FI56790C - FAERGLOESNINGSMEDEL FOER TRYCKKAENSLIGT REGISTRERINGSMATERIAL - Google Patents

Description

IT.'W. I Dr. ANNOUNCEMENT

ÄTLÄGGNI NGSSKMFT 5679Q

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Conventional recording materials consist of a stamping liquid, i.e., a dye and a solid, a reactive substance thereof, which is spread as evenly as possible on the color-bearing and dye-receiving paper, the separating barrier of which is removed by pressure. One such recording agent consists of a first paper containing, as uniformly as possible, pressure-breakable capsules in which no chromogenic substance is dissolved in the pouring liquid, and a second paper. The number and volume of capsules containing the stamping liquid are sufficient to form a continuous pattern when subjected to a pressure corresponding to the shape of the pattern.

The composition of the stamping liquid contained in the capsules of the first paper may vary. It is a prerequisite that the liquid compositions form a colored mark on reaction with the solid in the rabbit. Commonly desirable properties of the labeling fluid are easy filling of the capsules by conventional means, 56790 2 good shelf life in the capsules and not stability at relatively high temperatures. It is also important that the Trace of the Labeling Liquid-Solid Reaction develops rapidly, is resistant to fading, and resists capillary or other surface phenomena without draining or roughening the surface.

Preferably, the leaching fluid is a solution of a colorless or nearly colorless chromogenic material. Which dissolves color when in contact with and reacts with solid, sensitizing substances.

The advantage of such a material is that if it is accidentally broken on hands, clothes or other surfaces, it will not stain them.

The solid or sensitizing substances which react as rabbits in such labeling liquids are finely divided, acidic compounds which, in their neutral form, are also colorless or almost colorless. Usually organic polymers and inorganic clays are used, which are applied to the surface of the paper in a suitable paper coating adhesive, e.g. starch, casein, polymer or latex.

The function of the solvent is to act as a chromogen carrier and as a medium for the reaction between the chromogen and the acidic sensitizer. Generally, the chromogen is dissolved in a solvent to form a solution which, when encapsulated, can be applied to one side of the advertising paper. The solvent must be able to keep the chromogen dissolved in the capsule, transfer the labeling fluid to the sensitized paper when the capsule is broken, and promote or at least prevent the development of color in the reactive solid. As careless handling may accidentally break the capsule, in addition to the solution, it must be safe and must not damage the skin, clothing or the environment.

The solvent is an important factor in the quality of the recrystallization material, which is characterized by the heat and storage resistance of the paper, the rate of color development, the extent of color development and the stability of the film. However, there are in the field previously paid little attention to solvents And instead has focused on improving chorogens And sensitizers. Few compounds have been used as solvents, e.g. petroleum and their Jake, toluene, perchlorethylene, xylene, chlorinated paraffins, chlorinated diphenyls, alkylated diphenyls, hydrogenated terphenyls, doctyl phthalate and methyl salicylate. Although many of these solvents have achieved good results in fiveoctic applications, so far the important role of the solvent in the performance of the recoating material has not been fully taken into account.

Thus, it is an object of the present invention to provide improved solvents and solvent groups for use in a recoating agent to improve the rate, color intensity and durability of a label in paper. The invention and other objects will become apparent from the following description of the following 3,56790 and examples.

The improved solvents for the chromogens used in the pressure sensitive registration doors are alkyl-substituted aromatic hydrocarbons. The alkyl group is a straight hydrocarbon containing about 3 to 12 carbon atoms. The alkyl radical may be attached to an aromatic radical at any carbon atom in the chain. The present invention includes compounds of formula E 'H - CB - ir, wherein R is 2-n. A straight α. -Alkyl radical containing 11 carbon atoms, R · is hydrogen or 1-n. A straight alkyl radical of 6 carbon atoms, wherein the sum H ♦ Ä 'is about 2-11 carbon atoms And Ar is an aryl radical or a methyl-substituted aryl radical, In which the aryl is phenyl, diphenyl And naphthenic.

These solvents are more heat resistant and develop color faster on plastic or clay coated paper than their corresponding branched alkyl esters.

Pressure-sensitive recording papers, which use colorless dye solutions of chromogens and the improved solvents of the present invention, can be prepared by well-known, conventional methods. Descriptions of methods for making both color-bearing paper and substrate paper coated with plastic or clay can be found in the literature, and such methods do not form part of the present invention. However, the solvents disclosed herein can generally be used to replace conventional color releases for the production of improved advertising paper by such conventional methods.

