EP1030869A1 - Liants polyurethanes a faible teneur en monomeres volatils - Google Patents

Liants polyurethanes a faible teneur en monomeres volatils

Info

Publication number
EP1030869A1
EP1030869A1 EP98963418A EP98963418A EP1030869A1 EP 1030869 A1 EP1030869 A1 EP 1030869A1 EP 98963418 A EP98963418 A EP 98963418A EP 98963418 A EP98963418 A EP 98963418A EP 1030869 A1 EP1030869 A1 EP 1030869A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
component
groups
stage
polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP98963418A
Other languages
German (de)
English (en)
Inventor
Achim Hübener
Günter Henke
Andreas Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP06110268A priority Critical patent/EP1666513B1/fr
Publication of EP1030869A1 publication Critical patent/EP1030869A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C08G18/8019—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to a polyurethane binder, process for producing a low-viscosity, isocyanate group-bearing polyurethane binder which, despite its low viscosity, has only a low content of volatile residual monomers and essentially does not form any migrates.
  • the invention further relates to the use of a low-viscosity polyurethane binder which carries isocyanate groups (NCO groups) in the production of adhesives, in particular one- and two-component substances, for example for the application of sheet-like materials made of paper, plastic or aluminum, or mixtures of two or more of these, coatings, in particular sheets, emulsion paints and casting resins, and moldings.
  • NCO groups isocyanate groups
  • Polyurethane prepolymers with isocyanate end groups have been known for a long time. With suitable hardeners - mostly polyfunctional alcohols - they can be easily extended or crosslinked to form high molecular weight substances. Polyurethane prepolymers have gained importance in many fields of application, for example in the production of adhesives, coatings, casting resins and molded plastic.
  • polyurethane prepolymers with terminal I-socyanate groups it is customary to react polyfunctional alcohols with an excess of polyisocyanates, generally at least predominantly diisocyanates.
  • the molecular weight can be controlled at least approximately via the ratio of OH grapple to isocyanate groups. While a ratio of OH groups to isocyanate groups of 1: 1 or close to 1: 1 usually has high molecular weights, for example a ratio of about 2: 1 when using diisocyanates on average, add a diisocyanate molecule to each OH group, so that in the course of the reaction there is ideally no oligomer formation or chain extension
  • a content of such substances is particularly disruptive when it comes to volatile diisocyanates.
  • the vapors of these diisocyanates are often harmful to health, and the use of products with a high content of such volatile diisocyanates requires extensive effort on the part of the user M ⁇ took to protect the people processing the product, especially complex measures to clean the breathing air.
  • volatile is understood to mean those substances which have a vapor pressure of more than about 0.0007 mmHg or a boiling point of less than about 190 ° C (70 mPa) at about 30 ° C.
  • low volatile diisocyanates are used, in particular the widespread bicyclic diisocyanates, for example Diphenyimethane-isocyanates, as a rule, polyurethane binders are obtained with a viscosity that is usually outside the range that can be used for simple processing methods.
  • the viscosity of the polyurethane copolymers can be reduced by adding suitable solvents, but this contradicts the mostly required another possibility to lower the viscosity while avoiding L.
  • Solvents consist in the addition of an excess of monomeric polyisocyanates, which are incorporated in the coating or in the course of a subsequent curing process (after the addition of a hardener or by hardening under the influence of moisture) (reactive thinner).
  • Migrates are often intolerable, particularly in the packaging sector, because migration of the M. igrate through the packaging material would lead to contamination of the packaged goods and the consumer would inevitably have to come into contact with the migrants when consuming the goods.
  • EP-A 0 118 065 proposes to produce polyurethane prepolymers in a two-stage process.
  • a monocyclic diisocyanate is reacted with a polyfunctional alcohol in the ratio OH groups: isocyanate groups ⁇ 1 and then in a second step a bicyclic diisocyanate with polyfunctional alcohols in the ratio OH groups: isocyanate groups ⁇ 1 in Presence of the prepolymer prepared in the first step brought to reaction
  • a ratio of OH groups: isocyanate groups of 0.65 to 0.8, preferably 0.7 to 0.75 is proposed.
  • the prepolymers obtained in this way still have viscosities of 2500 mPas or 7150 mPas and 9260 mPas at high temperatures (75 ° C or 90 ° C).
  • DE-A 34 01 129 relates to a process for the production of mixed polyurethane prepolymers, in which polyfunctional alcohols are first reacted with the more rapidly reacting isocyanate group of an asymmetric Dusocyanate and the slower reacting group, and the reaction products are then reacted with be connected to a symmetrical diisocyanate, the equally reactive isocyanate groups of which, in turn, react more quickly than the slowly reacting groups of the first-mentioned multifunctional isocyanate compound.
