TWI225495B - Process for the coagulation of aqueous PU dispersions which contain dispersed reactive or post-crosslinkable polyurethane, products thus obtained and use thereof - Google Patents

Abstract

The invention relates to a process for the coagulation of PU dispersions, the coagulation products thus obtained and the use of the coagulated PU dispersions. Reactive or post-crosslinkable PU dispersions are suitable as PU dispersions for the process according to the invention. The processes according to the invention comprise the production of films, the coating of many different materials and the partial or complete impregnation of nonwoven, knitted or other fabrics for strengthening purposes.

Description

1225495 A7 B7 V. Description of the invention (丨) The present invention relates to a method for coagulating a PU dispersion, the obtained coagulation product, and the use of the coagulated PU dispersion. Reactive or post-crosslinkable PU dispersions are suitable as PU dispersions according to the method of the present invention. The method according to the invention comprises the production of a film, the coating of a number of different materials and, for the purpose of strengthening, / the impregnation of a non-woven fabric, a knitted fabric or other fabric, partially or completely. The coagulum produced according to the method of the present invention is suitable for use in, for example, fabrics, protective fabrics, uppers and padding materials, protective gloves, bags and furniture materials, metal coatings, medical and sanitary products. • Coated fabrics (eg, artificial leather) have been manufactured for some time. It applies one or more coating agents on the substrate by using a direct spread coating method or a conveyance coating method. Coated textiles can be used to produce outerwear, uppers and pads, bags and furniture materials, and more. It is known that latex dispersions can be used for manufacturing, for example, gloves, or in recent years, due to the emergence of latex hypersensitivity, polyurethane dispersions have been used. However, polyurethane dispersions for coagulation are particularly significant. Technical Issues 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in the production of two-quality coated fabrics, especially in terms of required comfort, stretchability, tensile strength, and softness play a decisive role because of the stiffness The fabric lacks comfort. If the combination of fiber crossing points cannot be avoided when manufacturing a stretch-coated fabric, the stretch will be lost, and the bond between the fabric and the bonding agent will be easily broken when subjected to bending pressure. The fabric is coagulated after being treated with an aqueous dispersion of an organic binder. The paper size applies to China 210X297 mm.) ^ 9BA ¥ ER > 1225495 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) ~ hour That is, avoid the combination between the fiber bundle and the line. In this way, the local tensile strength and the softness of the coated fabric can be improved. The following coagulation methods are known: • Tank coagulation method, in which the substrate is coated with a binding agent dissolved in an organic solvent (for example: DMf DMAC, DMSO, THF), and the resulting product is passed through a non-solvent ( For example: water) tank; when dissolved with insoluble materials, condensation occurs. Disadvantages of this method are the need for cost-effective safe handling, and the recovery and reuse of large amounts of solvents. • Burst coagulation method, which mainly uses volatile solvents and non-solvents with low volatility for the binding agent; under mild heating, it is best to exclude the solvent first. When the proportion of non-solvent gradually increases, the binding agent will condense ~; Disadvantages of this method In addition to using a large amount of solvent, it still requires a lot of technical support, and because of the processing parameters, the opportunity to reach the most appropriate conditions is very limited. • Salt, acid or electrolyte coagulation method, which consists of coated substrate, or in the case of gloves, the prototype is first immersed in dispersion, concentrated salt solution or acidified water, etc. Agent coagulation; the disadvantage of this method is that the technology is complicated and a large amount of polluted wastewater is generated. • Prepolymer method, in which the substrate of the isocyanate-coated polymer is immersed in water 'and then a polyurea with a porous structure is formed to release co2. Disadvantages of this method include the extremely high reactivity of the formulation and the relatively short reaction time; and • The temperature rise coagulation method, which is suitable for heat-sensitive binders that cannot be post-crosslinked often causes unacceptable results. In summary, the above method involves the complete removal of the solvent for a long time. Before you read (please read the precautions on the back first {马 页} installation, τ

