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    • 专利摘要:
    Compound for the manufacture of a water-based label in a textile sheet material and a composition, textile material, processes and corresponding uses. Composite for the manufacture of a water-based brand in a textile laminar material, of formula C-w-(a-w)m-(x-w)n-x-(w-a)p-w-c' Where W is a radical from tmdi, ipdi or hdi, Each x is a radical from peg, ppg, dimerdiol or dimethylolpropionic acid, independently of the remaining x, where w- (xw)n -xw has a molecular weight between 750-15,000 g/mol and an nco: oh ratio between 0.9 and 2.1, A is a radical derived from an amine, C and c 'are each, independently of the other, a radical derived from diethanolamine, ch3 -ch2-ch2 -ch2 -nh-ch2 -ch2 -ch2 -yes (och3 )3, glycine, taurine, homotaurine, 2-ethylhexanol, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, monomethylated polyethylene glycols, n, N-dimethylethanolamine, n, n, n'-trimethyl-n'-hydroxyethyl-bisaminoethylether, n, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, 2- (2-dimethylaminoethoxy) ethanol, n, n, n'-trimethylaminoethyl-ethanolamine, dimethylaminopropylamine, or a blocking agent of an isocyanate group, N > 0, m >= 0, p >= 0.
    公开号:ES2644165A1
    申请号:ES201630677
    申请日:2016-05-25
    公开日:2017-11-27
    发明作者:Josep Rocas Sorolla；Berta Solé Porta；Albert PUIGPINÓS COLILLAS
    申请人:Identity Mark S L；Identity Mark SL；
    IPC主号:
    专利说明:

    Field of the Invention
    The invention relates to a compound for the manufacture of a watermark in a textile laminar material with urethane bonds and, optionally, urea, and a composition comprising an emulsion in water of said compound, suitable for the manufacture of a brand water in a textile sheet material, so that a transparency effect on the fabric is achieved.
    The invention also relates to a textile laminar material with a watermark and its manufacturing process.
    State of the art
    In WO 2011/086224 A2 "Compound for the manufacture of a watermark on a textile laminar material and corresponding composition, material, process and use" various polyurethane-type compounds suitable for the manufacture of watermarks on fabrics are described .
    However, it is necessary to synthesize new products without flammable and / or harmful solvents but the same or more resistant to washing.
    Exhibition of the invention
    This purpose is achieved by a compound for the manufacture of a watermark in a textile sheet material, of formula
    C-W- (A-Wlm- (X-W) or-X- (W-A) p-W-C '
    where
    W is a radical from a compound of the group consisting of 2,2,4-trimethylhexamethylene diisocyanate (TMDI), 2,4,4.trimethyl-hexamethylene diisocyanate (TMDI, in fact TMOI is a mixture of the two isomers above) , Soforon diisocyanate <'POI) and hexamethylene diisocyanate (HDI),
    each X is a radical from a compound of the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), dimerdiol and dimethylolpropionic acid, regardless of the remaining X, where at least one X is a radical of a compound of the group formed by polyethylene glycol and polypropylene glycol, and where W- (XW) or XW has a molecular weight between 750-15,000 g / mol and a NeO: OH ratio between 0.9 and 2.1,
    A is a radical from a compound of the group formed by
    NH2-R-NH2 • where Res (CH2) n with n between 1 and 6,
    NHz-R-NH-R ', where R is (CHz) n with n between 1 and 6 and R' is CH, CH, CH, Si (OCH, h or (CH, hSO, H, and
    NHz-R "where R" is (-C Hz-k CH-COOH with n between 1 and 4,
    NH,
    C and 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine (OH-eHz-eHz-NH-eHz-eHz-OH), CH, -CH, -CH, -CH, - NH-CH, -CH, -CH, -Si (OCH, h (for example, the product sold as Dynasylan 1189), glycine (NH, -CH, -COOH), taurine (NH, -CH, CHZ-S03H) , homotaurin (NHr CHrCHrCHr S03H), 2-ethyl hexanol, N- (2-aminoethyl) -3aminopropyltrimethoxysilane (for example, the product marketed as Dynasylan DAMO), bis (trimethoxysilylpropyl) amine (for example the product marketed as Dynasylan 1124 by EVONIK ), monomethylated polyethylene glycols (PEGs) (H (-O-CH, CH2-) nO-CH3), N, N-dimethylethanolamine (DMEA, for example marketed by HUNTSMAN), N, N, N'-trimethyl-N'- hydroxyethyl-bisaminoethylether (for example the product marketed as Jeffcat ZF10 by HUNTSMAN), N, N-bis (3-dimethylaminopropyl) -Nisopropanolamine (for example the product marketed as Jeffcat ZR50 by HUNTSMAN), 2- (2-dimethylaminoethoxy) ethanol ( for example the product marketed as Jeffcat ZR70 by HUNTSMAN), N, N, N'-trimethylaminoethyl ethanolamine (for example the product marketed as Jeffcat Z110 by HUNTSMAN), dimethylaminopropylamine (DMAPA, for example marketed by HUNTSMAN) and a blocking agent of an isocyanate group,
    N> O,
    M> = O,
    P> = O.
    The link between W and X is a urethane type bond, which takes place between the isocyanate groups of the compounds from which W is derived and the OH groups of the compounds from which X is derived.
    The link between W and A is a urea type bond, which takes place between the isocyanate groups of the compounds from which W is derived and the NH2 groups of the compounds from which A.
    The link between W and C can be a urethane or urea type bond, which takes place between the isocyanate groups of the compounds from which W is derived and the OH groups
    or amine of the compounds from which C. comes
    In general, the compound according to the invention comprises a plurality of X. For a given compound it is not necessary that all X be the same, in fact, in many preferred solutions the different X within the same compound according to the invention they are different from each other, since, as will be seen later, in the manufacturing process of the compound according to the invention, W is reacted with a mixture of several different X (strictly speaking, of various compounds originating in X). Therefore, the result of the reaction will be a compound according to the invention in which the Xs that comprise it are also a mixture.
    Dimerdiol is the compound of formula
    OH
    OH
    and is marketed as Pripol 2033 by GRODA.
    The compound N- (2-aminoethyl) -3-aminopropyltrimethoxysilane can be both the origin of a radical A and a radical C or C '.
    The compounds according to the invention, based on polyurethane polymers, make it possible to avoid the use of flammable and / or harmful solvents since they are obtained as aqueous dispersions. They may have high resistance to washing.
    Preferably W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4. Trimethyl-hexamethylene diisocyanate.
    Advantageously, each X is a radical from a compound of the group consisting of polyethylene glycol of molecular weight 400 glmol, polypropylene glycol of molecular weight 2000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the rest
    x.
    Preferably W - (X-W) r. -X -W has a molecular weight between 750-1,000 g / molo and has a molecular weight between 6,000-11,000 g / mol. Be
    He has observed that these two subgroups of molecular weights are particularly advantageous for specific applications, depending on the characteristics of the tissue in which it is desired to make a watermark.
    5 Preferably W - (X-W) n -X-W has a NeO: OH ratio between 1.1 and 1.3 or has a NeO: OH ratio between 1.8 and 2.1.
    10 Advantageously A is a radical from a compound of the group consisting of ethylenediamine, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (such as Dynasylan DAMO), lysine, ethyldiaminopropyl sulfonate (EPS) and hexamethylenediamine, and it is particularly advantageous that A be a radical from ethylenediamine or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (such as Dynasylan DAMO).
    fifteen Preferably eoe 'is a radical from N, N-dimethylethanolamine, CH3-eH2CH, -CH, -N H-CH, -CH, -CH, -Si (OCH3h. N- (2-aminoetit) -3-aminopropyltrimethoxysitano and / or bis (trimethoxysilylpropyl) amine.