  • the polyurethane polymers described have high viscosities and thus high processing temperatures which only permit their use under conditions which allow high processing temperatures.
  • EP- ⁇ 0 019 120 relates to a method for producing elastic, weather-resistant flat structures.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane and diisocyanate
  • the actual polyurethane binders should be able to cure with water or with air humidity.
  • Composite foils are often used in areas with high temperatures, for example in the preparation of foodstuffs.
  • Composites made with traditional adhesives often show signs of delamination in the vaporizing area when the foils are exposed to temperatures, as is usually the case with to rule.
  • the object of the invention was therefore to provide a polyurethane binder .to available, the t lowest possible "viscosity and a möghchst succeed Restgeli of less than about 1 wt .-% comprising of highly volatile diisocyanates wherein the residual content of readily volatile isocyanate, in the case of toluene diisocyanate (TDI) should be less than about 0J% by weight.
  • TDI toluene diisocyanate
  • Another object of the invention was to provide a polyurethane binder which allows processing at the lowest possible processing temperature
  • Another object of the invention was to provide a polyurethane binder which has the lowest possible proportion of "migrates", i.e. the lowest possible proportion of monomeric polyisocyanates.
  • Another object of the invention was to provide a polyurethane binder with which film composites can be produced which have no or only a slight tendency to delaminate even at high temperatures.
  • a further aspect of the invention was to provide processes with which a polyurethane binder with the above-mentioned properties can be produced.
  • the invention relates to a polyurethane binder with a low content of volatile monomers bearing isocyanate groups, at least containing components A and B, in which
  • Isocyanate groups of which at least one .art has a lower reactivity than groups reactive with isocyanates than the other .art or the other types, and
  • low viscosity means a viscosity (measured according to Brookfield) that is less than 5000 mPas at 50 ° C.
  • Text is understood as a mixture of at least two isocyanate group-containing molecules in which the proportion of molecules with one Molecular weight of more than 500 is at least about 50% by weight, preferably at least about 60% by weight or about 70% by weight
  • Component A is a polyurethane prepolymer carrying at least two isocyanate groups, or a mixture of two or more at least two polyurethane prepolymers bearing isocyanate groups, which is preferably obtainable by reacting a polyol component with an at least difunctional isocyanate.
  • a "polyurethane prepolymer” is understood to mean a compound which results, for example, from the reaction of a polyol component with an at least difunctional isocyanate.
  • the term “polyurethane prepolymer” thus includes both compounds with a relatively low molecular weight and the like for example, from the reaction of a polyol with an excess of polyisocyanate, but oligomeric or polymeric compounds are also included.
  • Also encompassed by the term “polyurethane prepolymers” are compounds such as those e.g. are formed from the reaction of a 3 or 4-valent polyol with a molar excess of diisocyanates, based on the polyol. In this case, one molecule of the resulting compound carries several. Isocyanate groups.
  • molecular weight data relating to polymeric compounds relate to the number average molecular weight (M n ).
  • the polyurethane prepolymers used in the present invention have a molecular weight of about 500 to about 15,000, or about 500 to about 10,000, for example about 5,000, but in particular about 700 to about 2,500.
  • the two-isocyanate-bearing polyurethane prepolymer, or the mixture of two or more isocyanate-bearing polyurethane prepolymers has at least two differently bound types of isocyanate groups, at least one of which has less reactivity to groups reactive with isocyanates than the other or the other types of isocyanate groups.
  • Isocyanate groups with a comparatively lower reactivity towards groups reactive with isocyanates are also referred to in the following text as "less reactive socyanate groups", the corresponding isocyanate group with a higher reactivity compared with isocyanate groups .reactive compounds is also known as a "more reactive isocyanate group"
  • a difunctional polyurethane prepolymer can therefore be used as component A, which has two differently bonded isocyanate groups, one of the isocyanate groups being more reactive towards isocyanates r. active groups than the other I ⁇ cyanatzy.
  • a polyurethane prepolymer can be obtained, for example, from the reaction of a difunctional alcohol with two different, for example difunctional, compounds containing isocyanate groups, the reaction being carried out in such a way that on average each molecule of the difunctional alcohol with one molecule each of the different isocyanate group-bearing compounds responds.
  • component A it is also possible to use a tri-functional or higher-functional polyurethane prepolymer — component A, it being possible for one molecule of the polyurethane prepolymer to have, for example, a different number of less reactive and more reactive isocyanate groups.
  • Mixtures of two or more polyurethane prepolymers can also be used as component A in the context of the invention.
