DE2341113A1 - SELF-RECORDING PRESSURE SENSITIVE RECORDER SHEET - Google Patents

Description

PA7Et <TANWXi.'iE

DR. E. WIEGAND DiPL-IHG. tf, NO ONE

DR. M. KOHLER DIPL-ING. C. GERNHARDT 2341113

MÖNCHEN HAMBURG

TELEPHONE: 55 5476

TELEGRAM, CARPATENT 8000 MÖKCHEN 2, MATHILDENSTRASSE 12

V. 4-1 749/75 - Ko / Ke August 14, 1973

Photo Film Co., Ltd. Minami Äshigara-shi, Eanagawa (Japan)

Self-recording, pressure-sensitive recording sheet

The invention relates to a self-coloring recording sheet, d. H. a pressure-sensitive recording sheet which is a pressure-sensitive recording allowed using only one bow. In particular, the invention relates to a self-inking Recording sheet using new microcapsules containing a color former oil with an extremely low wall permeability of high strength, which are stable against pressure friction. The capsules are made by reacting a first wall-forming material with a second wall-forming material the inside of the oil droplets and simultaneous implementation a third wall-forming material, which

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outside of the oil droplets is present, with the first wall-forming Material made.

According to the invention, a pressure-sensitive recording sheet is specified, which consists of a carrier with a microcapsule layer thereon and a color developer layer on the same surface thereof; wherein the microcapsules develop by emulsifying an oily liquid which is suitable for reaction with the color development to form a color Color former contains a first wall film forming material and a second wall film forming material which is suitable for reaction with the first wall film forming material to form a high molecular compound, in a polar liquid which is suitable for forming a continuous phase, one third wall film forming material which is suitable with the first wall film forming material to form a high molecular weight compound and is added to the polar liquid before or after emulsification and formation the capsule is made around the oil droplets from the oil-like liquid, the capsule wall of aer inside of the oil droplets by the reaction between the first a wall-film-forming material and the second a wall-film-forming material and at the same time first by the reaction at the surface of the oil droplets between the a wall film forming material and the third wall film forming material is formed in the polar liquid.

Various proposals have already been made regarding self-inking pressure-sensitive recording sheets made. However, the usual arches are due to

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Color haze, d. H. the appearance of the color before use, unsatisfactory. The color haze is caused for several reasons, the most important of which is the porosity of the microcapsules to "should be considered. That is, a self-inking pressure-sensitive drawing sheet under use of conventional microcapsules, which, for example, by complex coacervation of gelatin and gum arabic will fog the entire sheet prior to use and result itself a decrease in the technical value of it. That's why it is necessary to apply a protective layer between the capsule layer and the color developer layer or to make the wall of the microcapsules twice as thick

It is therefore an object of the invention to provide a self-inking pressure-sensitive recording sheet, in which color haze is reduced and which is marked results in less staining and no staining caused by pressure or rubbing during handling.

As a result of extensive investigations gur achievement of the tasks outlined above, within the framework of the Invention found that extremely beneficial results with pressure sensitive recording sheets when applied the inventive microcapsules, which after he ^ - inventive method, as detailed below, are produced, can be achieved.

The invention relates to self-inking pressure-sensitive recording sheets comprising a support having a thereon contained microcapsule layer and a color developer layer on the same surface of the support. The microcapsules used in the microcapsule layer are unique in that they contain a color former oil droplets encapsulated within a wall

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materials, which from the reaction product of consists of three wall-forming materials, two of which are initially contained in the oily liquid phase and the third of these is initially contained in a polar liquid as a continuous phase. The inventive method microcapsules are formed, these materials forming the Walls of the microcapsules are reacted.

That is, the microcapsules used according to the invention are emulsified by emulsifying an oil-like liquid which contains a color former which is suitable for reaction with color developer to form a color, a first wall film-forming material and a second wall film-forming material which is suitable for reaction with the first Wall film-forming material is capable of forming a high molecular weight compound ϊ in a polar liquid which is suitable for the formation of a continuous phase containing a third, wall-film-forming material, which is to react with the first wall-film-forming material before or after Emulsification capable of forming a high molecular weight compound. As a result, the capsule wall is formed from the inside of the oil droplets by the reaction between the first wall film forming material and the second wall film forming material, and at the same time the capsule wall on the surface of the oil droplets through the reaction between the first wall film forming material and the third wall film forming material present in the polar liquid.

Figures 1 to 3 are graphs showing

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the dye haze of the self-inking pressure-sensitive Recording papers according to the invention (a) and according to show the prior art Cb).

The manufacturing process used according to the invention of the microcapsules is explained in detail below.

Palis a first wall film forming material and a second wall film forming material that is used for implementation is suitable with the first wall film-forming material in an oily liquid to be encapsulated are dissolved, the resulting mixture is emulsified in a polar liquid which forms a continuous phase and a third wall film forming material to be reacted with the first wall film forming material to form a high molecular weight material is added thereto, or if the oily liquid to be encapsulated in a polar liquid containing the third wall film-forming material, the oil-like oil-like material containing the first wall film forming material and the second wall film forming material Contains liquid, a capsule wall becomes attached to the surface of the oil droplets due to the reaction between the first wall film forming material and the third wall film forming material is formed and simultaneously forming the capsule wall also from the inside of the capsules by the reaction between the first wall film Material and the second wall film forming material formed.

As the first and second wall film-forming material that can be used according to the invention, all Compounds which react with each other to form a high molecular weight material which is found in the oily Liquid and insoluble in the polar liquid

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lien is to be used.

As a third wall film "forming material, the inventive is used, all compounds, which for dissolution or dispersion in a one continuous phase "forming polar liquid and to react with the first wall film "forming material to form a high molecular weight material, which is insoluble in the oily liquid and the polar liquid can be used.

As "preferred examples of the first and second Wall-film-forming materials to be used according to the invention are, for example, compounds with two or more functional groups, preferably three or more functional groups, most preferably three functional groups, such as isocyanate groups, isothiocyanate groups, Epoxy groups, acid chloride groups, chloroformate groups, hydroxyl groups, carboxyl groups, mercapto groups, Amino groups and the like., Indicated. The molar ratio of the first wall film forming material to the second Wall film forming material can vary. The applied Molar ratio is decided so that the number of functional or active groups of the first Wall film forming material is larger than that of the second wall film forming material.