-4- This paper size is applicable to China National Standards of Standards (CNS) eight-view grid (21GX297 public meal) 1225495 A7 B7 V. Description of the invention (: cost of separation and recovery of solvent and non-solvent uptake, water 'may not be formed every time you wish Acceptable quality W Salt waste 2 The purpose of providing is to provide a kind of production suitable for this method without the above-mentioned disadvantages σ_ 心 万 沄 and Μττα, should be a simple method, and should only be made with or without a small amount of organic solvents. High-quality products are obtained. And the use of salt, osmium, or electrolyte f has surprisingly been found, and the polyurethane dispersion obtained by cross-linking with water based on water-based method is achieved. Polyurethane " The word also includes polyurethane-polyurea. Therefore, the present invention provides a method for coagulating a post-crosslinkable dispersion, which is characterized by using a heating temperature of 50 to 120X: to make the post-crosslinkable dispersion The liquid precipitates to form a stable and at least partially crosslinked polyurethane or gel. The method according to the invention is preferably carried out at 75 to 98 ° C. The postcrosslinkable PU dispersion is coagulated according to the invention The method is characterized by the following Parts of the post-crosslinkable dispersion: a) 0.1 to 7.5% by weight (at 0.9 to 2.0 weight% /. Preferably) blocked isocyanate groups (calculated NCO = 42), and intellectual property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives b) at least one polyamine containing at least two (cyclic) aliphatic bonds of primary and / or secondary amine groups and / or hydroxylamines, a) blocked isocyanate groups and b) amine groups Equivalent ratio is 1: 0.5 to 1: 1.5, preferably 1: 0.7 to 1: 1.2, particularly preferably 1: 0.5 to 1: 1.1, at 50 to 120 ° C (preferably at 75 to 98 ° C) Heated to form a precipitate, which forms a stable and at least partially crosslinked polyurethane or gel. The paper size applies to the Chinese National Standard (cns) A4 (2i0x297). ^^ 0495

Description of the invention (4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention also provides a coagulum produced according to the method of the present invention. In the method of coagulating a post-crosslinkable dispersion according to the present invention, the crosslinkable dispersion Secret 5G to 1 delay and add ambiguity to form an at least partially cross-linked polyamine or _, which is characterized in that the dispersion used contains a) (U to 7.5% by weight of Fengrui isocyanate) Acetate (calculated and b) at least one polyamine and / or primary and / or secondary amine group containing at least two (cyclo) lipidic bonds via amine, a) blocked isocyanate moieties And b) the equivalent ratio of the amine group is 1: 0.5 to 1: 1.5, which can be post-crosslinked for a minimum of 75 to 98t, and then added to the temple to form a stable crosslinked polyaminocarboxylic acid. Or Gel, characterized in that the dispersion contains a) 0.25 to 5 wt% of blocked isocyanate groups (calculated NCO = 42), and w at least one polyamine and / or at least two polyamines (Cyclic) aliphatic-bonded-primary and / or secondary amine groups' a) Equivalent ratio of blocked isocyanate groups to b) amine groups is 1: 0.7 to 1: 1.2, which has particularly good characteristics When the post-crosslinkable Pu dispersion is added and subtracted at a temperature of 75 to 98 C, a stable and at least partially crosslinked polyamino acid or gel is formed. Its further characteristics are as follows: The dispersion used contains a) 0.7 to 2% by weight of blocked isocyanate groups (calculated nc0 = 42), and -6- this paper size applies to China National Standard (CNS) A4 (210X297 mm) (please first Read the notes on the back ^^ write this page) j equipment • Xiang Shiding ---- ^ printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Invention Description (5) b) at least one polyamine and / or hydroxylamine contains The equivalence ratio of at least two (cyclo) aliphatic primary and / or secondary amine groups, a) blocked isocyanate groups to b) amine groups is 1: 0.9 to 1: 1.1. A preferred aspect of the method for coagulating a post-crosslinkable dispersion liquid according to the present invention is to use a dispersion liquid mainly composed of a hydrophilic raw material, specifically, a hydrophilic polyhydric alcohol, so as to form a water vapor permeable condensate. The curable post-crosslinkable polyurethane alkane aqueous dispersion or emulsion used according to the method of the present invention is a reaction product of the following components: 1. at least one organic di- or polyisocyanate, 2. at least one molecular weight up to 16,000 Polyhydroxy compounds, 3 · ionic or potentially ionic hydrophilizing agents and / or nonionic hydrophilizing agents, 4. isocyanate-based blocking agents, and 5_ superimposed with low molecular weight monoamine, diamine or Triamine is used as a chain-stopping component, a chain-extending component, or a chain-branching component, which additionally contains a 6. polyamine cross-linking agent, which is contained in the dispersion, and the content of component 3) enables it to form a stable dispersion. The coagulable post-crosslinkable aqueous dispersion or emulsion-type polyurethane is preferably a reaction product of the following components: 1. 