    20 25 It is particularly advantageous that e or e 'is a radical from an isocyanate blocking agent. Indeed, the presence of the blocking agent allows, once the brand is being manufactured to water, isocyanates can be unlocked (for example, by raising the temperature), and these isocyanates allow for more cross-linking points that improve the fixation of the molecule in the tissue. Preferably the isocyanate blocking agent is a compound of the group pharmaceutized by pyrazole, 3,5-dimethylpyrazole, ketoximes, aliphatic esters, amides, midases and amines, and most preferably it is 3,5-dimethylpyrazole.
    Additionally, a plurality of particularly interesting compounds are specified in the dependent claims, namely:
    J O -a compound according to the invention in which
    W is a radical from isophane diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    C and C 'are a radical from CH3CH, CH, CH, NHCH, CH, CH, Si (OCH3) "
    M = 0,P = 0,and has a molecular weight between 9,100 and 10,100 g / mol.-a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    M = 0,P = 0,and has a molecular weight between 8,700 and 9,800 g / mol.-a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate, each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, regardless of the remaining X,
    A is a radical from ethylenediamine,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine and
    10 CH3CH, CH, CH, NHCH, CH, CH, Si (OCH3h.
    M> O.
    p> O. 15 and has a molecular weight between 7,300 and 8,300 g / mol.
    - a compound according to the invention in which
    20 W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine and
    CH 3CH, CH, CH, NHCH, CH, CH, Si (OCH3h. 30
    M = O.
    p = O.
    and has a molecular weight between 7,800 and 8,800 g / mol.
    - a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,
    C and C ' They areeveryone,independently of the other, aradical coming froma
    compound of thegroupformedbydielanolamineY
    CH, CH, CH, CH, NHCH, CH, CH, Si (OCH,) "
    M> 0,
    p> O,
    and has a molecular weight between 9,200 and 10,200 g / mol.
    - a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethyl
    hexamethylene diisocyanate,each X is a radical from a compound of the group formed byPolypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid,regardless of the remaining X,
    A is a radical from ethylenediamine,C and C 'are a radical from N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
    M> O,
    p> O,
    and has a molecular weight between 6,200 and 7,200 g / mol.
    -a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethyl
    hexamethylene diisocyanate,each X is a radical from a compound of the group formed by
    molecular weight polypropylene glycol 2,000 g / mol, dimerdiol and dimethylolpropionic acid,regardless of the remaining X,A is a radical from ethylenediamine,
    M> O,
    p> O,
    and has a molecular weight between 9,800 and 10,800 g / mol.
    - a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethyl
    hexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    C and C 'are a radical from N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,M = O,P = O,and has a molecular weight between 6,300 and 7,400 glmol. -a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g / mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X. A is a radical from ethylenediamine,
    C and C 'are CH, CH, CH, CH, NHCH, CH, CH, Si (OCH,) ,.M> O,p> O,
    and has a molecular weight between 8,500 and 9,500 glmol. -a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    X is a radical from polyethylene glycol of molecular weight 400 glmol,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of CH3CH2CH2CH2NHCH2CH2CH2Si (OCH3h, 2-ethylhexanol and glycine,
    M = 0,
    P = 0,
    And it has a molecular weight between 740 and 880 g / mol.
    - a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a compound of the group consisting of polyethylene glycol of molecular weight 400 g / mol, and dimerdiol,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of CH3CH2CH2CH2NHCH2CH2CH2Si (OCH3h. 2-ethylhexanol and glycine,
    M = O,
    P = O,
    and has a molecular weight between 780 and 880 glmol.
    -a compound according to the invention in which
    5 W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    each X is a radical from a polyethylene glycol compound of molecular weight 400 g / mol, and dimerdiol, of thegroupformedby
    10 e and e 'are each, independently of the other, a radical from the group compound formed by e H3e HzeHzeHzNHe HzeHzeHzSi (OeH3h. ethylhexanol and N, N-dimethylethanolamine,a 2
    fifteen M = 0, P = 0,
    and has a molecular weight between 780 and 880 g / mol.
    twenty -a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethylhexamethylene diisocyanate,
    25 each X is a radical from a polyethylene glycol compound of molecular weight 400 g / mol, and dimerdiol,of thegroupformedby
    JO e and e 'are each, independently of the other, a radical from a group compound consisting of bis (trimethoxysilylpropyl) amine, 2-ethylhexanol and N, N-dimethylethanolamine,
    M = 0,
    p = o.
    and has a molecular weight between 790 and 890 g / mol.
    - a compound according to the invention in which
    W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethyl
    hexamethylene diisocyanate,X is a radical from polyethylene glycol of molecular weight 400 glmol,
    and and e 'They areeveryone,independently of the other, aradical coming froma
    compound of thegroupformedby3.5dimethylpyrazole,
    CH, CH, CH, CH, NHCH, CH, CH, Si (OCH, h and DMEA.
    M = O.
    p = O.
    And it has a molecular weight between 750 and 850 g / mol.
    A subject of the invention is also a composition for the manufacture of a watermark in a textile sheet material comprising an emulsion of a compound according to the invention in water. Indeed, these compounds allow to generate an emulsion in water, which avoids the need to use flammable and / or harmful solvents. In some cases, the compounds according to the invention also allow to obtain watermarks that are more resistant to washing than the known compounds.
    A subject of the invention is also a textile sheet material which is formed with a transparent textile material characterized in that it comprises an area impregnated with a compound according to the invention, wherein said impregnated zone is a watermark.
    Another object of the invention is a process for manufacturing a watermark on a textile sheet material, which is formed with a transparent textile material, characterized in that it comprises a printing stage in which an area of said textile sheet material is impregnated. with a compound according to the invention (or a composition according to the invention), thus generating a watermark.
    Finally, the invention also aims at using a compound according to the invention (or a composition according to the invention), for impregnating an area of a textile sheet material, wherein said textile sheet material is formed with a transparent textile material, thus generating a watermark. Preferably the textile sheet material is a label and the watermark forms a security element. In the case of using the watermark as a safety element, it may be permissible that the watermark is not very resistant to washing, since its main function may be to inform the buyer of the origin of the garment, to "quality assurance certificate" mode. In this case, once the purchase has been made, it is no longer necessary for the security element to continue existing.
    Brief description of the drawings
    Other advantages and features of the invention can be seen from the following description, in which, without any limitation, preferred embodiments of the invention are mentioned, mentioning the accompanying drawings. The figures show:
    Fig. 1, an image by scanning electron microscope (SEM) of a polyester fabric.
    Fig. 2, an image by scanning electron microscope (SEM) of a cotton fabric, named "sample 1".
    Fig. 3, an image by scanning electron microscope (SEM) of another cotton fabric, called ~ sample 2 ".
    Fig. 4, a scanning electron microscope (SEM) image of a 65/35 polyester / cotton blend fabric of 122.6 g / m2.
    Fig. 5, an image by scanning electron microscope (SEM) of a 65/35 polyester / cotton blend fabric of 237.7 g / m2.
    Fig. 6, an image by scanning electron microscope (SEM) of a 65/35 polyester / cotton blend fabric of 410.8 g / m '.
    Fig. 7, table with a summary of the main characteristics of synthesized products.
    Fig. 8, table with the results of the applications on polyester.
    Fig. 9, table with the results of the applications on cotton.
    Fig. 10, table with the results of applications on polyester / cotton fabrics (65% / 35%).