Preferred examples of the third wall film-forming material are, for example, compounds with two or more functional groups, such as amino groups, hydroxyl groups, carboxyl groups, mercapto groups, alkali salts of hydroxyl group-containing aromatic compounds and the like. It is not a specific amount of the third wall film forming agent Material necessary for the first wall film-forming material, it is only necessary that it is present.

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Specific combinations of these compounds are listed in Table I below.

Table I.

First wall film-forming material

Polyisocyanates,
Polyisocyanate adducts
with remaining isocyanate group,
Polyisothiocyanates,
Polyisothiocyanate:
adducts with remaining isothiocyanate groups.

Epoxy compounds

Polyacid chlorides,
Polychloroformate

Second Vand-film-forming material

Polyhydroxy compounds, epoxy compounds, Polycarboxylic acids, polythiols

Epichlorohydrin

Polyamines, modified polyamines

Phenol-formaldehyde resins, polyhydroxy compounds, Polythiols, polycarboxylic acids.

Polyisocyanates, polyisocyanate adducts with the rest Isocyanate groups, polyisothiocyanates, polyisothiocyatad- · ducts with remaining isothioeyanate groups.

Third wall film forming material

Polyamines,
modified polyamines, polyhydroxy compounds, polycarboxylic acids, polythiols,

Polyamines, modified polyamines

Polyamines, modified polyamines, alkali salts of phenol-formaldehyde condensates, aromatic polyhydroxy compounds as alkali salts

Polyamines,
modified polyamines

The microcapsules according to the invention are characterized in that they are formed by the formation of the capsule wall of the inside of the oil droplets using ~ two Vandfilm-forming materials which react

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together to form a high molecular weight material are capable of which both in the oily liquid to be encapsulated and in the continuous Phase-forming polar liquid is insoluble, and at the same time the capsule wall also forms from the outside of the oil droplets by incorporation a wall film-forming material into the continuous phase-forming polar liquid, which is used for conversion with at least one of the two wall film-forming materials to form a material of high molecular weight, which both in the oily liquid and in the polar liquid which forms the continuous phase Liquid is insoluble, is suitable. The Vandfilm-forming materials used and the combinations thereof are not intended as a limitation in any way to the wall film-forming materials described above and combinations thereof. That is, all combinations of the first and second Wall film-forming materials suitable for dissolution or dispersion in an oily liquid and capable of reacting with each other to form a substance insoluble in the oily liquid can be used. Also all available for reaction with at least one in the oily liquid

ien

which wall film-forming material to form a substance which is insoluble in the oily liquid and in the polar liquid forming the continuous phase and for dissolution or dispersion in the continuous phase-forming polar liquid can be used as the third wall-forming material. The wall film-forming materials to be added to the oily liquid to be encapsulated are not necessary.

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maneuverable only limited to two materials, instead, if desired, more than two wall films can be used forming materials are used. For example, in addition to the two wall film forming Materials that react with each other, a wall film forming material, having a reactivity with one of the two wall film-forming materials can also be used herewith. You can also to the two wall film forming materials that react with each other, two wall film forming materials, each reacting with the two wall film forming materials can be used together.

Third, the film to be added to the polar liquid forming the continuous phase In addition to the use of the material forming a third wall film, two or more materials can be used more compounds capable of reacting with at least one of those in the oily liquid to be encapsulated existing wall film-forming materials to form a substance that is to be encapsulated in both the oily Liquid as well as the polar liquid forming the continuous phase is insoluble are used.

The concentration of the first wall film-forming material in the oily liquid is general in the range from about 0.5 to 100% by weight, preferably from about 1 to 40% by weight, based on the weight of the oil. The concentration of the second film-forming material in the oily liquid is decided so that the number of functional groups thereof is less than that of the first wall film-forming material are. The concentration of the third film-forming material, which is generally found in the polar solvent

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is set, is about 0.1 to 15 wt.%, Preferably about 0.4 to 8% by weight, based on the weight of the polar Solvent. These concentrations are neither critical nor limiting and are merely examples of Generally applicable quantities should be understood, since even when using concentrations of these three wall film-forming Materials outside of the above. listed preferred ranges the objects of the invention can be achieved.

Suitable polyisocyanates and polyisocyanate adducts which contain residual isocyanate groups are diisocyanates such as m-phenyl 1-diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, dialkylphenyl methane-4-, 4 -'-diisocyanate, 3 »3'-dimethoxy-4,4'-biphenyl diisocyanate, 3» 3'-dimethyldiphenyl-methane-4, 4 '-diisocyanate, xylene-1,4-diisocyanate, xylylene-1,3 -diisocyanate, 4,4'-Dipheny Ip ropandii socyanat, trimethylene diisocyanate, hexamethylene diisocyanate, propylene- Λ , 2-diisocyanate, butylene-1,2-diisocyanate, ethylidene diisocyanate, cyclohexylene ~ 1,2-diisocyanate, cyclohexylene-1 , 4-diisocyanate, and the like, diisothiocyanates such as xylylene-1,4-diisothiocyanate, ethylidene diisothiocyanate, hexamethylene diisothiocyanate and the like, ITriisocyanates such as 4,4 ', 4 "-triphenylmethane triisocyanate, toluene-2,4,6-triisocyanate, Polymethylene polyphenyl isocyanate and the like, tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5 * 5'-tetraisocyanate and adducts of these polyis ocyanates with polyamines, polycarboxylic acids, polythiols, polyhydroxy compounds, epoxy compounds and the like. The adducts obtained have two or more residual isocyanate groups per molecule and are suitable for reaction with the second and third wall film-forming material to form microcapsule walls.

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Suitable epoxy compounds are "for example aliphatic glycidyl ethers, such as diglycidyl ether, glycerine triglycidyl ethers, polyallyl glycidyl ethers with molecular weights from 150 to 50000 and the like, aliphatic «glycidyl ester, like the diglycidyl ester of linoleic acid dimer and the like, aromatic glycidyl ethers, such as bisphenol A diglycidyl ether, Trihydroxyphenylpropane triglycidyl ether, tetraphenylene ethane tetraglycidyl ether and the like, glycidyl ether / ester mixtures, such as 4,4'-bis (4-hydroxyphenyl) pentanoic acid diglycidyl ether ester and the like and similar compounds.

Examples of polycarboxylic acid chlorides are aliphatic and aromatic polycarboxylic acid chlorides, such as adipoyl chloride, sebacoyl chloride, phthaloyl chloride, Terephthaloyl chloride and the like. Listed.

Examples of polychloroformates are hexamethylene bis (chloroformate), p-phenylenebis-chloroformate) ■ and similar materials are listed.

