ES2265300B1 - "DERIVATIVES OF POLYURETHANS AND CORRESPONDING USES AND PROCEDURES OF MANUFACTURE OF BRANDS TO WATER". - Google Patents

Abstract

Polyurethane derivatives and corresponding uses and manufacturing procedures for watermarks. The invention relates to compounds and / or compositions for the manufacture of watermarks on paper, of general formula (I) RX- (AX) m - (- BX-) n-R '' (I) where, for example , R and R '' are polyethylene glycol, X, X '' and X '' '' are a diisocyanate, A is a polyester with a single branching, consisting of a carboxylic acid functional group, myn are 0 or 1, and B is a diol The molecular weight of the compound is greater than 550, and the NCO value is equal to 0. The invention also relates to methods of manufacturing watermarks and uses of compounds of general formula (I) and compositions containing them for manufacture of watermarks in cellulosic sheet materials.

Description

Polyurethane derivatives and uses corresponding and manufacturing procedures for brands Water.

Field of the Invention

The invention relates to compounds and / or compositions for the manufacture of watermarks in materials cellulosic laminar, in particular the invention relates to compounds of general formula (I)

(I) R-X- (A-X) m - (- B-X -) n - R '

and compositions containing them. The invention also relates to manufacturing processes of watermarks of cellulosic sheet materials and uses of compounds of general formula (I) and compositions that contain for the manufacture of watermarks in materials laminar cellulosic

State of the art

Various compositions are known and procedures for the manufacture of watermarks. But nevertheless it is usually necessary to use compositions containing more or less toxic substances and / or difficult to handle. Additionally they are suitable procedures for the manufacture of large series, so its application for the manufacture of medium and small series.

Summary of the invention

The invention aims to overcome these inconvenience This purpose is achieved by a compound of General Formula

(I) R-X - (- A-X '-) m - (- B-X' '-) n -R'

where

R and R 'are monoethylene glycol, polyethylene glycol molecular weight less than 1500, polyethylene glycol monoether weight molecular less than 1500, primary or secondary monoamine weight molecular less than or equal to 2000, or mixtures of the above,

X, X 'and X' 'are an aliphatic diisocyanate of molecular weight less than 1000, preferably less than 500,

A is a linear aliphatic polyester of weight molecular less than 1000, an aliphatic polyester with a single branching, consisting of a carboxylic acid functional group or a group -SO 3 H, of molecular weight less than 1000, a polyether linear aliphatic of molecular weight less than 1000, a polyether aliphatic with a single branch, consisting of a group functional carboxylic acid or a group -SO3H, by weight molecular less than 1000, a linear aliphatic polycaprolactone of molecular weight less than 1000, or an aliphatic polycaprolactone with a single branch, consisting of an acid functional group carboxylic or a -SO3H group, of molecular weight less than 1000,

m is 0 or 1

B is an aliphatic diol of lower molecular weight of 1000 and with a single branch, consisting of a group carboxylic acid functional or a group -SO3H,

n is 0 or 1,

where the molecular weight of said compound is greater than 550,

and where the value of NCO is equal to 0.

Indeed, the compounds of the general formula (I) allow to obtain a combination of properties that makes them particularly useful for use in the manufacture of brands the water. They are non-reactive oligouretans, since they have no groups NCO free. These compounds have a low viscosity (thanks at its reduced molecular weight, at low or no branching lateral and practically zero crosslinking), a high penetration into a cellulosic sheet material, low migration lateral and good solidity against water and solvents organic (thanks to the affinity of oligourethanes with the cellulosic material and, in the case of the presence of a group functional carboxylic acid or a side -SO3H group, thanks at their reactivity with the cellulosic material), they are soluble or dispersible in aqueous solutions and / or in organic solvents, they are  easy handling, etc. In addition, they have numerous ether groups or -CH_ {2} - which causes them to have a low refractive index, specifically they have a refractive index between 1.5 and 1.6. They preferably have an index close to 1.54 (for example between 1.52 to 1.56), which requires limiting the quantity of polar functional groups, so you must reach a compromise solution between the fixing capacity in the cellulosic material, refractive index and viscosity. All this allows to obtain a series of advantages, as is the fact of obtain a watermark with high transparency, contours well defined, which are relatively unaffected if they fall on top of a drop of water or some organic solvent (that is, the watermark is well anchored in the cellulosic material) and a simplicity in the subsequent cleaning of machinery and tools employees for the manufacture of the water brand. These compounds They are also very simple and versatile.