    Fig. 11, image of a sample of a cotton fabric printed with a watermark with the compound of example 3.
    Fig. 12, image of a sample of a polyester fabric printed with a watermark with the compound of example 11.
    Fig. 13, image of a sample of a polyester fabric printed with a watermark with the compound of example 12.
    Fig. 14, image of a sample of a polyester fabric printed with a watermark with the compound of example 13.
    5 Fig. 15, image of a sample of a cotton fabric printed with a watermark with the compound of example 19.
    Fig. 16, image of a sample of a polyester fabric printed with a watermark with the compound of example 20.
    10 Fig. 17, image of a sample of a cotton fabric printed with a watermark with the compound of example 22 with 35.0% solids.
    fifteen Fig. 18, image of a sample of a polyester fabric printed with a watermark with the compound of example 22 with 40.7% solids. Figs. 19 and 20, tables with a summary of the examples made.
    20 25 JO DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION In a first stage of the synthesis reaction of the compounds according to the reaction, a prepolymer (W- (XW) nXW) is formed by reacting the -OH groups of the compounds of which X proceeds with the -NCO groups of the compounds from which W. comes. In the second reaction stage the above prepolymer is dissolved in a THF (tetrahydrofuran), MEK (methyl ethyl ketone) and / or acetone (for example) solvent. , those marketed by PANREAC). These solvents preferably represent between 15% and 75% with respect to the weight of the prepolymer. Subsequently, an emulsion is formed with water, obtaining products containing between 20 and 80% solids.
    The above prepolymer can be elongated by reaction with compounds from which radical A will be obtained.
    Finally, the prepolymer (elongated or not) is capable of reacting with
    5 compounds from which the radicals e and e 'will be obtained. In part, the coating also takes place with water, preferably between 1 and 20% of the free NeO is coated with water.
    Compounds of this type can also be synthesized by blocking part or all of the
    10 isocyanate groups with a blocking agent (for example, pyrazole, 3,5-dimethylpyrazole, ketoximes, aliphatic esters, amides, imides and amino acids). Thus it will be possible to have more cross-linking points in the molecule that are fixed to the tissue once the isocyanate has been unlocked and reacted with the tissue. But it should be noted that the use of these compounds implies the need to subject the tissue to temperatures
    15 high for the release and reaction of these groups.
    The viscosity and particle size of the product as well as hydrophobia / hydrophilicity and the fabric of the fabric are very important parameters to take into account since they affect the speed of penetration of the product into the tissue. Apart from these 20 parameters, you should also take into account the treatments that have been done on the fabric, such as the softener finish that changes the hydrophilicity of cotton. In Figs. 1 to 6 various types of tissues are shown. As can be seen in these Figs., There are significant differences between the two cotton samples, sample 1 being busier than 2. This leads to some
    25 cases, within the same type of fabric, the products must also be adapted to act as a watermark. The weight is also important as can be seen in the 3 samples of polyester / cotton blend fabric (65% / 35%). All this makes it advisable to "customize" each compound for each type of fabric, in order to obtain optimal results.
    Examples of compound synthesis
    Example 1
    In a 700ml reactor 128.00g of molecular weight polypropylene glycol are added
    2000g / mol (Voranol 2000L, DOW), 3.90g of dimerdiol (Pripol 2033, CRODA) and 4.20g of DMPA (dimethylolpropionic acid, HUNTSMAN). At 120 'C and at 160rpm, it is done
    vacuum to remove the water that the polyols can contain and once dry the temperature is lowered to 60 ° C and 27.80g of IPDI (Isophorone Diisocyanate, Vestanat IPDI, EVONIK) are added. It is allowed to react at 85 ° C until it reaches an NCO = 1,167%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and in 5 minutes 44.339 of dry MEK (PANREAC), when the temperature reaches 55 ° C they are added with funnel of addition and in 20-35 minutes
    174.80g of dried acetone (PANREAC).
    Once the solvents have been added and at 20 ° C, 3,339 triethylamine (BASF) are added, the emulsion is immediately made with 245.00g of cold water in 30-40 minutes and at 250-400rpm. Subsequently, 0.329 of EDA (ethylenediamine, PANREAC) are added
    in 8.78g of water, at 3 minutes 0.55g of DEA (diethanolamine, PANREAC) in 8.78g
    of water and immediately 5.30g of N- (n-Butyl) -3-aminopropyltrimethoxysilane
    (Dynasylan 1189, EVONIK) in 5.30g of acetone. 10 minutes after the addition,
    distill the solvents at 50 ° C. A bluish white emulsion is obtained.
    Example 2In a 700ml reactor 53.73g of polyester (Hoopol S-1015-120,
    SYNTESIA) and at 120 ° C it is empty for 40 minutes to remove the water they may contain. Under a stream of nitrogen, 45.30g of HDI (Hexamethylene diisocyanate, Desmodur H, BAYER) are added. It is allowed to react at 80-85 ° C and at 160 rpm until it reaches an NCO = 18.062%, in this case the percentage of experimental NCO obtained by tritation is 17,390%. Then, the temperature is lowered to 60 ° C and
    add 7.81g of NPG (neopentyl glycol, PERSTORP) and 8.20g of DEG (diethylene glycol, PANREAC) in 8.28g of dry acetone (PANREAC). It is allowed to react until it reaches
    a NCO = 3.692%, in this case the percentage of experimental NCO obtained by tritation is 3.428%. At 50 ° C, they are added with addition funnel and in 20 · 35 minutes
    153. 17g of dried acetone. Once the solvent is added, 14.13g of EPS (ethyldiaminopropyl) are added
    sulphonate, RASCHIG) in 2.17g of 1N KOH (potassium hydroxide, PANREAC) and 13.86g
    of distilled water, the emulsion is immediately made with 222.66g of distilled water 5 in 30-40 minutes and at 250-400 rpm. The solvents are distilled at 10 ° C 10 minutes after the addition. A bluish white emulsion is obtained.
    10 Example 3 In a 700ml reactor 90.24g of molecular weight polypropylene glycol are added
    2000glmol (Voranol 2000L, DOW) and 2.74g of dimerdiol (Pripol 2033, CRODA). At 80'C
    and at 160 rpm, it is made empty to remove the water that the polyols can contain and once dry, 4.25g of DMPA (dimethylolpropionic acid, HUNTSMAN) is added with
    15 stream of nitrogen, leave stirring for 5 minutes and add 20.90g of IPDI
    (Isophorone diisocyanate, Vestanat IPDI, EVONIK). It is allowed to react until it reaches an NCO = O.875%, in this case the percentage of experimental NCO obtained by tritation is 0.766%. Then, the nitrogen is disconnected and the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and
    20 in 5 minutes 27.38g of dry MEK (PANREAC), when the temperature reaches 55'C
    75.38g of dried acetone are added with addition funnel and in 20-35 minutes
    (PANREAC). Once the solvents have been added and at 20 ° C, 3.36g of triethylamine (BASF) are added,
    The emulsion is immediately made with 261.4g of cold water in 30-40 minutes and at 250-400 rpm. The pH is checked to be above 8 (pH = 9.7) and 4.79g of N- (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) + 6.22g of MEK are added in 2-5 minutes. The solvents are distilled 10 minutes after the addition
    50'C.
    A bluish white emulsion is obtained.
    Example 4 Example 3 is repeated but adding, once the emulsion is made, 0.12g of EDA (ethitenediamine, PANREAC) in 10.03g of water, 0.21g of DEA (dietanotamine, PANREAC) in 10.01g of water and 1.97g of N- (n-Butit) -3-aminopropittrimethoxysilane (Dynasylan 1189, EVONIK) in 6.06g of acetone. 10 minutes after the addition,
    5 distil the solvents at 50 ° C.