Examples of polyhydroxy compounds include aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, hydroxy polyalkylene ethers and similar compounds. For example, suitable specific examples of such materials that can be used are catechol, resorcinol, hydroquinone, 1,2-dihydroxy-4-methylbenzene, Λ , 3-dihydroxy-5-methylbenzene, 3,4-dihydroxy-1-methylbenzene , 3 »5-dihydroxy-1-methylbenzene, 2,4-dihydroxyethylbenzene, 1,3-naphthalenediol, 1,5-haphthalenediol, 2,7-naphthalenediol, 2,3-naphthalenediol, 0,0'-biphenol, p, pj -'-biphenol, 1,1'-bis-2-naphthol, bisphenol A, 2,2'-bis- (4-hydroxyphenyl) -butane, 2,2'-bis- (4-hydroxyphenyl) -isopentane , 1,1'-bis- (4-hydroxyphenyl) -eyelopentane, 1,1'-bis- (4-hydroxyphenyl) -eyelohexane, 2,2'-bis- (4-hydroxy-3-methy! Phenyl) propane, bis (2-hydroxyphenyl) methane,

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Xylylene diol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-heptanediol, 1,7-heptanediol, 1,8-octanediol, 1,1,1-trimethylolpropane, Hexanetriol, pentaerythritol, glycerine, sorbitol, aromatic and aliphatic ^ polyhydric alcohols and similar compounds.

The hydroxypolyesters that can be used are "obtained, for example, from polycarboxylic acids and polyhydroxy compounds, The polycarboxylic acid components of the hydroxypolyesters are, for example, malonic acid, succinic acid, ' Glutaric acid, adipic acid, pimelic acid, maleic acid, isophthalic acid, terephthalic acid, gluconic acid and the like. specified. Those listed above are suitable as polyhydroxy compounds.

Suitable hydroxypolyalkylene ethers are, for example Condensation products between an alkylene oxide and a polyhydroxy compound. Suitable examples for alkylene oxides for the production of the hydroxy polyalkylene ethers are butylene oxide, amylene oxide and similar compounds. As the polyhydroxy compounds, those listed above can be used.

Polycarboxylic acids are, for example, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, Terephthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-sulfonyldibenzoic acid and the like. Listed.

Polythiols are condensation products of thioglycol, reaction products between a polyvalent one Alcohol and a suitable thioether glycol and the like. listed.

Examples of polyamine compounds and modified polyamine compounds are aromatic polyamine compounds, such as p-phenylenediamine, p-phenylenediamine, diaminonaphthalene, and the like, aliphatic ^ polyamine compounds

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fertilize, such as 1, 3-P ^ opyleB-diamine, diethylenetriamine, hexamethylenediamine and the like, adducts of these aromatic and aliphatic polyamines with epoxy compounds and the like Materials specified. Compounds such as gelatin with a plurality of amino groups can also be used here Be used per molecule. That is, such connections, which have two or more amino groups per molecule can be used as polyamine compounds or modified Polyamine compounds are used in the context of the invention.

Examples of alkali salts, aromatic hydroxy compounds, are the sodium salt of bisphenol A, the potassium salt of phenol-formaldehyde condensates and similar compounds are given. The sodium, potassium and lithium salts, preferably the sodium and potassium salts because of cost, can be used. Suitable Phenol-formaldehyde condensates are described in U.S. Patents 3,427,180, 3,455,721, 3,516,845, 3,634,121, 3,663,256 and 3,672,935 and <fer British patent specification 1 215 818 and the like.

The above-described materials are individually known in the art as wall film-forming materials U.S. Patents 3,429,827 and 3,577,515; and U.S. Pat British patents 1,091,076, 1,091,077 and 1 091 078 specified.

The third wall film-forming material can be added to the polar liquid before or after the oil-like liquid Solution containing the first and second wall film forming materials to be encapsulated is emulsified, can be added. However, the addition after emulsification is preferred because the oil droplets do not aggregate and the viscosity of the emulsion is not increased abruptly. This allows emulsification to be carried out easily,

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and microcapsules of more uniform size are obtained.

The most typical example of a polar liquid used to form a continuous phase is made up of water. Other polar liquids, such as alcohols and ketones, may be more suitable Way to be used. Alcohols such as monohydroxy alcohols, for example butyl alcohol, octyl alcohol and Like., glycols, such as ethylene glycol, and polyhydroxy alcohols, such as glycerine, water or mixtures of other polymeric materials with water can also be used are generally used.

The emulsification and dispersion of the oily solution, which is to be encapsulated in the polar liquid can be carried out using a protective colloid or a surfactant can be effected. The amount of the same can vary freely and it is just that Amount required that is necessary for emulsification. Examples of protective colloids are natural or synthetic hydrophilic high molecular materials such as gelatin, gum arabic, casein, carboxymethyl cellulose, Starch, polyvinyl alcohol and the like. Suitable surfactants are anionic surfactants such as Alkylbenzenesulfonates, alkylnaphthalene sulfonates, polyoxyethylene sulfonates onates, Turkish red oil and the like and non-ionic ones surface-active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, sorbitan fatty acid esters and the like

Although the reaction between the wall film-forming materials takes place without the need for a catalyst Acceleration and the like. Carried out for the purpose of accelerating the reaction between the wall film forming materials can be used, catalysts can also be used-

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The catalyst may be added to the oily liquid to be encapsulated or to the polar liquid constituting the continuous phase. The use of the catalyst enables the wall film formation reaction to be effectively accelerated, furthermore, the wall permeability is decreased, and the time required for the formation of the capsule wall is shortened. Even if the temperature of the reaction system is increased to accelerate the capsule formation reaction, the use of the catalyst allows encapsulation at lower temperatures, the use of a catalyst is known to those skilled in the art, and the amount of the catalyst used can be easily selected by those skilled in the art.

If polyisocyanates or adducts thereof with remaining isocyanate groups, for example, as the first wall film forming material can be used as catalysts for the addition reaction of Isoeyanat- ' known groups of catalysts, such as amines, organometallic compounds, tertiary phosphines and the like., Are used. As amines, which are used as catalysts according to the invention Trialkylamines such as triethylamine and tetraalkyldiamines may be mentioned, for example , such as N, N, N ', N' -tetramethyl-1,3-butanediamine and Like., amino alcohols such as dimethylethanolamine and the like., ethoxylated amines, ethoxylated diamines, ester amines, such as Bis (diethylethanolamine) adipate, and the like, triethylenediamine, N, N-dimethylcyclohe: xylamine derivatives, morpholine derivatives, such as N-methyimorpholine and the like, piperazine derivatives, such as N, N'-diethyl-2-methylpiperazine, Ν, Ν-bis (2-hydroxypropyl) -2-methylpiperazine and the like and similar compounds.

