JPS605463B2 - Composite of polyethylene foam and polyurethane and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite of polyethylene foam and polyurethane, in which crosslinked polyethylene foam and polyurethane are integrated by bonding with a fixing agent, and a method for producing the same.

Various types of composites are already known in the art.

For example, German Published Patent Application No. 1704647 describes thermoplastic foamed plastic materials in the form of strings, tapes, films or mixtures thereof and foamed duroplastic materials.
The proportion of thermoplastic foam is 10% and 90% (by weight) of the total composite foam.
Composite foams are described, preferably from 50 to 75% (by weight). By way of example, polyethylene can be used as the thermoplastic foam material, whereas polyurethane can be used as the foam duroplastic material. Composite foams known from the prior art are made as follows. That is, strings or tapes of thermoplastic foam are introduced into a suitable container in a completely random arrangement to form a tangled ball of the strings or tapes; Adds a hardenable and foamable duroplastic body,
Composite foams have also been produced by foaming using known foaming methods. Composite foams made by this method do not consist of a combination of various layers, but rather thermoplastic foams, such as polyethylene foam, are bonded together in a random arrangement in the form of strings, tapes or films. Encased in Duroplastic foam without any damage.

Various attempts have been made to combine polyethylene with polyurethane foam in a solid, rather than foamed, form, such as a polyethylene film.

It was found that almost no adhesion occurred between two plastics, so much so that polyethylene film was used as a release film in the polyurethane mold foaming process (see US Patent No. 318,706).
. If it is desired to integrate polyethylene film and polyurethane foam, an adhesion promoter, such as an adhesive, is required to obtain a suitable degree of adhesion in the composite. The use of fixatives is expensive on the one hand. This is because, in addition to requiring extra operations, the fixing agent is often expensive, and the use of a fixing agent always presents an economic disadvantage. Moreover, the use of adhesion promoters results in the formation of interlayers within the composite that affect the physical properties of the composite. It is therefore desirable to produce composites without the use of fixatives. Surprisingly, it does not have any intermediate layer to aid in adhesion.
The inventors have discovered a composite system that includes one or more pairs of layers of polyethylene foam and layers of polyurethane.

Accordingly, the present invention relates to a system comprising one or more pairs of crosslinked polyethylene foam layers and polyurethane layers, wherein the polyethylene foam layer and the polyurethane layer are bonded together through a fixing agent.

The composite foam according to the present invention is cross-linked and foamed by using a known chemical foaming agent for foaming and by irradiation with high-energy radiation such as Co-9 refraction radiation or accelerated electron beam or treatment with peroxide. It can be made using any polyethylene foam. Known methods for producing polyethylene foam include, for example, DE 1694130 and US Pat. No. 309/31.

In these manufacturing methods, an organic peroxide and a blowing agent are added to polyethylene, and the mixture is extruded into a sheet under conditions that neither crosslink nor decompose the blowing agent.

The sheet is first heated in a hot air oven to such an extent that a crosslinking reaction begins, and when the temperature is further raised, the foaming agent decomposes and the released gas causes the crosslinked polyethylene to foam. The polyethylenes used to make the above foam are low pressure polyethylene (density 0.94 to 0.97 m/cc) and high pressure polyethylene (density 0.91 to approximately 0.94 m/cc).
c), and high-pressure polyethylene is preferred. Suitable peroxides are, for example, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-
Hexane, 2,5-dimethyl-2,5-(tert-butylperoxy)-hexyne, tert-butyl hydroperoxide, cumyl tert-butyl/di-oxide, di-tert-butyl/g-oxide and bis[tert-butyl peroxy] Examples include organic peroxides such as [butylperoxyisopropyl]-benzene, preferably dicumyl peroxide. The above peroxide is used in an amount of 0.3 to 1.5% (by weight) based on the total mixture. Preferably, the polyolefin is mixed with a crosslinking agent and a blowing agent or a concentrated mixture thereof in an extruder and subsequently molded below the decomposition temperature of the peroxide.

The residence time in the extruder is approximately 5 minutes to ensure that the mixture to be foamed does not crosslink at this stage. Actual crosslinking reaction occurs at 160oo or higher, while foaming reaction occurs at 160oo or higher.
Occurs between 90 and 25,000.

Therefore, in a preferred embodiment, the present invention provides radiation crosslinked or peroxide crosslinked polyethylene foam,
Preferably, it relates to a composite made using a crosslinked polyethylene foam with a degree of crosslinking of 25% to 80%.

Polyethylene foam with a density of 20 to 200 kg/base is preferred.

Preferred composites according to the invention also include those made using low temperature curing, bare or semi-flexible, or rigid polyurethanes.

The present invention relates to a reactive mixture of polyisocyanates and at least one compound containing at least two or more reactive hydrogen atoms, or a polyurethane dispersion, solution,
It also relates to a method for producing a composite consisting of polyethylene foam and a homogeneous polyurethane layer, characterized in that a suspension or powder is coated on a layer of cross-linked polyethylene foam and left to cure by a known method. . In the present invention, suitable starting materials for making polyurethanes include cycloaliphatic, araljphatic, aromatic, heterocyclic polyisocyanates, such as W. Sief bag n J bitch tus Liebi saddle An armpit l
enderChemie No. 562 No. 75, No. 136
There are polyisocyanates of the type described on p.

