MXPA97005033A - Printing of images, resistant to wear, on surfaces of the - Google Patents

Abstract

A novel method and formulations for printing images on a latex rubber surface are provided. An ink containing natural or synthetic rubber, a pigment dispersion and an aromatically unsaturated solvent medium for the rubber is used. Image stability is improved by providing the ink rubber molecules with an agent such as an aryl diisocyanate that will form a tenacious, flexible and chemically resistant matrix between the rubber molecules of the ink, the base coat, if present, and the latex surface. A base coat can be used on the surface of the latex to fix the printing ink thereto. The base coat may comprise a natural rubber in an aromatically unsaturated solvent, and may also contain the aryl diisocyanate. The method can be improved by certain steps carried out after printing, such as heating or curing of the printed product.

Description

PRINTING IMAGES. RESISTANT TO WEAR, ON LATEX SURFACES FIELD OF THE INVENTION The printing of rubber articles made of rubber latex. TREATMENT OF THE PREVIOUS TECHNIQUE The printing of rubber articles that are manufactured from rubber latex, in particular natural rubber latex, is well known in the art. Balloons have been printed using natural rubber solutions in mineral spirits. These solutions provide an impression that can be easily removed by common household detergents and chemicals. Latex rubber ink or dye systems, in particular natural latex articles, and more specifically rubber latex gloves require a certain degree of chemical resistance that is not currently available on the market. In general, rubber gloves are exposed to a variety of household chemicals, including detergents, bleach, ammonia, oils and fats, polishing agents, disinfectants, etc. Any decorative system for rubber gloves must have a resistance to these common materials. Therefore, it would be useful to be able to offer a decorative technique comprising a printing system for the surface of such rubber articles, in which the printed image would have resistance to the common chemical substances in the home.

SUMMARY OF THE INVENTION A method is provided for printing images on a latex rubber surface comprising applying a dye containing natural or synthetic rubber, a pigment or pigment dispersion, as well as a solvent agent, in particular an aromatically unsaturated solvent for the rubber. In addition, the ink may comprise an aryl diisocyanate. When the rubber-containing ink is used above a natural rubber basecoat in such a solvent, the aryl diisocyanate may be present, either in the basecoat or in the ink. A natural rubber base coating in such a solvent is required when the rubber inside the ink is a synthetic rubber. The aryl diisocyanate, or also called aryl diisocyanate, may be present in the basic coating or in the ink. However, a portion of the solvent may be replaced by a terpene, a terpenoid or a high-boiling ketone that will effectively have a boiling point above 120 ° C, such as isophorone or the like. The printing efficiency can be improved by certain steps, which run before or after printing. One such additional step is to heat the printing surface. Another additional, highly convenient step is to place a base coat over the printing surface that receives the image. In one embodiment of the process, the base coat is allowed to dry to a sticky state before printing the image. As noted above, the base coating comprises natural rubber in an aromatically unsaturated solvent. A critical feature of the invention is the presence of an agent capable, at the time of curing, of forming a structure resistant to chemicals and abrasion, and which is nevertheless flexible, which integrates the rubber of the base coating where it is present, the rubbing the ink together with the pigment contained therein, as well as the rubber on the surface of the latex, at least in the base coat, or in the ink. The mechanism of this integration is not fully understood, but its creation of a surprising level of resistance thus achieved is unquestionably novel. Effectively such an agent is an aryl diisocyanate. The integrating agent may be present in the ink phase and / or in the base coat. The ink, like the base coat, can be applied with the use of a number of different common printing techniques, such as: printing by engraving, flexo-printing, silk-screen printing and printing with cushions. However, it has been found that cushion printing is superior for the inventive purposes, such as for printing specific rubber articles, such as rubber gloves.

