WO2005005565A1 - Procede de lamination au moyen d'adhesifs speciaux au polyurethane - Google Patents

Procede de lamination au moyen d'adhesifs speciaux au polyurethane Download PDF

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Publication number
WO2005005565A1
WO2005005565A1 PCT/EP2004/006650 EP2004006650W WO2005005565A1 WO 2005005565 A1 WO2005005565 A1 WO 2005005565A1 EP 2004006650 W EP2004006650 W EP 2004006650W WO 2005005565 A1 WO2005005565 A1 WO 2005005565A1
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Prior art keywords
adhesive
flexible substrate
groups
polyurethane
monomers
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PCT/EP2004/006650
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German (de)
English (en)
Inventor
Andre Burghardt
Karl Häberle
Ulrike Licht
Bernd Meyer-Roscher
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Basf Aktiengesellschaft
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Publication of WO2005005565A1 publication Critical patent/WO2005005565A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/042—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/10—Next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives

Definitions

  • the invention relates to a method for bonding flat, flexible substrates to non-flexible substrates (in short for laminating substrates), characterized in that the adhesive used for the adhesive bonding contains 0.0001 to 0.1 mol of carbodimide groups per 100 g of adhesive (Not including water or other organic solvents with a boiling point below 150 ° C at 1 bar), the adhesive is applied to the flexible substrate and the flexible substrate coated with adhesive is glued to the non-flexible substrate.
  • components are often laminated with a plastic film.
  • the substrate and / or the film to be laminated is coated with an adhesive from the production of the laminated component and, if appropriate after thermal activation of the adhesive, the two parts to be bonded to one another, generally using pressure.
  • the laminating film could not be coated by the manufacturer of the laminated component, but by the manufacturer of the laminating film, since the film manufacturer carries out a pre-treatment step anyway, e.g. the film is coated with an adhesion promoter.
  • the process of applying adhesive in a continuous process such as roller or roller application also offers the advantage of avoiding the so-called overspray when applying adhesive to the component to be laminated.
  • Aqueous polymer dispersions are often used as adhesives. It is also common practice to add a crosslinking agent to the dispersion in order to ensure sufficient heat resistance of the adhesive bond. Isocyanates are frequently used as crosslinking agents, but because of their short lifespan, which generally does not exceed one working day, they can only be added to the adhesive dispersion shortly before use. Even in the dry adhesive coating, the crosslinking agent reacts after a short time, so that it is not possible to produce laminated films that can be stored with adhesive.
  • Polyurethane dispersions containing carbodiimides are e.g. in DE-A-10000656 or DE-A-10001777.
  • the object of the present invention was a method for bonding flexible substrates, for example polymer films, to non-flexible substrates (lamination) in which the already coated flexible substrates can be stored and in which Tere bonding composites with high strength and durability, in particular also high heat resistance are obtained.
  • the adhesive used in the process according to the invention contains 0.0001 to 0.1 mol, preferably 0.0005 to 0.1 mol, particularly preferably 0.001 to 0.1 mol of carbodiimide groups per 100 g of adhesive; Water or other organic solvents with a boiling point below 150 ° C at 1 bar are not taken into account in the weight of the adhesive.
  • the content of carbodiimide groups is not higher than 0.05 mol / 100 g of adhesive.
  • Suitable compounds with carbodiimide groups generally contain on average 1 to 20, preferably 1 to 15, particularly preferably 2 to 10 carbodiimide groups.
  • the number average molecular weight M n is preferably 100 to 10,000, particularly preferably 200 to 5000 and very particularly 500 to 2000 g / mol.
  • the number average molecular weight is determined by end group analysis of the diisocyanates (i.e. consumption of the isocyanate groups by carbodiimide formation, see below) or, if end group analysis is not possible, by gel permeation chromatography (polystyrene standard, THF as eluent).
  • Carbodiimide groups are easily available from two isocyanate groups with the elimination of carbon dioxide:
  • carbodiimides with several carbodiimide groups and optionally isocyanate groups, in particular terminal isocyanate groups, are thus obtainable.
  • Suitable diisocyanates are, for example, diisocyanates X (NCO) 2 , where X is an aliphatic hydrocarbon residue with 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon residue with 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclo
  • TMXDI is particularly preferred.
  • the terminal isocyanate group makes the carbodiimides slightly hydrophilic, e.g. can be modified by reaction with amino or hydroxy acids. Hydrophilically modified carbodiimides are naturally easier to mix with aqueous adhesives or adhesives based on hydrophilic polymers.