Organometallic compounds include, for example, the organometallic compounds of tin, lead, cadmium, Cobalt, aluminum, potassium, chromium, zinc and the like, listed,

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Specific examples of organotin compounds,. the the The most typical representatives of the organometallic compounds described above are mbutyltin laurate, dibutyltin- (2-ethylhexoar) and similar connections.

As organic acid salts of various metals, for example, the salts of tin, lead, cadmium, cobalt, aluminum, potassium, chromium, zinc and the like. And organic acids such as oleic acid, naphthenic acid, caproic acid, octylic acid and the like., Listed. Specific examples of organic acids include, for example, Zinnsälz tin (II) oleate, tin äthylcaproat 2, Zi Tm naphthenate, tin octylate and the like.

Suitable examples of tertiary phosphines are trialky! Phosphine, dialkylbenzylphosphine and the like.

Alkali hydroxides or alkali salts of fatty acids can be used as alkali compounds.

Suitable agents which form free radicals are benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile and the like

These catalysts can be used individually or in combination. In particular, the joint use of an amine and an organometallic compound or a metal salt of an organic acid accelerates microencapsulation to a greater extent. Also, the temperature of the reaction system can be increased by heating to accelerate the reaction between the first wall film forming material and the second wall film forming material and the reaction between the first wall film forming material and the third wall film forming material. In this case, it is necessary to heat the reaction system to a lower temperature than the boiling point of the polar liquid agent constituting the continuous phase and the boiling point of the oily liquid to be encapsulated. The temperature range _t

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which can be generally used is about 0 ° C Ms about 100 ° C.

The microcapsules obtained in this way, which contain a color former oil, are carried on a carrier or a color developer layer applied to a support. The structural arrangement of the microcapsule layer and the color developing layer is not "particularly" limited and the order can be varied freely will. This means that with the usual microcapsules, a color developer layer and then a color developer layer must be placed on the carrier Microcapsule layer are applied so that the color haze is reduced as much as possible. However, according to the invention, there is also an opposite one physical arrangement possible so that this guard part is avoided both the microcapsules and the color developer simultaneously on the carrier, for example as a mixture the same are applied.

The color-forming oil encapsulated in the microcapsules is an oil that contains a color-forming compound contains dissolved, which is suitable for reaction with the color developer to form a color. The amount of color-forming compound depends on the density of the color desired in the color formation. Become generalities About 1 to 10% by weight, based on the oil, are used.

In practicing the invention, the color former is not particularly limited, and examples thereof are given. Nnectivity from triarylmethane, such as 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, ie, crystal violet lactone, 3> ^B is- 3- (p-dimethylaminophenyl) -phthali d, 3- (p-dimethylaminophenyl) -3 - (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl ^ -

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3- (2-methylindol-3-yl) -phthalide, ^ - (p-Dimethylaminophenyl) -3- (2-phenylindo.-3-yl) -phthalide, 3,3-bis- (1,2-dimethylindole -3-yl) -5-dimethylaminophthalide, 3 »3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3» 3-bis (9-ethylcarbazol-3-yl) -5- dimethylaminophthalide, 3,3-bis- (2-phenylindol-3-yl) -5-dimethylaminophthalide and 3-P-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide, diphenylmethane type compounds such as 4 , 4'-bis-dimethylaminobenzhydrinbenzyl ether, M-halophenylleucoauramine and N "-2, ^/ f, 5- ^ ichlorphenylleucoauramine, compounds of the xanthene type, such as ehodamine-B-anilinolactam, rhodamine-Bp-nitroanilinolactam, ehodamine-Bp-chloraniline, ^ i ^m öthylamino-2-metho3qs ^r fluoran, 7-diethylamino-2-methoxyfluoran, 7-diethylamino-3-methoxyfluoran, 7-diethylamino-3-chlorofluoran, 7-diethylamino-3-chloro-2-methylfluoran, 7 -Diäthylamino-2 _i 3-öimethylfluoran, 7 - diethylamino-3-acetylmethylamiiiofluoran, 7-diethylamino-3'-methylaminofluoran, 3,7-diethylaminofluoran, 7-diethylamino-3-dibenzylaminofluoran, 7-diethylamino-3-niethylbenzylarainofluoran, 7-diethylamino-3-chloroethylmethylaminofluoran and 7-diethylamino-3-diethylaminofluoran, compounds of the thiazine-nitro-methylene and spiro-benzylleu-type compounds, such as benzoblueylleu like 3-methylspiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzylspirodinaph.thopyran, 3-methylnaphtho- (3-methoxybenzo) -spiropyran and 3-i ³ 3? opyl-spiro-dibenzopyran.

All oils that have the property of Resolution and retention of the color former can be used as known in the art. Suitable examples of such oils are those with a medium and high boiling point, e.g. higher than about 170 ° C, synthetic oils, solvents and the like,

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such as paraffin oil, cottonseed oil, soybean oil, corn oil, Olive oil, castor oil, fish oil, bacon oil and chlorinated paraffin, chlorinated diphenyl, dibutyl phthalate, dioctyl phthalate, Tributyl phosphate, tricresyl phosphate, dibutyl maleate, o-dichlorobenzene, alkylnaphthalene, alkylbiphenyl, Alkyldiphenylmethane, hexahydroterphenyl, toluene, Benzyl alcohol and the like. Suitable alkyl naphthalenes, alkyl by-phenyls and alkyldiphenylmethanes are in US patent applications Ser. No. 174-518 of August 24, 1971, 172 593 of August 17, 1971 and 193 152 of October 27 1971 stated. The color former oil can be different Additives known in the art, for example ultraviolet light absorbers, fluorescent Lightening agents, antioxidants and the like. Contain.

Thus, the microcapsules containing the color picture oil are applied to a carrier as such or together with a binder such as polyvinyl alcohol, carboxymethyl cellulose, gelatin, gum arabic, starch or mixtures thereof, applied. A suitable amount of the binder can range from 0 to 100 weight percent based on weight of the microcapsule dispersion. Suitable carriers are those usually used, such as papers and plastic films or arches.