    A bluish white emulsion is obtained.
    Example 5
    10 Example 3 is repeated but adding, once the emulsion is made, 0.07g of EDA (ethylenediamine, PANREAC) in 10.00g of water, 0.52g of DEA (diethanolamine, PANREAC) in 10.41g of water and 2.49g of N - (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 8.90g of acetone. The solvents are distilled at 10 ° C 10 minutes after the addition.
    15 A bluish white emulsion is obtained.
    Example 6 In a 700mt reactor 55.91g of polyester (Priplast 3162, CRODA) are added and a
    20 120 ° C becomes empty for 40 minutes to remove the water they may contain. Under a stream of nitrogen, 45.19g of HDI (hexamethylene diisocyanate, Desmodur H, BAYER) are added. It is allowed to react at 80-85 ° C and at 160 rpm until reaching an NCO = 22,320%, in this case the percentage of experimental NCO obtained by tritation is 17,880%. Then, the temperature is lowered to 60 ° C and 7.81g of
    25 NPG (neopentyl glycol, PERSTORP) and 8.21g of DEG (diethylene glycol, PANREAC) in 8.49g of dry acetone (PANREAC). It is allowed to react at 60 ° C until it reaches an NCO = 4,022%, in this case the percentage of experimental NCO obtained by tritation is 3,468%. The reactor temperature is lowered to 50 ° C and 140.45g of dried acetone are added with addition funnel and in 20-35 minutes.
    Once the solvent is added, 14.62g of EPS (ethyldiaminopropyl sulfonate, RASCHIG) in 2.24g of 1N KOH (potassium hydroxide, PANREAC) and 22.51g of distilled water are added, after 15 minutes the emulsion is made with 239.02g of water in 30
    40 minutes and at 250-400 rpm. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish white emulsion is obtained.
    Example 7
    Example 6 is repeated but adding 2.69g of N- (n-Butyl) -3aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 34.45g of dried acetone before performing the emulsion.
    Example 8 In a 21 reactor, 315.25g of polypropylene glycol of molecular weight 2000 g / mol (Voranol 2000L, DOW), 12.09g of dimerdiol (Pripol 2033, GRODA), 10.21g of DMPA (dimethylolpropionic acid, HUNTSMAN) are added and 68.54g of IPDI (diisocyanate
    15 isophorone, Vestanat IPDI, EVONIK). It is allowed to react at 80'G and 110 rpm until it reaches
    at an NCO = 1.094%, in this case the percentage of experimental NCO obtained by tritation is 0.982%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C, 115.82g of dried MEK (PANREAC) is added with 15 funnel, when the temperature reaches 55 ° C they are added with addition funnel and
    20 in 20-35 minutes 419 .79g of dried acetone (PANREAG).
    Once the solvents have been added and at 20 ° C, 8.10g of triethylamine (BASF) are added, the emulsion is immediately made with 577.90g of cold water in 30-40 minutes and at 250-400 rpm. After 3 minutes the polymer is lengthened with 0.65g of ethylenediamine (EDA, 25 PANREAC) in 10.02g water, after 3 more minutes, the polymer is coated with
    1.30g of 98% diethanolamine (DEA, PANREAG) in 10.02g of water and with 10,969 of N (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 9,989 MEK. Be
    check that the pH is higher than 8, pH = 8.95 And after 10 minutes of the addition the solvents are distilled at 50 ° C.
    A bluish white emulsion is obtained.
    Example 9 In a 700ml reactor 57.07g of polyester (Priplast 3162, eRODA) are added and at 1200 e it is emptied for 40 minutes to remove the water they may contain. Under a stream of nitrogen, 39.89g of HDI (hexamethylene diisocyanate, Desmodur H, BAYER) are added. It is allowed to react at 80-85 ° C and at 160 rpm until it reaches an NCO = 15.66%, in this case the percentage of experimental NCO obtained by tritation is 15,090%. Then, the temperature is lowered to 60 ° C and 3.90g of NPG (neopentyl glycol, PERSTORP) and 8.21g of DEG (diethylene glycol, PANREAC) in 8.32g of dry acetone (PANREAC) are added. It is allowed to react at 60 ° C until it reaches an NCO = 4,426%, in this case the percentage of experimental NCO obtained by tritation is 3,807%. The reactor temperature is lowered to 50 ° C and 152.18g of dried acetone are added with addition funnel and in 20-35 minutes.
    Once the solvent is added, 14,019 EPS (ethyldiaminopropyl sulfonate, RASCHIG) in 2.19g of 1N KOH (potassium hydroxide, PANREAC) and 21.45g of distilled water are added, after 15 minutes the emulsion is made with 169.71g of water in 3040 minutes and at 250-400 rpm. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish white emulsion is obtained.
    Example 10 In a reactor of 21, 324.90g of polypropylene glycol of molecular weight 2000 g / mol (Voranol 2000L, DOW), 12.109 of dimerdiol (Pripol 2033, CRODA), 9.59g of DMPA (dimethylolpropionic acid, HUNTSMAN) and 68.60g are added of IPDI (isophorone diisocyanate, Vestanat IPDI, EVONIK). It is allowed to react at 80 ° C and 110 rpm until it reaches an NCO = 1.071%, in this case the percentage of experimental NCO obtained by tritation is 0.998%. Then, the temperature is lowered to 50 ° C, and when it is about 700 e, 115.78g of dry MEK (PANREAC) is added in 15 minutes, when the temperature reaches 55 ° and they are added with funnel of addition and in 20-35 minutes 420 .00g of dry acetone (PANREAC).
    Once the solvents have been added and at 20 ° C, 7.60g of triethylamine (BASF) are added, the emulsion is immediately made with 566.93g of cold water in 30-40 minutes and at
    250-400 rpm After 3 minutes the polymer is lengthened with 0.83g of ethylenediamine (EDA, PANREAC) in 10.06g water, after 3 more minutes, the polymer is coated with
    1.48g of 98% diethanolamine (DEA, PANREAC) in 10.03g of water and with 8.76g of N (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 10.00g of
    5 acetone The pH is found to be higher than 8, pH = 9.31 and at 10 minutes after the addition the solvents are distilled at 50 ° C.
    A white emulsion is obtained.
    10 Example 11
    In a 700ml reactor 90.28g of molecular weight polypropylene glycol are added
    2000 g / mol (Voranol 2000L, DOW) and 2.75g of dimerdiol (Pripol 2033, GRODA). TO
    120 ° C And at 140rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and 4.24g of DMPA (acid is added
    15 dimethylolpropionic, HUNTSMAN) is left stirring for 10 minutes and added
    19.81g of TMDI (2,2,4-Y 2,4,4-trimethyl-hexamethylene diisocyanate, Vestanat TMDI, EVONIK). It is allowed to react at 90 ° C until it reaches an NCO = 0.899%, in this case the percentage of experimental NCO obtained by tritation is 0.662%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with funnel of
    20 addition and in 5 minutes 27.96g of dry MEK (PANREAG), when the temperature arrives
    at 55 ° C they are added with addition funnel and in 20-35 minutes 74,909 of dry acetone
    (PANREAC).
    Once the solvents have been added and at 20 ° C, 3,369 triethylamine (BASF) are added,
    The emulsion is immediately made with 216.58g of cold water in 30-40 minutes and at 250-400 rpm. The pH is checked to be above 8 (pH = 9.82) and 3.31g of N- (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 4.31g of MEK are added in 2-5 minutes. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish white emulsion is obtained.