For example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,
Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, mixture of the above isomers, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (
German Patent No. 1202785), 2,41 and 2,
6-hexahydrotolylene diisocyanate, mixtures of the above isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4- and/or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, isomeric mixtures of the above, diphenylmethane-2,4- and/or -4,4-diisocyanate, Naphthylene-1,5-diisocyanate, triphenylmethane-4,4',4''-triisocyanate, polyphenylene-polymethylene polyisocyanate, and a type made by condensing aniline and formaldehyde to phosgenate. , for example British Patent Specification No. 8
Types described in Nos. 7443 and 848671,
For example, perchlorinated aryl polyisocyanates as described in German Patent No. 1,157,601, polyisocyanates containing carposimide groups of the type described in Proprietary Patent No. 1,092,007, and polyisocyanates of the type described in U.S. Pat. No. 92,330. diisocyanates, e.g. British Patent No. 7
61626, Belgian Patent No. 761626 and Dutch Patent Application No. 7102524, for example polyisocyanates containing allophaMt groups, such as German Patent No. 1022
78, 1222067, 1027394, DE 1929034, 2004048; Polyisocyanate containing a type of urethane group, German Patent No. 123077
Polyisocyanates having acylated urea groups as described in US Pat. Polyisocyanates, for example telomerization of the type described in Belgian patent no.
cation) reactions, such as British Patents Nos. 965474 and 1072956 and US Patent No. 3567763, German Patent No. 12316
88, and the reaction products of the above-mentioned isocyanates with acetals according to German Patent No. 1,072,385.

Also used are distillation residues containing isocyanate groups that are accumulated in the production of isocyanates on an industrial scale, and in some cases, products obtained by dissolving this in one or more of the above-mentioned isocyanates.

Mixtures of the aforementioned polyisocyanates may also be used. Generally speaking, readily available commercially available polyisocyanates,
For example, 2,4- and 2,6-tolylene diisocyanates and mixtures thereof (TDI''), polyphenylene-polymethylene polyisocyanates (TDI
It is particularly preferable to use monomodified polyisocyanates (") and polyinsyanates containing any one of carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups, and biuret groups. Other starting materials used in the production of polyurethanes according to the invention are compounds having at least two or more isocyanate-reactive hydrogen atoms and having a molecular weight between 400 and 10,000.

Compounds of this type include, in addition to compounds containing amino groups, thiol groups, and carboxyl groups, polyhydroxyl compounds, especially compounds containing 2 to 8 hydroxyl groups, especially those with a molecular weight of 800 or less. 10000, preferably 1000, 6000
For example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates, which are known for the production of homogeneous polyurethane foams, are used.
Polyesteramides containing at least two or more hydroxyl groups, generally none to eight, but preferably from two to four, are preferred. Suitable hydroxyl-containing polyesters include, for example, polyhydric, preferably dihydric, optionally trihydric alcohols and polyhydric, preferably dihydric, alcohols.
It is a reaction product with a polyvalent carboxylic acid.

Instead of using free polycarboxylic acids, esters of the corresponding polycarboxylic anhydrides or lower alcohols of the corresponding polycarboxylic acids or mixtures thereof may be used in the preparation of polyesters. The polycarboxylic acids can be aliphatic, alicyclic, aromatic and/or heterocyclic, and the polycarboxylic acids may optionally be substituted, for example with halogen atoms, and/or Or it may be unsaturated. Examples of polycarboxylic acids of this type are succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. , tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dibasic or tribasic fatty acids such as oleic acid, optionally monobasic Mixtures with fatty acids, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester, etc. can be used. Examples of suitable polyhydric alcohols include: i.e. ethylene glycol,
1,2- and 1,3-propylene glycol, 1,4
- and 2,3-butylene glycol, 1,6-hexanediol, 1,8-octanediol, neobentyl glycol, cyclohexanedimethanol (1,4-pisuhydroxymethylcyclohexane), 2-methyl-
1,3-p. Pandiol, glycerin, trimethylolpro/gun, 1,2,6-hexanetriol, 1,
2,4-butanetriol, trimethylolethane, bentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol,
Includes polypropylene glycol, dibutylene glycol, and polybutylene glycol. The above polyester may contain terminal carboxyl groups. It is also possible to use polyesters of lactones, such as f-caprolactone, or of hydroxycarboxylic acids, such as -hydroxycaproic acid. The aforementioned polyhydric glycol (molecular weight: 62, 400) can also be added as a crosslinking agent. Two or more, generally two, suitable for use in the present invention
Polyethers containing from 8 to 8, preferably 3, hydroxyl groups are also known, and such polyethers can be prepared by combining epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin as such in the presence of eg BF3. The polyethers are obtained by polymerizing these epipoxides, optionally mixtures thereof, or sequentially with starting materials containing reactive hydrogen atoms, such as alcohols or amines, such as water, ethylene glycol, etc. , 1, 3 one if < is 1,
It can also be obtained by chemical addition to substances such as 2-propylene glycol, trimethylolpropylene, 4,4'-dihydroxydiphenylpropylene, aniline, ammonia, ethanolamine, and ethylenediamine. For example, German patent nos. 1176358 and 10
Saccharose polyethers of the type described in No. 64938 may also be used in the present invention. In many cases, it is preferred to use polyethers of the type containing predominantly primary OH groups (up to 90% by weight, based on the total amount of OH groups in the polyether). For example, US Patent No. 3383351, 3304273, 3523093, 311069
Polyethers modified with vinyl polymers, such as polymerization of styrene and acrylonitrile in the presence of polyethers, as described in No. 5 and DE 1152536, are also suitable, as are polybutadienes containing hydroxyl groups.