In general, it is advantageous that the compound contain one (and preferably only one) acid functional group carboxylic or a group -SO 3 H, or, in general, a group functional anionic type. This way you can improve the solidity of the brand to the water without losing penetrability in the cellulosic material It is particularly advantageous that the group functional is carboxylic acid because of its weak acidity, which favors the passage of carboxylate (which is the way it has initially, when applied) to carboxylic in the substrate, which It is more solid in water and solvents than carboxylate.

Preferably the primary monoamines or Secondary ones comprise a solubilizing group which is advantageously a polyethylene glycol, a carboxylic acid or an acid sulfonic

Advantageously the molecular weight of the compound (I) is between 550 and 5000, preferably it is between 550 and 2500, and most preferably it is between 550 and 1500.

Advantageously, if the molecular weight of both R since R 'is greater than 1000, then m and n are equal to 0.

A preferred alternative is that the compound (I) be linear. In general, viscosity is a parameter of great importance for the manufacture of watermarks. A viscosity too low can cause problems of low solidity, excessive lateral migration, etc. On the other hand, a viscosity too elevated can give problems of little penetrability. A compound linear will generally have a viscosity less than a compound with ramifications. On the other hand, the ramifications will affect more or less at viscosity based on its properties: the presence of polar lateral groups (such as type - OH) will have as a consequence that bridge-type links are formed hydrogen, etc. (forming a certain degree of crosslinking), which greatly affects viscosity; the presence of others ionic or polar side groups can also affect quite a lot at viscosity such as, for example, carboxylic acid groups or -SO_ {3} H. Therefore, another preferred alternative is that the compound be linear with the only exception of having a group side comprising said carboxylic acid groups or -SO_ {3} H.

A preferred alternative is that the monoether of polyethylene glycol be monomethyl ether of polyethylene glycol by weight molecular less than 1500.

Another advantageous alternative is when R and R 'are linear and crystalline or semicrystalline polyethylene glycols, such as for example PEG 400, since a compound with viscosity is obtained adequate and with a refractive index close to that of the material cellulosic

Preferably the amine is monoethanolamine, diethanolamine, polyoxyalkylenemonoamine, methoxypropylamine, acid 2-aminoethanesulfonic acid (taurine), acid 3-aminopropanesulfonic acid (homotaurine), or acid aminoacetic (glycine). In particular, polyoxyalkylenemonoamine it is preferably a primary monoamine bound to a polyether, where the polyether is formed from a mixture of oxide of ethylene (EO) and propylene oxide (PO). These compounds are marketed by Huntsman Corporation under the general name Jeffamine®. Preferably the molar ratio between PO and EO is 911 and the molecular weight is 600 (marketed under the name XTJ-505 (M-600)), or the molar ratio between PO and EO is 3/19 and the molecular weight is 1000 (marketed under the name XTJ-506 (M-1000)), or the molar ratio between PO and EO is 2916 and the molecular weight is 2000 (marketed under the name XTJ-507 (M-2005)), or the molar ratio between PO and EO is 10/31 and the molecular weight is 2000 (marketed under the name Jeffamine® M-2070)).

Preferably X, X 'and X' 'are hexamethylene diisocyanate, isophoron diisocyanate, dicyclohexylmethyl diisocyanate, tetramethylxilylene diisocyanate, xylylene diisocyanate, or trimethylhexamethylene diisocyanate.

Advantageously the polyester is formed to from a linear aliphatic diol of the group formed by ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol, neopentyl glycol and acid 2,2- (bishidroxymethyl) propionic, and an aliphatic diacid linear. It is particularly advantageous that the diol is butanediol and that the diacid is adipic acid.

Preferably the polyester is crystalline or semi-crystalline because in this case you get a watermark of greater strength against water and organic solvents. Advantageously the polyether is formed from a diol linear aliphatic of the group consisting of ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol, and neopentyl glycol

Preferably polycaprolactone is formed from a gamma-caprolactone and using as an initiator of chain a linear aliphatic diol of the group formed by ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol, neopentyl glycol, and acid 2,2- (bishydroxymethyl) propionic. Is particularly interesting that polycaprolactone is formed from acid 2,2- (bishydroxymethyl) propionic as chain initiator. A An example of these polycaprolactones is the product marketed under the name of HC 1100® by Solvay Caprolactones (which is a division of Solvay S.A.), which is a caprolactone polyester that it has a diol included in the chain and it has an acid group free side. It has a molecular weight of 1000, an OH value of 100 mg KOH / g, an acid value less than 60 mg KOH / g and a point of fusion between 40 ° C and 45 ° C.

A preferred alternative is that A be a composed of the group consisting of hexanediol adipate, adipate of butanediol, neopentyl glycol adipate, adipate 2-methylpropanediol, diethylene glycol adipate, and mixtures of the above.