  • the mixtures mentioned can be polyurethane-P. act prepolymers in which individual molecules each carry identically bonded isocyanate groups, with a mixture of at least one more reactive and one less reactive isocyanate group. It is also possible for the mixture to contain, in addition to molecules which carry one or more identically bound isocyanate groups, further molecules which carry both one or more identically bound isocyanate groups and one or more differently bound isocyanate groups.
  • the polyurethane binder according to the invention also contains an at least difunctional isocyanate, the molecular weight of which is lower than the molecular weight of the polyurethane prepolymers contained in component A, and whose isocyanate groups are more reactive towards compounds reactive with isocyanates than the less reactive compounds contained in component A. .Type of isocyanate groups.
  • Component B generally has a molecular weight of up to about 1000, with molecular weights of up to about 720 or less, for example about 550, 500, 450, 400 or less, being preferred.
  • Suitable as component B are, for example, low-molecular diisocyanates with a molecular weight of up to about 300 or the reaction products of di- or higher-functional alcohols with an at least equimolar amount of such low-molecular diisocyanates, based on the OH groups of the di- or higher-functional Alcohol.
  • Also suitable as component B are, for example, the trimerization point (difunctional isocyanates), the isocyanurates.
  • the polyurethane binder according to the invention contains at least 5% by weight of component B, based on the total polyurethane binder.
  • the polyurethane binder according to the invention preferably has a content of volatile monomers bearing isocyanate groups of less than 2% by weight or less than 1% by weight or preferably less than 0.5% by weight. These limits apply in particular to volatile cocyanate compounds which have only a limited potential for degradation for persons involved in processing, for example for Isophorondii.socyanat (IPDI),
  • HDI Hexamethylene diisocyanate
  • TXDI tetramethylxylylene diisocyanate
  • cyclohexane diisocyanate With certain volatile isocyanate compounds, especially those which have a high risk potential for people involved in their processing, their content in the polyurethane binder according to the invention is preferably less than 0.3% by weight and particularly preferably less than 0J% by weight.
  • the latter isocyanate compounds include, in particular, tolylene diisocyanate (TDI).
  • TDI tolylene diisocyanate
  • the polyurethane binder has a TDI and .HDI content of less than 0.05% by weight.
  • the polyurethane binder according to the invention can contain, in addition to components A and B, as component H an at least trifunctional isocyanate.
  • Suitable as at least trifunctional isocyanates are, for example, the tri- and oligomerization products of the polyisocyanates already mentioned, as are obtainable with the formation of isocyanurate rings by suitable reaction of polyisocyanates, preferably diisocyanates. If oligomerization products are used, those oligomerization products with an average degree of ohgomerization of about 3 to about 5 are particularly suitable.
  • Isocyanates suitable for the production of trimers are the diisocyanates already mentioned, the trimerization products of the isocyanates being HDI, MDI or IPDI are particularly preferred.
  • polymeric isocyanates such as are obtained, for example, as a residue in the distillation bottoms from the distillation of 5 diisocyanates.
  • polymeric MDI as is available in the distillation of MDI from the distillation residue, is particularly suitable
  • Desmodur N 3300, Desmodur N 100, the IPDI-trimeric isocyanurate T 1890 ⁇ o (manufacturer: Bayer AG) or triphenylmethane triisocyanate are used, for example.
  • Component H is preferably used in an amount of approximately 1 to approximately 30% by weight, in particular between approximately 5 and approximately 25% by weight, for example approximately 12 to approximately 20% by weight.
  • component A is produced by an at least two-stage reaction in the
  • Prepolymer is produced, the NCO / OH ratio being less than 2 and free OH groups still present in the polyurethane prepolymer, and. 25 (d) in a second stage, another at least difunctional isocyanate is reacted with the polyurethane prepolymer from the first stage,
  • the further, at least difunctional isocyanate is added in a molar excess, based on free OH groups of component A, the portion not reacting with OH groups being further at least difunctional isocyanate component B.
  • component A is produced by an at least two-stage reaction in which
  • a polyurethane P in a first stage of an at least difunctional isocyanate and at least one first polyol component. is produced in the prepolymer, the NCO / OH ratio being less than 2 and free OH groups still present in the polyurethane prepolymer, and
  • the isocyanate groups of the isocyanate added in the second stage being more reactive towards compounds reactive with isocyanates than at least the predominant proportion of those in the polyurethane. ethane-P. prepolymers from the first stage present isocyanate groups.
  • the further at least difunctional isocyanate is added in molar excess, based on free OH groups of component A and the further polyol component, the portion of the further at least difunctional isocyanate which does not react with OH groups being component B. It is preferred in the context of the present invention if the OH: NCO ratio in the preparation of component A in the second stage is about 0.001 to less than 1, in particular 0.005 to about 0.8.