Among the polythioethers, the following may be mentioned in particular.

That is, it is a condensation product of thiodiglycol itself and/or other glycols, divalent carboxylic acids, formaldehyde, aminocarboxylic acids, and aminoalcohols. Such condensation products include polythio mixed ethers, polythioether esters, and polythioether ester amides, depending on the partner component to the thiodiglycol used in the reaction.

Examples of polyacetals include glycols such as diethylene glycol, triethylene glycol, 4,
4'-dioxyethoxydiphenyldimethylmethane, a compound obtained from hexanediol and formaldehyde.

Suitable polyacetals for use in the present invention are also obtained from cyclic acetals. Suitable known polycarbonates containing hydroxyl groups include, for example, diols such as 1,3-propanediol, 1,4-butanediol and/or 1,6-hexanediol diethylene glycol, triethylene glycol, tetraethylene glycol. For example, it can be obtained by reacting with diaryl carbonates such as diphenyl carbonate or phosgene.

The above-mentioned polyesteramides and polyamides include, for example, mainly linear condensates of polyvalent saturated and unsaturated carboxylic acids or their anhydrides with polyvalent saturated and unsaturated amino alcohols, diamines, polyamines, and mixtures thereof. It will be done. The polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols, such as castor oil,
Carbohydrates and starches can also be used.

Addition products of alkylene oxides and phenol-formaldehyde resins or urea-formaldehyde resins can also be used in the present invention. These compounds suitable for use in the present invention include, for example, Hi bait PolymeR Vol. XV1 “Polyuret
haneS Chemistry and Techn
ology” (written by Saders-Frisch, InterReclencePrice, Ne
wYork, London Vol. 1. Published in 1962), pages 32 to 42 and 44 to 54, and Vol. B 196 P year issue 5 no, 6 pages and 198 L, 199 pages, also kunSG
toff Kazuya n background h Vol, Vro (Vieweg-
HochUen, Carl-Yanser-Verlag
, Munich, published in 1966), for example, on pages 45 and 71. Catalysts are often also used in the present invention. Suitable known catalysts are, for example, triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N,N,N',N'-tetramethylethylenediamine, 1,4- Diazabicyclo(2,2,2)-octane, N-methyl-N'-dimethylaminoethylpiverazine, N,N-dimethylbenzylamine, bis(N
, N-diethylaminoethyl)-azibate, N,N-dimethylbenzylamine, bentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,
N,-N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-8-phenylethylamine,
These are tertiary amines such as 1,2-dimethylimidazole and 2-methylimidazole. Tertiary amines containing isocyanate-reactive hydrogen atoms include, for example, triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, and alkylene oxides of these and For example, there are reaction products with propylene oxide and/or ethylene oxide.

Other suitable catalysts include, for example, German Patent No. 12292
For example, silamines having a carbon-silicon bond such as 2,2,4-trimethyl-2-silamorpholene and 1,3-diethylaminomethyltetramethyldisiloxane described in No. 9' are included.

Other suitable catalysts include nitrogenous bases such as tetraalkylammonium hydroxides, and alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate, and alkali alcoholates such as sodium methylate. .

Hexahydrotriazine is also used as a catalyst. Organometallic compounds, especially organotin compounds, also find use in the present invention.

Preferred organotin compounds include tin(0) acetate, tin(0) octoate, tin(ro)ethylhexoate, and tin(ro)laurate.
0) and dialkyltin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate. Examples of suitable catalysts for use in the present invention and details regarding the operation of the catalysts can be found at Kunsts
toH-Handbuch Vol. VI1 (View
eg and Hochtlen, Carl-nse
r-VerlagMunich, published in 1966)
For example, on pages 96-102.

The catalyst is generally used in an amount of 0.001 to 10% by weight of a compound having a molecular weight of 400 to 10,000 and containing at least two or more isocyanate-reactive hydrogen atoms. In the present invention, a reaction retarder,
For example, acid-reactive substances such as hydrochloric acid or organic halides can be used, as well as retardants, pigments, dyes, and anti-aging agents such as trischloroethyl phosphate, ammonium phosphate, ammonium polyphosphate, etc. It is also possible to add film resistance imparting agents, plasticizers, fungicides, antibacterial agents, fillers such as barium sulfate, silica gel, carbon black, and chalk.

Other substances that can be used in the present invention, such as reaction retarders, stabilizers, oxidizing agents, plasticizers, coloring agents, fillers, fungicides, antibacterial agents, etc., may be used as necessary. Examples, as well as details regarding the use and action of additives of this type, can be found in Kunststoday Vol. V1 (
Vieweg Hada d HMhtlen, Car1-Ha
nser-Verlag, Munich, 1966), pages 103 and 113, for example.