Advantageously B is acidic 2,2- (bishydroxymethyl) propionic.

A preferred embodiment of the compound (I) is when n is 0 if m = 1 and A has a branching, consisting of a carboxylic acid functional group or a group -SO_ {3} H. It is particularly advantageous that the group Functional be carboxylic acid.

Another preferred embodiment of the compound (I) is when n is 1 if m = 0 or if m = 1 and A is linear. Indeed, in this case group B can provide the branching with the carboxylic acid functional group or with the group -SO_ {3} H.

Another preferred alternative of compound (I) is when m is 0 and n is 0.

Advantageously the compound (I) comprises a Colorant. Indeed, a preferred embodiment of the invention is obtained when a dye is included, so that The resulting watermark is colored. The dye can be included in such a way that it is chemically bonded with the compound (so that the compound, as a whole, understands the dye), or it may be included in the composition used for make the watermark, as another component of it. In Any case is advantageous to present a group suitable for react with the cellulosic substrate and with some functional group of the polyurethane, such as a reactive halogen group. Some Examples of these dyes are Drimaren dyes marketed by the Pigments and Additives division of Clariant Group In case the dye is chemically bonded to the compound (I), it is advantageous that it is attached to the compound through a urethane bond formed from an -OH group of the dye and an NCO group of the compound. Some examples of dyes from this type are Reactint® dyes marketed by Milliken Chemical, which is a division of Milliken & Company. Too it can be interesting to combine dyes of both types, in depending on the color you want to obtain.

Preferably the compound has the dye in a proportion less than or equal to 0.5% by weight, preferably less than or equal to 0.4% by weight with respect to the total weight of the compound, both in case the dye is chemically bound to the compound as in the case that both are dissolved and 10 dispersed in a composition. It has been observed that the use of higher percentages worsens the transparency quality of the water mark, since the index of refraction of the dye (in especially red and blue) is higher than the refractive index of  cellulosic material

A preferred embodiment of the invention is obtained when a composition is made and used comprising at least a first compound of general formula (I) according to the invention, where R, R ', X, X', X '', A, m, B, and n have the general meaning indicated above, and a solvent, preferably water, ethanol, isopropanol or methoxypropanol Indeed, to be able to manufacture and use the compound (I) in a suitable way it is convenient to dilute it and / or disperse it in a solvent. On the one hand, this facilitates its manufacturing and, on the other hand, this facilitates its application and penetration into cellulosic material.

Preferably the composition comprises minus a second compound of general formula (I), where the second Compound has a different molecular weight than the first compound. In this way it is possible to adjust the viscosity of the composition. Thus, for example, when the synthesis is done in two steps you can adjust the viscosity and fixing on the substrate (cellulose); that is, to achieve a balance between a viscosity Low and good anchor. Mixing is usually done between a product that has good adhesion or fixation on cellulose (but that is somewhat viscous for depending on what type of paper, especially thick and dense) and another that is more fluid and even gives something more transparency (because it is less functionalized, no has carboxylic groups or has fewer of them, has a refractive index even lower).

The composition may comprise a cosolvent which is preferably an alcohol, preferably ethanol, isopropanol or methoxypropanol. Alternatively it can be advantageous. that the cosolvent is N-methylpyrrolidone. Other alternative of interest is obtained when the main solvent It is an alcohol and has as a cosolvent, in small proportions, the Water. In this way, with a small amount of water, you can get a composition suitable for use with materials water sensitive cellulosics (for example, due to problems of wrinkled). It should be noted that the use of alcohols containing small amounts of water (as per example ethanol). In general, it is advantageous that the composition has a water content of less than 15% by weight with respect to total weight of compound of general formula (I) in the case of having to be used with cellulosic material that is affected by the Water.

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In the event that the compound is dispersed in an aqueous solution, preferably the particle size of the dispersion is less than 10 nanometers, to get a good penetration.

It is particularly advantageous that the composition be a mixture of a first compound of general formula (I) with a branching consisting of an acid functional group carboxylic or a group -SO 3 H and at least one second compound of general formula (I) with no branching consisting of a carboxylic acid functional group or a group -SO 3 H, wherein said second compound has m and n equal to 0.

Preferably, in the composition the concentration of compounds of general formula (I) is comprised between 50-70% by weight with respect to the total weight of compound of general formula (I). These concentrations are the most suitable for use in the manufacture of the watermark. Concentrations below 50% make the transparency of the water mark is insufficient since they are not filled sufficiently the pores of the cellulosic material with the compound of formula general (I). It is also advantageous that the concentration of compounds of general formula (I) is between 70-90% by weight with respect to the total weight of compound of general formula (I), and preferably is 80%. Indeed, these concentrations are more suitable for your manufacturing, transportation and distribution. More concentrations elevated make the composition excessively viscous for its handling during the manufacturing process.