    Example 12
    Example 10 is repeated with TMDI instead of IPDl so that the final product is more fluid. A more fluid bluish white emulsion is obtained than in the case of example 10.
    Example 13
    In a 700ml reactor 92.89g of molecular weight polypropylene glycol are added
    2000 glmol (Voranol 2000L, DOW) and 3.54g of dimerdiol (Pripol 2033, GRODA), se
    Connect the vacuum at 120 ° C for 30 minutes to dry the polyols. The vacuum is switched off and at 60 ° C 2.76g of DMPA (dimethylolpropionic acid, HUNTSMAN) and 18.38g of TMDI (2,2,4-Y 2,4,4-trimethyl-hexamethylene diisocyanate, Vestanat TMDI, are added,
    EVONIK). It is allowed to react at 80'G and 150 rpm until reaching an NGO = 1.002%, in
    In this case, the percentage of experimental NCO obtained by tritation is 0.948%. Then, the temperature is lowered to 50 ° C, and when it is about 700 G they are added
    with addition funnel and in 15 minutes 31,559 of dry MEK (PANREAG), when the
    temperature reaches 55 ° C are added with addition funnel and in 20-35 minutes
    124.00g of dried acetone (PANREAG).
    Once the solvents have been added and at 200 G, 2.20g of triethylamine (BASF) are added, the emulsion is immediately made with 205.05g of cold water in 30-40 minutes and at 250-400 rpm. After 3 minutes the polymer is coated with 0.39g of 98% diethanolamine
    (DEA, PANREAG) in 2.38g of water and with 4.149 of N- (n-Butyl) -3
    aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 8.25g of acetone. The solvents are distilled at 10 ° C 10 minutes after the addition. A white emulsion is obtained.
    Example 14 Example 10 is repeated with 4000 molecular weight polypropylene glycol instead of
    2000
    A more fluid bluish white emulsion is obtained than in the case of example 10.
    Example 15
    Example 11 is repeated with EDA and DEA.
    After 3 minutes of finishing the emulsion, the polymer is elongated with 2.07g of EDA in
    5.10g of water and the polymer is coated with 1.81g of DEA in 4.99g of water and with 3.76g
    of N- (n-Butyl} -3-aminopropyltrimethoxysilane in 9.49g of acetone The solvents are distilled at 50 ° C within 10 minutes of the addition.
    A bluish white emulsion is obtained.
    In this example, an excess of amino acids has been added so that the product is more soluble with the tissue but it is observed that over time it is not stable.
    Example 16 In a 700ml reactor, 2.70g of DMPA, 2.77g of dimerdiol and 92.589 of
    Polypropylene glycol of molecular weight 2000 g / mol. At 120 ° C and at 60rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and the stirring is raised to 190 rpm. In 10 minutes 17.58g are added
    of TMDI.
    It is allowed to react at 85 ° C until it reaches an NCO = O.889%, in this case the percentage of experimental NCO obtained by tritation is 0.872%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and in 5 minutes 27. 72g of dried MEK, when the temperature reaches 55 ° C they are added with funnel of addition 20-35 minutes 74.30g of dry acetone.
    Once the solvents have been added and at 20 ° C, 2.14g of triethylamine are added, the emulsion is immediately made with 117.52g of cold water in 30-40 minutes and at 250-400 rpm. It is verified that the pH is above 8 (pH = 10.37) and 0.139 of EDA are added in 2,379 of water, at 2-3 minutes 2.79g of N- (n-Bulil) -3aminopropyltrimethoxysilane in 7.79g of acetone. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish white emulsion is obtained.
    Example 17In a 700ml reactor, 2.67g of DMPA (dimethylolpropionic acid,
    5 HUNTSMAN), 2.74g of dimerdiol (PripoI2033, CRODA) and 92.51g of polypropylene glycol of molecular weight 2000 glmol (Voranol 2000L, DOW). At 120 ° C And at 60 rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and the stirring is raised to 190 rpm. In 10 minutes 17.57g of TMDI (2,2,4-Y 2,4,4-trimethyl-hexamethylene diisocyanate, Vestanat TMDI, EVONIK) are added.
    10 It is allowed to react at 90 ° C until it reaches an NCO = 0.909%, in this case the percentage of experimental NCO obtained by tritation is 0.867%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C, 26.75g of dry MEK (PANREAC) is added in 5 minutes, when the temperature reaches 55'C
    15 are added with addition funnel and in 20-35 minutes 74,459 of dry acetone (PANREAC).
    Once the solvents have been added and at 20 ° C, 2.11g of triethylamine (BASF) are added, the emulsion is immediately made with 144.00g of cold water in 30-40 minutes and at
    20 250-400 rpm. The pH is verified to be above 8 (pH = 1 0.50) and 3.44g of N- (n-Butyl) -3-aminopropyltrimethoxysilane (Dynasylan 1189, EVONIK) in 9.79g of acetone are added in 2-5 minutes. The solvents are distilled at 10 ° C 10 minutes after the addition.
    25 A bluish transparent emulsion is obtained.
    Example 18 Example 17 is repeated with 2.6% less DMPA and reducing the time to perform the emulsion in half.
    A bluish transparent emulsion is obtained.
    Example 19
    5 In a 700ml reactor 2.37g of DMPA, 2.82g of dimerdiol and 92.46g of polypropylene glycol of molecular weight 2000 g / mol are added. At 120 ° C And at 60 rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and the stirring is raised to 160rpm. In 10 minutes, 18.10g of TMDI are added.
    10 It is allowed to react at 90 ° C until reaching an NCO = 1,245%, in this case the percentage of experimental NCO obtained by tritation is 1,224%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and in 5 minutes 29.00g of dried MEK, when the temperature reaches 55 ° C they are added with addition funnel yen 20-35 minutes 77.49g of dried acetone.
    fifteen Once the solvents have been added and at 20 ° C 1.88g of triethylamine are added, the emulsion is immediately made with 154.06g of cold water in 30-40 minutes and at 250-400 rpm. The pH is checked to be above 8 (pH = 8.43) and 0.24g of EDA in 4.03g of water are added in 2-5 minutes and then 1.96g of N- (2Aminoethyl) -3-aminopropyltrimethoxysilane in 6.33g of acetone. The solvents are distilled at 10 ° C 10 minutes after the addition.
    twenty A bluish transparent emulsion is obtained.
    25 Example 20 In a 700ml reactor, 4,259 DMPA, 2,829 dimerdiol, 90,829 polypropylene glycol of molecular weight 2000 g / mol and 0.015g of a 6.21% phosphoric acid solution in acetone are added. At 120 ° C And at 60 rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and the stirring is raised to 160 rpm. In 10 minutes 19.64g of TMDI are added.
    JO It is allowed to react at 80 ° C until it reaches an NCO = O.819%, in this case the percentage of experimental NCO obtained by tritation is 0.817%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and in 5 minutes 29.35g of dried MEK, when the temperature reaches 55 ° C they are added with addition funnel yen 20-35 minutes 76.00g of dried acetone.
    Once the solvents were added and at 20 ° C 1,959 triethylamine were added, after 2 minutes 0.25g of ethylenediamine in 19.13g of water were added and then 1.84g of N- (n-Butyl) -3-aminopropyltrimethoxysilane in 7.97g of acetone. It is checked by infrared (IR) spectroscopy that NCO groups remain unreacted and the emulsion is immediately made with 129.65g of cold water in 30-40 minutes and at 250-400 rpm. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish white emulsion is obtained.
    Example 21 Example 19 is repeated but without EDA, of the equivalents of free NCO having the
    15% prepolymer is allowed to react with the water of the emulsion and 85% with the silane.
