CA1241142A - Coating agents of polyurethane dispersions and the use thereof for top coats and finishes - Google Patents

Coating agents of polyurethane dispersions and the use thereof for top coats and finishes

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Publication number
CA1241142A
CA1241142A CA000408850A CA408850A CA1241142A CA 1241142 A CA1241142 A CA 1241142A CA 000408850 A CA000408850 A CA 000408850A CA 408850 A CA408850 A CA 408850A CA 1241142 A CA1241142 A CA 1241142A
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Prior art keywords
weight
coating agent
molecular weight
agent according
component
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Application number
CA000408850A
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French (fr)
Inventor
Wilhelm Thoma
Klaus Noll
Klaus Nachtkamp
Josef Pedain
Walter Schroer
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Bayer AG
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Bayer AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/721Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06Homopolymers or copolymers of vinyl chloride
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31551Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/3158Halide monomer type [polyvinyl chloride, etc.]

Abstract

Mo-2402 LeA 21,088 COATING AGENTS OF POLYURETHANE DISPERSIONS
AND THE USE THEREOF FOR TOP COATS AND FINISHES
ABSTRACT OF THE DISCLOSURE
This invention relates to coatinq compositions based on aqueous polyurethane dispersions, as well as the use of the coating compositions for the production of top coats or finishes on flexible substrates, particularly on PVC.
Thc present coating agents contain an aqueous polyurethane dispersion having certain physico-chemical properties and the following composition of the solid substance:
(A) from about 30 to 60%, by weight, of a hexane diol-1,6-polyester diol having a molecular weight of from about 500 to 6000;
(B) up to about 8%, by weight, of a relatively low molecular weight triol having a molecular weight of from about 91 to 399;
(C) from about 3 to 30%, by weight, of one or more mono-or poly-functional compounds bearing cationic and/or anionic groups and/or containing non-ionic polyoxyethylene segments;
(D) from about 20 to 50%, by weight, of a diisocyanate corresponding to the following general formula:
wherein R1, R2 and R3, which may be the same or different, each represents hydrogen or a straight- or branched-chain aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms;
Mo-2402 (E) from about 2.5 to 20%, by welght, of other aliphatic and/or cycloaliphatic diisocyanates; and (F) from about 0.5 to 4%, by weight, of hydrazine; and optionally conventional additives,auxiliaries and catalysts.
Mo-2402

Description

COATING AGENTS OF POLYURETHANE DISPERSIONS
AND THE USE THEREOF FOR TOP COATS AND FINISH~S
BACKGROUND OF T~E I~VENTION

_eld of the Invention This invention relates to coating compositions based on aqueous polyurethane dispersions and to the use thereof for the production oftop coats or finishes on flexible substrates, in particular on PVC. The present coating agents comprise an aqueous polyurethane dispersion having 10 certain physico-chemical properties.
Descxiptlo f the Prior Art The production of polyurethane coatings on PVC is known in principle. Thus, for example, U.~. Patent Nos.
3,262,~05; 4,017,493 and 4,045,600 describe processes for 15 the coating of PVC using one- or two-component polyuxe-thane systems dissolved in organic solvents.
The use of solven~-containing coating agents is accompanied by numerous problems, however, and for economical and, in particular, ecological reasons, it is 20 nec~ssary to restrict as ~ar as possible or even to a~oid completely the use of organic solvents. It is known from Ger~an Offenlegungsschrit No. 1,769,387 (British Patent No. 1,191,260) to cement PVC with aqueous polyurethane dispersions. However, the aqueous polyurethane disper-25 sions could not be used as a top coat or finish on PVCas it has not been possible hitherto to provide products having, on the one hand, good adhesion to PVC and, on the other hand, the high level of quality demanaed in the coatings industry for top coats and finishes (high so~ten-30 ing point; hiyh mechanical strength; stability to hyclroly-sis and ageing; minimal swelling in plasticizers; blocking acti.on against the migration of the plasticizers contained in the PVC; avoidance of discoloration at the gelation temperatures of PVC pastes; and pleasant dry feel).
Mo-2402 LeA 21 088-US
~ ~dr~ ~