9 to 30% by weight of at least one organic diisocyanate, 2 · 40 to 85% by weight of at least one polyhydroxy compound having at least a difunctional group with a molecular weight of 350 to 4000, 3.4 to 22% by weight of an ionic or potentially ionic hydrophilizing agent and / or a nonionic hydrophilizing agent, paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) 1225495 V. Description of the invention (6 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0.5 to 5 mile / isocyanate end-capping agent, and 5.0 to 5% by weight of a low molecular weight mono-, di-, or triamine as a component of bond termination, chain extension, or chain branching, which additionally contains 6.1 to 6% by weight of a polyamine cross-linking agent, which is contained in the dispersion The content of the nonionic hydrophilicizing agent 3 · is 3% by weight. According to the method of the present invention, a reactive or post-crosslinkable dispersion liquid is used, and a PU dispersion liquid is preferred. The following can be used for these pu dispersion liquids Structural composition: organic one-and / or Gaseous acid, such as, for example: tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2, 'trimethylhexaene Methylene diisocyanate (THDI), dodecane methylene diisocyanate, diisocyanatomethylcyclohexane, 3-isocyanatomethyl-3,3,5_trimethylcyclohexyl isocyanate (Isophor Diisocyanate = IPDI), 4,4, _diisocyanobicyclohexylmethane (®Desmodur W), 4,4'-diisocyanobioxo_3,3, -dimethyldicyclohexyl Arsenic, 4,4'-diisocyanatobicyclohexylpropane_ (2,2), ι, 4_ monoisocyanatobenzene, 2,4- or 2,6-diisocyanatomethyltoluene Or a mixture of these isomers, 4,4'-, 2,4'- or 2,2'-diisocyanatobiphenyl methane or a mixture of isomers, 4,4'-di Isocyanatobiphenylpropane (2,2), p-xylylene diisocyanate and α, α, α ,, α, tetramethyl-m- or -p-xylylene diisocyanate (Tmxdi) and mixtures of these compounds. For modification, a small amount of the terpolymer of diisocyanate, urethane, condensation Step on, urea-based paper this scale applicable Chinese National Standard (CNS) a4 size (210X297 mm)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225495 A7 ---------- ____B7 V. Description of the Invention (7) ^^ ~~~-Formic acid vinegar or Ιιο methylol_. Pictures, DesmGdm, abdomen and / or IPDI are particularly good. 2. Per minute = Polyhydroxy compounds containing ^ to 8 (preferably h7 to M) meridians and (flat weight molecular weight up to 16,000 (up to 4,000,000) are preferred) & Suitable low-molecular weight light-weight compounds under the two definitions are, for example, ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trihydroxymethylpropane, glycerol, Part of hydrazine + 2 parts of propylene glycol reaction product, and molecular weight of 350 to 1 (), (preferably 840 to 3000) polymerized or polymerized polyhydroxy compounds. Higher molecular weight hydroxy compounds include polyurethane chemistry The hydroxy polyesters, hydroxy polyethers, hydroxy polythiol ethers, hydroxy polyacetals, hydroxy polycarbonates, and / or hydroxy polyester amidines known per se are preferably those having an average molecular weight of 350,000 to 4,000, Those having an average molecular weight of 84 to 3,000 are particularly preferred. Hydroxy polycarbonates and / or hydroxy polyethers are particularly preferred. These compounds can be used to produce coagulates that are particularly stable to hydrolysis. 3.a) have acid radicals and / Or a salt-type acid group and at least one isocyanate-reactive group, such as: -OH or -NH2 group ionicity Potentially ionically hydrophilizing agent. Examples are ethylenediamine-ethanesulfonic acid, Na salt (AAS salt solution), dimethylol malonic acid (DMDA), dimethylolbutyric acid, sodium phthalate according to DE-A 2 446 440 Groups of fatty diols, hydroxypivalic acid or 1 mol diamine (preferably isophorone diamine) and 1 mol α, lu-unsaturated weir acid (preferably acrylic acid) Adducts (see German patent application 19 750 186.9). With the last mentioned carboxylate and / or carboxyl or dimethylol propionic acid-free 9- This paper A degree is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back first (Fill in this page again)

5. Description of the invention (8 Α7 Β7 hydrating agent is preferred. Mono- and / or difunctional polyethylene oxide or polyethylene propylene oxide of 300 to 5_ non-ionic hydrophilizing agent. Especially those who It contains 35 to 85% by weight of ethylene oxide units and has a molecular weight of 900 to 250. It is a monobasic functional ethylene oxide based on n-butanol.