    A bluish white emulsion is obtained.
    Example 22 In a 700ml reactor, 2.38g of DMPA, 2.84g of dimerdiol, 92.52g of polypropylene glycol of molecular weight 2000 g / mol (Voranol 2000L, DOW) and 0.0989g of
    a solution of phosphoric acid (PANREAC) a2.14% in acetone. At 120 ° C And at 60 rpm, it is empty to remove the water that the polyols can contain and once dry, the temperature is lowered to 60 ° C and the stirring is raised to 160 rpm. In 10 minutes 18.09g of TMDI (2,2,4-Y 2,4,4-trimethyl-hexamethylene diisocyanate, Vestanat are added
    TMDI, EVONIK).
    It is allowed to react at 80 ° C until it reaches an NCO = 1,233%, in this case the percentage of experimental NCO obtained by tritation is 1,121%. Then, the temperature is lowered to 50 ° C, and when it is about 70 ° C they are added with addition funnel and
    in 5 minutes 28.52g of dry MEK (PANREAC), when the temperature reaches 55'C
    77.89g of dried acetone are added with addition funnel and in 20-35 minutes
    (PANREAC).
    Once the solvents were added and at 20 ° C, 1,919 triethylamine (BASF) was added and the emulsion was immediately made with 129,659 cold water in 30-40 minutes and at 250-400 rpm, after 10 minutes 0.239 ethylenediamine was added in 4,289 of a9ua and then 3,659 N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane (Dynasylan DAMO,
    5 EVONIK) in 7.09g of acetone. The solvents are distilled at 10 ° C 10 minutes after the addition.
    A bluish transparent emulsion is obtained.
    Example 23 Example 20 is repeated but with a lower proportion of DMPA, 22.6% less.
    A bluish white emulsion is obtained.
    Example 24 Example 22 is repeated but with a lower proportion of DMPA, 22.4% less.
    A bluish white emulsion is obtained.
    Example 25 In a 100ml reactor, 6.1971g of PEG400 (400 molecular weight polyethylene glycol, CAMP and JOVE) are added and dried for 30 minutes at 120 ° C. At 40 ° C, 0.0052g of DBTL (Dibutyl Tin Dilaurate, in English dibutyl tin dilaurate, EVONIK) in 0.2069g of dried MEK is added, then 6.6856g of TMDI is added and
    25 let react for 2 hours. 2.8294g of 2-ethylhexanol (PROQUIBASA) are added and allowed to react for a further 2 hours. 0.3525g of Dynasylan 1189 is added and allowed to react for 30 minutes. At 40 ° C and 400 rpm, 0.56079 glycine (PANREAC) in 0.1806g of NaOH (PANREAC) and 1.0000g of water are added. After 5 minutes, 10.7381g of water are added and left under stirring for about 12 hours.
    A transparent emulsion of moderate viscosity is obtained.
    Example 26
    In a 100ml reactor 1,56929 of dimerdiol and 5.46309 of PEG400 are added, the polyols are dried for 30 minutes at 120 ° C. At 40 ° C, 0.00849 of DBTL (dibutyl tin dilaurate, EVONIK) in 0.3326g of dry MEK is added, then 7.0770g of TMDI is added and allowed to react for 2 hours. 1.7264g of 2-ethylhexanol are added and allowed to react for a further 2 hours. 0.4241 9 of Dynasylan 1189 is added and allowed to react for 30 minutes. At 40 ° C and at 400 rpm 1.4029g of glycine (PANREAC) in 0.78559 of NaOH (PANREAC) and 4.0000g of water are added. After 5 minutes, 20.9834g of water are added and left under stirring for about 12 hours.
    A transparent emulsion of moderate viscosity is obtained.
    Example 27 In a 100ml reactor 1.5272g of dimerdiol and 5.4129g of PEG400 are added, the polyols are dried for 30 minutes at 120 ° C.
    At 40 'C and 100 rpm, 0.00839 of DBTL (dibutyl tin dilaurate, EVONIK) in 0.3257g of dry MEK is added, then 7.01239 of TMDI is added and allowed to react for 2-3 hours, it is verified by IR that the NeO signal remains stable. 0.80069 of 2-ethylhexanol are added and allowed to react for a further 2 hours, once the NCO signal becomes stable again, 0.4157g of Dynasylan 1189 is added and allowed to react for 30 minutes, 2.1522g of DMEA (N , N-dimethylethanolamine, HUNTSMAN) and once it has been verified by IR that there is no signal from the NCO group, the temperature is lowered to 30 ° C and the prepolymer is dissolved with 4,44619 THF (tetrahydrofuran, PANREAC), at 25 minutes 1.5281g of acetic acid (PANREAC) are added. At 25 minutes the emulsion is made at room temperature and at 400 rpm with 23.85169 of water and a transparent and moderate viscosity emulsion is obtained.
    Example 28 1.5611g of dimerdiol and 5.7329g of PEG400 are added in a 100ml reactor, the polyols are dried for 30 minutes at 120 ° C.
    At 40 ° C and 100 rpm, 0.0083g of OBTL (dibutyl tin dilaurate, EVONIK) in 0.3257g of dry MEK is added, then 7.30869 of TMDI is added and allowed to react for 2-3 hours, it is verified by IR that the NCO signal remains stable. 0.4335g of 2-ethylhexanol are added and allowed to react for another 2 hours, once the NCO signal becomes stable again, 0.5958g of Dynasylan 1124 (Bis (trimethoxysilylpropyl) amine, EVONIK) is added and allowed to react for 30 minutes, 2.5025g of DMEA (N, N-dimethylethanolamine, HUNTSMAN) are added and once it has been verified by IR that there is no signal from the NCO group, the temperature is lowered to 30 ° C and the prepolymer is dissolved with 6.2083g of THF (tetrahydrofuran, PANREAC), after 17 minutes 1.7691g of acetic acid (PANREAC) are added. At 25 minutes the emulsion is made at room temperature and at 400 rpm with 24.4380g of water and a transparent and moderate viscosity emulsion is obtained.
    Example 29 In a 100ml reactor 6.6221g of PEG400 is added and dried for 30 minutes at 120'C.
    At 40'C and 100 rpm, 0.00559 of DBTL (dibutyl tin dilaurate, EVONIK) in 0.2183g of dry MEK is added, then 7.05259 of TMDI is added and allowed to react for 2-3 hours, it is verified by IR that the NCO signal remains stable.
    1.63179 of 3.5 dimethylpyrazole (FLUOROCHEM) are added and allowed to react for 2 more hours, once the NCO signal becomes stable again, 0.3277g of Dynasylan 1189 is added and allowed to react for 30 minutes, 0.99259 of DMEA (N, N-dimethylethanolamine, HUNTSMAN) and once it has been verified by IR that there is no signal from the NCO group, the temperature is lowered to 30'C and the prepolymer is dissolved with 7.25729 THF (tetrahydrofuran, PANREAC), a 25 minutes are added 0.7211 9 acetic acid (PANREAC). At 25 minutes the emulsion is made at room temperature and at 400 rpm with 20.3459g of water and a transparent and moderate viscosity emulsion is obtained.
    In Figs. 19 and 20 show some tables with a summary of the examples
    made and in Fig. 7 shows a table with a summary of the main
    characteristics of synthesized products.
    5 In general, to reduce the tack (stickiness) that some of the products have
    synthesized additives type BYK-378 (marketed by BYK) can be used at about
    0.01 to 0.5% levels with respect to the total weight of the product. Also, if it were
    necessary to increase the viscosity of the product, type additives can be used
    Rheolate 278 (marketed by ELEMENTIS) at levels of 0.4 to 2%. Too
    10 moisturizers can be added at levels of 0.5 to 3% to increase penetration
    of the product in the fabric as EMPILAN KR 6/90. EMPILAN KI8 65 (both
    marketed by HUNTSMAN) and / or ANTAROX FM33 (marketed by RHODIA).