  • the carbodiimides can also be easily attached to polymers by combining the isocyanate group with a reactive group of the polymer, e.g. an amino group or hydroxyl group is reacted.
  • the adhesive used according to the invention can therefore e.g. as an additive or in a bound form, e.g. by binding to a polyurethane or a radically polymerized polymer.
  • the adhesive to be used according to the invention preferably contains further reactive groups which can undergo a crosslinking reaction with one another or with the carbodiimide groups.
  • Carboxyl or carboxylate groups are preferably present in an amount of 0.0001 to 0.5 mol, particularly preferably 0.0005 to 0.5 mol / 100 g of adhesive.
  • Carboxyl groups are also formed by transesterification reactions, so that crosslinking occurs even without an initial content of carboxyl groups in the polyurethane.
  • the adhesive to be used according to the invention essentially consists of at least one polymeric binder and optionally additives such as fillers, thickeners, defoamers etc.
  • the additives also include the carbodiimides, unless they are bound to a polymeric binder.
  • the polymeric binder is preferably present as a solution or dispersion in water or another solvent with a boiling point below 150 ° C. (1 bar). Water is particularly preferred. The water or other solvents are not included in the weight of the composition of the adhesive.
  • the polymeric binder is preferably a polyurethane, a free-radically polymerized polymer or mixtures thereof.
  • the polymeric binders are in the form of aqueous dispersions.
  • the polyurethanes predominantly consist of polyisocyanates, in particular diisocyanates on the one hand and as reactants, polyester diols, polyether diols or mixtures thereof on the other hand.
  • the polyurethane is preferably composed of at least 40% by weight, particularly preferably at least 60% by weight and very particularly preferably at least 80% by weight, of diisocyanates, polyether diols and / or polyester diols.
  • the polyurethane preferably has a softening point or melting point in the range from -50 to 150 ° C., particularly preferably from 0 to 100, and very particularly preferably from 10 to 90 ° C.
  • the polyurethane particularly preferably has a melting point in the above temperature range.
  • the polyurethane preferably contains polyester diols in an amount of more than 10% by weight, based on the polyurethane.
  • the polyurethane is preferably composed of:
  • diols of which bi ) 10 to 100 mol%, based on the total amount of diols (b), have a molecular weight of 500 to 5000 g / mol, b 2) 0 to 90 mol%, based on the total amount of diols (b), have a molecular weight of 60 to 500 g / mol,
  • monomers (a) are diisocyanates X (NCO) 2 , where X is an aliphatic hydrocarbon radical with 4 to 15 carbon atoms, an aloaliphatic or aromatic hydrocarbon radical with 6 to 15 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 Carbon atoms.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclo
  • Such diisocyanates are commercially available.
  • mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane are particularly important as mixtures of these isocyanates, the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene is particularly suitable.
  • mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to Is 1: 4.
  • isocyanates which, in addition to the free isocyanate groups, have other blocked isocyanate groups, e.g. Wear uretdione groups.
  • diols (b) which can be used are primarily higher molecular weight diols (b1) which have a molecular weight of about 500 to 5000, preferably of about 1000 to 3000 g / mol. It is the number average molecular weight Mn. Mn is obtained by determining the number of end groups (OH number).
  • the diols (b1) can be polyester polyols which are known, for example, from Ulimanns Encyklopadie der Technische Chemie, 4th edition, volume 19, pages 62 to 65. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated.
  • Examples include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, fatty acid, maleic anhydride, maleic anhydride, maleic anhydride.
  • Dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • polyhydric alcohols examples include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol , Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • Examples include ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Neopentyl glycol is also preferred.
  • polycarbonate diols such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
  • polyester diols based on lactone can also be used, which are homopolymers or copolymers of lactones, preferably terminal products having hydroxyl groups, which are addition products of lactones to suitable difunctional starter molecules.
  • Preferred lactones are those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also from a Cr to C 4 -alkyl radical may be substituted. Examples are e-caprolactone, ⁇ -propiolactone, g-butyrolactone and / or methyl e-caprolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the structural component for the polyester polyols.
  • the corresponding polymers of e-caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.
  • Polyether diols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, if appropriate in a mixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines , for example water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline.
  • Polypropylene oxide, polytetrahydrofuran with a molecular weight of 240 to 5000, and especially 500 to 4500 are particularly preferred.