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method is provided, as well as a formulation for printing images on latex rubber surfaces. It is desirable that the amount by weight of the aryl diisocyanate be 0.5 to 3.0 times greater than that of the total rubber in solution within the ink or within the base coat, or both. The rubber can be natural or synthetic rubber. The diisocyanate of the group consisting of toluene, methylene diphenyl and methylenediphenyl diisocyanates of polymeric type, as well as their mixtures, is selected efficiently. The rubber inside the ink can be natural rubber, or synthetic rubber, such as neoprene rubber or its mixtures, to achieve a good impression, the ink must have, at the time of printing, a viscosity at 20 ° C of between 800 at 3,000 cps. The use of synthetic rubber in the ink is preferred over the use of natural rubber, since its chemical resistance is greater. However, natural rubber, when mixed with the aryl diisocyanate will provide sufficient strength. The aryl diisocyanate, when cured by itself, will form a hard and cracking product. In the presence of rubber, it is integrated with this material to generate a structure or matrix resistant to chemical substances, flexible and tenacious, which provides the unique printing product associated with the present invention. The inks containing the diisocyanate should be used without delay after mixing, effectively within a time of 10 hours of preparation. The printing solvents according to the prior art generally use mineral spirits, such as aliphatic or alicyclic hydrocarbons. In contrast, the solvents used in the inks and in the preliminary coating of the invention are aromatically unsaturated solvents. Preference is given to the aliphatic esters of the aromatic acids, or to the higher liquid aromatic hydrocarbons. Particularly suitable is methyl naphthalene. The latter product, under certain conditions, can be partially replaced by terpenes or terpenoids, such as: dilimonen, or high-boiling ketones, such as isophorone. However, methyl naphthalene is preferred. The product called Glidsol 90, manufactured by SCM Glisol Organics, 210 Summit Ave., Montvale NJ 07645, is a terpene formulation that is especially preferred. Terpenes and terpenoids may be used in the basecoat, however, this is not preferred. It should be noted that, in fact, commercial methylnaphthalene is a complex mixture containing dimethylnaphthalene, ethylmethylnaphthalene and other coal tar, fractional and heavy type components. The actual amounts of the rubber, of the solvents and of the pigments used in the printing formulations of this invention, can vary greatly according to the desired consistency and the speed of drying. The desired viscosity range of ink at 20 ° C is in the range of 800 to 3,000 cps. Approximately an amount between 5% and 40% by weight of the pigment is contained in the ink composition. The image to be printed on the surface of the latex rubber according to the ink formulation of this invention does not specifically depend on any conventional printing method. The stability of the image is improved through the additional step of heating the printed surface. Effectively heating is achieved in a temperature range of approximately 95 to 130 ° C, for 10 to 20 minutes, or from 190 to 230 ° C for 3 to 8 seconds. Thermal cure can increase the chemical and abrasive resistance of the printed ink image to the commonly used household cleaner, Pine Sol®. A simple test of the resistance of the ink image is to rub the printed image with a cushion impregnated with Pine Sun with its recommended strength of household detergent. Regarding the neoprene resistance, and the inks containing natural rubber according to the present invention, are capable of withstanding 35 to 100 rubs. The above can be achieved with the ink formulations according to the invention, thanks to the presence of the aryl diisocyanate which, as mentioned above, is embedded intimately within the rubber molecules. The strength of the printed image can also be improved by certain steps executed before and after printing. A washing of the surface of the article can be done with water and a surfactant, followed by drying, or simply washing the surface with a hydrocarbon solvent will improve the printing process. However, the washing procedure is not recommended for gloves that contain flocculation on their internal faces. It is helpful to warm up the printed image for approximately 3 to 6 seconds at a temperature between 190 and 220 ° C. One of the rare and totally unexpected aspects of the present invention is the ability of the product with the printed image to become increasingly resistant to chemical attack and abrasion over time. It has been found that while the product with the printed image is stable to the contact immediately after the initial heating step, the chemical abrasion resistance continues to accumulate to a maximum after some prolonged time at room temperature. The tests have revealed that the product with its printed image reaches maximum efficiency after 20 and up to 60 days after printing. On the other hand, this slow curing does not pose any problem of commercialization, since the average time between the manufacture and arrival at the point of sale of a typical latex rubber glove, printed, is usually about 75 days. . The stability of the printed image is also improved by placing a base coat over the surface that receives the printed image. The base coat is applied and allowed to dry until a sticky condition is obtained. The image is then printed on the surface of the sticky base coat. The base coating may comprise natural rubber in an aromatically unsaturated solvent. Effectively this base coat also contains an aryl diisocyanate at a weight of approximately 0.5-3.0 times the amount of rubber in the solution. One method of printing an image on a latex rubber surface includes preparing a clear basecoat solution comprising natural rubber of about one to ten parts by weight in an aromatic hydrocarbon solvent of about 45 to 50 parts by weight. This clear basecoat solution is then mixed with a pre-mixed portion consisting of an aromatic hydrocarbon solvent of about 2 to 15 parts by weight containing an aryl diisocyanate of about 1 to 30 parts by weight. Then the above combination is mixed with a pigment that has an approximate weight between 0.3 to 5.0 times that of the rubber in solution. The components of this formulation, namely, the transparent coating, the premix and the pigment, are mixed at room temperature, and then printed on the latex rubber surface, preferably within 10 hours of the mixing.