Burned / propylene oxide. In combination, the weight of Q μ is at least 6% by weight. In particular, a non-ionic hydrophilicizing agent is preferred. 4. Isocyanate blocking agents, such as , 5-Dimethyl μ, Misal, San · Chuan ch acid ㈣ propyl ~ 酉 夂 C〗 (to C4 alkyl vinegar, ethyl acetic acid) or internal amine ⑻ hexamethylene amine). With dibutylamine, diisopropylamine, and u, heart vomiting is particularly good. The addition of polyamines as chain extenders provides special properties to the polymer backbone of post-crosslinkable dispersions. It includes, for example, the diamine functional hydrophilizing agent mentioned in the polyamine 3a) mentioned in item 6 is also suitable as an added chain extender. Ethylenediamine, IPDa and Hu MDA are particularly preferred. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. VII. Polyamine cross-linking agent for post-parent linkage under the action of X heat. The preferred one is aliphatic or cycloaliphatic diamine, but trifunctional or more than Bifunctional polyamines achieve special properties. In principle, polyamines containing other functional groups (for example: -OH groups) can also be used. When preparing the reactive partition solution, it can be directly mixed or mixed at a later time, which will not enter the polymer structure of the polyamine cross-linking agent at a normal ambient temperature to slightly higher than the ambient temperature (for example: 20 to 60 °). Suitable Examples of fatty polyamines are ethylenediamine, 1,2- and 1,3-propane-10- This paper is suitable for financial purposes g () Α4_ (210X297 mm 1225495 A7 B7 V. Description of the invention (10) 1 ·) t is especially good for isogasic acid 2 ·) is particularly good for poly (^) compounds 3. a) is particularly good for ionic hydrophilic agent 3. b) is particularly good for non-ionic hydrophilic agent 4) capping agent Particularly good 5 ·) Chain-extending polyamine Very good 6 ·) Polyamine cross-linking agent Very good Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Printed 9.0 to 30.0% by weight 13.0 to 20.0% by weight 40.0 to 85.0% by weight 55.0 to 75.0% by weight 1.0 to 5.0% by weight 2.5 to 4.0% by weight 3.0 to 17.0% by weight 6.0 to 12.0% by weight 0.5 to 5.0% by weight 1.5 to 4.0% by weight 0 to 5.0% by weight 0 to 1.5% by weight 1.0 to 6.0% by weight 2.0 to 4.0 wt% reactive post-crosslinkable dispersion Prepared by methods, for example, as follows. Pre-brain polymer is prepared in a single-step method in a single-shirt method, in which polyisocyanate (polyether / polycarbonate) (2.) is made from excess diisonitro acid. The presence of DMPA (3a) and monofunctional polyethylene oxide fluorene at 110 ° C to 110 ° C was shown to be dazzling and sorrowful for about 3 to 6 hours until the theoretical NCO content was measured. Then dilute the high-viscosity NC0 polymer with acetone, for example, the half of the NCO groups contained at about 45 ° C, and react with the end-capping agent (4.), and the remaining NCO groups with diamine ( For example: IPDA) Anti-12 'This paper size is applicable to Chinese National Standard (CNS) A4 specification (mm) 1225495 Printed by the Ministry of Economic Affairs and Intellectual Property, Production Bureau Employee Consumer Cooperative A7 B7 V. Invention Description (ii) ~ ^ -— -Should be used to extend the chain, or if a potentially ionic dispersant such as, for example, DMPA is not added in the previous polymer step, it should be compatible with a potentially ionic dispersant (e.g., iMoore IPDA and iMoprop) Adduct). As soon as NCO groups were no longer detected in this acetone solution, a polyamine cross-linking agent (6.) was added. The amount of the polyamine cross-linking agent is relative to the equivalent of the capped nc0 equivalent to 2 equivalents. In this case, the polyamine cross-linking agent also loosens the cationic role of forming a salt with the added retarding acid (3a) and, together with the structural component (3b), provides the hydrophilic properties required for the above-mentioned polyurethane. Water can now be added to the acetone / valley solution while stirring. As a result, a light blue dispersion was formed. After the acetone was removed under vacuum at 45 ° C, a ready-to-use reactive dispersion was obtained. This method is particularly preferable when a cross-linking agent (6 ·) is used simultaneously as a neutralizing agent for the ionic group of the compound (3a) to obtain an advanced coagulum or dispersion having particularly good coagulation properties. Another specific embodiment includes manufacturing a dispersion liquid by using the above method, and adding a polyamine crosslinking agent only before processing the dispersion liquid. In the above method, a method for producing a reactive dispersion using the acetone method has been described, which generally produces reproducible good product quality. However, other solvents (such as N-fluorenylpyrrolidone) can be used instead of acetone. For a discussion of PU dispersions and related methods, see "Rosthauser and Nachtkamp, Waterborne Polyurathane, Advances in Urethane Science and Technology, vol. 10, pp. 121-162 (1987)". The products according to the invention can in principle also be produced using organic solvents. It has been surprisingly found that the selection of suitable raw materials can also produce a reactive polyamine sulfide dispersion with good water vapor permeability and post-crosslinking. 