  • B ⁇ > includes only polyether diols which consist of less than 20% by weight of ethylene oxide.
  • Polyether diols with at least 20% by weight are hydrophilic polyether diols which belong to monomers c).
  • polyhydroxyolefins can also be used, preferably before 2 terminal hydroxyl groups, for example ⁇ , - ⁇ -dihydroxypolybutadiene, ⁇ , - ⁇ - Dihydroxypolymethacrylic ester or ⁇ , - ⁇ -dihydroxypolyacrylic ester as monomers (c1).
  • ⁇ , - ⁇ -dihydroxypolybutadiene ⁇ , - ⁇ - Dihydroxypolymethacrylic ester or ⁇ , - ⁇ -dihydroxypolyacrylic ester as monomers (c1).
  • suitable polyols are polyacetals, polysiloxanes and alkyd resins.
  • At least 95 mol% of the diols b 1 ⁇ are preferably polyether diols. Particularly preferred diols are used exclusively as polyether diols.
  • the hardness and the modulus of elasticity of the polyurethanes can be increased if, in addition to the diols (b1), low molecular weight diols (b2) with a molecular weight of about 60 to 500, preferably from 62 to 200 g / mol, are used as the diols (b) become.
  • polyester polyols The structural components of the short-chain alkanediols mentioned for the production of polyester polyols are primarily used as monomers (b2), the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms and pentane-1,5-diol and neopentyl glycol are preferred.
  • diols b 2) are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, but ⁇ n-1,4-diol, butyne-1,4-diol and pentane -1,5-dioI, neopentyl glycol, bis- (hydroxymethyl) cyclohexanes such as 1,4-bis- (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-dioI, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol , Polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Examples include ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Neopentyl glycol is also preferred.
  • the proportion of the diols (bi), based on the total amount of the diols (b), is preferably 10 to 100 mol% and the proportion of the monomers (b 2 ), based on the total amount of the diols (b), 0 to 90 mol -%.
  • the ratio of the diols (b1) to the monomers (b2) is particularly preferably 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 2: 1.
  • the polyurethanes contain different monomers (c) from components (a), (b) and (d), which contain at least one isocyanate group or at least one group which is reactive toward isocyanate groups and moreover at least one hydrophilic group or a group that can be converted into a hydrophilic group, as a structural component.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to "(potentially) hydrophilic groups”.
  • the (potentially) Hydrophilic groups react with isocyanates much more slowly than the functional groups of the monomers, which are used to build up the main polymer chain.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c), (d) and (e) is generally such that the molar amount of the (potentially) hydrophilic Groups, based on the amount by weight of all monomers (a) to (e), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • the (potentially) hydrophilic groups can be nonionic or preferably (potentially) ionic hydrophilic groups.
  • Particularly suitable nonionic hydrophilic groups are polyethylene glycol ethers composed of preferably 5 to 100, preferably 10 to 80, repeating ethylene oxide units.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6% by weight, based on the amount by weight of all monomers (a) to (e).
  • Preferred monomers with nonionic hydrophilic groups are polyethylene oxide diols with at least 20% by weight of ethylene oxide, polyethylene oxide monools and the reaction products of a polyethylene glycol and a diisocyanate which carry a terminally etherified polyethylene glycol residue.
  • diisocyanates and processes for their preparation are specified in the patents US-A 3905929 and US-A 3920598.
  • Ionic hydrophilic groups are above all anionic groups such as the sulfonate, carboxylate and phosphate groups in the form of their alkali metal or ammonium salts, and also cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • Potentially ionic hydrophilic groups are above all those which can be converted into the above-mentioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, e.g. Carboxylic acid groups or tertiary amino groups.
  • (Potentially) ionic monomers (c) are e.g. described in detail in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, pages 311-313 and, for example, in DE-A 1 495745.
  • cationic monomers (c) especially monomers with tertiary amino groups are of particular practical importance, for example: tris (hydroxyalkyl) - amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl dialkylamines, tris (aminoalkyl) amines, N, N'-bis (aminoalkyl) alkylamines, N-aminoalkyl dialkylamines, the alkyl radicals and Alkanediyl units of these tertiary amines independently of one another consist of 1 to 6 carbon atoms.
  • polyethers containing tertiary nitrogen atoms with preferably two terminal hydroxyl groups are obtainable in a conventional manner, for example by alkoxylation of two amines containing hydrogen atoms bonded to amine nitrogen, for example methylamine, aniline or N, N'-dimethylhydrazine.