  • the ratio OH: NCO in the second stage is approximately 0.2 to 0.6
  • the ratio OH: NCO is less than 1, in particular 0.5 to 0.7, in the first stage, it being possible, if appropriate, to maintain the ratios described for the second stage.
  • polyol component in the context of the present text encompasses a single polyol or a mixture of two or more polyols which can be used for the production of polyurethanes.
  • a polyol is understood to be a polyfunctional alcohol, i.e. a connection with melir. as an OH group in Molelcül.
  • polyol component for the production of component A.
  • these are aliphatic alcohols with 2 to
  • OH groups per Molelcül.
  • the OH groups can be either primary or secondary.
  • Suitable aliphatic alcohols include, for example
  • Ethylene glycol propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
  • the reaction products of low molecular weight polyfunctional alcohols with allcylene oxides, so-called polyethers can be used as the polyol component for producing component A.
  • the .Allcyleneoxides preferably have 2 to 4 carbon atoms.
  • the reaction products of ethylene glycol, propylene glycol, the isomeric butanediols or hexanediols with ethylene oxide, propylene oxide or butylene oxide, or mixtures of two or more thereof, are suitable.
  • the reaction products are also more polyfunctional.
  • Alcohols such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols, or mixtures of two or more thereof, with the allcylene oxides mentioned.
  • polyether polyols Suitable for polyether polyols. Polyether polyols with a molecular weight of about 100 to about 10,000 are particularly suitable. preferably from about 200 to about 5,000. Polypropylene glycol with a molecular weight of about 300 to about 2,500 is very particularly preferred in the Ralimen of the present invention.
  • polyether polyols such as those obtained from the polymerization of tetrahydrofuran.
  • the polyethers are reacted in a manner known to the person skilled in the art by reacting the starting compound with a .reactive hydrogen atom with .Allcylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • .Allcylene oxides for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • Suitable starting compounds are, for example, water, ethylene glycol, propylene glycol 1, 2 or -1, butylene glycol 1, 4 or -1 hexanediol-1, 6, octanediol-1,8, neopentyl glycol, 1,4-hydroxymethylcyclohexane, 2-methyl-1 , 3-propanediol, glycerol, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4 trimethylolethane, pentaerythritol mannitol, sorbitol, methylglycosides, sugar, phenol, isononylphenol, resorcinol, hydroquinone, 1 ⁇ 2- or l, 1,2-tris (hydroxyphenyl) ethane,.
  • ammonia methylamine, ethylenediamine, tetra- or hexamethyleneamine, triethanolamine, Aniline, phenylenediamine, 2,4- and 2,6-diaminotoluene and polyphenylrx) lymethylene polyamines, as can be obtained by .aniline-fo ⁇ naldehyde condensation, or mixtures of two or more thereof.
  • polystyrene are also suitable for use as the polyol polyethers which have been modifiaert by "Vlnylpolymere.
  • Such products are obtainable, for example, by, are polymerized in the presence of polyethers styrene or acrylonitrile, or a mixture thereof.
  • polyester polyols with a molecular weight of about 200 to about 10,000.
  • polyester polyols can be used which are formed by reacting low molecular weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone.
  • polyfunctional alcohols 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 1,2-butanetriol are suitable for the production of polyester polyols,
  • Triethylene glycol Triethylene glycol, tetraethylene glycol, polyethylene glycol, IDipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • polyester polyols can be prepared by polycondensation.
  • difunctional and / or trifunctional alcohols with a deficit of dicarboxylic acids and / or tricarboxylic acids, or their reactive derivatives can be condensed to give polyester polyols.
  • Suitable dicarboxylic acids are, for example, succinic acid and its higher homologues with up to 16 carbon atoms, furthermore unsaturated dicarboxylic acids such as maleic acid or fumaric acid and aromatic dicarboxylic acids, in particular the isomeric phthalic acids such as phthalic acid, isophthalic acid or terephthalic acid.
  • polyester polyols of at least one of the dicarboxylic acids and glycerol mentioned, which have a residual content of OH groups are particularly suitable according to the invention.
  • Particularly suitable are hexanediol, ethylene glycol, diethylene glycol or neopentyl glycol or mixtures of two or more thereof.
  • Particularly suitable acids are isophthalic acid or adipic acid or a mixture thereof.
  • the present invention is particularly preferred as a polyol component.
  • Polyols used to produce component A are, for example, dipropylene glycol and / or polypropylene glycol with a molecular weight of about 400 to about 2500, and polyester polyols, preferably polyester polyols, obtainable by polycondensation of hexanediol, ethylene glycol, or diethylene glycol Neopentyl glycol or mixtures of two or more thereof and isophthalic acid or adipic acid, or mixtures thereof.