According to the present invention, the reaction components are often
No. 764,565, the reaction can be carried out either by a one-stage process, a prepolymer process, or a semi-prepolymer process, using a machine of the type described in US Pat. The details of other processing machines used in the present invention can be found in
1 (Viewweg Hada d Hochtlen, Carl
-ratio nser-vetelag, Munich, 1966
For example, it is described on pages 121 and 205 of ``Published in 2015''. According to the invention, polyurethane dispersions can also be applied to polyethylene foams.

Both cationic and anionic polyurethane dispersions are suitable. Suitable cationic polyurethanes for use in the present invention include, for example, German Patent No. 1270276
using one or more components having one or more basic tertiary nitrogen atoms in the synthesis of polyurethanes, according to No.
It is obtained by reacting the chlorinated tertiary nitrogen atom in this polyurethane with an alkylating agent or an organic or inorganic acid.

In principle, the nitrogen atoms mentioned above may be attached anywhere in the polyurethane macromolecule. Conversely, it is also possible to react a ditertiary amine with a polyurethane containing a reactive halogen atom which can be quaternized.

Cationic polyurethanes are produced by "for example, a relatively high molecular weight diol and an isocyanate containing a reactive halogen atom, or a dihalogen urethane made from a diisocyanate and a halogen alcohol, and chain expansion performed by reacting this dihalogen urethane with a ditertiary amine. It can also be produced by a quaternization reaction.Conversely, a diaminourethane can be prepared from a compound having two isocyanate groups and a tertiary-amino alcohol, and then this diaminourethane can be reacted with a reactive dihalogen compound. Good. Of course, cationic polyurethane is
They can also be prepared from cationic salt starting materials, such as quaternary basic polyethers or isocyanates containing quaternary nitrogen. These manufacturing methods are described, for example, in German Patent Nos. 1184946, 1178586, 1179363L, US Patent No. 3686108,
Belgian Patent No. 653223, No. 658026,
No. 63679y, etc. Suitable starting materials for the synthesis of the salt polyurethanes mentioned above are also described in these publications. A suitable cationic dispersion in a mixture of dimethylformamide and water can be obtained, for example, as follows.

That is, a polyester having hydroxyl end groups is reacted with a diisocyanate to form a prepolymer, diluted with dimethylformamide, and then further reacted with N-methyljetanolamine.

Further quaternization with ~dichlorodirolle (1,4-bis-(chloromethyl)-benzene) and addition of phosphoric acid and an equal mixture of dimethylformamide and water. An anioso-type polyurethane (urea) dispersion is prepared by known methods.

Suitable anionic polyurethanes are described, for example, in DE 1237306, DE 1570556, DE 1720639, DE 1495847. In addition to the usual glycols and diamines, compounds containing anionic groups or groups that can later be converted into anionic groups can be used as in the preparation of cationic dispersions. Such compounds include, for example, hydroxy acids such as amino acids such as glyceric acid, citric acid, urea acid, diaminonaphthoic acid, and mercapto acids, 2-hydroxyethanesulfonic acid or P
- hydroxycarboxysulfonic acids such as sulfobenzoic acid, hydrazine sulfonic acid, aminosulfonic acids such as 2,4-diaminotoluene-5-sulfonic acid, aminoethylaminoethanesulfonic acid, phosphinic acid, phosphonic acid, Derivatives of phosphoric acid, such as phosphoric acid, phosphorous acid esters, or phosphoric acid bispropylene glycol esters, or their thio homologs, phthalic acid-
These include hydrazinedicarboxylic acid, diaminoamidecarboxylic acid, or a salt thereof, such as sodium bis-N,N-(r-aminof0.pyr)amide. The above-mentioned anionic dispersion is prepared by reacting a polyurethane containing free hydroxyl and/or amino groups with an aliphatic and/or aromatic aldehyde and simultaneously or subsequently reacting with a metal sulfite, metal halide sulfite, metal amino It can also be produced by reacting with carboxylates and metal aminosulfates. Finally, it is also possible to react polyurethanes containing free hydroxyl groups and/or amino groups with cyclic compounds having 3- to 7-membered rings with salts, atom groups, or groups capable of forming salts after ring opening. (cf. German Patent No. 1237306)
. Compounds of this type include, in particular, sultones such as 1,3-propane sultone, 1,4-butane sultone, 1,8 naphthosulfon, 6-propiolactone,
These include lactones such as r-butyrolactone and dicarboxylic anhydrides such as succinic anhydride. Suitable cationic or anionic polyurethanes for use according to the invention can also be prepared by disarmament of formaldehyde according to DE 1770068 A1.

In this method, a relatively high molecular weight polyisocyanate is combined with a compound having methylol end groups (e.g.
(amino-formaldehyde resin or phenol-formaldehyde resin), the reaction product containing methylol groups is dispersed in water, and finally the dispersion is heat-treated to form methylene crosslinks. . Furthermore, ``In the present invention, German Published Patent No. 1953
No. 345, No. 1953348, and No. 1953349
It is also possible to use dispersions of the type described in this issue.

