Its softening temperature is measured by JIS K-2548 by ring and ball softening point determinator.Softening temperature is measured as 83 ℃.With the tetrahydrofuran solution of the aqueous sodium carbonate titration resin of 1/10N, with measure Whitfield's ointment components contents in the resin, record be 14.3%(by weight).
Resin synthesizes example 7-29
Press the same quadrat method of the synthetic example 6 of resin, obtain various Whitfield's ointments-trialkyl benzene cocondensation resin, be shown in table 2-1 to table 2-4, be trialkyl benzene, α, α '-dialkoxy dimethylbenzene and catalyst consumption have been done change with respect to Whitfield's ointment, as show 2-1 to shown in the table 2-4, their kind and reaction conditions also change, and are shown in the same table.
Resin synthesizes example 30:
Pack in the reactor 13.8 the gram (0.1 mole) Whitfield's ointments, 24 the gram (0.2 mole) 1,3, the α of the right-uncle-octyl phenol of 5 Three methyl Benzenes and 20.6 grams (0.1 mole) and 33.2 grams (0.2 mole), α '-dimethoxy-right-dimethylbenzene then adds the tosic acid of 0.3 gram as catalyzer.After this, the reactant heating was also stirred, 150-160 ℃ of reaction 4 hours.In reaction process, steam methyl alcohol 11.2 grams altogether.After reaction is finished, add 200 milliliters of toluene with the solubilizing reaction mixture.Then, add 400 milliliters of warm water in the solution, the gained mixture refluxes and stirred 30 minutes down, and with lower floor, just water layer is removed.With the extraction of 400 milliliters of warm water with separate unreacted monomer, more than the operation repetition secondary, then under reduced pressure steam solvent, i.e. toluene like this.Pour out molten resin, obtain the light brown transparent resin.The resin that obtains like this, its weight-average molecular weight is 2,550, its softening temperature is with ring and ball softening point determinator, presses JIS K-2548 and measures.Measurement result is 72 ℃.With the tetrahydrofuran solution of the aqueous sodium carbonate titration resin of 1/10N, to measure salicylic content in the resin, the result is a 12.8%(weight).
Resin synthesizes example 31-36
Press the same method of the synthetic example of resin 30, expect various Whitfield's ointments-1,3,5 trimethylbenzenes-para-orientation phenol cocondensation resin are shown in table 3.Be 1,3,5 trimethylbenzenes, its para-orientation phenol, α, the amount of α '-dialkoxy dimethylbenzene and catalyzer is with respect to some change of Whitfield's ointment, and is as shown in table 3.Their kind and reaction conditions have also been done a little changes, are shown in the same table.
Resin synthesizes example 37:
13.8 Whitfield's ointments, 61.8 that restrain (0.1 mole) of packing in reactor restrain the right-uncle's octyl phenol of (0.3 mole) and the α of 33.2 grams (0.2 mole), and α '-dimethoxy-p-Xylol then adds the tosic acid that 0.5 gram is made catalyzer.Reactant heating then and make the solid matter dissolving after, reaction stirred.150-160 ℃ of reaction 4 hours.In reaction process, steam 12.2 gram methyl alcohol altogether.After reaction is finished, add 200 milliliters of toluene with the solubilizing reaction mixture.In solution, add 400 milliliters of warm water then.The mixture that obtains stirred 30 minutes under refluxing, and removed lower floor, i.e. water layer.With the extraction of 400 milliliters of warm water with separate unreacted monomer, this operation repeats more than the secondary.Then under reduced pressure steam solvent, promptly toluene is then poured out molten resin, obtains the light brown transparent resin.The resin weight-average molecular weight that obtains like this is 1,850.With ring and ball softening point determinator, recording softening temperature by JIS K-2548 is 54 ℃.With the tetrahydrofuran solution of the aqueous sodium carbonate titration resin of 1/10N, to measure the salicylic acid content in the resin, recording the result is 10.8%(weight).