  • Polyester polyols with a high molecular weight include, for example, the reaction products of polyfunctional, preferably difunctional, alcohols (optionally, together with small amounts of trifunctional alcohols) and polyfunctional, preferably difunctional, carboxylic acids.
  • polyfunctional, preferably difunctional, alcohols instead of free polycarboxylic acids, the corresponding polycarbonate anhydrides or corresponding polycarboxylic acid esters with alcohols with preferably 1 to 3 carbon atoms can also be used (if possible).
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic or heterocyclic, or both. She. can optionally be substituted, for example by alkyl groups, .alkenyl groups, ether groups or halogens.
  • polycarboxylic acids are, for example, bemsteimic acid, adipic acid, suberic acid, .alainic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimelamic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endogenous anhydride, tetracidic anhydride, endogenous anhydride, tetracetic anhydride, endogenous anhydride, tetracidic anhydride, tetracidic anhydride, endogenous anhydride, endogenous anhydride, tetracetic acid , Fumaric acid, dimer fatty acid or trimer fatty acid or mixtures of two or more thereof. If necessary, minor amounts of monofunctional fatty acids can be present in the reaction mixture.
  • polyesters can optionally have a small proportion of carboxyl end groups.
  • Polyesters available from .lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, can also be used.
  • Polyacetals are also suitable as the polyol component.
  • Polyacetals are understood to mean compounds such as are obtainable from glycols, for example diethylene glycol or hexanediol or a mixture thereof with formaldehyde, and polyacetals which can be used in accordance with the invention can also be obtained by the polymerization of cyclic acetals.
  • Polycarbonates are also suitable as polyols for the production of components A and B.
  • Polycarbonates can be obtained, for example, by the reaction of diols, such as .propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol, or mixtures of two or more thereof with diaryl carbonates, for example diphenylcarbonate or phosgene.
  • Polyacrylates bearing OH groups are also suitable as the polyol component for producing component A. These polyacrylates can be obtained, for example, by the polymerization of ethylenically unsaturated monomers which carry an OH group. Such monomers can be obtained, for example, from the esterification of ethylenically unsaturated carboxylic acids and difunctional alcohols, the alcohol generally being in a slight excess. Suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid.
  • Corresponding esters carrying OH groups are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy propyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate or 3-hydroxypropyl methacrylate or mixtures of two or more thereof.
  • the corresponding polyol component is in each case reacted with an at least difunctional isocyanate.
  • at least difunctional isocyanate both I are used for the production of component A.
  • Socyanate with at least two isocyanate groups in question but in general within the scope of the present invention, compounds with two to four isocyanate groups, in particular with two isocyanate groups, are preferred.
  • At least difunctional isocyanates which are suitable as the at least difunctional isocyanate for the production of components A are described below.
  • ethylene diisocyanate 1,4-tetramethylene diisocyanate 1,6-hexamethylene diisocyanate HDI
  • cyclobutane-l 3-diisocyanate cyclohexane-1,3- and -1,4-diisocyanate and mixtures of two or more thereof
  • 1,3- and 1,4-phenylene diisocyanate 2 4- or 2,6-tolylene diisocyanate diphenylmethane-2,4'-diisocyanate diphenylmethane-2,2'-di-isocyanate or diphenylmethan
  • suitable as socyanates for the production of component A are trivalent or higher-valent isocyanates, such as are obtainable, for example, by oligomerizing diisocyanates.
  • trivalent and higher polyisocyanates are the triisocyanurates from HDI or IPDI or their mixtures or their mixed triisocyanurates.
  • diisocyanates which have two cocyanate groups with different reactivity are used for the production of component A. Examples of such diisocyanates are 2,4- and 2,6-tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).
  • an isocyanate group generally reacts much faster with groups which are reactive toward isocyanates, for example OH groups, while the remaining isocyanate group is comparatively inert.
  • a monocyclic, non-symmetrical diisocyanate is used to produce component A, which has two isocyanate groups of the different reactivity described
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • a mixture of the two isomers is particularly preferred, but in particular the use of pure 2,4-TDI.
  • Component B is prepared using an at least functional isocyanate, which ensures that at least the majority of the isocyanate groups of component B remaining after completion of the reaction with the polyol component are more reactive than the majority of the isocyanate groups present in component A.
  • Difunctional cocyanates whose isocyanate groups have a largely identical reactivity are preferably used to prepare component B.
  • these are the symmetrical isocyanates, with the symmetrical, aromatic difunctional isocyanates being preferred.
  • the bicyclic, aromatic, symmetrical diisocyanates of the diphenylmethane series, in particular .MDI are very particularly preferred for the production of component B.