    Application on fabrics
    fifteen
    Synthesized products are applied on polyester and cotton fabrics with a
    24 ~ m applicator and at room temperature. Once applied they are made a
    heat treatment by placing them in the oven at 8DoC for 2 minutes. In the case of
    The compounds with blocked isocyanates the heat treatment is at 120 ° C.
    twenty
    Alternatively, the products can be printed on the fabric manually with
    a flat template that contains some recommended designs to assess the sharpness and
    penetration of prints, immediately undergo drying-curing in
    Branch at 80 ° C for 2 minutes and then iron at 11 DOC.
    25
    Simultaneously several products that are in the market have been studied to see
    if they have the same properties as synthesized products and check if
    They can also be used as a watermark. These products are adhesives
    based on high concentration aqueous aliphatic polyurethanes (between a
    JO 49-61% solids). The products studied are the following:
    BONDTHANE UD-375 60% solids
    BONDTHANE XP-158E 55% solids
    BONDTHANE XP-160D 55% solids ALBERDINGK U180VP 49-51% solids ALBERDINGK U199VP 59-61% solids ALBERDINGK U216VP 59-61% solids
    These products are applied on fabric following the same procedure described above.
    In Figs. 8, 9 and 10 there are some tables with the results of the applications on polyester, cotton and polyester / cotton (65% / 35%), respectively.
    In Figs. 11-18 are shown images of samples of fabrics printed with a watermark with a compound according to the invention.
    Wash resistance
    To check the wash resistance of the watermarks, weighed 5 9 of fabric with the mark and placed in a container next to 0.08 9 of liquid detergent and 45 ml of water at 60 ° C. The container is stirred with a mechanical stirrer for 1 h and the tissue is rinsed with water, the water is drained and allowed to dry. Once dry, it is checked whether the watermark has resisted washing. If you resist This procedure is repeated until the mark is observed in the water or until 20 washes are obtained without disappearing.
    The examples have been evaluated: 11, 12, 13, 15, 17, 19, 20, 22, 23, 24, 25, 26, 27, 28 Y
    29.
    All samples tested withstand 20 washes at 60 ° C except for examples 25 and 26. To increase the washing resistance of the products synthesized according to example 25 and 26, an external crosslinker must be added such as a blocked or unblocked isocyanate.
    From the above results it can be concluded that for polyester fabrics the best products are preferably those synthesized according to example 11, 12, 13, 15,
    17,20, 22 (40.7% solids) and 23. For cotton fabrics (sample type 1), the best products are preferably those synthesized according to example 3, 19, 22 (35.0% solids) and 24. For cotton fabrics (sample type 2), the best products are preferably those synthesized according to example 25, 26, 27, 28 and 29.
    5 For polyester / cotton blend fabrics (sample type 1,2 and 3), the best products are preferably those synthesized according to example 25, 26, 27, 28 and 29.
    权利要求:
    Claims (1)
    [1]
    1 -Composite for the manufacture of a watermark in a textile sheet material, of formula
    C-W- (A-W) m- (X-W) or-X- (W-A) p-W-C '
     where
    W is a radical from a compound of the group consisting of 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4. 1-dimethyl-hexamethylene diisocyanate, safaron diisocyanate and hexamethylene diisocyanate,
    each X is a radical from a compound of the group formed by
    polyethylene glycol, polypropylene glycol, dimerdiol and dimethylolpropionic acid, regardless of the remaining X, where at least one X is a radical of a compound of the group consisting of polyethylene glycol and polypropylene glycol, and where W- (XW) nXW has a molecular weight between 750-15,000 g / mol and a ratio
    NCO: OH between 0.9 and 2.1,
    A is a radical from a compound of the group formed by
    NH2-R-NH2, where Res (CH2) n with n between 1 and 6,
    NH2-R-NH-R ', where R is (CH2) n with n between 1 and 6 and R' is
    CH, CH, CH, Si (OCH3h or (CH, hS03H, and
    NH2-R "where R" is (-CHdn-CH-COOH with n between 1 and 4,
    NH,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine, CH3-CH2-CH2-CH2-NH-CH2-CH2CH2-Si (OCH3h, glycine, taurine, homotaurine, 2- ethyl hexanol, N- (2-aminoethyl) -3aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, polyethylene glycols
    5 monomethylated, N, N-dimethylethanolamine, N, N, N'-trimethyl-N'-hydroxyethyl-bisaminoethylether, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, 2- (2-d imethylamine and noethoxy) ethanol, N, N, N'-trimethylaminoethyl ethanolamine, dimethylaminopropylamine, and a blocking agent of an isocyanate group,
    10 N> O,
    M> = O.
    P> = O.
    Compound according to claim 1, characterized in that W is a radical from 2,2,4-trimethyl-hexamethylene diisocyanate and / or 2,4,4.trimethyl-hexamethylene diisocyanate.
    Compound according to one of claims 1 or 2, characterized in that each X is a radical from a compound of the group consisting of polyethylene glycol of molecular weight 400 g / mol, polypropylene glycol of molecular weight 2000 g / mol, dimerdiol and acid dimethylolpropionic, regardless of the remaining X.
    Compound according to any one of claims 1 to 3, characterized in that W - (X-W) n -X-W has a molecular weight between 750-1,000 g / mol.
    5 - Compound according to any one of claims 1 to 3, characterized in that W - (X-W) n -X-W has a molecular weight between 6,000-11,000 g / mol.
    6 - Compound according to any one of claims 1 to 5, characterized in that W - (X-W) or -X-W has a NeO: OH ratio between 1.1 and 1.3.
    7 - Compound according to any one of claims 1 to 5, characterized in that W - (X-W) n -X-W has an NCO: OH ratio between 1.8 and 2.1.
    8 - Compound according to any one of claims 1 to 7, characterized in that A is a radical from a compound of the group consisting of ethylenediamine, N (2-aminoethyl) -3-aminopropyltrimethoxysilane, lysine, ethyldiaminopropyl sulfonate and hexamethylenediamine.
    Compound according to claim 8, characterized in that A is a radical derived from ethylenediamine or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
    10 - Compound according to any of claims 1 to 9, characterized in that C or C 'is a radical from N, N-dimethylethanolamine.
    11 - Compound according to any one of claims 1 to 10, characterized in that C or C 'is a radical from CH3-CH2-CH2-CH2-NH-CH2-CH2-CH2
    Yes (OCH,) ,.
    Compound according to any of claims 1 to 11, characterized in that C or C 'is a radical from N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
    13 - Compound according to any of claims 1 to 12, characterized in that C or C 'is a radical from bis (trimethoxysilylpropyl) amine.
    14 - Compound according to any one of claims 1 to 13, characterized in that C or C 'is a radical from an isocyanate blocking agent.
    - Compound according to any one of claims 1 to 14, characterized in that said isocyanate blocking agent is a compound of the group consisting of pyrazole, 3, S-dimethylpyrazole, ketoximes, aliphatic esters, amides, imides and amines.
    16 - Compound according to any one of claims 1 to 15, characterized in that said isocyanate blocking agent is 3, S-dimethylpyrazole.
    17 - Compound according to claim 1, characterized in that
    W is a radical from isophoron diisocyanate,
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    M = 0,
    P = 0.15 and has a molecular weight between 9,100 and 10,100 glmol.