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are converted into the ammonium salts either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids, or by reaction with suitable quaternizing agents such as G 1 -C 6 -alkyl halides or benzyl halides, for example bromides or chlorides.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids
  • suitable quaternizing agents such as G 1 -C 6 -alkyl halides or benzyl halides, for example bromides or chlorides.
  • Monomers with (potentially) anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids which carry at least one alcoholic hydroxyl group or at least one primary or secondary amino group.
  • Dihydroxyalkylcarboxylic acids are preferred, especially those with 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054.
  • R 1 and R 2 are a C to C alkanediyl (unit) and R 3 is a C to C 4 alkyl (unit) and especially dimethylolpropionic acid (DMPA) is preferred.
  • DMPA dimethylolpropionic acid
  • dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid are also suitable.
  • dihydroxyl compounds with a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups, which are known from DE-A 3911 827. They are obtainable by reacting dihydroxyl compounds with tetracarbonic acid dianhydrides such as pyromellitic acid dianhydride or cyclopentantetracarboxylic acid dianhydride in a molar ratio of 2: 1 to 1.05: 1 in a polyaddition reaction. Particularly suitable dihydroxyl compounds are the monomers (b2) listed as chain extenders and the diols (b1).
  • Suitable monomers (c) with amino groups reactive towards isocyanates are amino carboxylic acids such as lysine, ⁇ -alanine or the adducts of aliphatic diprimeric diamines with ⁇ , ⁇ -unsaturated carboxylic or sulfonic acids mentioned in DE-A 2034479.
  • R 4 and R 5 independently of one another are a C to C 6 alkanediyl unit, preferably ethylene and X is COOH or SO 3 H.
  • Particularly preferred compounds of the formula (c 2 ) are the N- (2-aminoethyl) -2-aminoethane carboxylic acid and the N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding alkali metal salts, Na being a particularly preferred counterion.
  • aliphatic diprimeric diamines with 2-acrylamido-2-methylpropanesulfonic acid such as those e.g. are described in DE-B 1 954090.
  • monomers with potentially ionic groups are used, they can be converted into the ionic form before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture.
  • the sulfonate or carboxylate groups are particularly preferably in the form of their salts with an alkali metal ion or an ammonium ion as counter ion.
  • the monomers (d), which differ from the monomers (a) to (c) and which may also be constituents of the polyurethane, are generally used for crosslinking or chain extension.
  • Alcohols with a higher valence than 2 which can serve to establish a certain degree of branching or crosslinking, are, for example, trimethylolpropane, glycerol or sugar.
  • monoalcohols which, in addition to the hydroxyl group, carry another isocyanate-reactive group, such as monoalcohols having one or more primary and / or secondary amino groups, e.g. Monoethanolamine.
  • Polyamines with 2 or more primary and / or secondary amino groups are used above all if the chain extension or crosslinking is to take place in the presence of water, since amines generally react with isocyanates faster than alcohols or water. This is often necessary when aqueous dispersions of cross-linked polyurethanes or high molecular weight polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to disperse them rapidly in water and then to extend or crosslink them by adding compounds having several amino groups reactive towards isocyanates.
  • Amines suitable for this purpose are generally polyfunctional amines in the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two amino groups selected from the group of the primary and secondary amino groups.
  • Examples include diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
  • diamines such as diaminoethane, di
  • the amines can also be used in blocked form, for example in the form of the corresponding ketimines (see, for example, CA-A 1 129 128), ketazines (see, for example, US Pat. No. 4,269,748) or amine salts (see US Pat. No. 4,292,226).
  • Oxazolidines as are used, for example, in US Pat. No. 4,192,937, are masked polyamines which can be used for the production of the polyurethanes according to the invention for chain extension of the prepolymers.
  • capped polyamines When such capped polyamines are used, they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or part of the dispersion water, so that the corresponding polyamines are released hydrolytically.
  • Mixtures of di- and triamines are preferably used, particularly preferably mixtures of isophoronediamine (IPDA) and diethylenetriamine (DETA).
  • the polyurethanes preferably contain 1 to 30, particularly preferably 4 to 25 mol%, based on the total amount of components (b) and (d) of a polyamine with at least 2 amino groups reactive towards isocyanates as monomers (d).
  • divalent isocyanates can also be used as monomers (d).