  • a polyurethane binder with the devices according to the invention can in principle can be produced in a conventional manner. However, two methods have proven to be particularly advantageous and are described below.
  • polyurethane binder directly by producing component A, with a subsequent addition of component B.
  • Another object of the invention is therefore a process for the production of a low-viscosity, isocyanate group-containing polyurethane binder, comprising at least two stages, in which
  • a polyurethane prepolymer is prepared in a first step from an at least difunctional isocyanate and at least one polyol component, and
  • the majority of the isocyanate groups present after completion of the first stage have a lower reactivity towards groups reactive with isocyanates, in particular towards OH groups, than the. isocyanate groups of the at least difunctional kocyanate added in the second stage and the ratio OH in the second stage : NCO is about 0.2 to about 0.6
  • a further polyol component it is possible in principle to use polyol components already mentioned in the context of this text.
  • the ratio OH: NCO in the first stage of the process according to the invention was less than 1.
  • the ratio of OH groups to isocyanate groups in the first stage is about 0.4 to about 0.7, in particular more than 0.5 to about 0.7.
  • the reaction of a polyol component with the at least difunctional isocyanate in a first stage k can be carried out in any manner known to the person skilled in the art according to the general rules of polyurethane production.
  • the reaction can be carried out, for example, in the presence of [solvents.
  • Solvents which can generally be used as solvents in polyurethane chemistry, in particular esters, ketones, mogeninated hydrocarbons, allcans, alkenes and aromatic hydrocarbons. Examples of such solvents are methylene chloride, trichlorethylene, toluene, xylene and butyl acetate.
  • the reaction components themselves are liquid or at least one or more of the reaction components form a solution or dispersion of further, insufficiently liquid reaction components, then the use of solvents can be dispensed with entirely.
  • solvent-free reaction is preferred in the context of the present invention
  • the polyol if appropriate together with a suitable solvent, is initially introduced into a suitable vessel and genetically mixed. Anj5c. While the mixing is continued, the at least difunctional isocyanate is added. The temperature is usually increased to accelerate the reaction. As a rule, the temperature is raised to about 40 to about 80 ° C. The onset of exothermic reaction then ensures that the temperature rises.
  • the temperature of the .an ⁇ tzes is kept at about 70 to about 110 ° C, for example at about 85 to 95 ° C or in particular at about 75 to about 85 ° C, possibly the temperature is divided by suitable external measures, for example heating or cooling.
  • catalysts can be added to the reaction mixture to accelerate the reaction in polyurethane chemistry.
  • DABCO diazabicyclooctane
  • the catalyst is typically added to the reaction mixture in an amount of about 0.005% or about 0.01% to about 0.2% by weight of the total batch. admitted.
  • the reaction time for the first stage depends on the polyol component used, on the at least difunctional isocyanate used, on the reaction temperature and on the catalyst which may be present.
  • the total reaction time is usually about 30 minutes to about 20 hours.
  • Isophorone diisocyanate (IPDI), tetramethylxylylene diisocyanate (TMXD.I), hydrogenated diphenylmethane diisocyanate (MDIH ⁇ ) or tolylene diisocyanate (TDI) or a mixture of two or more thereof is preferably used as the at least difunctional isocyanM in the first stage to carry out the second stage of the invention
  • Procedure is in Mixture with the component A obtained in the first stage reacted at least one further at least difunctional isocyanate with a further polyol component. Any polyol from the group of the polyols listed above in the course of this text or a mixture of two or more thereof can be used as a constituent of the further polyol component.
  • a polypropylene glycol with a molecular weight of about 400 to about 2500, or a polyester polyol with at least a high, in particular a predominant proportion of aphatic dicarboxylic acids, or a mixture of these polyols is preferably used as the polyol component.
  • the at least one difunctional isocyanate used in the second stage of the process according to the invention is at least one polyisocyanate whose isocyanate groups have a higher reactivity than the majority of the isocyanate groups in the 5 prepolymers.
  • reactive isocyanate groups originating from the at least difunctional isocyanate originally used for the preparation of prepolymer A may still be present in the prepolymer; it is only essential to the invention in this context that the major proportion of the isocyanate groups present in the prepolymer A is one has lower reactivity than the isocyanate groups, furthermore at least difunctional isocyanate, which is added in the second stage of the process according to the invention.
  • a bicyclic, aromatic, symmetrical diisocyanate is preferably used.