    18 - Compound according to claim 2, characterized in that
    Each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    C and C 'are a radical from CH, CH, CH, CH, NHCH, CH, CH, Si (OCH,) "
    M = 0,P = 0,
    30 And it has a molecular weight between 8,700 and 9,800 glmol. 19 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine and CH, CH, CH, CH, NHCH, CH, CH, Si (OCH, h.
    M> O,
    P> O.
    And it has a molecular weight between 7,300 and 8,300 g / mol.
    20 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine and
    CH, CH, CH, CH, NHCH, CH, CH, Si (OCH, h.
    M = O.
    P = O.
    and has a molecular weight between 7,800 and 8,800 glmol.
    21 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,
    C and C 'are each, independently of the other, a radical from a compound of the group consisting of diethanolamine and CH 3CH, CH, CH, NHCH, CH, CH, Si (OCH3h.
    M> O.
    p> O.
    and has a molecular weight between 9,200 and 10,200 glmol.
    22 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 g mol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,C and C 'are a radical from N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
    M> O,
    P> O.and has a molecular weight between 6,200 and 7,200 glmol.
    23 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,
    M> O,
    p> O,
    And it has a molecular weight between 9,800 and 10,800 g / mol. 24 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X.
    C and C 'are a radical from N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
    M = O,p = O,and has a molecular weight between 6,300 and 7,400 glmol.25 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polypropylene glycol of molecular weight 2,000 glmol, dimerdiol and dimethylolpropionic acid, independently of the remaining X,
    A is a radical from ethylenediamine,
    C and C 'are CH, CH, CH, CH, NHCH, CH, CH, Si (OCH, h.
    M> O,
    p> O,
    and has a molecular weight between 8,500 and 9,500 glmol. 26 - Compound according to claim 2, characterized in that X is a radical from polyethylene glycol of molecular weight 400 glmol,
    C and C ' They areeveryone, independently of the other, aradical coming froma
    compound of thegrou poformedbyCH, CH, CH, CH, NHCH, CH, CH, Si (OCH,) "2
    ethylhexanol and glycine,
    M = 0,P = 0,and has a molecular weight between 740 and 880 g / mol.27 - Compound according to claim 2, characterized in thateach X is a radical from a compound of the group formed by
    polyethylene glycol of molecular weight 400 gl mol, and dimerdiol, C and C 'are each, independently of the other, a radical from a compound of the group consisting of CH3CH2CH2CH2NHCH2CH2CH2Si (OCH3h, 2-ethylhexanol and glycine,
    5 M = 0,
    P = 0,
    and has a molecular weight between 780 and 880 g / mol. 10 28 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polyethylene glycol of molecular weight 400 g / mol, and dimerdiol,
    15 C and C 'are each, independently of the other, a radical from a compound of the group consisting of CH3CH2CH2CH2NHCH2CH2CH2Si (OCH3h, 2-ethylhexanol and N, N-dimethylethanolamine,
    20 M = 0,
    P = 0,
    and has a molecular weight between 780 and 880 g / mol.
    29 - Compound according to claim 2, characterized in that
    each X is a radical from a compound of the group consisting of polyethylene glycol of molecular weight 400 g / mol, and dimerdiol,
    30 C and C 'are each, independently of the other, a radical from a compound of the group consisting of bis (trimethoxysilylpropyl) amine, 2-ethylhexanol and N, N-dimethylethanolamine,
    M = 0,P = 0,
    5 and has a molecular weight between 790 and 890 glmol. 30 - Compound according to claim 2, characterized in that
    10 X is a radical derived from 400 glmol molecular weight polyethylene glycol, and C 'are each, independently of the other, a radical from a compound of the group consisting of 3,5 dimethylpyrazole,
    CH, CH, CH, CH, NHCH, CH, CH, Si (OCH, h and DMEA, 15 M = 0,
    P = 0,
    20 And it has a molecular weight between 750 and 850 g / mol.
    Composition for the manufacture of a water-based brand in textile comprising an emulsion of a compound according to claims 1 to 30 in water.
    32-Textile laminar material that is formed with a material characterized in that it comprises an area impregnated with a
    a sheet material any of the
    transparent textile compound according
    any one of claims 1 to 30, wherein said impregnated zone is a watermark.
    33 -Procedure for the manufacture of a watermark in a textile sheet material, which is formed with a transparent textile material, characterized in that it comprises a printing stage in which an area of said textile sheet material is impregnated with a compound according to any of claims 1 to 30, thereby generating a watermark.
    34 - Procedure for manufacturing a watermark on a sheet material
    Textile, which is formed with a transparent textile material, characterized in that it comprises a printing stage in which an area of said textile sheet material is impregnated with a composition according to claim 31, thus generating a watermark.
    Use of a compound according to any one of claims 1 to 30. for impregnating an area of a textile sheet material, wherein said textile sheet material is formed with a transparent textile material, thus generating a watermark.
    - Use of a composition according to claim 31, for the impregnation of an area of a textile sheet material, wherein said textile sheet material is formed with a transparent textile material, thus generating a watermark.
    37 - Use according to one of claims 35 or 36, characterized in that said
    20 textile sheet material is a label and said watermark forms a safety element.
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    同族专利:
    公开号 | 公开日
    WO2017203081A1|2017-11-30|
    ES2644165B1|2018-09-11|
    EP3467194A1|2019-04-10|
    MA45170A|2019-04-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2008009388A1|2006-07-17|2008-01-24|Oliva Gurgui Antonia|Polyurethane derivates and corresponding uses and methods for producing watermarks|
    US20100304017A1|2007-05-07|2010-12-02|Antonio Oliva Gurgui|Urethane and oligourethane derivatives and corresponding uses and methods for producing water marks using the offset printing technique|
    ES2340756A1|2010-01-18|2010-06-08|Marca D'aigua, S.L.|A compound for making a watermark on a laminated textile material and corresponding composition, material, method and use|
    ES2386179A1|2012-06-13|2012-08-10|Antonio Oliva Gurgui|Compounds derived from urethanes and oligouretans and procedures for manufacturing brands to water through the offset printing technique and corresponding uses |
    GB9806788D0|1998-03-31|1998-05-27|Zeneca Ltd|Composition|
    DE19914884A1|1999-04-01|2000-10-05|Bayer Ag|Special polyurethane dispersion for coating glass fibres or other coating applications, made by reacting isocyanate prepolymer with chain extenders and monoamino-functional alkoxy-silane chain stopper|
    DE10339479A1|2003-08-27|2005-05-12|Basf Ag|Foam control agent based on cationic urethane oligomers|
    JP5864595B2|2010-10-29|2016-02-17|ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド|Aqueous cationic polyurethane dispersion|CN110951039A|2019-11-24|2020-04-03|华南理工大学|Environment-friendly self-extinction waterborne polyurethane and preparation method and application thereof|
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    ES201630677A|ES2644165B1|2016-05-25|2016-05-25|Compound for the manufacture of a watermark on a textile sheet material and a corresponding composition, textile material, procedures and uses|ES201630677A| ES2644165B1|2016-05-25|2016-05-25|Compound for the manufacture of a watermark on a textile sheet material and a corresponding composition, textile material, procedures and uses|
    EP17734128.6A| EP3467194A1|2016-05-25|2017-05-23|Compound for producing a watermark on a laminar textile material and corresponding composition, textile material, methods and uses|
    MA045170A| MA45170A|2016-05-25|2017-05-23|COMPOUND FOR THE MANUFACTURE OF A WATERMARK IN A TEXTILE LAMINARY MATERIAL AND CORRESPONDING COMPOSITION, TEXTILE MATERIAL, PROCESSES AND USES|
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