The coating agents descrlbed in German Offenlegungs-schrift ~o. 2,807,479 made it possible for the first time to provide aqueous polyurethane dispersions which almost met the above requirements and allowed the production of 5 coatings on PVC, in particular on foamed PVC, without the use o~ solvents.
However, these coating agents still have some dis-advantages which make them difficult to use:
The flex resistance of the final composite material 10 is often inadequate and the adhesion to the PVC is unsatis-factory.
In particular, however, the fact that the coating agents are composed of mixtures of two polyurethane dis-persions is a considera~le disad~antage. Such mixtures 15 are invariably expensive and complicated to produce and may give rise to errors , Moreover, the compatibility of the two systems must be guaranteed.
It has now been found that the disadvantages of the system according to German Offenlegungsschrift No.
20 2,807,479 may be overcome and that it is still possible, with uniform polyurethane dispersions, to produce coatings on PVC which have an exceptional level of quality if a dispersion of a certain composition is used. ~his is all the more surprising since it is quite impossible with the 25 individual dispersion components according to German ~ffenlegungsschrift ~o. 2,807,47g to produce coatings or finishes on foamed or non-foamed PVC which meet the essential requirements as regards ~uality.
---SVMMARY OF THE INVEMTION
.
The present invention relates to coating agents based on aqueous, polyurethane disperslons containing a solid/ composed of essentially linear polyester diols, diisocyanates, compounds which contain hydrophilic groups and are mono-and/or di-func-35 tional towards isocyanates, as well as optionally Mo-2402 ~2 relatively low molecular weight trifunctional components and difunctional chain-extenders, as well as optionally conventional additives, auxiliaries and catalysts, characterized in that the solid substance is 5 composed of:
(A) from about 30 to 60%, by weight, preferably from about 35 to 50%, by weight, of a polyester diol having a molecular weight of from about 500 to 6000 9 preferably from about 500 to 3000 and wherein the diol 10 component comprises at least about 80 mol % of hexane diol-1,6;
(B) from about 0.5 to 5%, by weight, of a relatively low molecular weight triol having a molecular weight of from about 92 to 399;
15 (C) from about 3 tv 30%, by weight, preferably from about 5 to 20%, by weight, of one or more mono- or polyfunctional compounds containing anionic groups and/or non-ionic polyoxyethylene segment~;
(D) from about 20 to 50%, by weight, preferably from 20 about 25 to 40%, by weight, of a diisocyanate corresponding to the ~ollowing general formula:
/~~~\ NCO
oC~ C ~ ~
25 wherein 1 3 Rl, R2 and R3, which ~ay be the same or dif-ferent, each represents hydrogen or a straight- or . ; branched-chain aliphatic hydrocarbon radical containing from l to 4 carbon atoms;
30 (E) from about 2.5 to 20%, by weight, preferably from about 4 to 18%, by weight, of other aliphatic or cyclo-aliphatic diisocyanates; and (F) from about 0.5 to 4%, by weight, preferably from about 0.8 to 3%, by weight 9 of hydrazine.

Mo-2402 DETAILED DESCRIPTION OF T~E INVENTION
The hexane diol-1~6-polyesters(A) to be used accord-ing to the present invention preferably contain as acid component aliphatic dicarboxylic acids, for example suc-S cinic acid, suberic acid, acelaic acid, sebacic acid,hexahydrophthalic acid anhydride, endomethylene tetra-hydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, fumaric acid, and preferably adipic acid.
In addition, carbonic acid is also preferred, but it is 10 obviously possible to use derivatives of carbonic acid, such as diesters, for example, diphenyl carbonate and diethyl carbonate, or also phosgene, for the prepara-tion of the polyesters.
The use of aromatic dicarboxylic acid, such as 15 phthalic acid, isophthalic acid and terephthalic acid, is less preferred. In addition to hexane diol-1,6, it is also possible, in a less preferred embodiment, to use amount-q of other diols, for example, butane diol-1,4, diethylene glycol or EO-(C~2)6-O-CO-(C~2)5-O~, but the 20 content thereof should not exceed approximately 20 mol %.
The molecular weight of the hexane diol-1,6-polyesters (A) should be from about 500 to 6000, preferably from about 500 to 3000.
The lower molecular weight triols (B) inc].ude, in 25 particular, glycerin, trimethylol propane, trimethylol ethane and the various isomeric hexane triols, as well as 1,3,5-tris-hydroxy-cyclohexane. The lower alkoxylation products thereof are also suita~le. The molecular weights should preferably be from about 92 to 399.
Suitable hydrophilic compounas (C) include structur-al components of the type ex~mplified in the literature concerning the production o~ a~ueous polyurethane disper-sions and solutions, which are mono- or difunctional, in particular difunctional, in the context of the 35 isocyanate addition reactions and which contain cationic Mo-2402 .