  • Commercially available compounds are, for example, the isocyanurate or the biuret of hexamethylene diisocyanate.
  • Monomers (e) which may be used are monoisocyanates, monoalcohols and monoprimary and secondary amines. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers. These monofunctional compounds usually carry further functional groups such as olefinic groups or carbonyl groups and are used to introduce functional groups into the polyurethane which enable the polyurethane to be dispersed or crosslinked or further polymer-analogously converted. Monomers such as isopropenyl-a, a-dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate are suitable for this.
  • TMI isopropenyl-a
  • TMI a-dimethylbenzyl isocyanate
  • esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate
  • Coatings with a particularly good property profile are obtained above all if essentially only aliphatic diisocyanates, cycloaliphatic diisocyanates or araliphatic diisocyanates are used as monomers (a).
  • This monomer combination is excellently supplemented as component (c) by diaminosulfonic acid alkali salts; very particularly by the N- (2-aminoethyl) -2-aminoethanesulfonic acid or its corresponding alkali salts, the Na salt being the most suitable, and a mixture of DETA / IPDA as component (d).
  • A is the molar amount of isocyanate groups and B the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction
  • the ratio A: B is very particularly preferably as close as possible to 1: 1.
  • the monomers (a) to (e) used usually carry on average 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups which can react with isocyanates in an addition reaction ,
  • the polyaddition of components (a) to (e) to produce the polyurethane is preferably carried out at reaction temperatures of up to 180 ° C., preferably up to 150 ° C. under normal pressure or under autogenous pressure.
  • carbodiimides with terminal isocyanate groups can be used as diisocyanates a) in the desired amount in the preparation of the polyurethanes.
  • the polymeric binder can also be a radical polymerized polymer, i.e. the polymer can be obtained by radical polymerization of ethylenically unsaturated compounds (monomers).
  • the polymer preferably consists of at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from Ci-Cao-alky methacrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic Hydrocarbons with 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • Examples include (Meth) acrylic acid alkyl esters with a CrCio-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are, for example, vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers examples include Vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
  • hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds ethylene, propylene, butadiene, isoprene and chloroprene may be mentioned.
  • Preferred main monomers are the C to CIO alkyl acrylates and methacrylates, in particular d to C 8 alkyl acrylates and methacrylates and vinyl aromatics, in particular styrene and mixtures thereof.
  • Methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and mixtures of these monomers are very particularly preferred.
  • the polymer may contain other monomers, e.g. Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups.
  • Carboxylic acid groups are preferred. For example, Acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • monomers are e.g. also monomers containing hydroxyl groups, in particular C -C-hydroxyalkyl (meth) acrylates, (meth) acrylamide.
  • Phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may also be mentioned as further monomers.
  • Crosslinking monomers may also be mentioned as further monomers. More preferably, the polymer comprises at least 40 wt .-%, especially at least 60 wt .-% and most preferably at least 80 wt .-% of C 1 -C 20 -, in particular C ⁇ -C ⁇ 0 alkyl (meth) acrylates.
  • the polymers are prepared by emulsion polymerization, so it is an emulsion polymer.
  • the manufacture can e.g. also by solution polymerization and subsequent dispersion in water.
  • the adhesive is preferably an aqueous adhesive.
  • the polymeric binder is preferably in the form of an aqueous dispersion. Further additives can easily be added to the aqueous dispersion of the polymeric binder.
  • An essential feature of the method according to the invention is that the adhesive is applied to the flexible substrate.
  • a flexible substrate is understood to mean a flat substrate which, with a substrate area of 50x50 cm, held on one side parallel to the surface of the earth, bends due to its own weight.
  • the flexible substrate is preferably flat substrates with a thickness of less than 10 mm, in particular less than 5 mm, particularly preferably less than 0.5 mm, very particularly preferably less than 3 mm.
  • it can be polymer films, metal foils, nonwovens made of synthetic or natural fibers, coated or uncoated paper or also veneers made of wood or imitation wood.
  • Polymer films e.g. Films made of polyester, such as polyethylene terephthalate, polyolefins such as polyethylene, polypropylene or polyvinyl chloride, made of polyacetate or ...
  • the flexible substrate can be pretreated, for example it can be coated with adhesion promoters.
  • the flexible substrate can also be constructed from several layers; For example, a carrier layer made of the above polymers and protective coatings or decorative coatings applied to this carrier layer on one or both sides.