According to the present invention, it is preferably used in combination with one or more conventional, normally colorless chromogens. One such chromogenic group consists of colorless, aromatic double-bonded organic compounds which, on contact with an acidic sensitizer, become more polar, conjugated, and colored. A highly preferred group of chromogens includes phthalide-type compounds, e.g. crystal violet lactone, i.e. 3, J-bis- (p-dimethylaminophenyl) -6-diaethylaminophthalide and malachtyl green lactone, i.

3,3-bis (p-dimethylaminophenyl) phthalide. Gold chromogenic phthalide Derivatives are J »3“ Me ~ (p ~ * ”diProPhyllainophenyl.) - i“ thalide,? 3-bs- (p-neylaminaminophenyl) phthalide, 3- (iyl)-3- (indole) 3-yl) salts, e.g. 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-4-yl) phthalide, 3,3-bis- (phenyl «indole) 3 * * yyAi) f or idites, e.g. 3- (3-bie- (1,2-dimethylindol-3-yl) phthalide, from 3- (phenyl-3-heterocyclic substituted) italides, e.g. 3- (p - 4 S6790 l dimethylphthalophenyl) -3- (1-methylpyr-3-yl) -6-dimethyl * inophthalide, indole, kerbateol-substituted phthalides, e.g. 3,3-bis- (1,2-dimethylindol-3 -yl) -5-dimethylaminophthalide and 313-bis- (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide and substituted indole phthalides, euim. 3- (1,2-Dimethyl-indol-3-yl) -3- (2-methyl-indol-3-yl) -phthalide.

Other chromogenic dye compounds useful in the practice of this invention include sprouts and indole-substituted pyroellitides, esla. 3,5-bis- (p-diethylphenophenyl) -3,5-bis- (1,2-dialylindol-3-yl) -pyroellitide, 3,7-bis- (p-diethylaminophenyl) -3, 7-Bβ- (1,2-dimethyl-indol-3-yl) -pyrroleellitide, 3,3,7 • 7 ”tstrakis- (1,2-diaethyl-indol-3H-yl) -pyrroleellitide, 3.3 , 5,5-tetrskis- (1,2-dialylindol-3-yl) -pyroaellitide, leucaurines And substituted leucaurines, e.g. p-xylyl-leucaurine and phenyl-leucuraine. These compounds also include orthohydroxybenzoaceto-phenone, 2,4-bis- [β- (p-dimethylaminophenylazo) -anilino] -6-hydroxy-sym-trazazine, R, 3, 3 “tri * ®tyl-indolino-benzoepiropyrans, and R, 3,3-triae-style «indolino - (l-naftoepiropyraanit.

T11Ä. In addition to said chromogens, an auxiliary dye can be used to prevent fading. For many phthalide compounds, pre. the crystal violet lactone is oasis of rapid color development And color fading over time. A suitable excipient is benzoyl leukoaethylene, which, on contact with paper, gradually oxidizes to a permanent blue color. With this phthalide dichromogen, and such a colorless, oxidizing auxiliary dye is obtained, which develops the color rapidly and boils without fading.

The solvent fractions of this invention are straight chain alkyl substituted aromatic compounds of the formula ka R-CH-Ar And mixtures thereof. The formula R is 2-n. A straight alkyl radical containing 11 carbon atoms, R 'is hydrogen or 1-n. Direct alkyl radical containing 6 carbon atoms. Where the sum E ♦ 8 'is about 2-3 * carbon atoms And Ar is an aryl radical or a methyl-substituted aryl radical, wherein the aryl is phenyl, diphenyl and naphthalene.

Preferred solvents in which R * is hydrogen or methyl can be prepared by alkylation of the appropriate aroma with a straight-chain alkyl halide or 1-olefin, respectively. Particularly preferred solvents are direct butyldiphenyl, direct hexyldiphenyl, direct octyldiphenyl, mixtures of direct C 8 -C 18 alkyldiphenyls, direct hexylnaphthalene, direct octylnaphthene, direct C 6 -C 6 alkylbenzene, mixtures of direct C 6 -C 6 alkylbenzene, straight Mixtures of ^ -alkylbenzenes, direct dodecylbenzenel And mixtures thereof.

The solvents of this invention may form mixtures with one or more of a solvent or diluent which are not straight chain alkyl aromatic compounds. In particular, the solvents of this invention can be mixed with e.g. O-n. 5 parts of a diluent for each solvent part, the lalentent being a mineral or vegetable oil, e.g. kerosene, paraffin oil, petrol fractions, cottonseed oil, coconut oil or rapeseed oil. These diluents have the function of altering the physical properties of the solvent, e.g., viscosity and vapor pressure, and may be undesirable for treatment and process reasons. Diluents may also reduce the overall cost of solvents and in some cases may improve the effectiveness of the solvent, especially with respect to fading or fluffing of the surface.