~2~

and/or anionic hydrophilic groups and/or non-ionic hydro-philic polyoxyethylene isocyanates. These are, for exam-ple, dihydroxy compounds; diamines or diisocyanates con-taining ionic or potential ionic groups (for example 5 tertiary amine groups which become ammonium groups when they are acidified or alkylated), or also monoalcohols, monoamines or monoisocyanates containing polyethylene oxide units.
The preferred hydrophilically modified structural 10 components (C) include, in particular, the aliphatic diols containing sulphonate groups according to German Offen~
legungsschrift No. 2,446,440 corresponding to the follow-ing general formula:
HO-[cH_cH2_O]n_cH2_cH2_cH_cH2_[o_cH2_cH]m-oH
X S8Me R
wherein R represents hydrogen or an organic radical containing from 1 to 8 carbon atoms;
n and m are integers of from 1 to 10; and 20 Me represents a quaternized ammonium ion or an alkali metal cation~ propoxylated addition product of sodium bisulphite to butene diol~
the cationic or anionic incorporable internal emulsifiers according to German Offenlegungsschrift No. 2 651 506 or diamino sulphonates 25 corresponding to the following formula:
NH2 (C~l2)2-6-NH-(CH2)2_3-S03 cation ~.

: The monofunctional, incorporable hydrophilic polyethers described inGerman Offenlegungsschrift No. 2651 501, which preferably have a 30 molecular weight of from about 200 to 3000 and a polyoxyethylene content of from about 60 to 95O. by weight~are also preferred.

The ammonium or alkali metal salts of organic dihydroxymonocarboxylic acids, for example the salt of Mo-2402 ^ - ~
2,2-dimethylol propionic acid, are a type of preferred, incorporable ionic compounds.
~ he dicyclohexyl alkane diisocyanates (D) to be used according to the present invention corresponding to the 5 following general formula:

Rl ~ ¦ ~ NCO

OC ~ ~ R3 wherein Rl, R2 and R3 represent H or Cl-C4 straight- or branched-chain alkyl radicals;
include the isomers (for example, 2,2'-, 2,4'- and 4,4'-15 isomers) and the cis/trans, cis/cis and trans/trans conformers of diisocyanato dicyclohexyl methane. ~owever, the representatives of the corresponding ethylidene, pro-pylidene, butylidene compounds, as well as other homo-logues are also included, for example 4,4'-diisocyanato 20 dicyclohexyl dimethylmethane. Diisocyanates wherein R3 does not represent hydrogen, but a monovalent hydrocarbon, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or t-butyl, are less preferred.
The diisocyanates (E) which are to be used pro-25 portionally but do not correspond to ~e above formulainclude tetramethylene diisocyanate, xylylene diisocyanate, as well as the perhydrated derivative thereof, cyclo-hexylene diisocyanate-1,3 and 1,4, as well as, particular-ly preferably, 3-isocyanatomethyl-3,5,5-trimethyl-cyclo-30 hexylisocyanate and hexamethylene-1,6-diisocyanate.
Other diisocyanates to be used include lysine methyl ester diisocyanate, 2,4- and/or 2,6-hexahydro toluylene diisocyanate, l,9-diisocyanato-5-methyl nonane, 1,8-diisocyanato-2,4-dimethyl octane. The cycloaliphatic 35 diisocyanates may be used as mixtures of the positional Mo-2402 isomers thereof as well as stereo isomers (conormers).
The hydrazine (F) is prefexa~ly used in the ~orm of its ke-tazines (reaction products with, for example, acetone or other ketones, such as methylethyl ketone) or 5 optionally also in the ~orm of its carbonic acid salts.
Additives and auxiliaries, as well as catalysts, which are conventional in polyurethane chemistry ma~ be added in the conventional manner and quantity. They are listed, ~or example, in German Auslegeschrift No. 2,854,384.
Processes for the production o~ stable aqueous polyurethane dispersions which are suitable accordiIlg to the present invention are described, for example, in German Auslegeschrift Nos. 1,178,586 (U.S. Patent No.
3,480,592), 1,495,745 (~.S. Patent No. 3,479,310) and 15 1,770,068 (U.S. Patent No. 3,756,992), German Offenlegungs-schrift Nos. 2,314,512 (U.S. Patent No. 3,905,929), 2,314,513 (U.S. Patent No. 3,920,598), 2,320,719 (sritish Patent No. 1,465,572), 2,446,440; 2,555,534 and 2,811,148 and also in "Angewandte Chemie" 82, 53 (1970) by D. Die-20 terich. The general principle o this process involvesincorporating hydrophilic centers as so-called "internal emulsifiers" into the chain of a polyurethane or poly-urethane urea macro-molecule. Anionic or cationic groups and/or -CH2-CH2-O-sequences may be 25 used as hydrophilic centers in this sense.
In order to proauce polyurethane dis~ersions, an NCO prepolymer having terminal NCO groups is generally produced first ~rom a relatively hiyh molecular weight hexane cliol polyester diol, a relatively low molecular 30 wei~ht triol and an excess o~ polyisocyanate, and is then converted by chain-extension, for example as in the pro-cesses in German ~uslegeschri~t No. 1,495,745 (U.S. Patent No. 3,479,310), German Offenlegungsschri~t Nos. 1,770,068 (U.S. Patent No. 3,756,992), 2,446,440 and 2,811,148 into 35 a polyurethane dispersion. The relatively high molecular Mo-2402 weight polyhydroxyl compound and the optional relatively low molecular weigh~ alcohol may contain ionic groups or groupings which may be converted to ionic groups, of the type listed, for examplef in German Offenlegungsschrift 5 Nos. 1,770,068 and 2,446,440. However, it is also possible, in addition to or instead of the ionically modified high and low molecular weight alcohol to incorporate into the macro-molecule monohydric alcohols or diols having ethy-lene oxide sequences as hydrophilic segments, as described, 10 for example, in German Offenlegungsschrift Nos. 2,314,512 (U.S. Patent No. 3,905,929); 2,551,094; 2,555,534 and 2,651,506. In principle, however, it is also possible to produce hydrophobic prepolymers (i.e. those without hydro-philic centers) and then to convert them by chain-ex-15 tension, for example with diamines or diols containingionic groups(German Offenlegungsschrift No. 2,035,732~
into polyurethanes or polyurethane ureas which are dis-persible in water.
During the production of the NCO prepolymers, the 20 reactants are generally used in proportions corresponding to a ratio of isocyanate groups to isocyanate-reactive hydrogen atoms, preferably hydroxyl groups, of from about 1.1:1 to 10:1, preferably from about 1.3:1 to 3:1.
The NCO prepolymers are preferably produced in the 25 melt at from about 30 to 190C, preferably from about 50 to 120~C. The prepolymers may obviously also be produced in the presence of or~anic solvents. Suitable solvents which may be used, for example, for lowering the ~iscosity of particularly highly viscous NCO prepolymers include, Mo-2402 ~2 ~
g ~or example, acetone, methylethyl ketone, ethyl acetate, cyclohexanone, toluene, optionally also dimethyl formamide or N-methylpyrrolidone.
The quantity of solvent may be calculated in such 5 a way that the chain-extension of the NCO prepolymers with hydrazine and optionally hydrophilic components may be carried out in the solvent and the resulting solution is of sufficiently low viscosity to be converted into a dispersion with water. In this process, it is advisable 10 to use a solvent having a boiling point far below that of water so as to simplify removal by distillation.
However, the dispersions according to the present invention are preferably produced by the process described in German Offenlegungsschrift No. 2,811,1~8. The NCO
15 prepolymer is mixed with an azine and may be converted into a dispersion with water without the use of a solvent.
Chain-extension takes place in the heterogeneous phase as the chain-extender hydrazine is li~erated slowly from the azine by water. Solvents may also be used in this 20 process, but they are usually only added to the prepoly-mer in small quantities, optionally to reduce the viscos-ity thereof or as a coalescing agent. In this case, it is even prefera~le to use high-boiling solvents.
The solid substances in the dispersion contain from 25 about 5 to 50, preferably from about 10 to 30, ~pseudo-) millie~uivalents of hydrophilic groups per 100 g of solid material. A "pseudomilliequivalent" is the quantity of ethylene oxide units in the polyurethane, preferably in a polyether chain which is lateral to the main chain o~
30 the polyurethane molecule, whose hydrophilizing propertiés correspond to one millie~uivalent of ionic groups.
By definition, 0.5~, by weight, of -CH2-CH2-O- units should correspond to one "pseudomillie~uivalent percent".
The compositions according to the present invention 35 contain the emulsifiers needed for the dispersion thereof ~o-2402 ~f~
- -in water in the f~rm of incorporated hy~rophilic groups of the type described above. While the addition of known external emulsifi~rs is obviously also possible, it is not preferred. How-ever, if external emulsi~iers are used, the content o~ incorporated emulsifier may be reduced.
The dispersions generally have a solids content of from about 20 to 60~, by weight, preferably from about 35 to 50%, by weight. The diameters of the particles in the dispersion may vary from about 20 nm to 1 ~m, but should generally be from about 50 and 200 nm.
The aqueous PU~ dispersions according to the present invention may be mi~ed with aqueous non-PUR dispersions and a~ueous solutions of other polymers, for e~ample with dispersions of vinyl and/or diene polymexs composed of vinyl chlorlde, vinylidene chloride, vinyl acetate, 15 vinyl alcohol, styrene, ~meth) acrylic acid ester, butadiene, isoprene, chloroprene; solutions of polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, starch, gelatines, casein; aqueous dispersions of nitrocellulose, etc.
The known agents for improving the feel as well as pigments, flow agents, thickeners and other auxiliaries may obviously also be added to the present coating compo-sitions. They may optionally also contain solvents, such as alcohols, amides or ketones (in quantities of prefer-25 ably less than about lO~, by weight, based on aqueous dispersion composition).
The coating agents according to the present inven-tion are suitable, in particular, as top coats or finishes in the coating of textiles with RVC. Three different 30 possible methods o:E applying the present composi~ions are to be described below as exampleg:
1. The dispersion composition according to the present invention is applied, for example, by spreading, spraying or printinri , to a solid, optionally textured or embossed, Mo-2~02 PVC film. The coating is generally dried at from about 70 to 190C for from a~out 20 to 200 seconds in a heating duct. Next, the synthetic leather material ob-tained in this way is optionally embossed mechanically and 5 then rolled.
2. The polyurethane dispersion composition is spread onto a sheet of release paper or another support material (for example a steel strip) and dried in a heating duct.
A degassed PVC paste is applied to the dried PUR film 10 using a doctor blade. The textile to be coated is a~plied onto the PVC paste. The PVC is caused to gel in a known manner in a heating duct. After cooliny, the sheet of release paper or the other support material is removed and the synthetic leather rolled.
15 3. The composition according to the present invention i9 spread on a sheet of release paper or another support material, such as a steel strip and is dried in the heat-ing duct. A PVC paste containing chemical blowing agents, such as azoisobutyric acid dinitrile and azodicarbonamide, 20 is spread onto the dried PUR film (c~., also, F. ~ober.
An~w. Chem. 64, 65 (1952); R. Reed, Plastics Progress 1955, 51; H. A. Scheurlen, Kunststoffe 47, 446 (1957))-A textile is inserted onto the P~C paste and then guided into a heating duct. The desired PVC foam is produced 25 during the gelation process. After cooling the material to a temperature which is generally below 80C, the sup-port material is removed and the resulting synthetic leather is rolled.

