ES2386179A1 - Compounds derived from urethanes and oligouretans and procedures for manufacturing brands to water through the offset printing technique and corresponding uses (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

Compounds derived from urethanes and oligourethanes and procedures for making water labels using the offset printing technique and corresponding uses. Compound of general formula **image** Where R es un radical c6-c16 2-alquil-alquilo, Y X is a radical derived from isophorone diisocyanate or trimethylhexamethylene diisocyanate. With these compounds are prepared compositions comprising a first compound of general formula (I), and, optionally, a second compound of general formula (I) of different molecular weight, and a non-polar solvent, such as for example white mineral oil. The composition may also include a thickener, such as for example silicon oxide. With these compounds and compositions water marks can be made on cellulose or textile sheet materials by the offset system. (Machine-translation by Google Translate, not legally binding)

Description

Compounds derived from urethanes and oligourethanes and watermark manufacturing processes using offset printing technique and corresponding uses.

Field of the Invention

The invention relates to a compound derived from urethanes and oligourethanes, of general formula

R-O-CO-NH-X-NH-CO-O-R (I)

and to a composition comprising at least a first compound of general formula (I).

The invention also relates to processes for manufacturing a watermark in a cellulosic or textile sheet material and to uses of the compounds and compositions according to the invention.

10 State of the art

The technique of making watermarks on cellulosic or textile materials by applying, on the cellulosic or textile material, a compound derived from urethanes and oligourethanes is known. This technique is described in PCT application WO 2008/135273.

However, by industrializing the compounds and compositions described in said PCT application, it has been observed that some drawbacks may occur.

On the one hand, in general, it is important to avoid solvents that are flammable and / or toxic.

On the other hand, it has been observed that, during the industrial application of these compositions, in some cases there is a “smoke” or “fog” effect on the impeller of the offset machines, in the surroundings of the application area, that could lead to problems of dirt and, eventually, health.

20 In any case, it is interesting to find those compositions that optimally combine the required properties.

In this sense, it should be remembered that the compositions to be used must comply with a plurality of properties (good penetration, adequate refractive index, low viscosity, good anchorage on the cellulosic or textile material, low or no lateral migration, the product must not remain on the surface of cellulosic material 25 or textile, resistance to water and organic solvents, avoid the need to use crosslinking agents, stability in time of the composition, resistance to light, simplicity in the subsequent cleaning of machinery and tools used for the manufacture of the watermark, etc.), which are obtained thanks to the combination of the properties of the various components that make up the composition (both urethane and oligourethane-derived compounds and solvents and / or other additives that of may include in the composition). These properties

30 frequently interfere with each other so it is not easy to obtain a combination that is finally suitable for the manufacture of watermarks by means of the offset system.

Summary of the invention

The object of the invention is to overcome these drawbacks. This purpose is achieved by a compound of general formula

35 R-O-CO-NH-X-NH-CO-O-R (I)

where

R is a C6-C16 2-alkyl-alkyl radical,

Y

X is a radical from isophoron diisocyanate (IPDI) or trimethylhexamethylene diisocyanate TMDI CAS No. 28679-1640 5).

Indeed, it has been observed that these compounds are the ones that allow to obtain the best results, in particular, the use of these compounds allows to avoid the problems of the “fog” or “smoke” effect and allows the preparation of compositions without flammable solvents and / or Toxic

Preferably R is 2-ethylhexyl or 2-butyloctyl.

A subject of the invention is also a composition comprising at least a first compound of the general formula (I) according to the invention, where R and X have the general meaning indicated above, and a non-polar solvent.

Preferably the composition comprises at least a second compound of general formula (I), wherein the second compound has a different molecular weight than the first compound. Indeed, in this way the properties of both compounds can be optimally combined. It is particularly advantageous that in the first compound X it is a radical from isophoron diisocyanate and in the second compound X it is a radical from trimethylhexamethylene diisocyanate, since this is the combination with the best properties, in particular as regards the Formation of "fog" or "smoke" and also allows the use of solvents that are neither flammable nor toxic.

Preferably the solvent is a mineral oil, and it is particularly advantageous that it is white mineral oil (called White oil, CAS No. 8042-47-5).

Preferably, the composition includes a solid thickening agent which, advantageously, is silicon oxide.

Advantageously the proportion, by weight, between the first compound and the second compound is comprised between

90:10 and 10:90.