As a color developer, all that can be used to react with the color former to form a colored Hateriales are suitable to be used. This means, all color developers commonly known and used as color developers for pressure-sensitive applications Recording papers used can be used. These color developers are generally acidic materials and include active clay materials, for example

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acid clay, attapulgite, zeolite, bentonite and the like, organic acidic materials, for example succinic acid, tannic acid, bile acid, pentachlorophenol, phenolic resins and the like, metal salts of aromatic acids, for example Zinc salicylate, zinc i-hydroxy-3-naphthoate, tin salicylate, Tin 2-hydroxy-3-naphthoate, zinc 3,5-di-tert-butyl salicylate and the like, mixtures of aromatic acids and metal compounds such as a mixture of 2-hydroxy-3-naphthoic acid and zinc oxide, a mixture of p-tert-butyl salicic acid and zinc hydroxide and the like, or mixtures of such materials. Suitable color developers and the production of such layers are for example listed in U.S. Patent 2,730-457.

If necessary, the color developer is used together with various additives or binders, the styrene-butadiene copolymers (Molar ratio 1: 1, molecular weight about 1000) applied as a latex. The color developer layer can be applied in any conventional and well known manner in the art.

The microcapsules obtained by the above process have an extremely low wall permeability and are extremely stable against pressure, friction and similar forces. Therefore, if an oily liquid included herein contains a color former, is encapsulated in the microcapsules and, together with a color developer, on the the same surface is applied, color former and color developer do not react with each other through the capsule wall, so that the entire surface of the bow is colored, and the bow does not even become partially self-contained colored by a slight pressure or friction during handling.

That is, the self-recording sheets have one

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extremely high technical value and can according to the invention can be obtained. In addition, occurs in the case of the invention Process no color haze even if the color former concentration is in the oily Fluid is increased. Therefore, recording sheets that have an extremely high color density after application local pressure, for example in the case of lettering or typing, have been obtained.

Even if the above-mentioned microcapsules containing the color former and the color developer mixed with each other and applied to the carrier, no color haze occurs. Thus can the desired self-inking recording sheets can be obtained using only one coating process.

The invention will hereinafter be more specifically preferred by way of the following non-limiting examples Embodiments of the invention-explained. If nothing otherwise indicated, all parts and percentages are by weight.

The color developer solutions, which are acidic clay, zinc-3,5-di-tert-butylsaliaylat or phenolic resins which were used as representative in the following examples Examples of suitable color developers used were prepared in the following manner:

8 cnr of a 20% aqueous solution of sodium hydroxide were added as a dispersant to 300 g of water added. To this end, 100 g of acid clay were added to the dispersion, followed by vigorous stirring. then 40 g of SBR latex (styrene-butadiene rubber latex, same molar ratio, 50% solids content) were used here as Binder was added. In this way, a color developer

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solution containing sour clay. 10 s polyvinyl alcohol (average degree of polymerisation 500; Degree of saponification 87%) was dissolved in 90 g of water. For this purpose, 60 g of zinc 3 »5-di-tert-butyl salicylate powder were added added to the dispersion with vigorous stirring. This created a color developing solution which contained zinc 3,5-di-tert-butylsalieylate.

20 g of a condensate of p-phenylphenol and formaldehyde (Molar ratio 1: 1, degree of condensation 1 to (mixture)) as a binder, 8 g of a styrene-maleic anhydride copolymer (Molar ratio 1: 1) were added to 200 g of water and the solid in it Powdered using a ball mill for 24 hours. This made a color developing solution that is a phenolic resin contained, manufactured.

example 1

0.7 g crystal violet Iac ton and 0.5 g benzoylleucoäthylenblau were dissolved as color former in J> 0 g of a diisopropylnaphthalene, as an oily liquid with heating to 80 ° C and the resulting mixture was cooled to room temperature, about 20 to 30 ° C. 7 g of the adduct to 3 moles of hexamethylene diisocyanate were added to this oily liquid which contained the color former; and 1 mole of trimethylolpropane, which contained residual isocyanate groups, was added as a first wall film-forming material and 1 g of a polyoxypropylene poly (average molecular weight 560; hydroxyl number 530) was added as a polyhydroxy compound as a second wall film-forming material, and then stirred to mix. 0.1 g of dibutyltin laurate was added as a catalyst for accelerating the reaction between the first and second wall film-forming materials. The obtained oily L5-

409809/0962

The solution was added, with vigorous stirring, to 60 g of water at 20 ° C. with a content of 2 g of carboxymethyl cellulose and 2 g of polyvinyl alcohol (average degree of polymerization 500; degree of saponification 87%) to form oil droplets 4 "to 10 microns in diameter were added. 80 grams of water was also added to dilute the solution admitted. As a third wall film-forming material, 6 g of an adduct of a polyamine (N content 18 to 21%) and an epoxy compound to dsm the continuous Phase-forming water was added.

During the operations outlined above, the temperature of the system was not at temperatures Maintained above 20 ° C so that the reaction was mild. To form the reaction between the first wall film Material and the second wall film forming material and the reaction between the first wall film forming Material and the third wall film forming materail became the temperature of the system to 85 ° C by heating to complete the encapsulation elevated. As a result, microcapsules, which were enveloped with a strong capsule wall and contained dipropylnaphthalene, obtain.

This microcapsule solution was made into an acidic clay coated paper applied and dried with heating to 50 ° C and a self-inking recording sheet obtain. The sheet obtained was white, showed no color haze and only turned blue when inscribed colored with print.

In addition, this sheet was markedly stable and stable to light, pressure or friction during handling was particularly resistant to color staining.

The density of the veil of color on this self-record sheet was made using a spectrophotometer

409609/0962

ORIGINAL INSPECTED

determined and the one in Pig. Graph shown in i (a) obtain. In Fig. 1 (a), the fog density at a wavelength of 610 mu, corresponding to blue, as low as 0.04-, which shows that the self-recording sheet according to the invention showed no color haze.

On the other hand, a self-recording sheet has become that of a single-sheet pressure-sensitive recording sheet which was prepared in the same manner as above but using microcapsules was that after the complex coacervation of gelatin and gum arabic using the most widely used Process in the field of pressure-sensitive copier paper had been prepared as in the US patent 2 800 457 described, altogether blue to such Colored to the extent that the sheet was of no practical use.