While process (].) represents direct coating of the composite PVC textile material with a polyurethane dispersion composition, processes (2) and (3) are so-called "reverse coatings". The thickness of the noly-35 urethane top coat is from about about 5 to 100 g/m , ~ h~.~,L~
--12--preferably rom about 8 to 25 g/m2, in all cases.
During the gelation of PVC pastes, temperatures o~
from about about 170 to 200C are generally applied. The melting point of a top coat on PVC should therefore be 5 above 200C. PVC is a plastlc which is extremely stable to hydrolysis. For this reason, the finish should also be as stable as possible to hydrolysis so that it is not decomposed before the PVC. It should be noted that, in the course of time, PVC gives off small quantities of 10 hydrochloric acid which have a detrimental effect on the stability of the top coat to hydrolysis. In addition, the metal salts (generally lead, cadmium or zinc compounds) used in the PVC to reduce the gelation temperature and as stabilizers may impair the stability to hydrolysis.
Furthermore, a small degree of swelling by the con-ventional commercial plasticizers for PVC is an important criterion for a good P~R top coat. It depends greatly on the type of plasticizer (generally esters of phthalic acid, adipic acid, phosphoric acid or alkyl sulphonic 20 acids with ~-ethyl hexanol, _-butanol, benzyl alcohol, phenol and/or cresol). Little swelling of the top coat - material by the plasticizer for PVC is, moreover r neces-sary for producing good adhesion on flexible PVC and for achieving increased flexibili:ty in the PUR surface layer.
25 However, to prevent excessive migration of plasticizers to the surface, the swelling of the finish should be as slight as possible.
All these criteria are surprisingly fulfilled in an optimum manner by the coating systems according to the 30 present invention.
The coating produced according to the present invention may obviously be embossed at any time. Thus~
the coated textile may be embossed directly after the Mo-2402 drying or gelation process, but optionally also after the coating has been stored for a relatively short or even prolonged period. With the reverse process, a suitable surface texture may be achieved durin~ the production of 5 the coating by the use of a sheet of embossed release paper or another support material.
The following Examples illustrate the present inven-tion. Unless otherwise indicated, details of quantities should be i~terpreted as parts, by wei~ht, or percentages, 10 by weight.