Preferably the composition comprises between 1% and 30% by weight, based on the total weight of the first compound and the second compound, of the mineral oil.

Advantageously, the composition comprises between 0.5% and 10% by weight, based on the total weight of the first compound and the second compound, of the solid thickening agent. In the case that the thickening agent is silicon oxide, the optimum range is between 2% and 7% by weight, with respect to the total weight of both compounds.

A subject of the invention is also a method of manufacturing a watermark in a cellulosic sheet material or in a textile material characterized in that it comprises a step of applying a compound of general formula (I) according to the invention, where R and X have the general meaning indicated above, on the cellulosic or textile sheet material by means of the offset system.

The object of the invention is also a method of manufacturing a watermark on a cellulosic or textile sheet material characterized in that it comprises a step of applying a composition according to the invention on the cellulosic or textile sheet material by means of the offset system.

Another object of the invention is the use of a compound of general formula (I) according to the invention, where R and X have the general meaning indicated above, for the manufacture of a watermark on a cellulosic or textile sheet material.

Finally, another object of the invention is the use of a composition according to the invention, for the manufacture of a watermark on a cellulosic or textile sheet material.

Detailed description of embodiments of the invention

ESSAYS

For the following tests, the product called Ecopolmark-8-100, which is a 2: 1 molecule of IPDI (isophoron diisocyanate) with 2-ethylhexanol and with 8% excess of 2-ethylhexanol, has been taken as a starting point. As already mentioned in PCT application WO 2008/135273, excess alcohol can perform certain solvent functions. Two lines of work are followed; the first is to make variants of the Ecopolmark-8-100 product by changing the isocyanate or the starting alcohol, the second line of work is the addition of additives to the Ecopolmark-8-100 product.

Table 1 shows the products synthesized following the first line of work:

Table 1: Summary of synthesized products

Isocyanate

Alcohol Excess alcohol Appearance Laboratory Application

Example 1

TMXDI Ethanol 5% Crystalline Do not

Example-2

TMXDI Methanol 5% Crystalline Do not

Example-3

TMXDI Isopropanol 5% Crystalline Do not

Example-4

TMXDI Isopropanol 30% Crystalline Do not

Example-5

IPDI Isopropanol 5% Crystalline Do not

Example-6

 IPDI Isobutanol 5% Very viscous transparent liquid Yes

Example-7

 IPDI 2-ethylhexanol / PEG 200 0% Clear viscous liquid Yes

Example-8

 IPDI 2-ethylhexanol / Capstane 62A2 0% Clear viscous liquid Yes

Example-9

HDI Isobutanol 0% Crystalline Do not

Example-10

IPDI Isobutanol 18% Viscous translucent liquid Yes

Example-23

TMDI 2-ethylhexanol 10% Translucent liquid Yes

Example-24 Example-25

TMDI TMDI / IPDI 2-ethylhexanol 2-ethylhexanol 0% 10% Translucent liquid Translucent liquid No Yes

Example-31

TMDI Isofol 12 (2-Butyloctanol) 0% Transparent liquid Yes

Example-32

TMDI Isofol 12 5% Transparent liquid Yes

Example-33

TMDI Isofol 12 10% Transparent liquid Yes

Example-37

IPDI 2-ethylhexanol 0% Viscous and translucent liquid Yes

Example-48

IPDI Isofol 12 0% Viscous and translucent liquid Yes

TMXDI: tetramethylxylene diisocyanate IPDI: isophoron diisocyanate HDI: hexamethylene 1,6-diisocyanate TMDI: trimethylhexamethylene diisocyanate Capstone 62AL: tridecafluoro-1-octanol CAS #: 647-42-7 A brief summary of the products can be seen without a summary of the products according to the second line of work: Table 2: Summary of the additives used.