To this end, 0.7 S crystal violet lactone and 0.5 S Benzoylleucomethylene blue in 30 g of diisopropylnaphthalene solved. The obtained oily solution was added to 30 g of water of 50 ° C containing 6 g of the acid-treated one Gelatin and 6 g of gum arabic with vigorous stirring to emulsify to form oil droplets with a 4 to 10 microns in diameter added. 200 g of water of 50 ° C were added to the emulsion for dilution and £ 0% acetic acid was used to adjust the added pH of the system to 4.5. This involved complex coacervation of gelatin and gum arabic and a film of gelatin and gum arabic began to separate around the oil droplets. The temperature the system was increased to 10 G for further execution of complex coacervation and gelatinization of the gelatin of the film is reduced. Then there were 2 cnr 37% formalin

409809/0962

To this end, 20% sodium hydroxide was added to harden the gelatin and to accelerate hardening added drop by drop to increase the pH of the system to 11. Then the system was set to 60 ° C heated to complete curing. In this way the capsule solution was prepared. As a result, microcapsules with a gelatin-gum arabic wall, which a oily liquid with color formers dissolved therein, for use in pressure-sensitive copier papers obtain. This microcapsule solution was applied to a paper and dried with heating. Farther a color developing solution containing acidic clay was applied to the same surface, followed by the microcapsule solution applied / ^ applied and dried with heating. The recording sheet thus obtained was over the entire sheet immediately after drying Tinted blue to such an extent that he-by no practical Was worth. The color density of this sheet was measured using a spectrophotometer and the graphical values shown in Fig. 1 (b) were obtained. In this graph, the fog density was at a wavelength of 610 mu, corresponding to blue, 0.54-j, which is more than 12 times that obtainable according to the invention Value of 0.04- was.

Even if the two specified after Procedure obtained capsule solutions with a color twirl solution that contained acidic clay and in the pre- ' had been prepared as indicated standing, were mixed and applied to paper and then were dried, the sheets using the microcapsules according to the invention showed no blue color haze, while the arches using the microcap

409809/0962

be with a gelatin gum .arabicum wall like her usually for the production of pressure-sensitive recording papers used, were colored altogether blue to such an extent that they were of no practical use Meaning were.

In the same way, if each of these microcapsule solutions showed was applied to a surface, followed by a coloring developer solution containing an acidic clay had been applied, the sheet obtained using the microcapsules according to the invention no color fogging, while obtained using the usual microcapsules with a gelatin-gum arabic wall The overall bow was colored blue to such an extent that it was of no practical value.

Example 2

A microcapsule solution according to the invention was made prepared as in Example 1 and drawn down on paper and dried. Then a color developing solution was which zinc 3,5-di ~ tert-butyl salicylate contained, which were prepared in the manner described above was, on the same surface, whereupon the microcapsule solution had been applied, raised and then dried. This pressure-sensitive recording sheet showed no color haze, was white and only colored blue when printed under pressure became. The dyeing mistake density of this recording sheet was determined using a spectrophotometer and the graph obtained in Fig. 2 (a) won. In this graph, the fog density was at the wavelength of 600 µm

409809/0962

correspondingly blue, as low as 0.04, which shows that practically no fog was formed on the recording sheet according to the invention.

On the other hand, a sheet prepared in the same manner as above but using the microcapsule solution having a gelatin-gum arabic wall obtained in Example Λ was colored blue as a whole to such an extent that it was of no practical value.

The stain density of this recording sheet became was measured using a spectrophotometer and the graph shown in Fig. 2 (b) was obtained. In In this graph, the maximum absorption density at 600 mu was as high as 0.66, which is more than 14 times the fog density of the recording sheet of the invention.

On the other hand, when these capsule solutions were applied as a mixture with a coloring developing solution, or when these capsule solutions were applied to a surface drawn up with the color developing solution was that of the veils formed on the arches using the microcapsules according to the invention are markedly lower than with the sheet, which uses the commonly used microcapsules with a gelatin-gum-arabic wall became.

Example 3

A microcapsule solution according to the invention, here. represents according to Example 1, was applied to a paper and dried. Then a color developing solution was used that a phenolic resin, as described above, contained

409809/0962

the same surface on which the microcapsules had been applied, peeled off and then dried. This pressure-sensitive recording sheet showed no color fogging, was white and only colored blue when it was written on under pressure. The fog density of this recording sheet was determined using a spectrophotometer, and ^a graph shown in Fig. 5 (a) was obtained. According to this graph, the fog density at a wavelength of 600 mja, corresponding to blue, was as low as 0.025, which shows that practically no fog was formed on the recording sheet according to the invention.

Even if the pressure-sensitive recording sheet according to the invention was exposed to sunlight, it was colored only slightly blue, but showed no serious yellowing. When this in sunlight When exposed sheets were written under pressure, distinctive color markings were obtained. The coloring ability the arc was thus not lost by exposure to sunlight.

In addition, the color density of this sheet was markedly high.

On the other hand, in the same manner as above using microcapsules with a Gelatin and gum arabic wall obtained according to Example 1 The sheet produced was colored blue to such an extent that it was not used by any practical Was use value.

The stain density of this recording sheet was determined using a spectrophotometer and the graph shown in Fig. 3 (b) was obtained. According to this representation, the maximum was

409809/0962

Absorption density at 600 mu 0.135 »what more than that 5 times the fog density of the self-recording sheet according to the invention. The sheath of the self-recording sheet according to the present invention therefore turned out to be remarkably low.

Example 4

0.5 g of 2,4-dimethyl-7-dimethylaminofluorane and 0.2 g of ehodamine-Bp-nitroanilinolactam were dissolved as a color former in 30 g of dipropyldiphenylmethane as an oily liquid with heating to 90.degree. After cooling, the oily solution to 20 ° 0 was added 5 g of the adduct of 3 Hol tolylene diisocyanate and Λ Hol trimethylol propane, and 2 g of the adduct of 2 Hol tolylene diisocyanate and 1 Hol dipropylene glycol added thereto forming Haterialien to Auslöung this first wall film. To this solution, 0.5 g of an Ethyleixdiamine-propylene oxide adduct with a number of hydroxyl groups of 500 mg KOB / g was then added as a second wall film-forming material. The resulting oil-like solution was added, with vigorous stirring, to 60 g of water at 18 ° C., which dissolved 3 drops of Turkish red oil, 3 g of gum arabic and 2 g of polyvinyl alcohol, as indicated in Example 1, to form oil droplets 6 to 10 microns in diameter added. Then 100 g of water was added for dilution. 3 S of an adduct of a polyamine and an epoxy compound as a third wall film-forming material and 2 g of an epoxy resin as a hardener were added to the water forming the continuous phase. During the procedures outlined above, the temperature of the system was maintained at temperatures not higher than 20 ° C. The system was left on for 24 hours at room temperature

409809/0962

stirred and thereby ended the encapsulation. As a result, microcapsules with a strong capsule tape, which the the oily liquid containing the color former was obtained. This microcapsule solution was treated with an acidic Clay containing the color developing solution, d. H. a zinc 3,5-di-tert-butyl salicylate containing developer solution, or with a phenolic resin containing color developer solution, in a mixing ratio of 1: 1, applied to paper, mixed and then dried so that each three self-recording test sheets were obtained. These Arches were all white and showed a pronounced red marking only in the areas below Print.