Resin synthesizes example 38-42
Press the same quadrat method of the synthetic example 37 of resin, obtain various Whitfield's ointments-para-orientation phenol cocondensation resin, be shown in table 4.Just changed para-orientation phenol, α, α '-dialkoxy-right-dimethylbenzene and catalyzer are shown in table 4 with respect to salicylic amount, and their kind and reaction conditions also change, and also are shown in table 4.
Metal-modified resin synthesizes example 1:
12.5 grams in flask, pack into by the synthetic example 2 resulting salicyclic acid resins of resin.Heat this resin and 150-160 ℃ of fusion.Give mixing 8.2 gram Zinc dibenzoates and 5 gram bicarbonate of ammonia earlier, and under agitation in this mixture is during 30 minutes, add in the molten resin gradually.Then, 155-165 ℃ of stirred reaction mixture 1 hour, reaction is finished.After reaction is finished, from flask, pour out molten resin, pulverize after the cooling.Obtain 18.5 gram powdered zinc-modified resin thus.The softening temperature of zinc-modified resin is by ring and ball softening point determinator, presses JIS K-2548 and measures, and the result is 125 ℃.
Metal-modified resin synthesizes example 2-40:
The same manner by the synthetic example 1 of metal modified resin obtains various metal-modified resins, be shown in table 5-1 to table 5-6, only be to use prepared salicyclic acid resin among synthetic example 3 of resin and the 5-42, changed the kind of conditioning agent and additive, be shown in table 5-1 to table 5-6.
Metal-modified resin synthesizes example 41:
The resin of synthetic example 1 gained of resin is got 10 grams pulverize, then it is dispersed in the 100 gram aqueous solution that contain 2 gram sodium hydroxide.When dispersion under agitation was heated to 70 ℃, resin is dissolving just.At this moment the temperature of keeping solution is at 45-50 ℃, and dropping is given the 3.8 gram Zinc Chloride Anhydrouss (purity 90%) that make earlier and is dissolved in the solution in 30 ml waters in 30 minutes time then.
Produced a kind of white precipitate.Reaction mixture is after said temperature has stirred 2 hours, with its filtration.Precipitation washes with water, and is dry then, obtains the white powder of 11.5 grams.The zinc salt of Here it is salicyclic acid resin.Zinc content is 15.2%.
Metal-modified resin synthesizes example 42-50:
The salicyclic acid resin that uses the synthetic example 1,12,18,24,30,37 and 38 of resin to obtain respectively makes various metal-modified resins by the synthetic example 41 same methods of metal modified resin, is shown in table 6.
Example 1-50:
Utilize synthetic resulting each the metal-modified Whitfield's ointment cocondensation resin of example 1-50 of metal-modified resin as developer, in sand mill, disperse respectively, make the suspension of following composition.
Umber (weight)
Developer 6
10% polyvinyl alcohol water solution 3
(PVAC polyvinylalcohol: " Kuraray well 117 ",
Kuraray company produces)
Water 22.5
Then, make the coating formula of following component respectively with above-mentioned suspension.
Umber (weight)
Starch 0.8
Synthetic rubber latex 0.8
Water 32.5
These coating formulas are coated in respectively on the high-quality rolled paper, make dry coating heavily be 5.0-5.5 gram/rice
2, obtain the paper that develops the color thus.
Embodiment 51-64:
With the developer suspension that the synthetic example 1,4,10,16,22,28,35,41 of metal-modified resin, 44-48 and 49 obtain, make the coating formula of following composition respectively.
Umber (weight)
Zinc oxide 2
Lime carbonate 8
Umber (weight)
Starch 0.8
Synthetic rubber latex 0.8
Water 32.5
These coating formulas are coated to respectively on the high-quality rolled paper, so that the heavy 5.0-5.5 gram/rice of dry coating
2, obtain the paper that develops the color thus.