The dispersion in question here is an aqueous dispersion of an ionic emulsion polymer obtained by radical emulsion polymerization of an olefinically unsaturated monomer in the presence of a cationic or anionic oligourethane or polyurethane. be. Also suitable are polyurethanes of the cationic or anionic type which, when used, can actually produce chemically crosslinked structures.

It is also possible to apply polyurethane suspensions to polyethylene foams.

Crosslinked polyurethane particles of this type can be made in various ways known in principle to those skilled in the art. Generally speaking, the crosslinked polyurethane particles can be prepared in suspension in a suitable organic solvent or water, or in the absence of a liquid vehicle. Furthermore, in these production methods, it is possible to directly obtain crosslinked particles by appropriately selecting the reaction components, or it is also possible to first prepare suitable linear thermoplastic polymer particles and then crosslink them later. You can also get it by doing There are many ways to make polyurethane pongee grains in aqueous media.

For example, polyurethane is dissolved in a solvent that is immiscible with water, dispersed in water using an emulsifier, and then the organic solvent is removed by distillation. One particularly preferred method is to
When an ionic and/or hydrophilic modified polyurethane is mixed with water in the presence or absence of a solvent, a dispersion is produced depending on both the composition and the reaction conditions. The preferred method is to use prepolymers with terminal isocyanate or methylol groups, and the reaction is carried out at very high concentrations or even in the absence of solvent. ,
Alternatively, it reacts with a polyamine dissolved in the aqueous layer and transforms into a high molecular weight polyurethaneurea suspension accompanied by chain increase and crosslinking reactions. Methi. Chain augmentation of prepolymers containing group groups is achieved, for example, by heating or by lowering the pH value. Suitable dispersions can also be prepared by spraying the high molecular weight polyurethane, or its reactive precursor, into water or an organic non-solvent. In principle, any method proposed so far for producing latex-like dispersions of polyurethane requires that this suspension settle or flocculate under the action of shear forces in order to produce a polyurethane suspension. It can be used as long as measures are taken to prevent it from happening.

This means that the initially formed initial suspension, which is not very high in molecular weight, must be kept in motion until the dispersed particles become non-adhesive.
To crosslink the dispersed particles, bifunctional or more functional starting materials, for example branched polyesters or polyethers, triisocyanates or triols, are used in the synthesis of polyurethanes or initially twilled NCO-prepolymers are used. That is, this is possible by reacting a prepolymer made from bifunctional components with a polyfunctional amine to produce a crosslinked polyurethaneurea. However, pure 2
Crosslinked particles can also be synthesized from functional components. The use of more than an equivalent amount of isocyanate to the hydroxyl or amine compound in the presence of water and/or diamine is sufficient to cause crosslinking. Linear high molecular weight polyurethanes cannot be crosslinked later, either by treatment with polyisocyanates, formaldehyde, or formaldehyde donors, either in suspension in a liquid medium or in powder form. It is possible.
Products with basic groups can be crosslinked, for example, with polyfunctional quaternizing agents or with acids, while products with acidic groups can be crosslinked with metal oxides or polyamines. Polyurethane having unsaturated double bonds can be crosslinked with, for example, known radical generators, sulfur, polymercaptan, and other at least bifunctional substances capable of reacting with double bonds. In order to produce crosslinked polyurethane particles without a solvent, the polyurethane elastomer may be pulverized using, for example, an impact pulverizer.

It is particularly preferable to crush such an elastomer immediately after it has been produced, at a time when the tackiness has already been lost but the reaction is not yet complete. Details regarding the production of suspensions of ionic crosslinked polyurethanes can be found, for example, in German Patent No. 1495745 (
U.S. Pat. No. 347,931), U.S. Pat. No. 1,282,963 (
Canadian Patent No. 837174), No. 1694129 (British Patent No. 1158088) and German Published Patent No. 1595687 (including US Patent No. 3714095) No. No. 1,175,339) and No. 1,770,068 (US Pat. No. 3,756,992).

Composites according to the invention are also produced by applying polyurethane powder.

Polyurethane powders with a melting point of 110 to 25,000, preferably 110 to 19,000 are particularly suitable for coating and lining polyethylene foams. In addition, the curve of the intrinsic viscosity index is an upward parabola such that the IMI-value changes from 2 pm/10 min to 50 pm/10 min in the temperature range from 5 to 5000, preferably from 10 to 40 qo. It is necessary to approximate a curve with a type slope. In addition to the above, polyurethanes (ureas) suitable for coating have an ionic group content of 1 to 15
It must have a milliequivalent/100 ohm and a volume resistivity of 1 to 1 to 4 ohm, c. According to the invention, polyurethane (urea) in powder form has the following properties: 1. Smooth, spherical surface, 2. Average diameter: 5, no, 20 mm, 3. Containing ionic groups, 1: no, 15 milliequivalents/ 100
E 4 Volume resistivity 1.

1 to 40hm, i.e. 5 1MI-curve is an upward parabola in the range from 110 to 25000, and the IM
2 evenings/1 fall in the temperature range of I value 5 to 50℃) et al. 5
Powdered polyurethane having a tendency to change over 0/1 minute is applied dry to the polyethylene foam, followed by crystallization and/or melting by heating, and continued as required. Calendar processing is performed.