In the same way, the above capsule solution was applied to a surface, whereupon a zinc-3,5-di- "tert-butyl salicylate containing color developer solution, the color developing solution containing the phenolic resin or the color developing solution containing the acid clay was applied and then dried. The arches received were all white and yielded pronounced red markings only in the areas that had been labeled under pressure.

' Example 5

3 drops of Turkish cane oil, 1 g of carboxymethyl cellulose and 2 g of polyvinyl alcohol were dissolved in 80 g of water, and as the third wall film-forming material, 2 g of one Epoxy resin as hardener, namely the adduct of 3,9-bisaminopropyl-2,4,8,10-tetraoxaspiro- (5,5) -undecane and acrylonitrile (2: 1 molar ratio, active hydrogen equivalent 85, viscosity 20 cP (20 ° C)) was added to this.

409809/0962

Separately, 0.8 g of crystalline violet lactone in 500 g of dipropylnaphthalene was used as an oily liquid dissolved with heating and then the solution cooled to 15 ° C. In this oily solution, 7 g of one aliphatic polyisocyanate adduct with remaining isocyanate groups, namely the adduct of cyclohexane isocyanate and trimethylolpropane (molar ratio 3: 1) as the first wall film-forming material, and 2 g of an epoxy compound (epoxy equivalent 190; molecular weight 380) was added as a second wall film-forming material. This oily solution became the above aqueous one Solution containing the third wall film-forming material with vigorous stirring to form oil droplets 5 "to 15 microns in diameter added. During the above According to the procedure described, the temperature of the system was kept at no more than 15 ° C. To the addition of 100 g of water at 30 ° C was the system heated to 80 ° C and stirring continued for 4 hours to complete the encapsulation. The received Capsule solution was applied to a paper and dried, and a color developing solution containing acid clay was applied was applied to the same surface on which the microcapsule solution was applied, and then dried. A self-recording sheet was thereby obtained. This bow was white and showed pronounced red markings only on the areas that had been labeled under pressure.

Example 6

1 S 3,7-bis- (dimethylamino) -fluoran wure as a color former in 30 g hexahydroterphenyl as an oily liquid

409809/0962

ability dissolved with heating and then cooled to room temperature. 8 g of an epoxy resin for paint use was made dissolved therein as the first wall film-forming material and furthermore 1 g of o-phenylenediamine was added to this as the second Wall film forming material added.

The obtained oily solution was added to 50 g of water containing 2 g of gelatin and 3 S polyvinyl alcohol as indicated in Example 1 with vigorous stirring so that oil droplets having an average diameter of 8 microns were formed. Furthermore, 100 g of water were added to this. Then, 6 g of diethylenetriamine was added to the continuous phase as a third wall film-forming material, and in order to accelerate the wall film-forming reaction, the temperature of the system was raised to 85 ° C and stirring was continued for 24 hours to complete the encapsulation. The resulting microcapsules were filtered off from the continuous phase. After the unreacted diethylenetriamine present in the continuous phase had been removed, 100 g of water, which contained 3 S polyvinyl alcohol in solution, were added to prepare the coating solution. This coating solution containing the microcapsules was applied to a paper and dried. An ear developer solution containing phenolic resin was then applied to it and dried, and a self-inking sheet was obtained. This sheet was white and was only colored dark green in the areas where it was written on under pressure.

In the foregoing, the invention has been described in detail on the basis of specific embodiments, without that it is limited to this.

409809/0962

Claims (8)