Solvents may also contain certain additives with the specific purpose of altering or adjusting the final properties of the liquid. Such additives include, for example, viscosity modifiers, vapor barrier modifiers, freezing point depressants, odorless, hepettumestal, colorants, and the like.

The chromogen is preferably dissolved in a suitable solvent as a recording fluid, which is capable of reacting with an acidic solid. The acidic substance may be a Levis acid-like compound, i. it receives an electron from the chaogenic, whereby the chromogen becomes colored · In addition, the acidic, solid material acts as an adnorbolnt wave of the lymph and the formed sign passes into it. Commonly used acid materials are leavened leavened clays and organic polymers, e.g. phenolic, fenoliasetyleeni-polyneerit, hartsimuovit maleic acid, partially or fully hydrolyzed styreeniäsieiinianhydridisekapolyneerit, eteenimalellnianhydridlsekapoly-polymers, carboxypolymethylene, partially or fully hydrolyzed vinyyliae-ether-malellnianhydridisekapolymeeri and mixtures thereof.

The following example describes the preparation of straight-chain alkyl-substituted aromatic solvent bases by conventional methods, in which case a certain aromatic is alkylated with 1-olefin.

Preparation of straight chain hexyldiphenyl.

To the reaction flask is added 462 g of diphenyl and heated to 80 ° C. Add 2.0 g of AlCl 2 and purge the flask with 5 x 5 g of hydrogen chloride gas. The temperature is maintained at 75 ° ~ 80 ° C while 151 g of benzene are slowly added over two hours. At the end of the addition of hexene, the reactants are eluted at the reaction temperature for 15 minutes and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction mixture is neutralized by adding 2.9 E of calcium hydroxide and 2.7 ml of water. The reaction product is filtered off and halated to give unreacted diphenyl and 197 E hexyldiphenyl as a colorless oil, b.p. 166 ° - 180 ° C / 530 Pe.

In a similar manner, euryl chain butyldiphenyl butene 6 is prepared

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and diphenyl. The product is obtained as a pale yellow distillate, b.p. 140 ° - 177 ° C / 21 '; Ta.

Straight-chain octylnaphthylene is prepared in a similar manner, but using heptane as the solvent. My octyl naphthalene is recovered from the reaction medium as a pale yellow distillate, b.p. 145 ° ** 167 ° C / 120 Pa.

The effect of different solvents on the rate and intensity of color development was determined by a laboratory method, and a test solvent was prepared.

In the following examples, a standard labeling liquid was prepared by dissolving 0.5 g of crystal violet lactone in 10 g of solvent with stirring and, if required, heating to 100 ° to 120 °. The solution was cooled to room temperature, otherwise seeded with chromogenic crystal and allowed to stand for several days, stirring occasionally, to prevent supersaturation.

In the business development experiment, the liquor was transferred by drip to a cross-sectional area 5.2 cm wide, coated with either clay or plastic. The stopwatch was started and the zone was applied with a shaving blade with a paper feather. At five-second intervals immediately after coating and at predetermined intervals thereafter, the paper reflectance was measured with a Photovolt reflectometer. The meter was calibrated to show 100 reflections by measuring the reflection of solvent-moistened paper on a white standard plate only. Final reflectance measurements of the dry labeled paper were performed after 16 hours, at which time the meter was calibrated to show 100 pounds of annealed paper on the dry, unlabeled paper. The "percentage color," or intensity of color development, was calculated to be the 100-reflection value, i.e. the percentage of euurempl in color, the darker the developed color.

The heat resistance of the baking netting was determined by slowly heating the liquid to 150 ° to 160 ° C and maintaining it at this temperature for about 15 to 60 minutes. Thereafter, the solution was allowed to cool to room temperature and any color changes in the liquid were noted. This IsImus rivet was then used as described above to determine the factors affecting the speed and intensity of the heat treatment of the heat shield compared to the slurry.

The results of these experiments are shown in Table I, which shows the superior performance of the solvents of this invention and the suitability of straight-chain alkyl-substituted aromatics compared to branched alkyl-substituent compounds. The Mines defined in the table are an example of vmln and the present invention is not limited thereto.

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Details of the solvents in Table I were solvent A. Prepared from butene-1x and butene-2.

Solvent B. Prepared from a 50t50 mixture of butene-1xn and butene-2 / p-tert-butyldiphenyl.

Solvent C. Prepared from octene-1 *

Solvent D. Prepared from diisobutylene.

Solvent E. Prepared sec. -amyylihalogenidista.

Solvent E. Prepared from hexene-1.

Solvent G. Prepared from a mixture of hexene-octene-ltn and decene-ltn.

The values in Table I illustrate the following effects associated with the present invention.