1.1 Production of the PUR dispersion Mixture:
554 g hexane diol-1,6-polyadipate (OH-No. 134) 23.0 g trimethylol propane 53.0 g dimethylol propionic acid 33.0 g triethylamine 200 g 1,6-hexane diisocyanate 310 g 4,4'-dicyclohexyl methane diisocyanate 69.5 g acetone azine 1860 g deionized water Preparation:(~ccarding to German Offenlegungsschrift No.
2,811,148).
The trimethylol propane, the dimethylol propionic acid and 25 the triethylamine are mixed with the hexane diol poly-adipate dehydrated at 120C, and the diisocya~ates are added at 60C. The mixture is stirred at 80C until a constant NCO value is reached. The mixture is then allowed to cool to 50C and the aceton0 azine is stirred 30 into the moderately viscous NCO prepolymer melt, while the temperature drops sliyhtly and the viscosity continues to decrease. The water is now added with thorough stirring and the mixture is stirred for a further two hours.
The dispersion formed has a solids content of 40%

Mo-2402 and a Ford cup viscosity (4 mm nozzle) of 16 seconds a~d a pH of 7.5, The solid contains 32 milliequivalent percent o carboxyl groups.
Prop~rties of films:
5 Sof~ening range 200C
Shore A hardness 92 100% modulus 17~a 1.2 Production of a top coat for foamed PVC
The dispersion described under 1.1 is applied 10 together with a polyacrylic acid thickener onto a sheet of commercial release paper (for example Transkote*VEM
ClS manufactured by S.D. Warren) using a roller spreader incorporating a doctor blade in such a way that a film of 10 g/m is formed after drying at from 15 80 to 150C.
Spreading paste:
100 parts, by weight, 40% PUR dispersion from Example 1.1 1 part, by weight, polyacrylic acid 20 thickener (Mirox~ AM, Fa. Stockhausen, D-Krefeld).
5 parts, by weight, aqueous pigment preparation adjusted to pH 8 using ammonia (Helioecht-Gelb-Feinteig*, Bayer AG, D-5090 Leverkusen).
A PVC blowing ~oam mixture of the following 25 type is applied to the dried PUR film:
55 parts, by weight, of a PVC paste, (for example Solvic* 336) 9 parts, by weight, of dioctylphthalate plasticizer 36 parts, by weight, of didecylphthalate plastici.zer 10 parts, by weight, chalk 1 part, by weight, SiO2, powder 1 part, by weight, azoisobutyric acid 35 dinitrile 1 part, by weight, Cd/Zn stearate 5 parts, by weight, iron oxide yellow pigment.
* Trademark Mo-2402 f~

The PVC foam paste is laminated in a quantity of 200 9/m2 with a cotton fabric and is thoroughly heated for 1.5 minutes at 19~C. The fabric is then cooled and separated From the paper.