A generally preferred method of printing an image on a latex rubber surface comprises the step of applying a base coat on the rubber surface containing natural rubber in an approximate weight range of between 5 to 15 parts in a solvent that is present in an approximate weight range of 80 to 120 parts, with an aryl diisocyanate that is present in an amount of 0 to 45 parts by weight. The image is then printed on the base coat using an ink, which formulation comprises natural or synthetic rubber in an amount of about 1 to 10 parts by weight; a rubber solvent in an amount of between 30 to 60 parts, and a pigment of about 0.3 to 5.0 parts by weight of the rubber, as well as an aryl diisocyanate in the weight range of about 0 to 30 parts. The rubber solvent in the above formulation may be an aromatic hydrocarbon, a terpene, a terpenoid, a ketone boiling above 120 ° C, or a mixture of the foregoing. The rubber solvent in the base coat may be an aromatic hydrocarbon solvent comprising about 60 to 90 parts by weight, a terpene or terpenoid solvent in a weight of about 0 to 60 parts. The rubber solvent in the ink can be an aromatic hydrocarbon solvent consisting of about 30 to 50 parts by weight, with a terpene or terpenoid solvent occupying about 0 to 30 parts by weight.

Various combinations of basecoat and ink compositions are within the scope of the present invention. In one such embodiment, the ink comprises synthetic rubber in about 1 to 10 parts by weight; an aromatic hydrocarbon solvent in about 30 to 80 parts by weight, and a pigment occupying 0.3 to 5 parts by weight. The base coating may comprise natural rubber in an approximate weight of between 5 to 15 parts; an aromatic hydrocarbon solvent in about 80 to 120 parts by weight; and an aryl diisocyanate in a weight of approximately 1 to 5 parts. In another embodiment, the ink comprises synthetic rubber in a weight of approximately 1 to 10 parts; an aromatic hydrocarbon solvent of about 30 to 60 parts by weight; a pigment in an approximate weight of 0.3 to 5.0 parts; and an aryl diisocyanate of about 1 to 30 parts by weight. The base coat may comprise natural rubber in an amount of about 5 to 15 parts by weight within an aromatic hydrocarbon solvent comprising from about 80 to about 120 parts by weight. In another embodiment, the ink comprises synthetic rubber in about 1 to 10 parts by weight; an aromatic hydrocarbon solvent of about 15 to 60 parts by weight; a terpene or terpenoid solvent in a weight range of approximately 5 to 40 parts; and a pigment of about 0.3 to 5.0 parts by weight. The base coating comprises natural rubber in an amount of about 5 to 15 parts by weight, an aromatic hydrocarbon solvent in an approximate weight range of 80 to 120 parts; and an aryl diisocyanate of about 1 to 45 parts by weight. In yet another embodiment, the ink comprises synthetic rubber in a weight range of approximately 1 to 10 parts; an aromatic hydrocarbon solvent of about 15 to 60 parts by weight; a terpene or terpenoid solvent of about 5 to 40 parts by weight; a pigment in a weight range of 0.3 to 5.0 parts, and an aryl diisocyanate in a weight range of approximately 1 to 30 parts. The base coat comprises natural rubber of about 5 to 15 parts by weight in an aromatic hydrocarbon solvent of about 80 to 90 parts by weight. It should be reiterated that the aromatic hydrocarbon of choice in the above formulations is commercial grade methylnaphthalene. EXAMPLES Printing Methodology A series of printing stations each comprise a cushion printer. The printer stations are aligned to provide sequential processing. A first printing station is loaded with the base coating and the pigmented printing ink is loaded in the second printing station. A number of colors can be printed by placing cushion printing stations online, all subsequent to the first basecoat printer. It was found that improved results are obtained by not allowing the base coat to dry completely before applying the pigmented ink. There should be a slight degree of stickiness of the base coat when the rubber glove passes below the subsequent printing stations. Heat is applied to the printed surface by heating by contact with a heater with Teflon-coated aluminum plate at a temperature of about 215 ° C for 5 seconds. The heating process helps in the curing of the printing ink, which influences its ability to resist chemical attack and abrasion. A further improvement is obtained by placing the rubber gloves in an oven heated at 120 ° C for about 15 minutes. Stability Test A test was developed to compare the capacity of ink formulations, in order to resist exposure to common household chemicals. It was found that Pine Sol®, manufactured by IMFC of Clorox Co., Oa land, CA, directly attacked the rubber ink systems. A 50% solution of Pine Sol® in water was applied on a commercial paper napkin. The saturated paper napkin was rubbed against the printing surface by applying light hand pressure. The number of rub cycles that would erase the image was recorded. Each cycle of rubbing consisted of a reciprocating rub movement, comprising a distance of 4 centimeters in length. It was found that as an example, a printed image comprising ink in a balloon, disappeared in as little time as a cycle. In the subsequent Results Tables, certain abbreviations are used: SMRL: Standard Malaysian Rubber Light (Latex) (Malaysian Standard Light Rubber (Latex)); Alean Rubber «Se Chemical Inc., New York, NY DABCO: T-12 (Dibutyltin Dilaurate): Air Products & Chemicals Inc., Allentown PA PAPI 2021: Polymethylene polyphenylisocyanate, manufactured by Dow Chemical Company, Plastics Div., Midland MI. Pigments of Di-XXXX: 25% Pigment, 75% Dinonylphthalate; manufactured by Cardinal Color Inc., Paterson NJ 07524. NEOPRENE G: Dupont Co., Elastomer Div., Wilmington DE. STALITE S: R.T. Vanderbilt, Norwalk, CT. Solutions were prepared using a Versa ix mixer, model MW5, with a gallon capacity, or 3.75 liters, which was obtained from Ross & Co., Long Island, N.Y. Mixing was carried out using a slow agitation speed, whose system was applied for five days. As used in these Results Tables, the term "parts" refers to parts by weight.