13- This paper applies to Chinese national standards (CNS) A4 Specifications (210X297mm) " (Please read the precautions on the back before filling this page) Install! D, η'- 口 «ϋ-ϋ m · mu · 1225495 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the invention description (12 liquids. At this time, polyurethane, hydrophilic or glycol, Or hydrophilic polyethylene oxide / polypropylene oxide = or / or polyester polyester-based hydrophilic polyesterdiol or triol = alcohol and ethyl alcohol as components (2 ·). Hydrophilicity can also be used alone Polyols from four unique polyols 2), or a combination of hydrophobic polyols 2). _) Is a better concrete, and the water-based component 2), 3a), and / or 3b) are contained in the polyurethane which can be coagulated ^. The solid content of the dispersion used in accordance with the present invention may be between $ 0 'and a dryness of about ㈣ to 100 Pas. The dryness can be adjusted using 増 _1 = For example: Mirox ^ AM, Walocel® MT 6000 PV, Rheo1w, etc., and can be diluted with water as needed to meet the requirements of the dispersion, processing conditions and final product requirements quality. The reactive post-crosslinkable polyurethane dispersion used according to the present invention can be further modified according to the application mode of the final product. Thus, for example, dyes, pigments and / or carbon black, ultraviolet filter substances, antioxidants, process modifiers, etc. can be used. Other dispersions can also be used, such as, for example, polyurethane dispersions, polyacrylates, polypropionitrile, polyglycerides, polyepoxides, polybutadiene, polystyrene dispersions according to previous techniques Liquid, etc., it is preferred to use up to 50%, up to 25%, to achieve specific properties. The coagulum obtained according to the present invention can be directly processed into a flat material in situ during the reaction and / or reflex. The quantity should be customized. I m-= a-m 1 line -14- Chinese paper standard (CNS) A4 (21 × 297 mm) 1225495 A7 B7 applicable to each paper size V. Description of the invention (13) The flat material obtained by the invention can also be subsequently dyed by known methods. The identification of the dispersion liquid used according to the present invention is to measure the non-volatile matter content, viscosity, and to determine the stress and tension properties of the drawn film strip. The reactive post-crosslinkable dispersion liquid used according to the present invention can be applied by, for example, a flow coating method, a spray method, a dipping method, a laminating roll method, or a film spreader or a roll press or a paddle type machine. Cloth, and the dispersion can be used in the form of a liquid or foam. Pass ¥. After coating according to one of the methods above, it will be coagulated. It is immersed in hot water at 50 ° C to 120 ° C (preferably at 75 ° C to 98 ° C). Hot water steam is used in special applications. Then, fill the molded component with hot water, heat the model to 120 ° C to 13 ° C, or use radiation or a high-frequency dryer in an oven, and then at 60 ° C to 180 ° C (at 100 °.) : It is better to 160 °.) Drying and condensation. Flat substrates of fabric, metal, glass, ceramic, leather and plastic such as: PVC, polyolefin, polyurethane or the like are suitable as supporting materials. The term "fabric" in the definition of the present invention refers to, for example: woven and knitted fabrics, bonded and unbonded non-wovens. Fabrics can be made from synthetic or printed fibers and / or mixtures of the consumer cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A fabric made of any fiber is basically suitable for the method according to the present invention. The special effect of the method according to the present invention is to apply a coating on the support material, coat the substrate, and make a flat and shaped film, such as, for example, gloves , Protective cover, etc. And the general final modification for different operation methods. -15- 1225495 A7 B7 V. Description of the invention (The resistance of the coagulum produced by M makes it applied to saponification and ⑽_% NaOH), and can be made into microfibers. Perform a sinking operation, in which a part of the contained polyester is saponified and dissolved. As a result, a soft fabric with a particularly comfortable operation feeling is formed.-The fabric coated or filled on one or both sides is then polished and then particularly soft .Mechanical treatments on drum-type money machine towels will also increase the softness. ° ^ Example Example 1 (in accordance with the present invention) The following describes the method for preparing a reactive PU dispersion, which is based on the removal of isocyanate as the isocyanate component and methyl ethyl ketone. The oxime is used as a capping agent, and 4,4, _diaminodicyclohexylmethane is used as a polyamine post-crosslinking agent. A polyether polyol having a mixture of 0H and 56, and OH is produced by a method of trimethylolpropane propion oxidation. Polycarbonate number 56, polypropylene glycol based on 丨, 6-dihydroxyhexane as the main OH number. Read the note on the back first