The comparative example 1:
170 p-phenyl phenols that restrain, 22.5 of packing in glass reactor restrain 80% Paraformaldehyde 96, the tosic acid and the 200 gram benzene of 2.0 grams.Mixture heating up also stirred, and the water of generation becomes constant boiling mixture to distill from reactive system with benzene, 70-80 ℃ of reaction 2 hours.After the reaction, add the aqueous sodium hydroxide solution of 320 grams 10% and benzene is steamed by steam distillation.Reaction mixture then drips dilute sulphuric acid then.After the filtration, the right-phenyl phenol formaldehyde polymkeric substance of collecting precipitation washes drying then with water, obtains 176 gram white powders thus.With right-phenyl phenol formaldehyde polymkeric substance, obtain the paper that develops the color with the same quadrat method of embodiment 1-64.
Evaluation result by example 1-64 and comparison example 1 resulting colour developing paper performance is shown in table 7-1 to table 7-7.
Claims (6)
1, a kind of production method of linear salicylic acid copolymers, this multipolymer comprises the structural unit (I) of 5-60% (mole), the structural unit (II) of 30-50% (mole), the structural unit (III) of 0-60% (mole) and the structural unit (IV) of 0-60% (mole), and weight-average molecular weight is 500-30,000, when using Whitfield's ointment (I), α, the mixture cocondensation of α '-dialkoxy dimethylbenzene (II) and trialkyl benzene (III) and/or para-orientation phenol (IV) is when producing said linear copolymers, above-mentioned structural unit (I), (III), or (IV) and structural unit (I), (III), or in (IV) inequality that by structural unit (II) coupling, when reacting under the situation of not having (III) and (IV), then said structural unit (I) and structural unit (II) coupling, above-mentioned structural unit (I), (II), (III) and (IV) uses formula I down respectively, (II), (III) and (IV) representative:
R in the formula
1, R
2And R
3Refer to have 4 or respectively less than the alkyl of 4 carbon atoms, R
4Represent alkyl, cycloalkyl, aralkyl or phenyl, production method comprises:
(I) Whitfield's ointment, (II) α, α '-dialkoxy dimethyl (alkoxyl group: C
1-C
4Alkoxyl group) with optional (III) trialkyl benzene (alkyl: can be identical also can be different C
1-C
4Alkyl) and/or the mixture of (IV) para-orientation phenol (para-orienting group: alkyl, cycloalkyl, aralkyl or phenyl), in the presence of 110-240 ℃ and acid catalyst, react, in the said mixture, the consumption of compound (II) is each mole compound (I), (III) and (IV) total amount 0.1-1.0 mole; If with compound (III), then its consumption is that every mole compound (I) needs with 0.1-20 mole (III) in the reaction; As using (IV), then its consumption is that every mole compound (I) needs use the 0.1-15 mole in the reaction.
2, according to the production method described in the claim 1, wherein reaction does not add trialkyl benzene and para-orientation phenol when carrying out.
3, production method according to claim 1, wherein reaction does not add para-orientation phenol when carrying out.
4, production method according to claim 3, wherein compound (II) is α, α '-dialkoxy is a pair of-dimethylbenzene.
5, production method according to claim 1, wherein compound (III) is that 1, compound (II) they are α, α '-dialkoxy is a pair of-dimethylbenzene.
6, production method according to claim 1, wherein compound (II) is α, α '-dialkoxy is a pair of-dimethylbenzene, reaction is carried out middle compound (III) and is not existed.