  • the bicyclic isocyanates include, for example, the diisocyanates of the diphenylmethane series, in particular the 2,2'-diphenylmethane- ⁇ > cyanate 2,4'-diphenylmethane diisocyanate and 4,4-Diphenylmemane diisocyanate Among the diisocyanates mentioned, the use of diphenylmethane diisocyanate 0, in particular 4,4'-diphenylmethane diisocyanate, is at least the other difunctional isocyanate is particularly preferred in the second stage of the process according to the invention
  • the further at least difunctional isocyanate is in the second stage in an amount of about 5 to about 95% by weight, preferably about 20 to about 95% by weight and in particular in an amount of about 40 to about 90% by weight. %, based on the total amount of the polyisocyanates used in all stages of the process according to the invention
  • the ratio OH: NCO in the second stage is about 0.2 to about 0.6, in particular up to about 0.5. This is to be understood as the ratio OH: NCO of the components added in the second stage, and isocyanate groups originating from prepolymer A are not taken into account here
  • a polyurethane binder with the advantages according to the invention can also be produced by mixing individual components C, D and E.
  • the invention therefore also relates to a process for the preparation of a low-viscosity polyurethane binder containing isocyanate groups and having a low gel content of volatile monomers containing isocyanate groups, comprising the mixing of three components C, D and E, in which
  • component C a polyurethane prepolymer carrying bocyanate groups, obtained by reacting a polyol component with an at least difunctional isocyanate
  • Polyol component with a further at least difunctional isocyanate whose isocyanate groups have a higher reactivity towards have groups reactive with isocyanates than the isocyanate groups of component C and
  • component E a further at least difunctional isocyanate whose molecular weight is lower than that of components C and D and whose isocyanate groups have a higher reactivity towards groups reactive with isocyanates than the isocyanate groups of component C,
  • component E is used, the amount of component E being such that after completion of the mixing process and after completion of all the reactions which may occur between components C, D and E, at least 5% by weight, in particular at least 10% by weight, of component E in the polyurethane binder.
  • the polyurethane binders according to the invention and the polyurethane binders produced according to the invention preferably have a viscosity of less than 5000 mPas (measured with Brookfield RT DVU (The ⁇ nosell), spindle 27, 20 rpm, 50 ° C.).
  • all reactions possibly taking place between components C, D and E are understood to mean reactions of isocyanate groups with functional groups which have hydrogen atoms which are reactive towards isocyanates.
  • the addition of component E generally leads to a reaction of the isocyanate groups of component E with the free OH groups. This results in a reduction in the content of component E. Accordingly, if reactions are to be expected which can lead to a reduction in the proportion of component E, component E must be added in such an amount that, after all of these reactions the required .Minimum amount of component E in the polyurethane binder.
  • polyols and mixtures of two or more of the polyols mentioned can be used as the polyol component for producing components C and D in the process according to the invention.
  • the polyol components which were mentioned as particularly suitable for producing component A in the context of this text are preferably also used in the context of the process according to the invention
  • component B applies analogously to the at least difunctional I isocyanate to be used as component E, the molecular weight of which is lower than that of components C and D, and the isocyanate groups of which have a higher reactivity than the I. isocyanate groups of component C.
  • a further, at least trifunctional isocyanate can be added as component H following the two stages already described.
  • Suitable at least trifunctional isocyanates are the polyisocyanates with at least three NCO groups already described above or the tri and polymerization products of the difunctional isocyanates specified above.
  • the polyurethane binder according to the invention and the polyurethane binder produced according to the invention are distinguished in particular by the fact that they have an extremely low content of volatile monomers bearing isocyanate groups, which is less than 2% by weight, or less than 1% by weight, less than 0% 5 wt .-% and in particular less than about 0J wt .-%.
  • the process according to the invention manages without separate process steps for removing volatile diisocyanate components
  • Another advantage of the polyurethane binders produced by the process according to the invention is that they have a viscosity which is within a very favorable range for processing.
  • the viscosity of the polyurethane binders produced by the process according to the invention is in particular less than 5000 mPas (measured with Bro ⁇ kfield RT DVU ( The ⁇ nosell), spindle 27, 20 rpm, 50 ° C).
  • polyurethane binders according to the invention are suitable in bulk or as a solution in oman solvents, for example in solvents as described above, for coating objects, in particular for sealing objects.
  • the invention therefore also relates to the use of a polyurethane binder according to the invention or a polyurethane binder which has been produced by a process according to the invention in the production of adhesives, in particular one- and two-component adhesives, coatings, in particular paints, emulsion paints and casting resins and moldings, as well as for coating and in particular covering objects, in particular for covering foils and for producing composite foils.
  • adhesives in particular one- and two-component adhesives, coatings, in particular paints, emulsion paints and casting resins and moldings, as well as for coating and in particular covering objects, in particular for covering foils and for producing composite foils.