Starting product

Type of Additive % Additive Appearance Laboratory Application

Example-11

Ecopolmark-8100 Tegoglide 100 5% Transparent and viscous Yes

Example-12

Ecopolmark-8100 Tegoglide 432 5% Transparent and viscous Yes

Example-13

Ecopolmark-8100 DF253 5% Transparent and viscous Yes

Example-14

Ecopolmark-8100 Baysilone OL17 5% Transparent and viscous Yes

Example-15

Ecopolmark-8100 BYK333  5% Transparent and viscous Yes

Example-16 Example-17

Ecopolmark-8100 Ecopolmark-8100 Crodamide EBS Crodamide EBS 5% 2% White and viscous White and viscous Yes Yes

Example-18

Ecopolmark-8100 Tegoglide 482 5% White and very viscous Yes

Example-19

Ecopolmark-8100 GN-516 fluid 5% Transparent and viscous Yes

Example-20

Ecopolmark-8100 GN-526 fluid 5% Transparent and viscous Yes

Example-21

Ecopolmark-8100 Wacker AK 0.65 5% Transparent and viscous Yes

Example-22

Ecopolmark-8100 Wacker Belsil DM 1 plus 5% Transparent and viscous Yes

Example-26

Ecopolmark-8100 Ceraflour 970 5% Translucent and viscous Yes

Example-27

Ecopolmark-8100 Ceraflour 998 2% White and viscous Yes

Example-28

Ecopolmark-8100 Ceracol 609N 2% Translucent and viscous Yes

Example-29

Ecopolmark-8100 Cerafak 5% White and viscous Yes

Starting product

Type of Additive % Additive Appearance Laboratory Application

Example-30

Ecopolmark-8100 BYK-378 0.1% Transparent and viscous Yes

Example-34

Ecopolmark-8100 BYK 337 5% Transparent and viscous Yes

Example-35

Ecopolmark-8100 Cerafluor 997 5% Translucent and viscous Yes

Example-36

Ecopolmark-8100 / Example-31 (50/50) - - Viscous and transparent liquid Yes

Viscous liquid

Example-38

Example-37

GN-516 fluid

5%

Yes

and translucent

Example-39

Example-37 GN-526 fluid 5% Viscous and translucent liquid Yes

Example-37 /

Example-40

Example-24 GN-516 fluid 5% Translucent liquid Yes

(50/50)

Example-37 /

Example-41

Example-24 GN-526 fluid 5% Translucent t liquid Yes

(50/50)

Example-42

Example-37 GN-516 fluid 10% Viscous and translucent liquid Yes

Example-43

Example-37 GN-526 fluid 10% Viscous and translucent liquid Yes

Example-44

Example-37 / Example-24 (50/50) GN-516 fluid 10% Translucent liquid Yes

Example-45

Example-37 / Example-24 (50/50) GN-526 fluid 10% Translucent liquid Yes

Example-56 /

Example-46

Example-50 GN-526 fluid 5% Translucent liquid Yes

(50/50)

Example-37 /

Example-47

Example-31 GN-516 fluid 5% Translucent liquid Yes

(50/50)

Example-49

Example-47 GN-516 fluid 5% Translucent liquid Yes

Starting product

Type of Additive % Additive Appearance Laboratory Application

Example-50

Example-42 + 5% Isofol GN-516 fluid 10% Translucent liquid Yes

Example-51

Example-48 GN-516 fluid 5% Translucent liquid Yes

Example-52

Example-48 + 5% Isofol12 GN-516 fluid 5% Translucent liquid Yes

Example-53

Example-48 + 10% Isofol GN-516 fluid 5% Translucent liquid Yes

Example-54 Example-55

Example-48 + 5% Isofol12 Example-48 + 8% Isofol12 GN-516 fluid 10% Translucent liquid Translucent liquid Yes Yes

Example-56

Example-37 + 10% Isofol GN-516 fluid 5% Translucent liquid Yes

Example-57

Example-37 + 10% Isofol GN-516 fluid 10% Translucent liquid Yes

Example-58

Example-37 + Example-48 (1/1) Translucent liquid Yes

Example-59

Example-37 GN-516 fluid 22% Translucent liquid Yes

Example-60 Example-61

Example-37 + Example-48 (1/1) Example-37 Liquid GN-516 White Oil Aerosil 200 5% 25% 5% Translucent liquid Viscous and translucent liquid Yes Yes