The thus-obtained coated article is characterized ~y a dry surface ~eeland high flex resistance; the PUR film adheres very well to the PVC foamed coat.

The lacquer acts as a good barrier against the entry of the plasticizers into the foam as it only swells slightly in them. The pigmented top coat does not change color at high temperatures as the PUR film forming the basis thereo~ does not discolor at the gelation temperature of the PVC foam.

15 2 1 Production of the PUR disPersion Mixture: -485 g hexane aiOl-l, 6-polyadipate (OH No. 134) 20 g trimethylol propane 85 g propoxylated adduct of 2-butene diol-1,4 and NaHSO3 (molecular weight 425) 365 g 4,4'-dicyclohexylmethane diisocyanate 67 g 1,6-hexane diisocyanate 50 g acetone azine 107 g N-methyl pyrrolidone 1500 g deionized water Preparation: (see Example 1.1; cf. German Offenlegungsschrift No. 2,811,148).
The thus-obtained dispersion has a solids content of 40%, a Ford cup viscosity (4 nlm nozzle) of 19 seconds and a pH of 6.8. The solid contains 19 milliequivalent percent of SO3(-) groups.
A Eilm produced from the dispersion has a Shore A
hardness of 94, a 100% modulus of 20 MPa, and the film softens above 200~C.

Mo 2402 2.2 Production of a top coat for foamed PVC
Spreadinq paste:
100 parts 40~ PUR dispersion 2.1 2.0 parts polyacrylic acid thickener (see example 1) 10 parts a~ueous pigment preparation adjusted to pH 8 using ammonia (see example l) The PUR/PVC coated article produced according to Example 1.2 has a very dry feel, a very ~ood flex resistance an~ excellent ad-hesion to the PVC foam.
The top coat acts as a good barrier against the entry of the plasticizers contained into the foam, as it only swells slightly in them. The pigmented top coat does not change color at high temperatures as the PUR film on which it is based does not 15 discolor at the gelation temperature of the PVC foam.
EX~MPLE 3 3.1 Production of the PUR dispersion _ Mixture:
650 g 1,6-hexane diol ~olycarbonate (OH No~ 112) 13.4 g trimethylol propane 85 g propoxylated adduct of 2-~utenediol-1,4 and NaHSO3 (molecular weight 425) 315 g 4,4'-dicyclohexyl methane diisocyanate 44.4 g isophorone diisocyanate 33.6 g 1,6-hexane diisocyanate 52.8 g acetone azine 1780 g deionized water Preparation: (see Example 1.1, cf. German Offenlegungsschrift No. 2,811,148).

Mo-2~02 The thus-obtained dispersion has a solids content of 40~, a Ford viscosimeter viscosity (4 mm nozzle) e~uivalent to 20 seconds and a pH of 7.5. The solid material contains 17 mllliequivalent percent of SO3( ) groups.
The film produced from the dispersion has a Shore A
hardness of 92, a 100% modulus of 16 MPa and the film softens above 200~C.
3.2 Production of a top coat or fi~ish on PVC
Spreading paste:
100 parts 40% PUR dispersion 3.1 1.0 parts polyacrylic acid thickener (see example 1) 15 parts aqueous pigment preparation adjusted to p~ 8 using ammonia (see example 1) The PUR/PVC coated article produced according to 15 Example 1.2 has a very dry feel, good fle~ resistance and very good adhesion to the PVC foam.
The top coat acts as a good barrieragainst the entry of the plasticizers contained in the foam as it only swells slightly in them. The pigmented top coat does 20 not change color at high temperatures as the PUR filrn on which it is based does not discolor at the gelation temperature of the PVC foam.