Example I A printing ink is prepared as follows: PARTS * Neoprene GW 17.0 Methylnaphthalene # 5 41.33 Limonene 145 41.33 Pigment dispersion: Blue DI-6112 20.0 Agerite-Stalite 0.34 Total 120 An image was printed on a latex surface using the above formulation. The rubbing test mentioned above was carried out, using cushions impregnated with Pine Sol®. The test was carried out 12 days after printing. The printed image was cured in the air. Only one rub was required to remove the image. Example II In the ink formulation presented in Example 1, 17 parts of PAPI 2020 were added to the ink. After printing an image on the latex surface, a test with Pine Sol® was carried out after 12 days. The printed image was cured with air at room temperature. 6 rubs were needed to erase the image. EXAMPLE III A base coat is prepared as follows: PARTS * Std. Malaysian Rubber Light (small) (Malaysian Standard Lightweight Rubber (small) (Latex)); (Latex) 8.85 Dabco T12 0.6 Methylnaphthalene # 5 91.15 Total 100.57 The above-mentioned base coat was applied to a natural rubber surface just before applying the ink shown in Example II. A rub test was carried out with Pine Sol® after 12 days. About 12 to 22 rubs were taken to remove the printed image. This test was performed additionally using a 60-day cure. The image required 40 rubs for deletion.

EXAMPLE IV Natural Rubber Ink The composition of Example III was as follows: PAPI 2020 8 parts Blue: Blue Di-6112 20 parts The rub test with Pine Sol® was carried out after the printed image had been cured for 9 days. The image was removed after 16 rubs. Example V An ink of Example IV was applied over a base coat of Example II. The rub test with Pine Sol was carried out after a 9-day cure of the printed image. 36 rubs were required to remove the printed image.

Example VI Results of other Tests: RUBBER INK FORMULATIONS IN FOUR COLORS, STANDARD TYPE.

All the colors printed together were applied in a pattern according to the design.

Healing time: 60 days. Test with Pine Sol: It needed more than 40 rubs for the deletion.

Example VII NATURAL RUBBER INKS - NO BASE Example VIII NATURAL RUBBER TINS WITH BASE LINING EXAMPLE IX FORMULATIONS WITH STANDARD NEOPRENE INK The above inks were printed together in a pattern according to the design above a base coat as described in the second part of the previous Example VIII. The Healing Time was 60 days. A rub test with Pine Sol * required 40 rubs to erase the printed image.