  • the non-flexible substrate can be a shaped body whose external shape remains the same, even if this shaped body is loaded with its own weight, e.g. by holding the molded body freely suspended only at a single arbitrary point.
  • the above information relates to normal conditions (21 ° Cm 1 bar).
  • the non-flexible substrate can be made of wood or plastic, e.g. ABS (acrylonitrile butadiene styrene). For example, trade solid wood or plywood.
  • it can be molded parts which are made up of synthetic or natural fibers or chips.
  • the advantages can have any shape.
  • the flexible substrate is coated with adhesive.
  • the coating can be carried out using customary application methods. After coating, drying is carried out, preferably at room temperature or at temperatures up to 80 ° C., in order to remove water or other solvents.
  • the amount of adhesive applied is preferably 0.5 to 100 g / m 2 , particularly preferably 2 to 80 g / m 2 , very particularly preferably 10 to 70 g / m 2 .
  • the substrate coated with adhesive can then be stored; for this purpose it can be wound up on rolls, for example.
  • the coated substrate is preferably wound up.
  • Storage or transport generally takes place before further processing, so that a time of more than one week or more than 3 weeks, in particular also more than 6 weeks or more than 10 weeks passes before further processing.
  • the coated substrate is stable on storage, i.e. Even after several weeks of storage, the coated substrate can be processed with unchanged good results.
  • the temperature in the adhesive layer is preferably 20 to 200 ° C, particularly preferably 30 to 180 ° C.
  • the coated flexible substrate can suitably be heated to appropriate temperatures.
  • the bonding is preferably carried out under pressure, for example the parts to be bonded can be pressed together with a pressure of 0.05 to 5 N / mm 2 .
  • the composites obtained are characterized by high mechanical strength even at elevated temperatures (heat resistance) or under rapidly changing climatic conditions (climatic resistance). These good results are also achieved if the coated flexible substrate is used for a long time, e.g. has been stored for more than 3 months. The strengths are even higher compared to the usual methods (coating of the non-flexible substrate).
  • the method according to the invention is of particular importance in the automotive or furniture industry, e.g. when gluing flexible substrates to car interior parts such as dashboards, door linings and parcel shelves.
  • a solution of 250 g of an NCO-terminated carbodiimide from TMXDI with an NCO was added to a solution of 59 g (0.5 mol) of hydroxypivalic acid and 60.0 g (0.593 mol) of triethylamine (TEA) in 100 g of acetone while stirring -Content of 7.8% by weight in 50 g of acetone. After stirring for 240 min at 60 ° C., the mixture was diluted with 1200 g of water and the acetone was stripped off in vacuo. Then the solids content was adjusted to 20% by adding water. A colloidal, aqueous solution of a carbodiimide with an LD value (light transmittance as a measure of particle size) of 100 is obtained.
  • LD value light transmittance as a measure of particle size
  • the chain was extended with 42.2 g of a 50% strength aqueous solution of the aminoethylaminoethanesulfonic acid Na salt and dispersed with 1050 g of water.
  • the acetone was distilled off in vacuo at temperatures up to 43 ° C. and the solids content was adjusted to 45%.
  • Airflex ® EP 17 (adjusted to pH 7.5 with NaOH; (protective colloidal aqueous dispersion based on a vinyl acetate-ethylene copolymer,
  • thermoplastic polyolefin film from Benecke, VOLVO P2X TS 503520SF
  • wet application weight 100 g / cm 2 by means of a 2 mm wire doctor and dried at room temperature for 2 hours.
  • the coated film is stored at room temperature and laminated after various storage times (see table 1).
  • the film is placed on a hardboard and pressed using a laminating press at a pressure of 0.05 N7mm 2 .
  • the upper heating plate of the laminating press is heated to 120 ° C.
  • the heat resistance is tested in a static peeling test.
  • the 2.5 cm wide film test strips are loaded with a weight of 500 g and hung up in a 180 ° peel test at a temperature of 50 ° C in the heating cabinet. If the film loaded by the weight is not peeled off, the temperature is increased every 30 minutes by 10 ° C up to a maximum temperature load of 120 ° C. The resulting heat resistance results from the highest temperature, which did not result in the laminating film peeling off.