Mo-2402

Claims (14)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A coating agent based on an aqueous, poly-urethane dispersion containing a solid substance comprising, based on the weight of the solid substance, (A) from about 30 to 60%, by weight, of a polyester diol having a molecular weight of from about 500 to 6000 and wherein the diol component comprises at least about 80 mol % of hexane diol-1,6;
(B) from about 0.5 to 5.0%, by weight, of a relatively low molecular weight triol having a molecular weight of from about 92 to 399;
(C) from about 3 to 30%, by weight, of at least one mono- or poly-functional compound within the context of the isocyanate-polyaddition reaction bearing anionic groups and/or containing non-ionic polyoxyethylene segments;
(D) From about 20 to 50%, by weight, of a diisocyanate corresponding to the following general formula.
wherein R1, R2 and R3 which may be the same or different, each represents hydrogen or a straight- or branched-chain aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms;
(E) from about 2.5 to 20%, by weight, of other aliphatic and/or cycloaliphatic diisocyanates; and (F) from about 0.5 to 4%, by weight, of hydrazine.
2. The coating agent according to Claim 1 wherein the polyester diol component (A) is a hexane diol-1,6-polyadipate and/or hexane diol-1,6-polycarbonate.

Mo-2402
3. The coating agent according to Claim 1 or 2 wherein the lower molecular weight triol (B) is glycerin and/or trimethylol propane.
4. The coating agent according to Claim 1 or 2 wherein component (C) is a non-ionic mono-functional polyether having a molecular weight of from about 500 to 3000 and a polyoxyethylene content of from about 60 to 95%, by weight.
5. The coating agent according to Claim 1 or 2 wherein component (C) corresponds to the following general formula:
wherein R represents hyarogen or an organic radical having from 1 to 8 hydrocarbon atomsi m and n represent integers of from 1 to 10; and Me is a quaternizea ammonium ion or an alkali metal cation.
6. The coating agent according to Claim 1 or 2 whexein component (C) is an ammonium and/or alkali metal salt of an organic dihydroxy carboxylic acid.
7. The coating agent according to Claim 1 or 2 wherein in the compound corresponding to the following general formula:

R1, R2 and R3 represent hydrogen atoms.
8. The coating agent according to Claim 1 or 2 wherein the diisocyanate (E) is 3-isocyanatomethyl-3,5,5-trimethyl cyclohexylisocyanate and/or 1,6-diisocyanato-hexane.
Mo-2402
9. A coating agent based on an aqueous, poly-urethane dispersion containing a solid substance comprising, based on the weight of the solid substance, (A) from about 30 to 60%, by weight, of a polyester diol having a molecular weight of about 500 to 6000 and selected from the group consisting of hexane diol-1,6-polyadipate, hexane diol-1,6-poly-carbonate and mixtures thereof;
(B) from about 0.5 to 5%, by weight, of glycerin and/or trimethylol propane;
(C) from about 3 to 30%, by weight, of at least one mono- or poly-functional compound within the context of the isocyanate-polyaddition reaction bearing anionic and/or non-ionic polyoxyethylene segments;
(D) from about 20 to 50%, by weight, of a diisocyanate corresponding to the formula:
wherein R1, R2 and R3 represent hydrogen atoms;
(E) from about 2.5 to 20%, by weight, of 3-isocyanatomethyl-3,5,5 trimethyl cyclohexylisocyanate and/or 1,6-diisocyanatohexane; and (F) from about 0.5 to 4%, by weight, of hydrazine.
10. The coating agent according to Claim 9 wherein component (C) is a non-ionic mono-functional polyether having a molecular weight of from about 500 to 3000 and a polyoxyethylene content of from about 60 to 95%, by weight.
11. The coating agent according to Claim 9 wherein component (C) corresponds to the general formula Mo-2402 formula:
wherein R represents hydrogen or an organic radical having from 1 to 8 hydrocarbon atoms;
m and n represent integers of from 1 to 10; and Me is a quaternized ammonium ion or an alkali metal cation.
12. The coating agent according to Claim 9 whereîn component (C) is an ammonium and/or alkali metal salt of an organic dihydroxy carboxylic acid.
13. A process for the direct or reverse coating of non-foamed or foamed PVC which comprises using the coating agent of Claim 1, 2 or 9.
14. A coated, non-foamed or foamed PVC
substrate which has been coated with the coating agent of Claim 1, 2 or 9.
Mo-2402
CA000408850A 1981-08-28 1982-08-06 Coating agents of polyurethane dispersions and the use thereof for top coats and finishes Expired CA1241142A (en)

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US4594385A (en) 1986-06-10
ES515315A0 (en) 1983-12-16
DE3274648D1 (en) 1987-01-22
EP0073392B1 (en) 1986-12-10
DE3134161A1 (en) 1983-08-11
HU196231B (en) 1988-10-28

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