Vftrinkehltysnopeus. Comparing point A to point B and point C to point 1), it is found that "straight" alkyl compounds develop color faster than "branched" compounds.

Intensity of color development. The color developed by the straight alkyl solvents of lime is about 60 to 64 when the corresponding value of the "branched" alkyl solvents is 44 to 58 f>. Comparing point A to point B and point C to point D, it is observed that the direct compounds develop color slightly, clearly better than the corresponding branched compounds.

Color fastness of the dye solution. Comparing the heated and unheated samples at A, B, C, and P, it is found that heating in all cases adversely affects the rate and intensity of color development, but such a disadvantage is clearly less with direct alkylcine A and C than with branching with alkyl waves B and D. Thus it is clear that the direct compounds are more heat resistant than the corresponding branched compounds.

The better impact resistance of direct alkyl aromatics is also evident from the heat-induced discoloration of the labeling liquid itself. Comparing points A, B, C and D of Table I, it is observed that when heated, the straight alkyl compounds turn pale amber or pale yellow while the corresponding branched compounds turn darker amber.

In addition, the TIU shows that the color developed with direct alkyl aromatic dye solvents is more fading than the color developed with the corresponding branched alkyl compounds. For example, direct butyldiienyl (solvent A), which had a maximum color value of 60, had not faded at all after four months, while branched butyldiphenyl (solvent B) had faded from 58 to 56. From the heated samples, the direct compound faded from 58 to 54 and branched. compound from 53 to 48.

Although a preferred embodiment of the present invention is a double-sheet system. Where the acidic aluata-Alnes is in action in the orc and krcmo- β ·· η1 & And the solvent-containing lslme.usnsste is in the second sheet, of which

9 567'JO

the labeling fluid is released to the acidic material under pressure, the invention is not limited to such systems. The only important requirement in a pressure-sensitive recording system is that before the pressure is applied, the cryogenic and acidic sensitization troughs are separate, i.e., in an unreacted state, and that the new solvents of the present invention are released so that the cryogenic and acidic substances react with each other. Thus, it is possible to store the cryogenic And acidic substance in a dry and unreacted state with some common area substance And a simple solvent on a separate medium. When pressure is applied, the solvent is released into the mixture of chromogenic and acidic material and promotes local reaction and color development.

It is contemplated that many other arrangements, shapes, and relationships of the solvent and leaching vessel may be contemplated when encapsulating and placing them on a substrate sheet or web, and such arrangements are within the scope of the present invention. That's right. it is possible to coat a single paper or substrate with all the components of the system to form a self-contained unit which, when printed with a pen or other object, finds the paper on the surface. Such papers are particularly well suited for use in unearthed recording devices.

Thus, within the scope of the present invention are pressure-sensitive recording paper system rolls in which a cryogenic agent, an acidic sensitizer pressure and a solvent, which is a straight-chain alkyl aromatic compound, are used as the main constituents of the reaction. Ko. It will be apparent to one skilled in the art that in the manufacture of a pressure sensitive recording paper system, these reactants can be varied and combined in many ways. Such variations and combinations will depend on the type of chromogenesis selected, the nature of the coating and how it is applied, the amount of substrates used and the intended use of the system. Accordingly, the present invention is not limited to the details of the above description and examples.

Claims (6)

10 $ 6790 Claims p A pressure-sensitive registration system, characterized in that it comprises a) a zona or arkXi region material, b) a ketone component formed next to each other on a substrate, which consists of a chromoccnia reaction and a reactive hinge of said chromogenic blue, a type of electron from an acceptor reactant which, upon reactive contact, forms a labeling marker, and (c) a solvent-free solvent liquid of said chronoene component constituting said moiety, which is a compound of formula H * j, R - CH - Ar »of formula R having from 2 to about 11 carbon atoms the alkyl radical »R 'is hydrogen or a straight alkyl radical having 1 to about 6 carbon atoms, the sum of R ♦ R' being about 2 to 11 carbon atoms and Ar is an aryl radical or a methyl-substituted oryl radical in which the aryl is phenyl» diphenyl or naphthalene. The system according to claim 1, characterized in that the LcviUmpot-type eltrtroninkEoptor material is acidic clay or acidic orgas polymers. A system according to claim 1, characterized in that the cranogenic substance is dissolved in the solvent liquid before the solvent is released under pressure. 1 ». The inukinous system of claim 1, characterized in that the components forming the label and the solvent are on the same substrate paper. The system according to claim 1, characterized in that the chromogenic substance is a phthalide compound. System according to Claim 1, characterized in that the solvent liquid is direct butyldiphenyl, direct hexyldiphenyl, a mixture of direct C 1 -C 4 alkyldiphenyls or direct octylnaphthalene. 11 S6790 Patantkravj