  • Table 1 Table 1 :

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé de collage de substrats plats, flexibles sur des substrats non flexibles (c'est-à-dire de lamination de substrats), caractérisé en ce que l'adhésif utilisé pour le collage renferme entre 0,0001 et 0,1 mol de groupes carbodi-imide pour 100 g d'adhésif (eau ou tout autre solvant organique de point d'ébullition inférieur 150 °C pour 1 bar, non inclus), en ce que l'adhésif est appliqué sur le substrat flexible, et en ce que le substrat flexible enduit d'adhésif est collé avec le substrat non flexible.
PCT/EP2004/006650 2003-07-07 2004-06-19 Procede de lamination au moyen d'adhesifs speciaux au polyurethane WO2005005565A1 (fr)

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DE10330748A DE10330748A1 (de) 2003-07-07 2003-07-07 Verfahren zur Kaschierung mit Verwendung spezieller Polyurethan-Klebstoffe
DE10330748.6 2003-07-07

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Cited By (7)

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WO2007082826A2 (fr) * 2006-01-19 2007-07-26 Basf Se Adhésif à polyuréthane comprenant des groupes siliane et carbo-diimide
US7981954B2 (en) 2005-01-28 2011-07-19 Basf Aktiengesellschaft Anti-corrosion coatings containing thioamide groups
US8123899B2 (en) 2006-07-12 2012-02-28 Basf Aktiengesellschaft Polyurethane adhesive with a silane compound as an additive
US8268404B2 (en) 2007-06-20 2012-09-18 Basf Se Method for applying corrosion protection coatings to metal surfaces
US8420219B2 (en) 2006-04-26 2013-04-16 Basf Se Method for the application of corrosion-resistant layers to metallic surfaces
US8460445B2 (en) 2007-06-11 2013-06-11 Basf Se Corrosion protection coatings
CN109749053A (zh) * 2018-12-29 2019-05-14 华南理工大学 一种含聚碳化二亚胺的聚氨酯分散体及其制备方法

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DE102004063380A1 (de) 2004-12-23 2006-07-06 Basf Ag Verfahren zur Kaschierung unter Verwendung spezieller Vernetzer mit Carbodiimid-gruppen
ES2394520T3 (es) 2006-12-22 2013-02-01 Basf Se Microcápsulas que contienen compuestos con grupos carbodiimida
DE102010043486A1 (de) 2009-11-16 2011-05-19 Basf Se Kaschierverfahren unter Verwendung von Carbodiimid- und Harnstoffgruppen enthaltenden Klebstoffen
WO2013190839A1 (fr) 2012-06-20 2013-12-27 日泉化学株式会社 Film de résine et feuille de bois de placage tranché utilisant celui-ci et élément intérieur d'automobile

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WO1998012275A1 (fr) * 1996-09-20 1998-03-26 Ppg Industries Ohio, Inc. Adhesif a base d'eau utile pour la stratification sous vide
DE10001777A1 (de) * 1999-02-03 2000-08-10 Basf Ag Verfahren zur Herstellung von Verklebungen mittels carbodiimidhaltiger Dispersionen unter Wärmeaktivierung
DE19960864A1 (de) * 1999-12-17 2001-06-28 Basf Ag Carbodiimide in Emulsionspolymerisaten
DE10000656A1 (de) * 2000-01-11 2001-07-12 Basf Ag Carbodiimide mit Carboxyl- oder Carboxylatgruppen
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7981954B2 (en) 2005-01-28 2011-07-19 Basf Aktiengesellschaft Anti-corrosion coatings containing thioamide groups
WO2007082826A2 (fr) * 2006-01-19 2007-07-26 Basf Se Adhésif à polyuréthane comprenant des groupes siliane et carbo-diimide
WO2007082826A3 (fr) * 2006-01-19 2008-01-24 Basf Ag Adhésif à polyuréthane comprenant des groupes siliane et carbo-diimide
US8420219B2 (en) 2006-04-26 2013-04-16 Basf Se Method for the application of corrosion-resistant layers to metallic surfaces
US8123899B2 (en) 2006-07-12 2012-02-28 Basf Aktiengesellschaft Polyurethane adhesive with a silane compound as an additive
US8460445B2 (en) 2007-06-11 2013-06-11 Basf Se Corrosion protection coatings
US8268404B2 (en) 2007-06-20 2012-09-18 Basf Se Method for applying corrosion protection coatings to metal surfaces
CN109749053A (zh) * 2018-12-29 2019-05-14 华南理工大学 一种含聚碳化二亚胺的聚氨酯分散体及其制备方法

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