Example X AIR CURING, HOT STAMPING, 200 ° C, 3 SECONDS BASE COATING: SMRL 8.85 Methylnaphthalene # 5 91.15 DABCO T-12 0.6 TOTAL 100.6 Example XI INK MIXTURES WITH NATURAL AND SYNTHETIC RUBBER Hypalon Dupont ™ - Chloridesulfonated Polyurethane Rubber (CSM rubber). G = 75% blend of B-133, 25% of A-133 = Neoprene / Natural Rubber. H = 75% mixture of C-133, 25% of A-133 = Hypalon / Natural Rubber. B and C printed above the Base, G and H there was no base.

In view of the fact that other modifications and changes varied to conform to certain operational requirements in particular and that the environment will be apparent to those skilled in the art, the invention is not considered limited to the examples selected for the purposes of the disclosure, and therefore, it covers all changes and modifications that do not constitute overreaching the true spirit and scope of the present invention. Having thus described the invention, what is desired to be protected by a patent is presented in the following appended claims.

Claims (51)

1. A method for printing an image on a latex rubber surface comprising preparing an ink comprising: a) a transparent coating comprising: natural rubber and an aromatic hydrocarbon solvent, b) a premixed portion comprising: a hydrocarbon solvent aromatic and an agent capable of forming, after curing, a structure resistant to chemicals and abrasion, of flexible and tenacious structure, which integrates the rubber of the transparent coating with the rubber of the latex surface, and c) a pigment, and mixing the transparent coating with the pigment and the premix at room temperature, and then printing the image on the surface after combining the components of the mixture.

2. The method according to claim 1, wherein the agent is aryl diisocyanate.

3. The method according to claims 1 and 2, wherein the approximate weight of the aryl diisocyanate is 0.5 to 3 times that of the rubber in the ink.

The method according to claims 1 to 3, wherein: a) the transparent coating comprises natural rubber: from 1 to 10 parts by weight, and an aromatic hydrocarbon solvent in an amount of 45 to 55 parts by weight, b) the premixed portion comprises an aromatic hydrocarbon solvent of 2 to 15 parts by weight, and the agent is aryl diisocyanate in a proportion of 30 parts by weight, and c) the pigment comprises 0.3 to 5.0 parts by weight, and then print the image on the surface within 10 hours of combining the components of the mixture.

The method according to claims 1 to 4, wherein the diisocyanate is selected from the group consisting of toluene, methylenediphenyl, and polymeric methylene-phenyl diisocyanates and mixtures thereof.

The method according to claims 1 to 5, wherein the viscosity of the ink at the time of printing is in the range of 800 to 3,000 cps at 20 ° C.

7. A method of printing an image on a latex rubber surface comprising applying to the surface: a) a base coat coating comprising natural rubber and a solvent for the rubber, and b) printing the image onto the base coat with an ink comprising: natural or synthetic rubber; a solvent for the rubber and the pigment; with the understanding that an agent capable of curing is present, of forming a tenacious and flexible structure, resistant to chemical substances and to the abrasion that integrates the rubber of the base coating, the rubber of the ink and the rubber of the surface of latex in at least one copy of the base coat and the ink.

The method according to claim 7, wherein the agent is aryl diisocyanate.

The method according to claims 7 and 8, in which the approximate weight of the aryl diisocyanate is between 0.5 and 3 times that amount equivalent to the sum of the rubber in the base coating and in the ink.

The method according to claims 7 to 9, wherein: a) the coating of the base layer comprises natural rubber in a proportion of 5 to 15 parts by weight, a solvent for the rubber of 80 to 120 parts by weight, and aryl diisocyanate as the agent in an amount of 0 to 45 parts by weight; and b) the ink comprises natural or synthetic rubber: from 1 to 10 parts by weight; a solvent for the rubber; from 30 to 80 parts by weight; the pigment in 0.3 to 5.0 parts by weight; and aryl diisocyanate as the agent in 0 to 30 parts by weight, it being understood that the aryl diisocyanate in the above range is present in at least the base coat and / or the ink.

11. The method according to claims 7 to 10, wherein the solvent for the rubber is at least one member of the group consisting of an aromatic hydrocarbon solvent, a terpene, a terpenoid or a ketone that weeds above 120 ° C.

The method according to claims 7 to 11, wherein the diisocyanate selected from the group consisting of toluene, methylenediphenyl and polymeric methylene diphenyl diisocyanates and mixtures thereof.

