FI56646C - TRYCKKAENSLIGT KOPIERINGSSYSTEM - Google Patents

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flX-oö *, .... Patent meddelat 45 ^ ^ (51) Kv.ik. * / int.ci. * B 41 M 5/12 SUOMI — FINLAND (21) p * tentt, h *, bemu * - p * tenun, 0, tnln * 2893/72 (22) Hakemispllvi - Ansttknlngsdag 19 * 10.72 (FI) (23) AlkupUvS — Glltighetsdag 19 * 10 * 72 (41) Become Public - Bllvlt offentllg 21.0¾. 7 3

Patents and registries / 44) Date of NihtivUuipano and KuL | -

Patent and Registration Office Anadkan utlagd oeh utl.jkrtftan publlcerad 30.11.79 ^ (32) (33) (31) Claim Requested — Begird prlorltet 20.10.71 USA (US) I9IO53 (71) Monsanto Company, 800 North Lindbergh Boulevard, St Louis,

Missouri, USA (US) (72) James Kern Sears, Webster Groves, Missouri, USA (7 ^) Oy Kolster Ab (5¾) Compression-sensitive copy system - Tryckkänsligt kopieringssystem

The invention relates to a pressure-sensitive reproduction system in which diaryl or triaryl compounds with alkylene bridges are used as solvents.

Conventional pressure-sensitive copying agents comprise, in combination, a dye solution or dye and a solid co-reactive agent applied mainly in continuous coatings to the dye-bearing surface and the dye-receiving surface and separated by a physical boundary removed by pressure applied to the surfaces. One such reproduction material comprises one sheet material having a continuous coating on its surface by squeezing breakable capsules containing as a colorant a solution of a color-generating agent in a solvent, and a second sheet material comprising a uniform coating of the first sheet against the capsules of a solid reaction product. There are enough capsules containing toner liquid in number and volume to provide a continuous image reproduction when the toner liquid is run by squeezing out of the capsules with the compression provided by the image model.

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The colorant contained in the capsules of the first sheet may be any of a wide variety of liquid combinations, provided that they give a colored imprint upon contact with a solid co-reactive agent. The generally desirable properties of a color liquid are that it is easily encapsulated by conventional methods, that it is highly resistant to storage in encapsulated form, and that it is stable at reasonably elevated temperatures.

It is also important that the trace resulting from the reaction between the dye liquid and the solid co-reactant develops rapidly, is non-fading, and is resistant to discoloration or reference spreading as a result of capillary action or other surface phenomena.

The dye liquid is preferably a solution of a colorless or substantially colorless dye-generating agent in a solvent and develops the dye upon contact and reaction with a solid co-reactive agent or sensitizer. Such materials have the advantage that they do not stain the hands, clothing or other surfaces with accidental damage.

Solid co-reactants or sensitizers for such color liquids are finely divided acidic compounds which are also colorless or almost colorless in their natural form. Commonly used materials include organic polymers and inorganic clays which are applied to the surface of the paper in a suitable paper coating binder such as starch, casein, polymer or latex.

The solvent acts as a carrier for the colorant and as a medium for the reaction between the colorant and the acid sensitizer. It is common practice for a color-generating agent to be dissolved in a solvent to form a solution that is encapsulated and applied as a coating to another surface of the copy paper. The solvent must be able to keep the color-generating agent in solution inside the capsule, transport the colorant to the sensitized paper in the event of a capsule rupture, and at least promote or not prevent color development with the solid co-reactant. In addition, since inconspicuous breakage of the capsule is possible as a result of careless handling, the solvent must be harmless to the substance, the skin, clothing or the environment.

Solvent is an important factor in determining the performance of a copy transfer product in terms of paper heat resistance and storage time, color development rate, degree of color development, and trace resistance. However, the industry has so far paid very little attention to the issue of solvents and has instead focused on improving colorants and sensitizers using solvents taken from a limited number of compounds such as fuel oils and their distillates, toluene, perchlorethylene, xylene, chlorinated paraffins, chloro-56646 alkylated diphenyls, hydrogenated terphenyls, dioctyl phthalate and methyl salicylate. Although many of these solvents have given good results in applications to date, the full potential of the solvent as a positive contribution to the performance of the replica transfer product has not been fully realized.

The reproduction system according to the invention uses solvents which are better for use in reproduction transfer products than currently known, known solvents and which advantageously affect the properties of the paper.