The polyurethane (urea) powder used in the present invention is an NCO prepolymer having ionic groups and a primary and/or
Alternatively, it may be obtained by reacting a secondary diamine (containing an aliphatic amino group) and/or dicarboxylic acid-bishydrazide in the presence of water.

The NH:NCO ratio in the chain augmentation reaction is preferably between 0.1 and 0.95, particularly preferably between 0.25 and 0.25.
It is 85. The content of ionic groups in the NCO prepolymer is such that the final product has a required ionic group content of 1 to 15 meq/100 units, preferably 2 to 10 meq/100 units. must be selected. By preparing a solution of a prepolymer containing both isocyanate groups and ionic groups in an organic solvent, mixing this solution with an aqueous solution containing a chain extender, and finally removing the organic solvent, preferably by distillation. good.

In this way, the powder used in the present invention is obtained in the form of a settling aqueous dispersion. One of the features of this method is that it does not necessarily require a high-speed concentration machine; instead,
The advantage is that the NCO-prepolymer and chain extender can be combined by simply mixing the two components at low speeds.

The above-mentioned prepolymers, which simultaneously contain free isocyanate groups and ionic groups, are compounds known for the production of emulsifier-free polyurethane dispersions. It is preferable to use NCO prepolymers of the type having an average molecular weight of 300 to 25,000, further 800 to 15,000, especially 2,000 to 7,000. The properties of the polyurethane foam powders obtained in this way can be varied within a wide range by suitable methods.

This is especially true for hardness and particle size. The possibility of changing the nature of the various properties lies primarily in the synthesis of ionic preducts containing isocyanate groups.

The synthesis is carried out according to known methods (Belgium Patents No. 653,228 and No. 730,543) using the starting materials described in the above-mentioned patents. However, in addition to the compounds mentioned in the above patents, French patents 136181 and 1300981, German patent 1122254 and US patent 288843y also describe compounds containing ami/groups of the type described herein. It can be used as a relatively high molecular weight compound containing a hydrogen atom. The particle size is basically determined by the content of ionic groups in the preduct, while its hardness is mainly a function of the chemical properties of the polyisocyanate and the compound with active hydrogen atoms used in the production of the NCO-prepolymer. I'll settle down. If these compounds have a molecular weight of 50
If the compound is limited to a compound with a low molecular weight of about 0 or less, a relatively hard polyurethane can be obtained, whereas if the compound has a relatively high molecular weight of up to 10,000, a product that tends to be soft can be obtained. Any mixing ratio between these extremes is possible.

Since the formation of preaducts takes place in the presence of a relatively large excess of isocyanate (NCO
The molar ratio of the groups is best between 4 and 1.1, preferably between 2 and 1.4); in other words, the molecular weight of the prepolymer does not become very high, so the linearity of the chain is not very high. Not a problem. However, the powder has 2
Preference is given to making it from a linear NCO-prepolymer having aliphatic isocyanate groups. For this purpose, it is desirable to react the prepolymer with a chain extender that is water-soluble or in an aqueous dispersion.

As an exception, the chain extender can also be added during dispersion into the organic solvent solution. Basically, the polyurethane powder used in the present invention is preferably produced by the method for producing polyurethane dispersions without using emulsifiers, as described in Belgian Patents No. 653,223 and No. 730,543. Suitable chain extenders are in particular diamines containing primary and/or secondary aliphatic amino groups, dicarboxylic acids-bis! ÷ Drazid is also good.

(As far as the second type of chain extenders is concerned, it may be assumed that the amino group at the 3-position relative to the carbonyl group essentially reacts with the NCO-prepolymer; therefore, the dicarboxylic acid-pisuhydrazide may be considered as a bifunctional chain extender). Suitable diamines include, for example, in particular ethylene diamine, 1,2-propylene diamine, N-methylpropylene diamine, butylene diamine,
Hexamethylenediamine, Piverazine, 2-methylpiverazine, dimethylpiverazine, N,N'-dimethylethylenediamine, N,N'-diethyldiethylenediamine, N,N'-diisopropyl-1,2-bropylenediamine, N,N'-bis-hydroxyethylethylenediamine, N-hydroxyethylethylenediamine, N-
Hydroxypropylethylenediamine, N,N-bis-
(Hydroxypropyl)-ethylenediamine, N,N'
-dimethylhexamethylene diamine, 1,3-propylene diamine, r,r'-bis-aminopropyl sulfide, r,r-bis-aminopropylmethylamine, N,N-bis(r-aminopropyl)aniline, N
, N'-bis-(r-aminopropyl)-m-tolidine and the like having a molecular weight of 250 or less are preferable. Other suitable chain extenders include ether diamines, ester diamines, as well as diamines of the type formed during the hydrogenation reaction of cyanoethylated diols, and difunctional dihydroxy polyesters or dihydres. There is xypolyether.
The above diamines may be used as salts such as carbonates or acetates.

Salt formation is only partially necessary, for example to improve solubility. In the case of primary amines, salt formation leads to decreased reactivity. Suitable dicarboxylic acid-bishydrazides mentioned above include carboxylic acid-bishydrazides,
Included are bis-hydrazides of low molecular weight dicarboxylic acids having a molecular weight of 250 or less, such as oxalic acid-bis-hydrazide, succinic acid-bis-hydrazide, adipic acid-bis-hydrazide, terephthalic acid-bis-hydrazide, and tetrahydrophthalic acid-bis-hydrazide.