Example-62

Example-37 Redtack-1 * 4% Viscous and translucent liquid Yes

Example-63

Example-37 Redtack-2 ** 4% Viscous and translucent liquid Yes

Example-64

Example-37 Redtack-3 *** 4% Viscous and translucent liquid Yes

Example-65

Example-37 Redtack-3 *** 10% Viscous and translucent liquid Yes

Split product

from Type of Additive % Additive Appearance Laboratory Application

Example-66

Example-37 White Oil Fluid GN-516 15% 10% Viscous and translucent liquid Yes

Example-67

Example-52  White oil 10% Viscous and translucent liquid Yes

Example-68

Example-54 Redtack-1 * 4% Viscous and translucent liquid Yes

Example-69

Example-58 Redtack-1 * 4% Viscous and translucent liquid Yes

Example-70

Example-37 White Oil Aerosil 200 20% 5% Viscous and translucent liquid Yes

Example-71

Example-37 White Oil Aerosil 200 15% 5% Viscous and translucent liquid Yes

Example-72

Example-37 White Oil Aerosil 200 15% 3% Viscous and translucent liquid Yes

Example-73

Example-48 White Oil Aerosil 200 15% 5% Viscous and transparent liquid Yes

Example-74

Example-48 White Oil Titanium Oxide 6.6% 0.6% White viscous liquid Do not

Example-75 Example-76

Example-37 Example-37 White Oil Micronized clay White Oil Micronized clay 20% 1% 20% 1% Viscous and brown liquid Viscous and brown liquid Nerd

Example-77

Example-37 / Example-24 (50/50) White Oil Aerosil 200 20% 5% Viscous and translucent liquid Yes

Example-78

Example-37 / Example-24 (75/25) White Oil Aerosil 200 20% 5% Viscous and translucent liquid Yes

Example-79

Example-37 / Example-24 (50/50) White Oil Aerosil 200 10% 5% Viscous and translucent liquid Yes

Split product

from Type of Additive % Additive Appearance Laboratory Application

Example-80

Example-37 / Example-24 White Oil Aerosil 200 10% 5% Viscous and translucent liquid Yes

(75/25)

Example-81

Example-37 / Example-24 (25/75) White Oil Aerosil 200 20% 5% Viscous and translucent liquid Yes

Example-82

Example-37 / Example-24 (25/75) White Oil Aerosil R812 5% 5% Viscous and translucent liquid Yes

Example-83

Example-37 / Example-24 White Oil Aerosil R812 10% 5% Viscous and translucent liquid Yes

(25/75)

Example-84

Example-24 White Oil Aerosil R812 2.5% 5% Viscous and translucent liquid Yes

* Redtack-1: 89% White Oil, 10% Soybean Oil and 1% R972 Aerosil. ** Redtack-2: 85% White Oil, 8% Soybean Oil, 3% rice starch and 4% Aerosil 200. *** Redtack-3: 95% White Oil and 5% rice starch.

5 LABORATORY APPLICATION.

All synthesized products are applied except those that are crystalline. The Ecopolmark-8-100 product that will be used as a reference also applies. The products are applied on a glass sheet and a cellulose paper is adhered on top. The process is repeated on another stainless steel sheet.

The quantity of product applied is the same for each product.

10 The adhesion of the paper is checked 5 minutes after the application and after 24 hours.

Finally, the products are applied on paper with a buffer and compared with the application of the Ecopolmark-8-100 product to see if they have the same transparency properties, penetration speed, absence of migration and good registration.

OFFSET MACHINE APPLICATION

15 Synthesized products that have given good results in the laboratory are applied by offset printing technique. The following section shows the results obtained.

RESULTS LABORATORY APPLICATION

Table 3 shows the classification used for accession:

Table 3: Adhesion classification.

Low

Moderate high

Accession

one 2 3

Table 4 shows the results obtained: Table 4: Summary of the results obtained from the applications in the laboratory.

Product

Iron adhesion Glass adhesion Paper application

Example-6

3 3 Does not penetrate

Example-7

one one okay

Example-8

one one okay

Example-11

 one one okay

Example-12

one 2 okay

Example-13

one 2 okay

Example-14

one one okay

Example-15

 2 one okay

Example-16

2 one okay

Example-17

2 2 okay

Example-18

one one okay

Example-19

 one one okay

Example-20

one one okay

Example-21

one one okay

Example-22

one one okay

Example-23

 one one Migrate too much

Example-25

one one okay

Example-26

2 2 okay

Example-27

2 2 okay

Example-28

 2 2 okay

Example-29

2 2 okay

Example-30

2 2 okay

Example-31

one one okay

Example-32

 one one okay

Example-33

one one okay

Example-34

2 2 okay

Example-35

2 2 okay

Product

Iron adhesion Glass adhesion Paper application

Example-36

one one okay

Example-37

2 2 okay

Example-38

2 2 okay

Example-39

 2 2 okay

Examples-40-84

one one okay

OFFSET MACHINE APPLICATION

The following table shows the results obtained in offset machine applications. The fog formation is evaluated from 1 to 10 during the application, with 0 being the non-fog formation and 10 the maximum fog formed, the smell intensity of the product, the penetration rate, the transparency, the registration and the Brand migration to water.