The invention thus relates to a pressure-sensitive reproduction system comprising a) a carrier paper sheet, b) imprint-forming components arranged in close proximity to each other and carried by the paper sheets, the components comprising a color-generating agent and an acidic sensitizer capable of reacting with the color-generating agent; reacting with each other in a reactive manner, and c) a liquid solvent released by compression for said color-generating agent.

The system of the invention is characterized in that the solvent used therein comprises diphenylalkanes, C 1-8 alkyl-substituted diphenylalkanes, or mono- or dibenzyl-C 1-8 aryl compounds in which the aryl group is biphenyl, terphenyl, phenyl, tolyl, xylyl, ethyl or naphthyl.

These solvents cause color to develop rapidly on resin or kaolin coated paper.

Compression-sensitive copy paper systems using colorless dye solutions containing a color-generating agent as well as a solvent can be prepared according to well-known conventional methods. Descriptions of manufacturing methods for both color-bearing and receiving paper coated with either resin or kaolin can be found in the literature, and such methods are not within the scope of this invention. Admittedly, the solvents disclosed herein can generally replace conventional solvents to provide improved copy paper systems in accordance with such conventional methods.

The solvents are preferably used in combination with one or more conventional coloring agents in a normally colorless form.

One such group of color-generating agents comprises colorless aromatic double-bonded organic compounds that change to a 56646 higher polarized conjugated and colored form when reacted with an acidic sensitizer. Particularly preferred color-generating agents are phthalide-type compounds such as crystal violet lactone, which is 3β-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and Mala-prawn green lactone, which is 3,3-bis (p-dimethylaminophenyl) phthalide.

Other phthalide-derived coloring agents include 3,3-bis (pm-dipropylaminophenyl) phthalide, 3,3-bis (p-methylaminophenyl) phthalide, 3- (phenyl) -3- (indol-3-yl) phthalides, such as 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3,3-bis (phenylindol-3-yl) phthalides such as 3,3-bis (1,2- dimethylindol-3-yl) phthalide, 3- (phenyl) -3- (heterocyclically substituted) phthalides such as 3- (p-dimethylamino-phenyl) -3- (1-methylpyrr-2-yl) -6-dimethylaminophthalide , indole and carbazole-substituted phthalides such as 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide and 3,3 "bis (9-ethylcarbazol-3-yl) - 5-methylmethylamino phthalide and substituted indole phthalides such as 3- (1,2-dimethylindol-3-yl) -3- (2-methylindol-3-yl) phthalide.

Other color-generating compounds useful in this invention include indole-substituted pyromellitides such as 3,5-bis- (p-diethylamino-phenyl) -3,5-bis- (1,2-dimethyl-indol-3-yl) -pyromellitide, 3 , 7-bis- (p-diethylaminophenyl) -3,7-bis- (1,2-dimethylindol-3-yl) pyromellitide, 3,3,7,7-tetrakis- (1,2-dimethylindole) -3-yl) pyromellitidi; as well as leuko-auramines and substituted leukoauramines such as p-xylyl-leukoauramine and phenyl-leukoauramine. These also include orthohydroxybenzoacetophenone, 2, H-bis / β- (p-dimethylaminophenylazo) aniline-6-6-hydroxymymtriazine, N, 3,3-trimethylindoline benzospiropyrans and N, 3,3-trimethyl- indoline-β-naphthospiropyrans.

The auxiliary dye can be used with the color-generating agents described above to provide resistance to fading when fading is a problem. Many phthalide compounds, such as crystalline violet lactone, are characterized by rapid color development with a ~ normal tendency to fade over time. One suitable auxiliary dye is benzoyl leukomethylene blue, which oxidizes on paper to slowly form a permanent blue color. The combination of a color-generating phthalide compound and such a colorless oxidizable auxiliary dye forms a product with rapid color development and non-fading.