Difunctional polyesters having terminal carboxylic acid hydrazide groups can also be used.

Suitable solvents for the preparation of the products used in the invention include, in particular, solvents with a boiling point of 10,000, such as acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate and the like.
The following compounds that are miscible with water are preferred.

Non-aqueous solvents may also be used after the reactants are thoroughly mixed by appropriate mixing. Examples of this type of solvent include benzene and toluene. Solvents with a boiling point of 100 oo or higher, such as toluene, chlorobenzene,
Dimethyl formamide, dimethyl sulfoxide, etc. can also be used, although they are expensive to remove from the final product. The polyurethane powder used in the present invention may be produced as described below.

The ionic NCO prepolymer has a known molecular weight of 50.
Using a dihydroxyl compound of 0 and 5000, a diisocyanate, and an optional chain extender, the diisocyanate was prepared with an adduct of 1 and 4 by weight.
% of free NCO groups.

The NCO-prepolymer shall also have from 1 to 15 meq/100 quaternary nitrogen or carpoxylate or sulfonate groups. An acetone solution of an ionic NCO prepolymer of 30 to 90% by weight (with a viscosity of approximately 30 to 8
To 00. P. ) is mixed with an aqueous solution of an aliphatic amine having primary and/or secondary amino groups.

Thereafter, the acetone is distilled off to obtain polyurethaneurea powder as a precipitated aqueous dispersion. The final product is obtained in pure form by simple filtration. Although it may be redispersed in water afterwards, it is better to apply the dry powder using a dry knife method or a screen method. During the chain growth reaction, an aqueous solution may be added to an acetone solution, and an acetone solution may be added to an aqueous solution, but stirring is required in both cases.

The mixing is preferably carried out continuously using a suitable device while introducing the two types of liquids into a mixing tank using a pump or the like. In the simplest case, the mixing tank is equipped with a mulcher and an overflow port, so that the water-acetone dispersion overflows into the distiller. The temperature of the dispersion is 20°C to 60°C, preferably 35°C to 55°C. The amount of water required for the dispersion in which diamine is dissolved is 0.8 to 3 times the amount of ionic NCO-prepolymer.
Preferably it is 1 to 2 times. In the case of continuous multiplex mixing, it is more preferable to use a high-speed Takamoto machine or a Kazusa machine capable of producing high shearing force.

Screw mixers, in particular multi-screw mixers, internal mixers, high- or low-pressure countercurrent mixers, ultrasonic dispersers, etc. are known to those skilled in the art as suitable mixers. When using these types of mixers, it is possible to work with fluid prepolymers without any solvent, but it is preferable to use a 70% solution or a 90% solution. The properties of the polyurea powder initially accumulated as a suspension are influenced not only by the chemical composition of the polyisocyanate preduct but also by the dispersion conditions. The most important factors are the type and amount of chain extender, the amount of water, the type and amount of organic solvent, the reaction temperature which can vary from the pH value of 0°C to the boiling point of the organic solvent, and if necessary the reaction can be carried out under pressure. Sometimes it is done. Another important factor is the manner in which the aqueous and organic phases are mixed, i.e. whether the mixing is done simultaneously, such as by a continuous mixer, or whether the organic phase is added to the aqueous phase or the aqueous phase is added to the organic phase. That's it.

However, it is once again emphasized that it is possible to obtain useful products even by simple methods, for example by admixing the aqueous phase with the organic phase using a conventional rinsing machine. The organic solvent is removed by distillation during or after mixing. The final powder is obtained from an aqueous polyurethane dispersion by filtration. Polyurethane powder can be applied to polyethylene foam using the usual coating method.
That is, it is applied using an air knife coater, a comb blanket coater, especially a doctor roll coater, a roll coater or a reverse roll coater.

The coating may be colored in a variety of ways.

The polyurethane powder may be mixed with carbon black, titanium oxide, aluminum bronze, iron or cadmium pigments prior to coating. The composites according to the invention are particularly suitable for travel goods, leather substitutes, floor coverings, and are also used as crash pads, etc., for example in lacquered form and in deep-drawn form. It will be done.

For example, applying a polyurethane reaction mixture to a polyethylene foam used in the form of a foam sheet is not particularly difficult and can be done by any method.

Of course, it is also possible to use a machine. Composites according to the invention include one or more polyethylene foam and polyurethane layers.

The invention also encompasses systems containing a plurality of such combinations. In this connection, the layer of polyethylene foam and the layer of polyurethane must always be bonded together by an adhesion promoter. Example 1 10 parts by weight of butanediol adibate, 9.5 parts by weight of 1,4-butanediol, 37.5 parts by weight of 4,4
- After preparing a polyurethane polymer (1) consisting of diphenylmethane diisocyanate, it was mixed with 1% Si02
It was coextruded and pelletized, followed by milling in nitrogen to a powder.