Preferably the composition comprises, additionally, a volatile amine that forms a salt with said acid carboxylic acid or -SO3H, and most preferably said amine Volatile is ammonia or triethylamine. The salt thus obtained is soluble in water or water dispersible and soluble in an organic solvent (for example an alcohol) if used in the appropriate amount. A once applied to the cellulosic material, and when the solvent, the volatile amine is also removed and the compound is self-acidify Accordingly, the compound in its acid form is fixes cellulosic material better and is more difficult to redisolve.

The invention also aims at a use of a compound of general formula (I) according to the invention, where R, R ', X, X', X '', A, m, B, and n have the general meaning indicated above, for the manufacture of a watermark in a cellulosic sheet material.

The object of the invention is additionally the use of a composition according to the invention, for the manufacture of a watermark on a sheet material cellulosic

In general, in the present description and claims, when it is indicated that A and B (or the compound in its set) are linear or have a single consistent branching in a carboxylic acid functional group or a group -SO 3 H is must understand in the sense that A and B have no other Branches capable of generating crosslinking. In general, the Branches capable of generating cross-linking are known for An expert in the field. In the case of crosslinking the viscosity increases significantly, which acquires a value too high Therefore, A and B may include other ramifications, preferably alkyl type but also ramifications that include some additional functional group as long as there is no crosslinking due to this group additional functional. In particular, A and B can have groups -CH 3 {laterals.

The invention also aims at a manufacturing process of a watermark on a material cellulosic laminar characterized in that it comprises a stage of application of a compound of general formula (I) according to the invention, or of a composition according to the invention, about the cellulosic sheet material by flexography or gravure. Indeed, the brand is conventionally manufactured to water during the papermaking process. To do this they use rollers with embossed drawings, generally arranged in one point before the continuous wet paper roll enters the dryers In this way the cellulose fibers of the roll continuous move horizontally (in the direction of the paper itself) so that the paper becomes thinner and, consequently, more transparent in the area of the watermark or watermark. For the therefore, the rollers with embossed drawings "deform" the paper wet so that this deformation is permanently in The paper after drying. Another conventional manufacturing method of watermarks or watermarks, and that is also done in the papermaking moment consists in the use of a band fitted around a roller and embossing the drawing or configuration of the watermark. This relief drawing gets in touch with the wet paper, which still has a certain plasticity, which allows compression. The paper zone compressed has a smaller amount of trapped air and so therefore, a lower refraction of light, so it increases its transparency. As a result of all this, currently watermarks are manufactured during the manufacturing process of the paper and are black and white (that is, in general, in monochrome depending on the color of the paper) since they only play with the transparency, shadows and opacity.

The present invention allows the manufacture of watermarks on paper (in general, sheet materials cellulosic) already manufactured, at a corresponding later stage to print. In addition, the present invention allows the manufacture of colored watermarks. Indeed, the Compounds and compositions according to the invention are suitable to be used as inks for flexography and / or gravure (also called rotogravure). These printing techniques they use liquid inks (of low viscosity) that consist basically in a solvent and a series of additives (dyes, resins, pigments, waxes or plasticizers, etc.). Inks liquids are applied on the cellulosic support material and the solvent is evaporated. By using the compounds and compositions according to the invention, these penetrate inside the cellulosic material reducing its refraction and thus achieving generate a brand to the water.

Detailed description of some embodiments of the invention

Example one

150.00 grams of CAPA HC1100 (Solvay) se heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until Approach up to an NCO of 5.44. 90.00 were then added grams of PEG 300. When the NCO was equal to 0 the reaction was cooled up to 60 ° C and 12.34 grams of were added triethylamine Subsequently, 76.67 grams of methoxypropanol The reactor was cooled to room temperature and He terminated the reaction.

It is, therefore, an example in the that:

R = R '= PEG 300

X = X '= IPDI

A = LAYER HC1100

m = 1

n = 0

Example 2

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Blue X3LV (Milliken) was heated to 100 ° C with constant flow of N2 for ½ hour to extract Water. It was subsequently cooled to 80 ° C to add 66.69 grams of  IPDI It remained at this temperature until we approached up to NCO of 5.44. 90.00 grams of PEG 300 were then added. When the NCO was equal to 0 the reaction was cooled to 60 ° C and they added 12.34 grams of triethylamine. Later 76.67 grams of methoxypropanol were added. The reactor was cooled to room temperature and the reaction was terminated.