Particularly preferred solvents for use in the replication system of the invention are benzyl and dibenzyl aryl compounds such as benzyl, benzylbenzene, benzyltoluene, benzylxylene, N-C 1-4 alkylbenzylaryl compounds such as o (-methylbenzyltoluene, c O (-C 1-6 alkylbenzyl) aryl compounds such as bis (o (-methylbenzyl) toluene, bis (o (-methylbenzyl) xylene), 5 56646 bisoxymethylbenzyl) benzene and bis (oC-methylbenzyl) ethylbenzene, bis (C 1 -C 4 alkyl-C 1 -C 4 alkylbenzyl) aryl compounds such as bis (oC-methyl-3-ethylbenzyl) xylene and mixtures thereof. Mixtures of benzyl and dibenzyl aryl compounds with other solvent combinations within the scope of this invention, such as 2, L-diphenyl-2-methylpentene, are also preferable are preferred, readily available substances derived from styrene alkylation reactions. combinations that give particularly good performance to conventional pressure-sensitive copying systems. Particularly preferred solvent combinations are those having from 10 to 50% by weight of 2, L-diphenyl-2-methylpentene and up to 90% by weight of a benzyl or bibenzyl derivative such as mono- or dibenzyltoluene and mixtures thereof or mono- or dibenzylxylene and mixtures thereof, or mono- or dibenzyl-ethylbenzene and mixtures thereof, or mono- or dibenzylcumene and mixtures thereof.

The solvents of this invention are also useful in mixtures with one or more solvents or diluents which are compounds other than the solvents of this invention. In particular, the solvents of the present invention may be mixed with, for example, 0 to 3 parts of diluent for each part of solvent, the diluent being a mineral or vegetable oil such as fuel oil, paraffin oil, petrol, castor oil, hoof oil, whale oil, lard oil, olive oil, olive oil, olive oil, rapeseed oil, or an organic solvent such as aromatic mountain oil or alkylbenzene. The purpose of these diluents is to alter the physical properties of the solvent, such as viscosity and vapor pressure, which may be advantageous for treatment or process. In some cases, when the solvent compound solidifies, crystallizes, or becomes very tough at working temperatures, the diluent can act as a second solvent for such compounds. Diluents can also reduce the overall cost of solvents in the system and improve solvent performance, especially in terms of text fading or deterioration.

Solvents may also contain certain additives specifically intended to alter or control the final properties of the liquid, such as viscosity regulators, vapor pressure regulators, freezing point depressants, odor masking agents, antioxidants, colored dyes, etc.

The color-generating agent is preferably dissolved in a suitable solvent to form a color solution that is reactive with an acidic solid co-reactive agent. The acidic substance can be any compound that meets the definition of a Lewis acid, i.e., an electron-accepting substance relative to the color-generating substance, which promotes the polarization of the color-generating substance to a colored 56646 form. The solid acidic substance still acts as a dye liquid absorbent to receive the transferred image. Commonly used acidic substances include acid clays and acidic organic polymeric substances such as phenolic polymers, phenolic acetylene polymers, maleic acid resins, partially or completely hydrolyzed styrene-maleic anhydride mixed polymers and ethylene-maleic anhydride, ethylene-maleic anhydride or partially hydrolyzed vinyl methyl ether, maleic anhydride copolymer and mixtures thereof.

The effect of different solvents on the rate and degree of color development was determined by a laboratory method comprising preparing a color liquid with a solution of a color-generating agent in the test solvent, applying the liquid to a receiving paper coated with a reactive clay or resin reactor and color developing. _

In the following examples, a standard dye liquid was prepared by dissolving 0.5 g of crystal violet lactone (CVL) in 10 g of solvent with stirring and heating to 100-120 ° C if necessary to promote dissolution.

The solution was cooled to room temperature, a few crystals of a color-generating agent were added to the crystal embryos, and the solution was allowed to stand for several days with occasional shaking to ensure that the solution was not supersaturated.

The color development test involved pipetting a dye liquid droplet across a 3.18 cm wide, either clay-coated or resin-coated receiving paper strip. The stopwatch was started and the razor was cut along the paper strip with the help of a batch of my razor. 5 seconds after coating and at predetermined intervals thereafter, the paper reflectance was measured with a Photovolt-Reflect meter. This was calibrated to show 100% reflection on a specific test paper moistened with solvent alone and backed by a standard white porcelain plate. Final reflectance readings on dry, labeled paper were measured after 2k hours, at which time the reflectometer was calibrated to show a 100% reflectance ratio on dry, unlabeled paper. The degree of color development was expressed by the term "percent color", which was calculated as the difference of 100 minus the reflection ratio: i.e., the higher the color value, the deeper the color developed.

The experimental results for evaluating the representative solvent combinations are shown in Table I and show the improved results obtained with the solvents used in the system according to the invention.