Table 5: Summary of the results of the applications in offset machine.

Smoke (1 to 10)

Odor Penetration Transparency Registry Migration

Example-22

5 Light Slow okay okay Do not

Example-23

5 Do not Snapshot okay okay If much

Example-24

6 Do not Very fast okay okay Something

Example-25

8 Much Snapshot okay okay Do not

Example-31

5 Very little Snapshot okay okay Little

Example-34

7 Yes Slow Low Very good Little

Example-36

7 Yes Slow okay Very good Do not

Example-40

9 Little bit Slow Good okay A bit

Example-41

6 Yes Fast Good Good Casino

Example-42

2 Little bit Slow Irregular Good Minimum

Example-43

3 Little bit Slow Irregular Good Do not

Example-46

7 Yes Fast Good Good Do not

Example-47

5 Little bit Fast Good Good Do not

Example-48

3 Very little Slow Very good Very good Do not

Example-49

5 Little bit Fast Very good Very good Something

Example-50

4 Little bit Slow Homogeneous Very good Do not

Example-51

7 Very little Slow Homogeneous Very good Do not

Example-52

8 Do not okay Not uniform okay Do not

Example-53

7 Do not Fast okay okay A bit

Example-54

5 Do not Fast Not uniform okay A bit

Smoke (1 to 10)

Odor Penetration Transparency Registry Migration

Example-55

8 Do not Fast Regular okay Do not

Example-56

 3 Do not okay Homogeneous Good Do not

Example-57

5 Do not okay okay okay Do not

Example-58

 6 Do not okay okay Good Do not

Example-59

6 Do not Do not Do not Do not Do not

Example-60

2 Very little Fast okay okay A bit

Example-61

0 Do not Fast Good Good Minimum

Example-62

2 Do not Does not penetrate Does not penetrate Does not penetrate Does not penetrate

Example-63

2 Do not Does not penetrate Does not penetrate Does not penetrate Does not penetrate

Example-64

4 Yes Does not penetrate Does not penetrate Does not penetrate Does not penetrate

Example-65

4 Yes Does not penetrate Does not penetrate Does not penetrate Does not penetrate

Example-66

2 Little bit Very slow okay No ok Yes

Example-67

one Little bit Fast okay No ok Yes

Example-68

 one Little bit Very fast okay No ok Little

Example-69

one Very little Very fast okay No ok Minimum

Example-70

 0 Do not Fast Weak Good Do not

Example-71

0 Do not Slow Irregular Good Do not

Example-72

 0 Little bit Slow Good Good Casino

Example-73

0 Little bit Fast Good okay Yes

Example-77

 0 Do not Very fast okay okay Do not

Example-78

0 Do not Very fast okay okay Do not

Example-83

 0 Do not Very fast okay okay Do not

Example-84

0 Do not Very fast okay okay Do not

CONCLUSIONS

During the tests performed, it has been found that it is particularly advantageous to decrease the adhesion of the compounds and / or compositions employed. This can be achieved by selecting compounds,

5 "suitable" solvents and additives. In addition, the use of flammable and / or toxic solvents has been avoided. From table 5, where the results obtained in offset machine applications are shown, it can be concluded that there are several products that meet the required properties: absence of fog formation during application, absence of strong and annoying odor, rapid penetration, Good transparency, good registration and absence of migration of the brand to water on paper.

10 Of all the examples tested on offset machines, examples 77,78, 83 and 84 stand out as best products.

List of additives used:

Tegoglide 100: sliding and leveling additive. Polyether polysiloxane copolymer. Marketed by Evonik.

Tegoglide 432: sliding and anti-blocking additive. Polyether polysiloxane copolymer. DF253: Leveling Baysilone OL17: Additive for improving surface extensibility and smoothness. Methylpolysiloxane

modified with polyether. Marketed by Borchers. BYK 333: Surface additive. Copolymer of Polydimethylsiloxane modified with polyether. Marketed by BYK. BYK 378: Surface additive. Polyether modified polydimethylsiloxane. Co-commercialized by BYK. BYK 337: Surface additive. Polyether modified polydimethylsiloxane. Marketed by BYK. Crodamide EBS: Anti-blocking. Fatty amide derived from natural resources. Marketed by Croda. Tegoglide 482: sliding and anti-blocking additive. Polydimethylsiloxane Marketed by Evonik. GN516 fluid: (GODOSIL E-304) Very low viscosity additive for elimination of stickiness.

Decamethylcyclopentasiloxane. Commercialized by Comercial Godó.

Fluid GN526: (GODOSIL 310) Additive for elimination of stickiness. Phenylmethylpolysiloxane. Comercialized by

Commercial Godó.

Ceraflour 970: Improves surface properties. Wax Additive Marketed by BYK.

Ceraflour 998: Improves surface properties. Wax Additive Marketed by BYK.

Ceraflour 997: Improves surface properties. Wax Additive Marketed by BYK.

Ceracol 609N: Improves surface properties. Wax Additive Marketed by BYK.

Cerafak: Improves surface properties. Wax Additive Marketed by BYK.

Aerosil 200: Silicon dioxide. Marketed by Evonik.

Aerosil R812: Silicon dioxide. Marketed by Evonik.

White Oil: (SABITOL) Technical white oil derived from petroleum. Marketed by Brugués.

Wacker AK 0.65: Polydimethylsiloxane. Marketed by Wacker.

Wacker Belsil DM1 plus: Polydimethylsiloxane. Marketed by Wacker.

Claims (2)

1 -Compound of general formula R-O-CO-NH-X-NH-CO-O-R (I) where R is a C6-C16 2-alkyl-alkyl radical, and X is a radical from isophorone diisocyanate or trimethylhexamethylene diisocyanate. 2 - Compound according to claim 1, characterized in that R is 2-ethylhexyl. 3 - Compound according to claim 1, characterized in that R is 2-butyloctyl. 4 -Composition comprising at least one first compound of general formula (I) according to any of the claims 1 to 3, wherein R and X have the general meaning indicated above, and a non-polar solvent. 5. Composition according to claim 4, characterized in that it comprises at least a second compound of general formula (I), wherein said second compound has a different molecular weight than said first compound. 6 - Composition according to claim 5, characterized in that in said first compound X is a radical from isophoron diisocyanate and in said second compound X is a radical from trimethylhexamethylene diisocyanate. 7 - Composition according to any of claims 4 to 6, characterized in that said solvent is an oil mineral. 8 - Composition according to claim 7, characterized in that said solvent is white mineral oil. 9 - Composition according to any of claims 4 to 8, characterized in that it additionally comprises a solid thickening agent. 10 - Composition according to claim 9, characterized in that said thickening agent is silicon oxide. 11 - Composition according to any of claims 6 to 10, characterized in that the proportion, by weight, between said first compound and said second compound is comprised between 90:10 and 10:90. 12 - Composition according to any of claims 7 to 11, characterized in that it comprises between 1% and 30% by weight, based on the total weight of said first compound and said second compound, of said oil mineral. 13 - Composition according to any of claims 9 to 12, characterized in that it comprises between 0.5% and 10% by weight, based on the total weight of said first compound and said second compound, of said agent solid thickener. 14 - Composition according to claim 10, characterized in that it comprises between 2% and 7% by weight, with respect to the total weight of said first compound and said second compound, of silicon oxide. 15 - Method of manufacturing a watermark on a cellulosic sheet material characterized in that it comprises a step of applying a compound of general formula (I) according to any one of claims 1 to 3, wherein R and X have the general meaning indicated above. , on said cellulosic sheet material by means of the offset system. 16 - Method of manufacturing a watermark on a cellulosic sheet material characterized in that it comprises a step of applying a composition according to any of claims 4 to 14 on said cellulosic sheet material by means of the offset system. 17 - Use of a compound of general formula (I) according to any one of claims 1 to 3, wherein R and X have the general meaning indicated above, for the manufacture of a watermark on a cellulosic sheet material. 18 - Use of a composition according to any of claims 4 to 14, for the manufacture of a watermark on a cellulosic sheet material. 19 - Method of manufacturing a watermark on a textile sheet material characterized in that it comprises a step of applying a compound of general formula (I) according to any one of claims 1 to 3, wherein R and X have the general meaning indicated above. , on said textile sheet material by means of the offset system. 5 - Method of manufacturing a watermark on a textile sheet material characterized in that it comprises a step of applying a composition according to any of claims 4 to 14 on said textile sheet material by means of the offset system. 21 - Use of a compound of general formula (I) according to any one of claims 1 to 3, wherein R and X have the general meaning indicated above, for the manufacture of a watermark on a textile sheet material. 10 - Use of a composition according to any of claims 4 to 14, for the manufacture of a watermark on a textile sheet material. SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 201230926 SPAIN Date of submission of the application: 06.13.2012 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: See Additional Sheet RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