Example 3

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Red X65 (Milliken) were heated to 100 ° C with constant flow of N2 for ½ hour to extract Water. It was subsequently cooled to 80 ° C to add 66.69 grams of  IPDI It remained at this temperature until we approached an NCO of 5.44. 90.00 grams of PEG 300 were then added. When the NCO was equal to 0 the reaction was cooled to 60 ° C and they added 12.34 grams of triethylamine. Later 76.67 grams of methoxypropanol were added. The reactor was cooled to room temperature and the reaction was terminated.

Example 4

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Yellow X15 (Milliken) was heated to 100 ° C with constant flow of N2 for ½ hour to extract the Water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI It remained at this temperature until we approached an NCO of 5.44. 90.00 grams of PEG 300 were then added. When the NCO was equal to 0 the reaction was cooled to 60 ° C and they added 12.34 grams of triethylamine. Subsequently, 76.67 grams of methoxypropanol were added. Be cooled the reactor to room temperature and terminated the reaction.

Example 5

150.00 grams of CAPA HC1100 (Solvay) se heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until Approach up to an NCO of 5.44. 90.00 were then added grams of PEG 300. When the NCO was equal to 0, 4.00 was added grams of Drimaren Blau HF-RL (Clariant). ½ hour The reaction was then cooled to 60 ° C and added. added 12.34 grams of triethylamine. They were subsequently added 76.67 grams of methoxypropanol. The reactor was cooled to temperature ambient and the reaction was terminated.

Example 6

150.00 grams of CAPA HC1100 (Solvay) se heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until Approach up to an NCO of 5.44. 90.00 were then added grams of PEG 300. When the NCO was equal to 0, 4.00 was added grams of Drimaren Rot HF-G (Clariant). ½ hour The reaction was then cooled to 60 ° C and added. added 12.34 grams of triethylamine. They were subsequently added 76.67 grams of methoxypropanol. The reactor was cooled to temperature ambient and the reaction was terminated.

Example 7

150.00 grams of CAPA HC1100 (Solvay) se heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until Approach up to an NCO of 5.44. 90.00 were then added grams of PEG 300. When the NCO was equal to 0, 4.00 was added grams of Drimaren Gelb HF-R (Clariant). ½ hour The reaction was then cooled to 60 ° C and added. added 12.34 grams of triethylamine. They were subsequently added 76.67 grams of methoxypropanol. The reactor was cooled to temperature ambient and the reaction was terminated.

Example 8

150.00 grams of Butanediol Adipate weight molecular 1000, 9.91 grams of acid 2,2- (bishidroxymethyl) propionic (DMPA) and 9.91 grams of N-methylpyrrolidone (NMP) was heated to 100 ° C with constant flow of N2 for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 74.65 grams of IPDI. Be maintained at this temperature until we approached a NCO of 4.01. An additional 168.48 grams of IPDI was added and then 521.94 grams of PEG 300. When the NCO was equal to 0, the reaction up to 60 ° C and 7.10 grams of triethylamine were added. Subsequently, 223.81 grams of methoxypropanol were added. Be the reactor was cooled to room temperature and the reaction.

In this example you have to:

R = R '= PEG 300

X = X '= IPDI

A = polyester formed from adipate of butanediol

m = 1

B = DMPA

n = 1

Example 9

150.00 grams of polypropylene glycol (PPG) 1000 molecular weight, 20.12 grams of DMPA and 20.12 grams of NMP are heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 100.00 grams of IPDI. It remained at this temperature until Approach up to an NCO of 4.66. They were added below 90.00 grams of PEG 300. When the NCO was equal to 0, the reaction to 60 ° C and 14.42 grams of triethylamine were added. Subsequently, 73.51 grams of methoxypropanol were added. Be the reactor was cooled to room temperature and the reaction.

Example 10

300.00 grams of PEG 600 were heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 55.57 grams of IPDI. It remained at this temperature until we approached a NCO of 0. The reaction was cooled to 60 ° C and 88.89 grams of methoxypropanol The reactor was cooled to room temperature and was given The reaction is over.

Example eleven

300.00 grams of PEG 600 together with 4.00 grams of Reactint Blue X3LV (Milliken) were heated to 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 55.57 grams of IPDI. Be maintained at this temperature until we approached a NCO of 0. It cooled the reaction to 60 ° C and 88.89 grams of methoxypropanol The reactor was cooled to room temperature and He terminated the reaction.

Example 12

300.00 grams of PEG 600 together with 4.00 grams of Reactint Red X65 (Milliken) were heated to 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 55.57 grams of IPDI. Be maintained at this temperature until we approached a NCO of 0. It cooled the reaction to 60 ° C and 88.89 grams of methoxypropanol The reactor was cooled to room temperature and He terminated the reaction.