A polyethylene foam (polyethylene foam) manufactured by a continuous method of dicumyl peroxide crosslinking and azodicarponimide foaming is produced by passing the powder from which particles with a particle size of 200 French or less have been separated and removed through a ring.
Density 35k9/) with (a} sliced surface and {b} non-sliced surface transferred or dispersed, sintering temperature of polyurethane polymer in infrared field about 25%, then 30%)
An adhesive film was formed by heating to 14yo+ (25 to 30°C) and curing. It is recommended that you repeat this method several times and apply at least 50 tano to each item. Its upper limit weight is determined by the heat capacity of the infrared field. Adhesion was tested according to DIN 53357.

Polyethylene foam was used as the material. Example 2 5 parts by weight of ethylene-butylene-glycol adibate, 5 parts by weight of hexanediol polycarbonate,
Polyurethane polymer (b) consisting of 1 part by weight of 1,4-butasodiol and 4 parts by weight of 4,4'-diphenylurethane diisocyanate (b) was dissolved in a mixture of 3 parts by weight of dimethyl formamide and 2 parts by weight of methyl ethyl ketone. to make a 25% solution.

The above solution was colored with a standard pigment, coated on a standard release layer to a thickness of 60 mm, and dried according to a conventional method. The polyurethane polymer (1) obtained in Example 1 was streaked onto this film for 100 min/pillow thickness and sintered in the same manner as described above. Polyethylene foam (density 35 kg/) manufactured by dicumyl peroxide crosslinking, azodicarponamide foaming, and continuous manufacturing method and having [a-slice surface and 'b] non-slice surface is the above lie. The composite of polyurethane polymer (b)/polyurethane polymer (1)/polyethylene foam was mechanically peeled off from the mold release layer after being placed on the plastic surface of bound polyurethane polymer (1), gently pressurized, and cooled. . Adhesion was tested according to DIN 53357.

The material was cut in polyethylene foam. Example 3 Hexane polycarbonate 482.5 times, 1,6-diisocyanate hexane 76 times, acetone 596.5 times,
A polyethylene foam produced by dicumyl peroxide crosslinking, azodicarbonamide foaming, and a continuous production method of a powdered polycarethane polymer (m) consisting of 4 parts of N-methyldiethanolamine and 3.1 parts of dimethyl sulfate. 25% less than the sintering range of the polyurethane polymer, and 3500%
When sintered in a hot air bath at high temperatures, at least 5
0 evening/A film with a uniform coating thickness was formed.

In this example, the temperature of the tank was approximately 200°C and the enrichment time was approximately 1 minute.

Adhesion was tested according to DIN 53357. Material fracture occurred in polyethylene foam. Example 4 4,040 liters of butanediol polyadibate (OH number 64) and 114 liters of 4,4'-diphenylmethane diisocyanate were reacted in 5,180 liters of perchloroethylene.

A prepolymer with an NCO content of 1.85% was obtained.
To this prepolymer 896 was added using a gear pump a solution of 40 parts of 4,4'-diaminodiphenylmethane dissolved in 150 parts of dioxane. After thorough mixing with a suitable mix head, the reaction mixture was sprayed onto chemically expanded peroxide crosslinked polyethylene foam. For example, the spray can be
It can also be carried out with ranepo1201-Pistole (registered trademark). After coating, the whole was placed in a dryer at 80 CO for 30 minutes to react. Adhesion was tested according to DIN 53357.

The material was cut with polyethylene foam. Example 5 10 parts by weight of ethanediol polyadibate (OH value 56.2, oxidation 0.7) was vacuum dehydrated at 135°C.
000 and mixed with 18 parts of naphthylene diisocyanate.

After a few minutes the temperature reached 126°C and the reaction mixture was briefly degassed and 2 parts of 1,4-butanediol were added and mixed well. The hot reaction mixture (12500) was poured to a thickness of 3 willows onto a polyethylene foam prepared by a peroxide-crosslinked, chemical foaming continuous manufacturing process, and the resulting composite was post-treated for one period at 110oC. After cooling, the above composite material showed high strength and high adhesion as measured by DIN 53357. The material was cut with polyethylene foam. Example 6 455 parts of fatty acid-based polyester blended with ketone resin, 9 parts of molecular sieve (zeolite), 395 parts of barium sulfate, 32 parts of hydrogenated castor oil, 60 parts of diacetone alcohol, pigments (e.g. titanium oxide) A reactive mixture consisting of 6 parts (a mixture of iron oxide, iron oxide, and chromium oxide), 185 parts of diphenylmethane diisocyanate, and 22 parts of diphenylmethane diisocyanate was subjected to continuous peroxide crosslinking and chemical foaming using a standard compressed air spray gun. It was applied to a polyethylene foam produced by the manufacturing method.

The elasticity could be changed by adjusting the isocyanate component. The reactive mixture took about 1 bait hour to cure. Adhesion was tested with D-melon 53357.

Claims (1)

[Claims] 1. It has at least one set of a crosslinked polyethylene foam layer and a homogeneous polyurethane layer, and the polyethylene foam layer and the polyurethane layer are integrally bonded without a fixing agent. A composite of polyethylene foam and polyurethane. 2. A reactive mixture of polyisocyanate and at least one compound having at least two or more reactive hydrogen atoms, or a dispersion, solution, suspension, or powder of polyurethane is applied to a crosslinked polyethylene foam. ,
A method for producing a composite of polyethylene foam and polyurethane, which comprises curing by a known method.