X

EN 2294965 A1 (ANTONIO OLIVA GURGUI), the whole document, especially claims 1-18,30,32, examples 1-6,15,17,19,21

TO

claims 19-29,31,33 7-14,16,18,20,22

TO

EN 2340756 A1 (MARCA D AIGUA), the whole document 1-22

TO

CAPLUS Database in STN (Chemical Abstracts Service), accession number 2009: 1363036 & JP 2009258410ª (KONICA MINOLTA), summary 1-22

 TO

M EL-MOLLA et al, Indian Journal of Fiber & Textile Research, September 2011. "Nanotechnology to improve coloration and antimicrobial properties of silk fabrics" 4-22

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 17.07.2012

Examiner M. Fernández Fernández Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201230926 CLASSIFICATION OBJECT OF THE APPLICATION  C07C275 / 60 (2006.01) C07C265 / 14 (2006.01) C08G18 / 75 (2006.01) B41M3 / 06 (2006.01) Minimum documentation sought (classification system followed by classification symbols) C07C, C08G, B41M Electronic databases consulted during the search (name of the database and, if possible, search terms used) INVENES, EPODOC, WPI, ESPACENET, CAS, PAJ State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201230926 Date of Completion of Written Opinion: 07.17.2012 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims 7-14,16,18,20,22 Claims 1-6,15,17,19,21 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims 7-14,16,18,20,22 Claims 1-6,15,17,19,21 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201230926  1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

ES 2294965 A1 (ANTONIO OLIVA GURGUI) 04.01.2008

D02

claims 19-29,31,33

 2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The application refers to the compounds of general formula (I) of claim 1: R-O-CO-NH-X-NH-CO-O-R where X comes from isophoron diisocyanate (IPDI), to the composition comprising at least one compound of formula (I) and / or a second compound of formula (I) different from the first in a mineral oil as solvent (claims 4-14) and to the use of the compounds of general formula ( I) for the manufacture of a watermark on a cellulosic or textile sheet (claims 17,18,21 and 22). A method of manufacturing a watermark on a cellulosic or textile sheet characterized in that it comprises an application stage of a compound of general formula (I) (claims 15,16,19 and 20) is also claimed. Document D1 discloses urethane derivatives of general formula (I): R-O-CO-NH-X-NH-CO-O-R see claim 1, where n is zero (claim 8), R and R 'are alkyl radicals such as hexyl or octyl (claim 9 of D1) and X is hexamethylene, trimethylhexamethylene, isophoron ... (claim 7), in the examples repeatedly uses the isophoron diisocyanate (IPDI), that is, the compounds of claim 1 of the application are analogous to those disclosed in the prior art, as well as their use in watermark manufacturing processes (claims 30 to 33 of D1), therefore claims 1-6, 15,17,19 and 21 are not new. Claims 19 to 24 of D1 disclose a composition comprising one or two compounds of formula (I) in a non-polar solvent, such as benzene, toluene and derivatives. In the composition of claims 7-14 of the application the non-polar solvent used is a mineral oil, which has the advantage of not being flammable or toxic, problems that benzene and derivatives present. Therefore claims 7-14 of the application present novelty and inventive activity, since they solve a technical problem in the compositions of inks for printing on cellulosic and / or textile materials and this solvent has not been disclosed with compounds of the type of those of claim 1. Consequently, it is concluded that claims 1-6,15,17,19 and 21 are new and claims 7-14,16,18,20 and 22 have novelty and inventive activity, as provided in Art. 6.1 and 8.1 of Patent Law 11/1986. State of the Art Report Page 4/4