Applications Claiming Priority (16)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP648286A JPH0617462B2 (en) | 1986-01-17 | 1986-01-17 | Salicylic acid resin and method for producing the same |
| JP6482/1986 | 1986-01-17 | ||
| JP18027/1986 | 1986-01-31 | ||
| JP61018027A JPS62176875A (en) | 1986-01-31 | 1986-01-31 | Color developing sheet for pressure-sensitive copy paper |
| JP2025186 | 1986-02-03 | ||
| JP20252/1986 | 1986-02-03 | ||
| JP20251/1986 | 1986-02-03 | ||
| JP61020252A JPS62178388A (en) | 1986-02-03 | 1986-02-03 | Developing sheet for pressure sensitive copying paper |
| JP20250/1986 | 1986-02-03 | ||
| JP61020250A JPS62178387A (en) | 1986-02-03 | 1986-02-03 | Developing sheet for pressure sensitive copying paper |
| JP61305332A JPH0771866B2 (en) | 1986-02-03 | 1986-12-23 | Color-developing sheet for pressure-sensitive copying paper |
| JP305332/1986 | 1986-12-23 | ||
| JP61306207A JPH0733111B2 (en) | 1986-12-24 | 1986-12-24 | Color-developing sheet for pressure-sensitive copying paper |
| JP306207/1986 | 1986-12-24 | ||
| JP308026/1986 | 1986-12-25 | ||
| JP61308026A JPH0733112B2 (en) | 1986-12-25 | 1986-12-25 | Color-developing sheet for pressure-sensitive copying paper |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108003 Division CN1018908B (en) | 1986-01-17 | 1987-01-17 | Color-developing sheets using in pressure-sensing carbon paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100709A CN87100709A (en) | 1987-09-02 |
| CN1007814B true CN1007814B (en) | 1990-05-02 |
Family
ID=27571580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87100709A Expired CN1007814B (en) | 1986-01-17 | 1987-01-17 | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of copolymers, and color-developing sheets employ in agents |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1007814B (en) |
| CA (1) | CA1274338A (en) |
| DE (1) | DE3777209D1 (en) |
-
1987
- 1987-01-08 DE DE8787100116T patent/DE3777209D1/en not_active Expired - Fee Related
- 1987-01-16 CA CA000527524A patent/CA1274338A/en not_active Expired - Fee Related
- 1987-01-17 CN CN87100709A patent/CN1007814B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3777209D1 (en) | 1992-04-16 |
| CA1274338A (en) | 1990-09-18 |
| CN87100709A (en) | 1987-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1065536A (en) | Non-acidic barrier coating | |
| AU603615B2 (en) | Salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of the copolymers and color-developing sheets employing the agents | |
| CN1031235A (en) | The preparation method of polyvalent metal modified salicylic acid resin uses this resin and the suitable pressure-sensitive carbon paper unit that is used in the developer in the pressure-sensitive carbon paper and uses this developer | |
| CN1276299A (en) | Color developing composition, aqueous dispersion liquid, recording paper and color developing ink | |
| US4783521A (en) | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal-resins of the copolymers | |
| CN1296024A (en) | Partial esterification products of aromatic hydroxy-carboxylic resin and use thereof | |
| CN1007814B (en) | Linear salicylic acid copolymers and their metal salts, production process thereof, color-developing agents comprising metal salts of copolymers, and color-developing sheets employ in agents | |
| CN1018908B (en) | Color-developing sheets using in pressure-sensing carbon paper | |
| JPH01133780A (en) | Preparation of multivalent metal compound of salicylic acid resin | |
| CN1109075A (en) | Polyvalent metal salt of salicyclic acid resin and process for preparing it | |
| CN1040377A (en) | Polyvalent metal modification odorlessness product manufacture method of salicylic acid copolymers and uses thereof | |
| JPS62176875A (en) | Color developing sheet for pressure-sensitive copy paper | |
| CN1593937A (en) | Thermosensitive recording materials | |
| JPS62187078A (en) | Color forming sheet for pressure-sensitive copy paper | |
| JPS63160877A (en) | Color developer sheet for pressure sensitive paper | |
| JPS63115782A (en) | Color developer sheet for pressure-sensitive copying paper | |
| JPS63186729A (en) | Salicylic acid resin adducted polyvalent metal, its production and use as color developer of pressure-sensitive copying paper | |
| KR101484413B1 (en) | Urea developer composition for thermal recording medium and method thereof | |
| JPH0771866B2 (en) | Color-developing sheet for pressure-sensitive copying paper | |
| JPS63182181A (en) | Color developer sheet for pressure-sensitive paper | |
| JPH0712735B2 (en) | Developer composition for pressure-sensitive copying paper | |
| JPS6372588A (en) | Color developing sheet for pressure-sensitive copying paper | |
| JPH02153779A (en) | Color developing sheet for pressure-sensitive copying paper | |
| JPS62178387A (en) | Developing sheet for pressure sensitive copying paper | |
| JPH0579040B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |