Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
  • C08G18/4269—Lactones
  • C08G18/4277—Caprolactone and/or substituted caprolactone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/10—Watermarks
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
  • C08G18/348—Hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/08—Polyurethanes from polyethers

Definitions

• the invention relates to compounds and/or compositions for producing watermarks in cellulosic sheet materials, in particular the invention relates to compounds having the general formula (I)
• the invention also relates to methods for producing watermarks on cellulosic sheet materials and to uses of compounds having the general formula (I) and compositions containing them for producing watermarks on cellulosic sheet materials.
• compositions and methods for producing watermarks are known. However, it is usually necessary to use compositions containing substances that are more or less toxic and/or difficult to handle. In addition, they are methods that are suitable for manufacturing large batches, and therefore they are expensive to apply to the production of small or medium size batches.
• Document ES 2.115.002 describes printing inks based on polyurethane resins that have a high molecular weight. These resins have some dense portions in urethane links and other scarce portions in urethane links and they are particularly designed for use on plastic bags and packaging containers.
• Document US 6.933.329 describes some inks for ink jet printing systems that comprise some polyurethanes with molecular weights between 4791 and 7530.
• Document US 5.973.062 describes the chemical combination between some colouring agents and some polyurethanes for producing inks for rotogravure printing.
• the aim of the invention is to overcome these drawbacks. This purpose is achieved by means of a compound having the general formula
• R and R' are monoethyleneglycol, polyethyleneglycol having a molecular weight less than 1500, polyethyleneglycol monoether having a molecular weight less than 1500, primary or secondary monoamine with a molecular weight less than or equivalent to 2000, or mixtures thereof,
• X, X' y X" are an aliphatic diisocyanate with a molecular weight less than 1000, preferably less than 500,
• A is an aliphatic linear polyester with a molecular weight less or equal than 1000, an aliphatic polyester with single branching, consisting of a functional carboxylic acid group or a -SO 3 H group, with a molecular weight less or equal than 1000, an aliphatic linear polyester with a molecular weight less or equal than 1000, an aliphatic polyester with single branching, consisting in a functional carboxylic acid group or a -SO 3 H group, with a molecular weight less or equal than 1000, an aliphatic linear polycaprolactone with a molecular weight less or equal than 1000, or an aliphatic polycaprolactone with a single branching, consisting of a functional carboxylic acid group or a -SO 3 H group, with a molecular weight less or equal than 1000,
• n 0 or 1
• B is an aliphatic diol with a molecular weight less than 1000 and with a single branching, consisting in a functional carboxylic acid group or a -SO 3 H group,
• n 0 or 1
• the molecular weight of said compound is between 550 and 4000, preferably excluding that it has a molecular weight of 1000,
• the compounds having general formula (I) allow a combination of properties to be obtained, which makes them particularly suitable for use in the production of watermarks.
• They are non-reactive oligourethanes, since they do not have any free NCO groups.
• These compounds have a low viscosity (owing to their reduced molecular weight, the few or non-existent side branching and the virtually nonexistent cross-linking), a high penetration level in a cellulosic sheet material, a low sideways migration and a good solidity with respect to water and organic solvents (thanks to the oligourethane affinity to cellulosic material and, in the case where a functional carboxylic acid group or -SO 3 H lateral group is present, thanks to their reactive nature with the cellulosic material), they are soluble or can disperse in aqueous solutions and/or in organic solvents, they are easy to handle, etc.
• ether groups or -CH 2 - which means that they have a low refraction index, in fact their refraction index is between 1.5 and 1.6.
• they Preferably they have an index value close to 1.54 (for example, between 1.52 and 1.56), which requires limiting the amount of functional polar groups, and therefore a compromise solution must be reached between the attachment capacity to the cellulosic material, the refraction index and the viscosity.
• the compound contains a (and preferably only one) functional carboxylic acid group or a -SO 3 H group, or, in general, a functional anionic type group.
• the functional group be carboxylic acid owing to its weak acidity, which favours the conversion of carboxylate (which is its initial format, when applied) into carboxylic on the substrate, which, in the presence of water and solvents, has a solider structure than the carboxylate.
• the primary or secondary monoamines comprise a solubilising group that advantageously is a polyethyleneglycol, a carboxylic acid or a sulfonic acid.
• the molecular weight of compound (I) is between 550 and 2500, and preferably between 550 and 1500.
• compound (I) is linear.
• the viscosity is a very important parameter when producing watermarks. If viscosity is too low it can lead to problems of insufficient solidity, and excessive sideways migration, etc. On the other hand, if viscosity is too high it can create problems of poor penetrability.
• a linear compound will have a lower viscosity than a branched compound. For its part, branching will affect viscosity to a greater or lesser degree according to the properties thereof: the presence of lateral polar groups (such as for example -OH type) will consequently form hydrogen bridge type links, etc.
• the compound be linear with the sole exception of having a lateral group comprising the said carboxylic acid or -SO 3 H groups.
• polyethyleneglycol monoether be polyethylene monomethlyether with a molecular weight less than 1500.
• R and R' are linear and crystalline or semicrystalline polyethyleneglycols, such as for example PEG 400, as a compound is obtained that has a suitable viscosity and a refraction index close to that of the cellulosic material.
• the amine is monoethanolamine, diethanolamine, polyoxyalkylenemonoamine, metoxypropylamine, 2-aminoethanesulfonic acid
• taurine 3-aminopropanesulfonic acid (homotaurine), or aminoacetic acid (glycine).
• the polyoxyalkylenemonoamine is preferably a primary monoamine linked to a polyether, where the polyether is made from a mixture of ethylene oxide
• EO ethylene glycol
• PO propylene oxide
• EO propylene oxide
• PO propylene oxide
• molar ratio between PO and EO is 9/1 and the molecular weight is 600 (sold under the name of
• X, X' and X" are hexamethylene diisocyanate, isoforon diisocyanate (IPDI), dicyclohexylmethyl diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, or trimethylhexamethylene diisocyanate.
• IPDI isoforon diisocyanate
• dicyclohexylmethyl diisocyanate dicyclohexylmethyl diisocyanate
• tetramethylxylylene diisocyanate tetramethylxylylene diisocyanate
• xylylene diisocyanate or trimethylhexamethylene diisocyanate.
• the polyester is made from an aliphatic linear diol from the group made up of ethyleneglycol, hexanediol, butanediol, propyleneglycol, diethyleneglycol, methylpropylglycol, neopentylglycol 2,2-
• diol (bishydroxymethyl)propionic acid, and an aliphatic linear diacid. It is particularly advantageous that the diol be butanediol and that the diacid be adipic acid.
• the polyester is crystalline or semicrystalline as in this case a watermark is obtained that has a more solid structure in the presence of water and organic solvents.
• the polyester is made from an aliphatic linear diol from the group made up of ethyleneglycol, hexanediol, butanediol, propyleneglycol, diethyleneglycol, methylpropylglycol, and neopentylglycol.
• the polycaprolactone is made from a gamma-caprolactone and using as the chain initiator an aliphatic linear from the group containing ethyleneglycol, hexanediol, butanediol, propyleneglycol, diethyleneglycol, methylpropylglycol, neopentylglycol, and 2,2-(bishydroxymethyl)propionic acid. It is particularly interesting that the polycaprolactone be made from 2,2-(bishydroxymethyl)propionic acid as chain initiator.
• An example of these polycaprolactones is the product sold under the name of HC 1 100® by Solvay Caprolactones (which is a division of Solvay S.
• A. which is a caprolactone polyester that includes a diol in the chain and which has a free lateral acid group. 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 melting point between 4O 0 C and 45 0 C.
• a preferable alternative is that A be a compound from the group containing hexanediol adipate, butanediol adipate, neopentylglycol adipate, 2- methylpropanodiol adipate, diethyleneglycol adipate, and mixture of these.
• Advantageously B is 2,2-(bishydroxymethyl)propionic acid.
• compound (I) Another preferable alternative of compound (I) is when m is 0 and n is 0.
• colouring agent comprises a colouring agent.
• a colouring agent can be included so that it is chemically linked to the compound (so that the compound, overall, comprises the colouring agent), or it can be included in the composition used to make the watermark, as a further component thereof.
• these colouring agents are the Drimaren colouring agents sold by the Pigments and Additives division, of the Clariant Group.
• the colouring agent is chemically linked to compound (I)
• Some examples of the colouring agents of this type are the Reactint® colouring agents, sold by Milliken Chemical, which is a division of Milliken & Company. It may also be interesting to combine colouring agents of both types, depending of the colour to be obtained.
• the compound contains the colouring agent is a proportion less than or equivalent to 0.5% by weight, preferably less than or equivalent to 0.4% by weight with respect to the total weight of the compound, both in the event that the colouring agent is chemically linked to the compound and in the event that both are dissolved and/or dispersed in a composition. It has been observed that using higher percentages deteriorates the quality of the transparency of the watermark, because the refraction index of the colouring agent (particularly red and blue) is higher than the refraction index of the cellulosic material.
• a preferable embodiment of the invention is obtained when a composition is prepared and used that comprises at least a first compound having the general formula (I) according to the invention, where R, R', X 1 X', X", A, m, B, and n have the general meaning indicated above, and a solvent, preferably water, ethanol, isopropanol or metoxypropanol.
• a solvent preferably water, ethanol, isopropanol or metoxypropanol.
• the composition comprises at least a second compound having general formula (I), where the second compound has a different molecular weight to the first compound.
• the viscosity of the composition is adjusted. So, for example, when the synthesis is done in two stages the viscosity and attachment to the substrate (cellulose) can be adjusted; in other words, a balance is achieved between a low viscosity and a good fixation.
• the mixture is made between a product that has adheres or fixes well to cellulosic (but is quite viscose depending on the type of paper, particularly thick, dense paper) and another one that is more fluid and which even gives more transparency (because it is less functionalized, does not have carboxylic groups or has less of them, and has an even lower refraction index)
• the composition can comprise a cosolvent which, preferably is an alcohol, preferably ethanol, isopropanol or metoxypropanol.
• a cosolvent which, preferably is an alcohol, preferably ethanol, isopropanol or metoxypropanol.
• the cosolvente is N-methylpyrrolidone.
• Another interesting alternative is obtained when the main solvent is an alcohol and it has water as its cosolvent, in small proportions. This way, with a small amount of water, a composition can be obtained that is suitable for using with water sensitive cellulosic materials (for example, owing to wrinkling problems). It must be taken into account that it is very normal to use alcohols that contain small amounts of water (such as for example, ethanol).
• the composition has a water content less than 15% by weight with respect to the overall weight of the compound having general formula (I) in the event that it has to be used with a cellulosic material that is affected by water.
• the particle size of the dispersion is less than 10 nanometers, to obtain a good penetration.
• the composition be a mixture of a first compound having general formula (I) with a branch consisting of a functional carboxylic acid group or a -SO 3 H group and at least one second compound having general formula (I) with no branch consisting of a functional carboxylic acid group or a -SO 3 H group, where said second compound has m and n equal to 0.
• the concentration of compounds having general formula (I) is between 50-70% by weight with respect to the overall weight of the composition having general formula (I). These concentrations are the most suitable for use in the production of watermarks. Concentrations less than 50% make the watermark transparency insufficient because the pores of the cellulosic material are not filled sufficiently with the compound having general formula (I). It is also It is also advantageous that the concentration of compounds having general formula (I) be between 70-90% by weight with respect to the overall weight of the composition having general formula (I), and it is preferably 80%. In fact, these concentrations are more suitable in terms of production, transport and distribution. Higher concentrations make the composition too viscose to be handled during the production method.
• the composition comprises, in addition, a volatile amine that forms a salt with said carboxylic acid or -SO 3 H, and very preferably said volatile amine is ammonium or triethylamine.
• the salt obtained in this way is water soluble or dispersible and soluble in organic solvents (for example, an alcohol) if an appropriate amount is used.
• the invention also relates to the use of a compound having 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 producing watermarks on a cellulosic sheet material.
• the invention also relates to the use of a composition according to the invention, for the production of a watermark on a cellulosic sheet material.
• a and B when it is indicated that A and B (or the compound on the whole) are linear or have a single branch consisting of a functional carboxylic acid group of a -SO 3 H group, it must be understood in the sense that A and B do not have other branches capable of producing cross-linking.
• the branches capable of producing cross-linking are known by a person skilled in the art. In the event cross-linking occurs, viscosity is increased considerable, which acquires too high a value.
• a and B can include other branches, preferably of the alkylic type but also branches that include some additional functional group providing that cross-linking does not occur because of said additional functional group. Particularly, A and B can have -CH 3 lateral groups.
• the invention also relates to a method for the production of a watermark on a cellulosic sheet material characterized in that it comprises a stage of applying a compound having general formula (I) according to the invention, or a composition according to the invention, to the cellulosic sheet material using flexography or an intaglio printing process.
• a compound having general formula (I) according to the invention or a composition according to the invention, to the cellulosic sheet material using flexography or an intaglio printing process.
• the watermark is produced during the paper manufacturing method.
• rollers with relief drawings are used, generally arranged at a point before the continuous web of wet paper enters the dryers. This way, the web's cellulosic fibres move horizontally (in the direction of the actual paper) so that the paper is thinner and, consequently, more transparent in the area bearing the motif or watermark.
• the rolls with relief drawings "deform" the wet paper so that this deformation remains permanently on the paper after drying.
• Another conventional method for producing motifs or watermarks, and which is also carried out when producing the paper consists in using a tight band around a roller, which bears a relief drawing or the configuration of a watermark.
• This relief drawing comes into contact with the wet paper, which still has a certain degree of plasticity, which allows it to be compressed.
• the area of compressed paper has a smaller amount of trapped air and, therefore, a lower light refraction, which increases the paper's transparency. Consequently, watermarks are currently produced during the paper manufacturing process and they are white and black (in other words, generally, in one colour according to the colour of the paper) because they only deal with transparency, shading and opacity.
• This invention provides for the production of watermarks on papers (generally, cellulosic sheet materials) that have already been produced, in a subsequent stage corresponding to the printing phase. Also, this invention provides for the production of watermarks in colours.
• the compounds and compositions according to the invention can be used as inks for flexography and/or intaglio printing (also known as rotogravure printing). These printing techniques use liquid inks (with a low viscosity) that essentially consist of a solvent and a series of additives (colouring agents, resins, pigments, waxes or plastifying agents, etc.). The liquid inks are applied to the cellulosic support material and the solvent evaporates. When using the compounds and compositions according to the invention, these penetrate inside the cellulosic material reducing its refraction, therefore managing to produce a watermark.
• CAPA ® HC 1100 is a commercial name of a polycaprolactone polyester diol with a pendant carboxylic functional group commercialised by Solvay. It has a molecular weight of 1000 and a typical OH value of 110 mg KOH/g.
• Example 4 150.00 grams of CAPA HC1 100 (Solvay) together with 4.00 grams of Reactint Yellow X15 (Milliken) were heated to 100 0 C with a constant flow of N 2 during 14 hour to extract the water. It was then cooled to 8O 0 C to add 66.69 grams of IPDI. It was kept at this temperature until an NCO of approximately 5.44 was obtained. Then 90.00 grams of PEG 300 were added. When the NCO was equal to 0 the reaction was cooled to 6O 0 C and 12.34 grams of triethylamine were added. Then 76.67 grams of metoxypropanol were added. The reactor was cooled to room temperature and the reaction was considered to have been completed.
• Example 7 150.00 grams of CAPA HC1100 (Solvay) ) were heated to 100 0 C with a constant flow of N 2 during V 2 hour to extract the water. It was then cooled to 80 0 C to add 66.69 grams of IPDI. It was kept at this temperature until an NCO of approximately 5.44 was obtained. Then 90.00 grams of PEG 300 were added. When the NCO was equal to 0, 4.00 grams of Drimaren GeIb HF-R (Clariant). Then V 2 hour later the reaction was cooled to 6O 0 C and 12.34 grams of triethylamine were added. Then 76.67 grams of metoxypropanol were added. The reactor was cooled to room temperature and the reaction was considered to have been completed.
• Example 22 100.00 grams of Hoopol 523 (Synthesia) (butanediol polyadipate with a molecular weight of 1000), 14.19 grams of PEG 300 and 13.41 grams of DMPA were heated to 100 0 C with a constant flow of N 2 during Vi hour to extract the water. It was then cooled to 8O 0 C to add 63.87 grams of IPDI. It was kept at this temperature until an NCO of approximately 1.75 was obtained. The reaction was cooled to 6O 0 C and 47.87 grams of metoxypropanol were added. Then 9.61 grams of triethylamine were added. The reactor was cooled to room temperature and the reaction was considered to have been completed.
• Example 23 100.00 grams of Hoopol 523 (Synthesia), 30.00 grams of PEG 300 and 26.83 grams of DMPA were heated to 100 0 C with a constant flow of N 2 during ⁇ A hour to extract the water. It was then cooled to 8O 0 C to add 133.37 grams of IPDI. It was kept at this temperature until an NCO of approximately 4.66 was obtained. The reaction was cooled to 60 0 C and 72.55 grams of metoxypropanol were added. Then 19.23 grams of triethylamine were added. The reactor was cooled to room temperature and the reaction was considered to have been completed.
• the composition obtained is substantially a mixture of the compositions in Examples 1 and 17 above.
• this example is a specific case of a particularly advantageous embodiment of the invention, both from the point of view of the composition and from the point of view of the production method used.
• compositions that contain a mixture of one component that has a lateral carboxylic acid group, forming a salt with the triethylamine and one component without any lateral carboxylic acid group.
• the colouring agents can be added at the end, with the metoxypropanol, at 0.2 % in the case of yellow, (2 g in the 200 g of metoxypropanol for the 800 g of material), and at 0.1 % in the case of red and blue (1 g in the 200 g of metoxypropanol for the 800 g of material), the colours being Reactint Blue X3LV, Reactint Red X65, and Reactint Yellow X15, all by Milliken.
• the compounds according to the invention can also be used for the production of watermark using the offset system.
• the invention also relates to a method for producing a watermark on a cellulosic sheet material characterized in that it comprises a stage of applying a compound having general formula (I) according to the invention, or a composition according to the invention, where R, R', X, X', X", A, m, B, and n have the general meaning indicated above, to the cellulosic sheet material using offset.
• the properties of a material suitable for use in flexography must be different to the properties of a material that is suitable for use in offset.
• the products must be hydrophobic and soluble in organic, non-polar solvents.
• a suitable choice of R, R', X, X 1 , X" A, B, m and n enables products suitable for use in offset to be obtained.
• the products will have a low molecular weight (between 550 and 1500).
• the composition will have to use non- polar solvents, such as for example alkylobenzenes, to be suitable for use in offset.

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• 2006
  • 2006-07-17 ES ES200601897A patent/ES2265300B1/es active Active
• 2007
  • 2007-07-13 EP EP07786055A patent/EP2061824A1/en not_active Withdrawn
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