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Example 13

300.00 grams of PEG 600 together with 4.00 grams of Reactint Yellow X15 (Milliken) were heated to 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 55.57 grams of IPDI. Be maintained at this temperature until we approached a NCO of 0. It cooled the reaction to 60 ° C and 88.89 grams of methoxypropanol The reactor was cooled to room temperature and He terminated the reaction.

Example 14

300.00 grams of PEG 600 were heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 55.57 grams of IPDI. It remained at this temperature until we approached a NCO of 0 4.00 grams of Drimaren Blau HF-RL was added (Clariant) ½ hour later the reaction was cooled to 60 ° C and added 88.89 grams of methoxypropanol. The reactor was cooled to room temperature and the reaction was terminated.

Example fifteen

300.00 grams of PEG 600 together with 4.00 grams of Reactint Blue X3LV (Milliken) were heated to 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 55.57 grams of IPDI. Be maintained at this temperature until we approached a NCO of 0 added 4.00 grams of Drimaren Rot HF-G (Clariant) ½ hour later the reaction was cooled to 60 ° C and added 88.89 grams of methoxypropanol. The reactor was cooled to room temperature and the reaction was terminated.

Example 16

300.00 grams of PEG 600 together with 4.00 grams of Reactint Blue X3LV (Milliken) were heated to 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 55.57 grams of IPDI. Be maintained at this temperature until we approached a NCO of 0 added 4.00 grams of Drimaren Gelb HF-R (Clariant) ½ hour later the reaction was cooled to 60 ° C and added 88.89 grams of methoxypropanol. The reactor was cooled to room temperature and the reaction was terminated.

Example 17

300.00 grams of PEG 300 were heated to 100 ° C with constant flow of N2 for ½ hour to extract the Water. It was subsequently cooled to 80 ° C to add 111.14 grams of IPDI It remained at this temperature until we approached an NCO of O. The reaction was cooled to 60 ° C and 102.78 grams were added. of methoxypropanol. The reactor was cooled to room temperature and The reaction was terminated.

Example 18

300.00 grams of PEG 400 were heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 83.36 grams of IPDI. It remained at this temperature until we approached a NCO of 0. The reaction was cooled to 60 ° C and 95.84 grams of methoxypropanol The reactor was cooled to room temperature and was given The reaction is over.

Example 19

300.00 grams of PEG 1000 were heated to 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 33.34 grams of IPDI. It remained at this temperature until we approached a NCO of 0. The reaction was cooled to 60 ° C and 83.33 grams of methoxypropanol The reactor was cooled to room temperature and was given The reaction is over.

Example twenty

300.00 grams of PEG 1500 were heated to 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 22.23 grams of IPDI. It remained at this temperature until we approached a NCO of 0. The reaction was cooled to 60 ° C and 83.33 grams of methoxypropanol The reactor was cooled to room temperature and was given The reaction is over.

Example twenty-one

300.00 grams of PEG 800 were heated to 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 41,675 grams of IPDI. It remained at this temperature until we approached a NCO of 0. The reaction was cooled to 60 ° C and 83.33 grams of methoxypropanol The reactor was cooled to room temperature and was given The reaction is over.

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Example 22

100.00 grams of Hoopol 523 (Synthesia) (Butanediol polyadipate of 1000 molecular weight), 14.19 grams of PEG 300 and 13.41 grams of DMPA were heated at 100 ° C with flow N2 constant for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 63.87 grams of IPDI. Be maintained at this temperature until we approached a NCO of 1.75. The reaction was cooled to 60 ° C and 47.87 grams of methoxypropanol Subsequently, 9.61 grams of triethylamine The reactor was cooled to room temperature and was given The reaction is over.

Example 2. 3

100.00 grams of Hoopol 523 (Synthesia), 30.00 grams of PEG 300 and 26.83 grams of DMPA were heated to 100 ° C with constant flow of N2 for ½ hour to extract water. Be subsequently cooled to 80 ° C to add 133.37 grams of IPDI. Be maintained at this temperature until we approached a NCO of 4.66. The reaction was cooled to 60 ° C and 72.55 grams of methoxypropanol Subsequently 19.23 grams of triethylamine The reactor was cooled to room temperature and was given The reaction is over.

Example 24

150.00 grams of CAPA HC11O0 (Solvay) se heated at 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of isophoron diisocyanate (IPDI). He kept this temperature until approaching a NCO of 5.44. They were added 82.91 additional grams of IPDI and then 313.78 grams of polyethylene glycol (PEG) 300. When the NCO was equal to 0 it cooled the reaction to 60 ° C and 12.34 grams of triethylamine were added. Subsequently 153.34 grams of methoxypropanol were added. Be cooled the reactor to room temperature and terminated the reaction.