Ordered by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 110.0 grams (0 · 110 grams equivalent) 110.0 grams (0 · 110 grams equivalent) 80.0 grams (0.080 grams equivalent) 49.5 grams (0.022 grams equivalent) 76.5 grams (0.612 grams equivalent) Polyether polyol (dispersant) with a unit number of 25, manufactured by the ethoxylation method and the propion oxidation method of n-butanol (block 50/50%), 4, diisocyanatobibenzidine (MDI) -16- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 1225495 A7 B7 V. Description of the invention (1S) 12 · 18 grams (0.14 grams equivalent) 60.40 grams (〇 · 15 Gram equivalent) 14.70 grams (0.14 grams equivalent 533.57 grams butanone oxime dispersion (30% aqueous solution of the adduct of 1 mol acrylic acid and 1 mol IPOA), 1 ΝΗ / ΝΗ2 equivalent = 403 grams, 1 COOH equivalent = 806g) 4, cardiodiaminodicyclohexylmethane (Η12, j MDA or PACM 20) Water Please read the notes on the back-S Fill out this page m 1046.85 g dispersion (45%) 471 · 00 g solids Theoretical value of 575.77 grams of water content of 23 ° C viscosity: about 600mPas The above dispersed polyaminophosphonate (100%) contains: 1.25% by weight of blocked NCO groups, calculated NCO is 42 • 0.47% by weight of NH2 groups, calculated NH2S 16 method, taking anhydrous polyol (including monofunctional "polyethylene oxide dispersant" ) Stir into the full amount of MDI. The reaction mixture is heated to 85.0. After about 5 hours of reaction, the NCO content is measured at 2.7% and the theoretical value is 2.86%. The mixture is cooled to about 6 ° C with 500 grams. Diluted with acetone, and added butanone oxime with stirring at 45 C. After stirring at 45 ° C for about 30 minutes, it was found that the NCO content was 0.59%, and the theoretical value was 0.67 ° /.. Aqueous dispersant solution was added at 45 ° C Continue to stir for 1 hour until NC0 is no longer detected -17- To the fullest paper standard General China National Standard (CNS) A # specifications (21 οχ297 mm) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives 1225495 Α7 Β7 Five The Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the invention description (16)-group. Then add the full amount of H12MDA at a time, and at short intervals, pour water into the acetone solution, stir well and disperse it in water. After acetone is distilled off (45 ° C, 250 to 20 mbar (About 3 to 4 hours) to obtain a milky blue dispersion with a viscosity (23.00 about 600 mPas and a solid content of 45%). Example 2 (according to the present invention) This reactive dispersion differs from the dispersion according to Example 丨 only in that it is a capping agent. Now use 13.44 g (0.14 g equivalent) of 3,5-dipyridylpyrazole instead of butanone oxime. This blue dispersion has a solids content of 45% and a viscosity of 23 ° C) of approximately 4400 mPas. Example 3 (according to the present invention) This reactive dispersion differs from the dispersion according to Example 1 only in the capping agent, and now 14.14 g (0.4 g equivalent) of diisopropylamine is used instead of butanone oxime. The stable blue dispersion has a solid content of 45% and a viscosity (23 ° C) of about 2200 mPas. Example 4 (According to the present invention) The method for preparing a reactive PU dispersion is described below, which uses IPPI as the isocyanate component and 1,2,4-Trisalyl is a capping agent, and 4,4'-diaminodicyclohexylmethane is a polyamine cross-linking agent. Mixture 185.0 g polyether polyol with a number of 56, (0.185 g equivalent) 230.0 g (0.230 g equivalent) made by the trimethylolpropane oxidation method. Polybutanediol with a number of 56-this paper Standards are applicable to Chinese National Standards (CNS) A4 specifications (2 丨 〇 < 297 mm) 1225495 A7 B7 Polyethylene glycol with a number of 56 and manufactured from propoxy-ethoxylated water (block about 50/50) %) Polyether polyol with a unit number of 25 (dispersant, see Example 1) Isophorone diisocyanate (IPDI) 1,2,4-triazole Potential ionic dispersant isophorone di according to Example 1 Amine (IPDA) 4,4'-Diaminodicyclohexylmethane (Η12 MDA or PACM 20) Demineralized water dispersion (40%) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (17) 70.0 g (0.070 g equivalent) 34.0 g (0.015 g equivalent) 100.0 g (0.90 g equivalent) 12.07 g (0.175 g equivalent) 60.45 g (0.150 g equivalent) 6.37 g (0.075 g equivalent) 18.40 g (0.175 g equivalent) ) 968.68 g 1684.97 g 673.97 g 1011.00 g method solid content theoretical value water content viscosity (23 ° C): l〇〇〇mPas the IPDI with a dehydrating hydroxy compound reacted together for about 5 hours at 105 ° C, until the NCO content was reduced to 2.67% stopper, the theoretical value of 2.7%. Then add the white flakes of triazole, and stir the mixture at 100 ° C for about 1 hour 19- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1225495 A7 B7 V. Description of the invention (18 ), The NCO content was found to be 1.4%, and the theoretical value was 1.49%. It was then diluted with 500 g of acetone, about 45% aqueous dispersant solution was added, and IPDA was added after 15 minutes. Stirring was continued for 30 minutes at 45 ° C, no more NCO groups were detected (IR spectrum). Polyamine cross-linking agent PACM 20 can now be added with stirring. After 10 minutes, it is dispersed with water. After the acetone was distilled off (45 ° C, 250 to 20 mbar, about 3 to 4 hours), a milky blue dispersion with stability (50 ° C) was obtained. The viscosity (23 ° C) was about 1000 mPas and the solid content was 40%. . Example 5 (According to the present invention) A method for producing a reactive PU dispersion is described below, and the coating is water vapor permeable. Its structure is only slightly different from Example 1. The change lies in the composition of the three polyols listed below. All other ingredients correspond to the amounts and properties of the ingredients described in Example 1. 100.0 g (0.100 g equivalent) of a polyether polyol with an OH number of 56 produced by the propoxylation method of trimethylolpropane 100.0 g (0.100 g equivalent) of a polycarbonate with an OH number of 56 based on 1,6-dihydroxyhexane 100.0 g (0.100 g equivalent) based on alkane Polypropylene / ethylene glycol with OH number 56 (polyethylene < glycol content of about 50%) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This blue dispersion is almost a solution , Solid content 35%, viscosity (23 ° C) is about 2000mPas. Application Example 1 Strengthening of non-woven fabrics. Non-woven fabrics mainly composed of polyamide and polyester fibers without pre-treatment, which are diluted with water to 10% solids content. Dispersion liquid according to Example 1-20- This paper Standards apply to Chinese National Standard (CNS) A4 specifications (210X297 mm)