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The values in Table I indicate that the compounds used in this invention are particularly effective solvents for color-generating agents and are useful in the preparation of pressure-sensitive imitators. In particular, these compounds promote rapid color development, good color depth or darkness, and good resistance to fading, as demonstrated by the remaining color depth after 2k hours of surface exposure.

In many cases, these compounds can be advantageously combined with a diluent or solvent which is not an aromatic substance containing alkylene bridges. Such combinations may be advantageous in order to optimize the physical properties of the solvent, such as viscosity, melting point or volatility, and thus to facilitate the use of the solvent in the preparation of a pressure-sensitive replicator. In such combination solvents, the diaryl or triaryl compound containing alkylene bridges is the primary solvent and the substance mixed with it is the secondary solvent. Typical and descriptive secondary solvents were evaluated as solvent combinations alone and the results obtained are shown under the heading "solvent combinations 15" in Table I. These results show that the secondary solvents have no use as solvents alone and that the excellent results obtained as primary-secondary solvent combinations the presence of a solvent, although the performance of the primary solvent may in some cases be improved by the action of the secondary solvent.

Chlorinated biphenyl with about b2% chlorine is a well-known commercial dye solvent that can be used alone or in combination with a diluent such as fuel oil. The performance of these substances is described by the values given under the heading "solvent combination 1U" in Table I.

A comparison of these values with the results obtained for solvents using the compounds of the invention shows that aryl compounds containing alkylene bridges are in most cases as good or better in general performance than chlorinated biphenyl.

Although a preferred embodiment of the present invention has a two-sheet system in which the acidic receiving agent is on one sheet and a dye liquid having a color-generating agent and a solvent on the second sheet, the dye liquid is released on the surface of the acidic substance by pressing on the sheets, the invention is not limited to such systems . The only essential requirement for a pressure-sensitive reproduction method is that the color-generating agent and the acidic sensitizer remain in a separate or unreacted state until the pressure is applied to the system and that the new solvents used in the system are released as a result of the color-generating agent and the acidic reaction. Thus, it is possible that the color-generating agent 'S6646 and the acidic substance are present in dry and unreacted form on a common carrier and that the solvent is on a separate sheet whose surface pressure releases the solvent into the mixture of color-generating agent and acidic substance and causes local reaction and color development.

It will be appreciated that many other arrangements, forms and connections may be provided for the solvent and tracers with respect to their encapsulation and location on the carrier sheet or sheet, but such arrangements are within the scope of this invention. For example, it is possible to coat a simple paper or carrier with all the components of this system and form a simple independent unit which can be marked by moving the drawing or some other means of compression - on the surface of the paper. Such papers are particularly useful in inkless marking machines.

The invention thus encompasses pressure-sensitive copy paper systems using a color-generating agent, an acidic sensitizer, and a solvent formed by a diaryl or triaryl compound containing alkylene bridges as essential tracers. Many variations and combinations of these reactants in making a pressure sensitive copy paper system will be readily apparent to one skilled in the art and will depend on such factors as the type of colorant selected, the nature and application of the coating used, the number of substrates used and the intended use of the system. Thus, the invention need not be limited to the specific details set forth in the foregoing explanations and examples.

Claims (6)

15 S & 646 A pressure-sensitive reproduction system comprising a) a carrier paper sheet, b) imprint-forming components arranged in close proximity to each other and carried by the paper sheets, the components comprising a color-generating agent and an acidic sensitizer capable of reacting with the color-generating agent to form a mark or label. and - c) a liquid solvent released by compression for said color-generating agent, characterized in that the solvent comprises diphenylalkanes, C 1-6 alkyl-substituted diphenylalkanes, or mono- or dibenzyl-C aryl compounds in which the aryl group is biphenyl, terphenyl, phenyl, tolyl, xylyl, ethylphenyl, cumyl or naphthyl. System according to Claim 1, characterized in that the acidic sensitizer is clay or acidic organic polymers. A system according to claim 1, characterized in that the color-generating agent is in solution in a liquid solvent before release by compression. U. A system according to claim 1, characterized in that the color-generating agent is a phthalide compound. System according to one of the preceding claims, characterized in that the imprint-forming components and the liquid solvent are on a single, support sheet. A system according to any one of claims 1 to h, characterized in that it comprises a first carrier paper sheet coated with a solvent released under pressure and a second carrier paper sheet coated with a sensitizing agent.