In this case, the composition obtained is substantially a mixture of the compositions of examples 1 and 17 above.

In fact, this example is a concrete case of a particularly advantageous embodiment of the invention, both from the point of view of the composition and from the point of view in view of the manufacturing procedure used. Effectively, very good results are obtained in the case of compositions that they comprise a mixture of a component that has an acidic group lateral carboxylic, forming a salt with triethylamine and a component without any side carboxylic acid group.

Example 25

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Blue X3LV (Milliken) was heated to 100 ° C with constant flow of N2 for ½ hour to extract the Water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI It remained at this temperature until we approached an NCO of 5.44. An additional 82.91 grams of IPDI was added and a continued 313.78 grams of PEG 300. When the NCO was equal to 0 The reaction was cooled to 60 ° C and 12.34 were added. grams of triethylamine Subsequently 153.34 grams were added. of methoxypropanol. The reactor was cooled to room temperature and  He terminated the reaction.

Example 26

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Red X65 (Milliken) were heated to 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until we approached a NCO of 5.44. An additional 82.91 grams of IPDI was added and a continued 313.78 grams of PEG 300. When the NCO was equal to 0 The reaction was cooled to 60 ° C and 12.34 were added. grams of triethylamine Subsequently 153.34 grams were added. of methoxypropanol. The reactor was cooled to room temperature and  He terminated the reaction.

Example 27

150.00 grams of CAPA HC1100 (Solvay) along with 4.00 grams of Reactint Yellow X15 (Milliken) was heated to 100 ° C with constant flow of N2 for ½ hour to extract the water. It was subsequently cooled to 80 ° C to add 66.69 grams of IPDI. It remained at this temperature until we approached a NCO of 5.44. An additional 82.91 grams of IPDI was added and then 313.78 grams of PEG 300. When the NCO was equal to 0, the reaction up to 60 ° C and 12.34 grams of were added triethylamine Subsequently 153.34 grams of methoxypropanol The reactor was cooled to room temperature and He terminated the reaction.

Claims (38)

1. Compound of general formula

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(I) R-X - (- A-X '-) m (-B-X '' -) n - R ' where R and R 'are monoethylene glycol, polyethylene glycol molecular weight less than 1500, polyethylene glycol monoether weight molecular less than 1500, primary or secondary monoamine weight molecular less than or equal to 2000, or mixtures of the above, X, X 'and X' 'are an aliphatic diisocyanate of molecular weight less than 1000, preferably less than 500, A is a linear aliphatic polyester of weight molecular less than 1000, an aliphatic polyester with a single branching, consisting of a carboxylic acid functional group or a group -SO 3 H, of molecular weight less than 1000, a polyether linear aliphatic of molecular weight less than 1000, a polyether aliphatic with a single branch, consisting of a group functional carboxylic acid or a group -SO3H, by weight molecular less than 1000, a linear aliphatic polycaprolactone of molecular weight less than 1000, or an aliphatic polycaprolactone with a single branch, consisting of an acid functional group carboxylic or a -SO3H group, of molecular weight less than 1000, m is 0 or 1 B is an aliphatic diol of lower molecular weight of 1000 and with a single branch, consisting of a group carboxylic acid functional or a group -SO3H, n is 0 or 1, where the molecular weight of said compound is greater than 550, and where the value of NCO is equal to 0. 2. A compound according to claim 1, characterized in that its molecular weight is between 550 and 5000, preferably between 550 and 2500, and most preferably between 550 and 1500. 3. Compound according to one of claims 1 or 2, characterized in that it is linear. 4. Compound according to any of claims 1 to 3, characterized in that said polyethylene glycol monoether is polyethylene glycol monomethyl ether of molecular weight less than 1500. 5. A compound according to any of claims 1 to 4, characterized in that said amine is monoethanolamine, diethanolamine, polyoxyalkylene amine, methoxypropylamine, 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, or aminoacetic acid. 6. Compound according to any one of claims 1 to 5, characterized in that X, X 'and X''are hexamethylene diisocyanate, isophoron diisocyanate, dicyclohexylmethyl diisocyanate, tetramethylxilylene diisocyanate, xylylene diisocyanate, or trimethylhexamethylene diisocyanate. 7. Compound according to any of claims 1 to 6, characterized in that said polyester is formed from a linear aliphatic diol of the group consisting of ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol, neopentyl glycol and 2,2- (bishydroxymethyl acid) ) propionic, and an aliphatic diacid
linear. 8. A compound according to claim 7, characterized in that said diol is butanediol and said diacid is adipic acid. 9. Compound according to any of claims 1 to 8, characterized in that said polyether is formed from a linear aliphatic diol of the group consisting of ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol, and neopentyl glycol. 10. A compound according to any one of claims 1 to 9, characterized in that said polycaprolactone is formed from a gamma-caprolactone and using as a chain initiator a linear aliphatic diol of the group consisting of ethylene glycol, hexanediol, butanediol, propylene glycol, diethylene glycol, methylpropyl glycol , neopentyl glycol, and 2,2- (bishydroxymethyl) propionic acid.