Description of the invention (Condensation under C, opening and closing points ^. Then two types of wrestling are completed at 15Θ to 16-times. F The strength of the dryer is strong enough to pass through: and resistant membrane :: : =: = It will not move on the surface. It will prevent the water from moving on the surface and add the final repair agent barrel: dry, polished, or ^, it changes by 70%. It is similar to leather. ς 'Cracks the non-woven fabric, it is easy to adjust the straightness of the non-woven fabric. Take the degummed non-woven fabrics mainly composed of amine and polyester fiber, and use the additive content = dilution = 1G% 1] according to the content of the fabric manufactured in Example Dispersion solution I, in a tank containing 3% sodium hydroxide solution, coagulated at 95 to 10 (Tc, " on the same day, the polyester fiber contained in the non-woven fabric was saponified and dissolved. Treatment The time is 45 minutes. Then wash the strips thoroughly with water, squeeze and dry at 120 ° C. Then condense at 160 ° C. Each side is polished once or twice. A soft fabric with a particularly pleasant operating feel is obtained. Application Example 3 Oblique coating of metal and / or fish glass bottles to obtain metal or glass articles directly or indirectly using heated liquid To 90-100 ° C, immersed in the dispersion made according to Example 3 and diluted to 20%. It is easy to control the film thickness using the soaking time and the concentration of the PU dispersion -21- This paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm)

1225495 A7 -----—___ B7 V. Description of the invention (20) ~ Degrees. The resulting gel was condensed at 60 ° C without contacting each other. ,then

Adding an aqueous pigment preparation, you get a series of interesting shades. The coating is characterized by excellent adhesion. D Application Practice i Set of textile ferritic coatings The textile blank was pulled into a glove shape and immersed in the dispersion made according to Example 5 'using a commercially available thickener product to adjust to about 2000 to 3000 mPas. The thickening of the dispersion prevents the dispersion from penetrating into the fabric during soaking. After immersion, the outer layer was immersed in hot water at 60 to 95 ° C for 10 seconds, then dried at 120 ° c and condensed at 160 ° c. If necessary, pigment preparations can be added to the post-crosslinkable dispersion to make colored gloves. Application Example 5 Unsupported Gloves or Nylon Cover Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Take a prototype heated to 80-120 ° C and immerse it in the dispersion made in Example 4 and diluted to 25% solids. Depending on the required film thickness, the residence time is 5 to 20 seconds. The gel was then dried on the prototype at 80 to 100 t: and then condensed at 160 ° C. The produced film has no pores and has excellent elasticity and strength. -22- This paper size applies to China National Standard (CNS) A4g (210X297 mm)

Claims (1)

Patent Application No. 8812037 Received by RoC Patent Application No. 88210037 Amended Claims in Chinese-Encl. (T) '(Chinese version) (Appendix dated May 17, 1993) ( Submitted on May 17, 2004) 10 'A method for coagulating a post-crosslinkable PU dispersion, which is characterized in that = the post-crosslinkable dispersion is heated at 50 to i2 (rc at rc and sinks =, forming a stable and At least partially crosslinked polyurethane or gel 'wherein the dispersion used contains: a) 0.1 to 7.5% by weight of blocked isocyanate groups (calculated NC = 42), and 15 b) at least one polyamine and / or hydroxylamine, which contains at least two rings (aliphatic) 2. Bonds, primary, secondary and / or secondary amine groups, a) blocked isocyanate groups and b) amines The base equivalent ratio is from 1: 0.5 to 1: 1.5. 2 The method for coagulating a post-crosslinkable PU dispersion according to item 1 of the scope of patent application, which is characterized in that the post-crosslinkable dispersion is precipitated by heat treatment at 75 to 98 C, forming a stable and at least Partially crosslinked poly 20 urethane or gel. 3. The method of making the post-crosslinkable Ke dispersing liquid condensate in accordance with the scope of the patent application, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, characterized by making the post-crosslinkable dispersion at 75 to 98 C. Under heat treatment, Shen Dian forms a stable and at least partially crosslinked urethane or gel, which is further characterized by the use of a dispersion of 25 liquids containing: a) 0.25 to 5% by weight of blocked isocyanate groups (Calculated NC0 = 42), and b) at least one polyamine and / or hydroxylamine, which contains at least two (cyclic) lipids 88426B-th-23-1225495 A8 B8 C8 D8 The equivalent ratio of primary and / or secondary amine groups, a) blocked isocyanate groups to b) amine groups is ι: 0 · 7 to 1: 1.2. 