The method according to claims 7 to 12, wherein the solvent for the rubber in the base coat is an aromatic hydrocarbon solvent in 60 to 90 parts by weight, and a terpene or terpenoid solvent in 0 to 60 parts by weight; and the rubber solvent within the ink is an aromatic hydrocarbon solvent in 30 to 50 parts by weight, and a terpene or terpenoid solvent in 0 to 30 parts by weight.

The method according to claims 7 to 13, wherein the viscosity of the ink at the time of printing is in the range of 800 to 3,000 cps at approximately 20 ° C.

15. The method according to claims 7 to 14, wherein the surface is a natural latex rubber surface.

16. The method according to claims 7 to 15, which comprises allowing the base coat to become tacky before being printed with the ink.

The method according to claims 7 to 15, which comprises allowing the base coat to dry before being printed with the ink.

18. The method according to claims 7 to 17, wherein the base coat comprises natural rubber in 5 to 15 parts by weight; an aromatic hydrocarbon solvent in 80 to 120 parts by weight, and aryl diisocyanate in 1 to 45 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 30 to 80 parts by weight; and a pigment in 0.3 to 5 parts by weight.

19. The method according to claims 7 to 17, wherein the base coat comprises natural rubber in 5 to 15 parts by weight; and an aromatic hydrocarbon solvent in 80 to 120 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 30 to 60 parts by weight, pigment in 0.3 to 5.0 parts by weight, and aryl diisocyanate in 1 to 30 parts by weight.

The method according to claim 18, wherein the base coating comprises natural rubber in 5 to 15 parts by weight; an aromatic hydrocarbon solvent in 80 to 120 parts by weight; and an aryl diisocyanate of 1 to 45 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 15 to 60 parts by weight, a terpene or terpenoid solvent in 5 to 40 parts by weight; and a pigment in 0.3 to 5.0 parts by weight.

The method according to claim 19, wherein the base coat comprises natural rubber in 5 to 15 parts by weight; and an aromatic hydrocarbon solvent in 80 to 90 parts by weight; and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 15 to 60 parts by weight, a terpene or terpenoid solvent in 5 to 40 parts by weight; a pigment in 0.3 to 5.0 parts by weight, and aryl diisocyanate in 1 to 30 parts by weight.

22. The method according to claims 7 to 21, comprising the additional step of heating the printed surface.

The method according to claim 22, wherein the heating is carried out in a time and temperature range of 95 ° C to 130 ° C for 10 to 20 minutes.

The method according to claim 22, wherein the heating is carried out in a time and a temperature range of 190 to 230 ° C for 3 to 8 seconds.

25. The method according to claims 7 to 21, further comprising allowing the printed surface to cure at ambient conditions for 5 to 60 days.

26. The method according to claims 22 to 24, which further comprises allowing the printed heated surface to be cured at ambient conditions for 5 to 60 days.

27. The method according to claims 1 to 26, wherein the aromatic hydrocarbon is commercial grade methylnaphthalene.

28. A formulation for printing an image on a latex rubber surface that is resistant to abrasion and chemical attack which comprises as components: a) a clear coating comprising: natural rubber and an aromatic hydrocarbon solvent, b) a premix portion comprising: an aromatic hydrocarbon solvent and a curable agent capable of forming a tough chemical and abrasion resistant structure, which integrates the rubber of the transparent coating with the rubber of the latex surface and c) pigment, mixing these components before printing the image on the surface.

29. The formulation according to claim 28, in which the agent is the aryl diisocyanate.

30. The formulation according to claims 28 and 29, wherein the approximate weight of the aryl diisocyanate is between 0.5 and 3 times that of the rubber in the ink.

The formulation according to claims 28 to 30, wherein: a) the clear coat comprises natural rubber in 1 to 10 parts by weight, and an aromatic hydrocarbon solvent in 45 to 55 parts by weight, b) the pre-mixed portion comprises : an aromatic hydrocarbon solvent in 2 to 15 parts by weight, and the agent is aryl diisocyanate in 1 to 30 parts by weight; and c) the pigment comprises 0.3 to 5.0 parts by weight.

32. The formulation according to claim 31, wherein the diisocyanate is selected from the group consisting of toluene diisocyanate, methylenediphenyl and polymeric methylene diphenyl.

33. The formulation according to claims 28 to 32, wherein the viscosity of the ink at the time of printing is in the range of 800 to 3,000 cps at 20 ° C.