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11. Compound according to any of claims 1 to 6, characterized in that A is a compound of the group consisting of hexanediol adipate, butanediol adipate, neopentyl glycol adipate, 2-methylpropanediol adipate, diethylene glycol adipate, and mixtures of the foregoing. 12. Compound according to any of claims 1 to 11, characterized in that said polycaprolactone is formed from 2,2- (bishydroxymethyl) propionic acid as a chain initiator. 13. Compound according to any of claims 1 to 12, characterized in that B is 2,2- (bishydroxy- acid
methyl) propionic. 14. A compound according to any one of claims 1 to 13, characterized in that n is 0 if m = 1 and A has a branching, consisting of a carboxylic acid functional group or a -SO3H group. 15. Compound according to any of claims 1 to 13, characterized in that n is 1 if m = 0 or if m = 1 and A is linear. 16. Compound according to any of claims 1 to 13, characterized in that m is 0 and n is 0. 17. Compound according to any of claims 1 to 16, characterized in that it comprises a dye. 18. Compound according to claim 17, characterized in that said dye is linked to said compound through an -OH group of the dye and an NCO group of the compound. 19. Compound according to one of claims 17 or 18, characterized in that said compound has said dye in a proportion less than or equal to 0.5% by weight, preferably less than or equal to 0.4% by weight with respect to the total weight of the compound . 20. Composition comprising at least one first compound of general formula (I) according to any of the claims 1 to 19, wherein R, R ', X, X', X '', A, m, B, and n they have the general meaning indicated above, and a solvent, preferably water, ethanol, isopropanol or methoxypropanol 21. Composition according to claim 20, characterized in that it comprises at least a second compound of general formula (I), wherein said second compound has a different molecular weight of said first compound. 22. Composition according to one of claims 20 or 21, characterized in that it comprises a cosolvent. 23. Composition according to claim 22, characterized in that said cosolvent is an alcohol. 24. Composition according to claim 23, characterized in that said alcohol is ethanol, isopropanol or methoxypropanol. 25. Composition according to claim 22, characterized in that said cosolvent is N-methylpyrrolidone. 26. Composition according to any of claims 20 to 25, characterized in that it has a water content of less than 15% by weight with respect to the total weight of the compound of the general formula (I). 27. Composition according to any of claims 20 to 26, characterized in that it comprises a dye. 28. Composition according to claim 27, characterized in that said dye has a proportion less than or equal to 0.5% by weight, preferably less than or equal to 0.4% by weight with respect to the total weight of compound of general formula (I) . 29. Composition according to any one of claims 20 to 28, characterized in that it is a mixture of a first compound of general formula (I) with a branching consisting of a carboxylic acid functional group or a -SO3H group and at least a second compound of general formula (I) with no branching consisting of a carboxylic acid functional group or a -SO 3 H group, wherein said second compound has mn equal to 0. Composition according to any one of claims 20 to 29, characterized in that the concentration of compounds of general formula (I) is comprised between 50-70% by weight with respect to the total weight of compound of general formula (I). Composition according to any one of claims 20 to 29, characterized in that the concentration of compounds of general formula (I) is comprised between 70-90% by weight with respect to the total weight of compound of general formula (I), and preferably is of 80% 32. Composition according to any one of claims 20 to 31, characterized in that it additionally comprises a volatile amine which forms a salt with said carboxylic acid or -SO 3 H, preferably ammonia or triethylamine.

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33. 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 19, wherein R, R ', X, X' , X '', A, m, B, and n have the general meaning indicated above, on said cellulosic sheet material by flexography. 34. 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 20 to 32 on said cellulosic sheet material by flexography. 35. 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 19, wherein R, R ', X, X' , X '', A, m, B, and n have the general meaning indicated or above, on said cellulosic sheet material by gravure. 36. 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 20 to 32 on said cellulosic sheet material by gravure. 37. Use of a compound of general formula (I) according to any of claims 1 to 19, wherein R, R ', X, X ', X' ', A, m, B, and n have the indicated general meaning previously, for the manufacture of a watermark in a cellulosic sheet material. 38. Use of a composition according to any of claims 20 to 32, for the manufacture of a brand at water in a cellulosic sheet material.