4. The method for coagulating the post-crosslinkable pu dispersion according to item 丨 of the scope of the patent application, which is characterized in that the post-crosslinkable PU dispersion is heat-treated at a temperature of 75 5 to 98 C and formed. A stable and at least partially crosslinked polyurethane or gel, which is further characterized in that the dispersion used contains: a) 0.7 to 2% by weight of blocked isocyanate groups (calculated NCO = 42), And 10 b) at least one polyamine and / or hydroxylamine containing at least two (cyclo) aliphatic bond primary and / or secondary amine groups, a) equivalent ratio of blocked isocyanate group to b) amine group From 1: 0.9 to 1: 1.1. 5. The method for coagulating a post-crosslinkable pu dispersion according to item 1 of the scope of the patent application, which is characterized by using a dispersion mainly composed of a hydrophilic raw material (especially a hydrophilic 15-polyol) to form water vapor. Penetrating Condensate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, a type of polyaminophosphonate dispersion that can be post-crosslinked and made in accordance with item 1 of the scope of patent application, which is characterized by the reaction of the following ingredients The product is in the form of an aqueous dispersion or emulsion: 20 1. at least one organic di- or polyisocyanate, 2. at least one polyhydroxy compound having a molecular weight of up to 16,000, 3. ionic or potentially ionic hydrophilicizing agents and / or non-ionics Hydrophilic hydrophilizing agent, 4 · isocyanate blocking agent, and 25 5 · select low molecular weight monoamine, diamine or triamine as chain-24-this paper size applies Chinese national standard (CNS ) A4 size (210x297 mm) 1225495 Α8 Β8 C8 -------- VI. Patent application suspension component, chain extension component or chain branch component, which also contains 6. · polyamine cross-linking agent, which contains In the dispersion liquid, the content of the component 3) is sufficient to form a stable dispersion liquid. 7. The curable, post-crosslinkable polyamine 5 carbamate dispersion according to claim # 6, which is characterized in that it is a reaction product of the following ingredients and is in the form of an aqueous dispersion or emulsion: 1 9 to 30% by weight of at least one organic diisocyanate, 2.40 to 85% by weight of at least one molecular compound having a molecular weight of 35 to 40% and containing up to the last B energy group, 10 3 · 4 to 22% by weight % Of ionic or potentially ionic hydrophilizing agent and / or non-ionic hydrophilizing agent, 4.0 to 5 wt% of isocyanate-based blocking agent, and 5.0 to 5 wt% of low molecular weight Early, di or triamine, as a component of bond termination, bond extension or bond branching, 15 which additionally contains 6.1 to 6% by weight of a polyamine cross-linking agent, which is contained in the dispersion, nonionic hydrophilization The content of the agent 3) was 3% by weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Or the reaction product of 1 mol diamine and 0.5 to 2 mol acrylic acid is used as the hydrophilizing agent 3). 9. A curable, post-crosslinkable polyurethane dispersion according to item 6 of the scope of the patent application, characterized in that it contains butanone oxime, diisopropylamine and / or triazole as capping agent 4). 25 10. Condensable and post-crosslinkable polyamine-25 according to item 6 of the scope of patent application-This paper size applies to China National Standard (CNS) A4 (210 X297 mm) A8 B8 C8 D8 The succinic acid vinegar dispersion is characterized in that it contains dimethylsulfalic acid as a capping agent 4). 11. The curable and post-crosslinkable polyurethane dispersion according to item 6 of the patent application, which is characterized in that the polyamine used as the crosslinking agent 6 is additionally used as the acid-based neutralizer of the component 3). Features. 12. The curable and post-crosslinkable polyurethane dispersion according to item 6 of the application, which is characterized by containing isophorone diamine, TCD diamine, Laromin C260, PACM 20 and / or Ethyl triamine is used as the crosslinking agent 6. 10 15 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 13. Condensable and post-crosslinkable polyurethane dispersion according to item 6 of the scope of patent application, which is characterized by component 2) partial or complete Composed of hydrophilic polyols, condensate that is saturated with water vapor is obtained. 14. A method of coagulating a post-crosslinkable PU dispersion according to item 1 of the scope of the patent application, thereby obtaining a coagulable dispersion for coating a surface. 15_ The method of coagulating a post-crosslinkable pu dispersion according to item 1 of the scope of patent application, thereby obtaining a coagulum. 16. A method of coagulating a post-crosslinkable pu dispersion according to item 1 of the scope of the patent application, thereby obtaining a condensate that can be penetrated by water vapor. 17. A method for coagulating a post-crosslinkable PU dispersion according to item 1 of the scope of the patent application, thereby obtaining a coagulable dispersion for coating a surface. 18. · The method of coagulating the post-crosslinkable pu dispersion according to item 丨 of the scope of the patent application, thereby obtaining a coagulable dispersion for strengthening non-woven fabrics 0 -26-This paper is applicable to China ^^^^ 10x297--