- 53 - Patent claims r \.) Pressure-sensitive recording sheet, ordered from a carrier with a microcapsule layer attached to it and a color developer layer on the same surface, characterized in that the microcapsules are emulsified by emulsifying an oil-like liquid that contains a color former, which is used to react with the color developer Formation of a paint is suitable, a first wall film-forming material and a second wall-film-forming material, which is suitable for reaction with the first wall-film-forming material to form a high molecular weight compound, in a polar liquid, which is suitable for forming a continuous phase , contains, a third wall film forming material capable of reacting with the first wall film forming material to form a high molecular weight compound is added to the polar liquid before or after emulsification, and a capsule wall around the oil droplets the oil-like liquid forms, wherein the capsule wall on the inside of the oil droplets made by reaction between the first wall film forming material and the second wall film forming material and at the same time by reaction on the surface of the oil droplets between the first wall film forming material and the third wall film forming material has been formed in the polar liquid. 2. Pressure-sensitive recording sheet according to claim 1, characterized in that the first wall filter forming material and the second wall film forming material each composed of a combination of two or more 409809/0962 functional groups from the group of isocyanate groups, Isothiocyanate groups, epoxy groups, acid chloride groups, Chloroformate groups, hydroxyl groups, carboxyl groups, Mercapto groups or amino groups. 3. Pressure-sensitive recording sheet according to Claim 1 or 2, characterized in that the third wall film-forming material consists of a compound with two or more functional groups from the group of amino groups, hydroxyl groups, carboxyl groups and mercapto groups or an alkali salt of a hydroxy IgruppehaItigen aromatic compound consists. 4. Pressure-sensitive recording sheet according to claims 1 to 3, characterized in that the first wall film-forming material consists of a polyisocyanate, a polyisocyanate adduct containing residual isocyanate groups, a polyisothiocyanate, a polyisothiocyanate adduct containing residual isothiocyanate groups, an epoxy compound, a polyacid chloride, a polychloroformate or an epichlorohydrin, the second wall film-forming material consists of a polyhydric oxy compound, an epoxy compound, a polycarboxylic acid compound, a polythiol, a polyamine, a modified polyamine, a phenol-formaldehyde resin, a polyhydroxy compound, a polyisocyanate, a polyisocyanate containing residual isocyanate groups Adduct, a polyisothiocyanate or a polyisothiocyanate adduct containing residual isothiocyanate groups, and the third wall film-forming material consists of a polyamine, a modified polyamine, a polyhydroxy compound g, a polycarboxylic acid, a polythiol, an alkali salt of a phenol-iormaldehyde condensate or an alkali salt of an aromatic polyhydroxy compound. 409809/0962 5 · Pressure-sensitive recording sheet according to Claim 4, characterized in that the polyisocyanate consists of a diisocyanate, a triisocyanate or a tetraisocyanate, the remaining isoeyanate groups containing polyisocyanate adduct of an adduct of a diisocyanate, a triisocyanate or a tetraisoeyanate with a polyamine, a polycarboxylic acid, a polythiol, a polyhydroxy compound or a Epoxy compound consists, the polyisothiocyanate from a polydiisothiocyanate, which the remaining isothiocyanate groups containing polyisothiocyanate adduct of an adduct of a polydiisothiocyanate with a polyamine, a Polycarboxylic acid, a polythiol · a polyhydroxy compound or an epoxy compound, the epoxy compound consists of an aliphatic glyeidyl ether, a aliphatic glycidyl ester or an aliphatic glycidyl ether / ester mixture consists, the polycarboxylic acid. Chloride from an aliphatic polycarboxylic acid chloride or an aromatic polycarboxylic acid chloride, the polychloroformate consists of an alkylene chloroformate or an arylene chloroformate, the polyhydroxy compound from an aliphatic, polyhydric alcohol, an aromatic, polyhydric alcohol, a hydroxypolyester or a hydroxypolyalkylene ester, the carboxylic acid consists of an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid and the polyamine compound from an aromatic polyamine, an aliphatic polyamine or from a polymeric amino group containing compound exists. 6. Pressure sensitive recording sheet according to claim 4, characterized in that the polyisocyanate from m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene 409809/0962 1, 4-diisocyanate, Malkylphenylmethan ^^ '- diisocyanates, 3' 3 'dimethoxy-4,4' -biphenyldiisocyanat, 313' -Dimethyldiphenylmethan ^{1-4,4-diisocyanate,} xylylene diisocyanate, 1,4-xylylene-1 , 3-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, ethylidene diisocyanate; cycloliexylene-1,2-diisocyanate, cycloliexylene- Λ , 4-diisocyanate , 4,4 ', 4 "-iriphenylmethane triisocyanate, toluene-2,4,6-triisocyanate, polymethylene polyphenyl isocyanate or 4,4 ^I -dimethyldiplienylmetliaii-2,2 ^I , ^ i ^' - ^ etraisocyanai ;, the polyisocyanate adduct containing the remaining I cyanate groups from an adduct of such a polyisocyanate with a polyamine, a polycarboxylic acid, a Polythiol, a polyhydroxy compound or an epoxy compound, the polyisothiocyanate from xylylene-1,4-diisotniocyanate, Ethylidene diisothiocyanate or hexamethylene diisothiocyanate, the epoxy compound from a diglyeidyl ether, G-lycerol triglycidyl ether, Polyallyl glycidyl ether, diglycidyl ester of linoleic acid dimer, bisphenol A diglycidyl ether, G? Rihydroxyphenylpropane Triglyc i dyläther, Tetraphenylenäthantetraglycidylätlier or 4,4'-bis (4-hydroxyphenyl) pentanoic acid diglycidyl ether ester, the polycarboxylic acid chloride from adipoyl chloride, sebacoyl chloride, phthaloyl chloride or terephthaloyl chloride, the polychloroformate from hexamethylene bis-chloroformate) or p-phenylenebis-chloroformate), the polyhydroxy compound from catech o3, resorcinol, hydroquinone, 1 ^ -dihydroxy ^-1,3-methylbenzene, -5-methylbenzene, 3i ^Z ^ -I ⁾ ihydroxy-1-methylbenzene _ί 3 »5- ^l) ihydroxy-1-methylbenzene, 2,4-dihydroxyethybenzene, 1,3-naphthalenediol, 1,5-naphthalenediol , 2,7- ^ apb-thalindiol, 409809/0962 2,3-naphthalenediol, ο, ο'-biphenol, ρ, ρ ¹ -biphenol, 1,1'-bis-2-naphthol, bisphenol-A, 2,2 · -Βί8- (4 ~ 1 $ ΓαΓθΧ3Γρ] ιβ ^ 1) -butane, 2,2'-bis - (^ - hydroxyphenyl) -isopentane, 1,1 '-bis- (4-hydroxyphenyl) -eye lopentane, 1,1' -bis - ^ - hydroxyphenyl) -cyclohexane , 2,2'-bis (4-hydroxy-3-met3iylplienyl) propane, bis (2-hydroxyphenyl) methane, xylylene diol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5- Pentanediol, 1,6-heptanediol, 1,7-heptanediol, 1,8-octanediol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol, glycerol, sorbitol or a reaction product of a polycarboxylic acid and at least one such polyhydroxy compound, the polycarboxylic acid from the group of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, isophthalic acid, terephthalic acid and gluconic acid is selected, the polycarboxylic acid from pimelic acid, suberic acid, Azelaic acid, sebacic acid, phthalic acid ', terephthalic acid, 4,4'-biphenyldicarboxylic acid or 4,4'-sulfonyldibenzoic acid, the polythiol from the condensation product of thioglycol or the reaction product between a polyhydric alcohol and a thioether glycol, the polyamine compound of o-phenylenediamine, p-phenylenediamine, Diaminonaphthalene, 1,3-propylenediamine, diethylenetriamine, Hexamethylenediamine, adducts these water polyamines with an epoxy compound or gelatin and the alkali salt of the aromatic hydroxy compound from the sodium or potassium salt of bisphenol A or the sodium or potassium salt of a phenol-s ormaldehyde condensate. 7 · Pressure-sensitive recording sheet according to claim 1 to 6, characterized in that the molar ratio of the first wall film forming material increases 409803/0962 the second wall film-forming material is such that the first wall-film-forming material is in excess, based on Equivalence basis exists. 8. Pressure-sensitive recording sheet according to claim 1 to 7 »characterized in that the polar liquid is additionally a protective colloid or a surface-active one Contains funds. 9 · Pressure-sensitive recording sheet according to claim 1 to 8, characterized in that the oily liquid or the polar liquid also has a catalyst for catalyzing the reaction between materials forming the wall film. ΊΟ. Pressure-sensitive recording sheet according to Claims 1 to 9> characterized in that the color former from a triaryl methane compound, a diphenyl methane compound, a xanthene compound, a thiazine compound, a spiro compound or mixtures thereof and the color developer in the color developer layer consists of an active tone material, an organic one acidic material, a metal salt of an aromatic acid, a mixture of an aromatic acid and a metal compound or mixtures thereof. 409809/0 9 62