34. A formulation for printing an image on a latex rubber surface that is resistant to abrasion and chemical attack which comprises as components: a) a base coating comprising natural rubber and a rubber solvent, and b) an ink that comprises natural or synthetic rubber; a solvent for rubber and pigment, understanding that an agent capable of forming at the time of curing a structure resistant to chemical products and abrasion, of tenacious and flexible character, which integrates the rubber of base coating, the rubber of the ink and the Rubber from the latex surface is present, either in the base coat and / or in the ink.

35. The formulation according to claim 34, wherein the agent is aryl diisocyanate.

36. The formulation according to claims 34 and 35, wherein the approximate weight of the aryl diisocyanate is between 0.5 and 3 times that of the sum of the rubber in the base coat and in the ink.

37. The formulation according to claims 34 to 36, wherein: a) the base coating comprises natural rubber in 5 to 15 parts by weight, a solvent for rubber in 80 to 120 parts by weight, aryl-diisocyanate as a crosslinking agent in 0 to 45 parts by weight; and b) the ink comprises natural or synthetic rubber in 1 to 10 parts by weight; a rubber solvent, 30 to 80 parts by weight; pigment in 0.3 to 5.0 parts by weight; and aryl diisocyanate, as the crosslinking agent, in 0 to 30 parts by weight; it being understood that the aryl diisocyanate in the above range is present, either in the base coat and / or in the ink.

38. The formulation according to claims 34 to 37, wherein the solvent for the rubber is at least one member of the group consisting of an aromatic hydrocarbon, a terpene, a terpenoid or a ketone boiling above 120 ° C.

39. The formulation according to claims 34 to 38, wherein the diisocyanate is selected from the group consisting of toluene, methylene diphenyl and methylene phenylene polymer diisocyanates and mixtures thereof.

40. The formulation according to claims 34 to 39, in that solvent for the rubber in the base coat is an aromatic hydrocarbon solvent in 60 to 90 parts by weight; a terpene or terpenoid solvent in 0 to 60 parts by weight, and the solvent for the rubber in the ink is an aromatic hydrocarbon solvent in 30 to 50 parts by weight, as well as a terpene or terpenoid solvent in 0 to 30 parts in weigh.

41. The formulation according to claims 34 to 40, wherein the base coat comprises natural rubber in 5 to 15 parts by weight; an aromatic hydrocarbon solvent in 80 to 120 parts by weight; and aryl diisocyanate in 1 to 45 parts by weight, and the ink comprises synthetic rubber at 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 30 to 80 parts by weight; and pigment in 0.3 to 5 parts by weight.

42. The formulation according to claims 34 to 40, wherein the base coat comprises natural rubber in 5 to 15 parts by weight; and an aromatic hydrocarbon solvent in 80 to 120 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 30 to 60 parts by weight, pigment in 0.3 to 5.0 parts by weight, and an aryl diisocyanate in 1 to 30 parts by weight.

43. The formulation according to claim 41, wherein the base coating comprises natural rubber in 5 to 15 parts by weight; an aromatic hydrocarbon solvent in 80 to 120 parts by weight, and aryl diisocyanate in 1 to 45 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts by weight; an aromatic hydrocarbon solvent in 15 to 60 parts by weight; a terpene or terpenoid solvent in 5 to 40 parts by weight, and pigment in 0.3 to 5.0 parts by weight.

44. The formulation according to claim 42, wherein the base coat comprises natural rubber of from 5 to 15 parts by weight, and an aromatic hydrocarbon solvent in from 80 to 90 parts by weight, and the ink comprises synthetic rubber in 1 to 10 parts. in weigh; an aromatic hydrocarbon solvent in 15 to 60 parts by weight; a terpene or terpenoid solvent of 5 to 40 parts by weight; pigment in 0.3 to 5.0 parts by weight, and aryl diisocyanate in 1 to 30 parts by weight.

45. The formulation according to claims 1 to 44, wherein the aromatic hydrocarbon is commercial grade methylnaphthalene.

46. A rubber latex object having a design printed thereon by the method of claim 1.

47. A rubber latex object having a design imprinted therein by the method of claim 7.

48. A glove of natural rubber latex according to claim 46.

49. A natural rubber latex glove according to claim 47.

50. A natural rubber latex glove having a design imprinted thereon according to the method of the claim 4.

51. A rubber latex glove having a design printed on it by the method according to claim 10.