  • the polyurethane binder according to the invention or the polyurethane binder produced by one of the methods according to the invention is used in particular for gluing plastics and particularly preferably for laminating plastic foils, plastic foils vapor-coated with MetaU or with MetaU oxides, and metal foils, in particular aluminum foils.
  • the curing ie the crosslinking of the individual polyurethane binder molecules via the free isocyanate groups, can only be carried out without adding hardener Humidity can be controlled.
  • polyfunctional crosslinking agents for example .amines or in particular polyfunctional alcohols, are added as hardeners (two-component systems).
  • Film composites produced with the products produced according to the invention show high processing reliability when heat-sealing. This is due to the reduced. similar, low-molecular-weight products in the polyurethane binders.
  • an advantageous processing temperature for the adhesives produced according to the invention is between about 30 and about 90 ° C.
  • the invention also relates to an adhesive containing two components F and G, wherein
  • any polyurethane binding agent according to the invention can thus be used as component F, as described in the context of the above text.
  • component G a compound having at least two functional groups which are reactive toward the isocyanate groups of component F and having a molecular weight of up to 2,500, or a mixture of two or more such compounds, is preferably used.
  • .Amino groups, mercapto groups or OH groups are particularly suitable as at least two functional groups which are reactive toward the isocyanate groups of component F, compounds, which can be used in component G, having amino groups, mercapto groups or OH groups, respectively, or having a mixture thereof can.
  • component G The functionality of the compounds that can be used in component G is generally at least about two.
  • Component G preferably has a proportion of more highly functional compounds, for example with a functionality of three, four or more.
  • the total (average) functionality of component G is, for example, approximately two (for example if only different compounds are used as component G) or more, for example approximately 2.1, 2.2, 2.5, 2.7, or 3. If necessary, component G can have an even higher functionality, for example about 4 or more.
  • Component G preferably contains a polyol carrying at least two OH groups.
  • Polyols mentioned in the context of the preceding text are also suitable for use in component G provided they meet the restrictive criterion of the upper limit of the molecular weight.
  • Component G is generally used in an amount such that the ratio of isocyanate groups of component F to functional groups in component G which are reactive with isocyanate groups of component F is about 5: 1 to about 1: 1, in particular about 2: 1 to about 1 : 1 is.
  • the adhesive according to the invention generally has a " viscosity of about 250 to about 10,000 mPas, in particular about 500 to about 8,000 or up to about 5,000 mPas (Brookfield RVT DVU, spindle 27, 20 rpm, 40 ° C.).
  • the K. Lebstoff still contain additives.
  • the additives can have a proportion of up to about 30% by weight of the total adhesive.
  • additives that can be used in the context of the present invention include, for example, plasticizers, stabilizers, antioxidants, dyes, photo-stabilizers or fillers.
  • plasticizers for example, plasticizers based on phthalic acid are used, in particular diaucyl phthalates, phthalic esters which have been esterified with a 5 linear .Allcanol having about 6 to about 12 carbon atoms being preferred as plasticizers. Dioctyl phthalate is particularly preferred
  • plasticizers for example sucrose benzoate, diethylene glycol dibenzoate and / or diethylene glycol benzoate, in which about 50 to about 95% of the hydroxyl groups have been esterified, phosphate plasticizers, for example t-butylphenyldiphenylphosphate, polyethylene glycols and their derivatives, in particular polyphenylene (ethylene) liquid resin derivatives, for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their 5 polymerization products.
  • phosphate plasticizers for example t-butylphenyldiphenylphosphate
  • polyethylene glycols and their derivatives in particular polyphenylene (ethylene) liquid resin derivatives, for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their 5 polymerization products.
  • Antioxidants include hindered high molecular weight (M) phenols, polyfunctional phenols, and sulfur and phosphorus phenols.
  • Phenols which can be used as additives in Ralimen 0 of the invention are, for example, 1,3,5- Trimemyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyben2yl) benzene; Pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; n-octa-decyl-3,5-di-tert-butyl-4-hydroxyphenyl) propionate 4,4-methylenebis (2,6-di-tert-butyl-phenol); 4,4-thiobis (6-tert-butyl-o-cresol); 2,6-di-tert-butylphenol; 6- (4-hydroxyphenoxy) -2,4-bis (n-oc
  • Suitable photostabulators are, for example, those which are commercially available under the name Thinuvin® (manufacturer: Ciba Geigy).
  • thermoplastic polymers or copolymers can be present in the adhesives according to the invention, for example ethylene vinyl acetate (EVA), ethylene acrylic acid, ethylene methacrylate and ethylene-n-butyl acrylate copolymers, which optionally give the woven fabric additional flexibility, toughness and strength.
  • EVA ethylene vinyl acetate
  • ethylene acrylic acid ethylene methacrylate
  • ethylene-n-butyl acrylate copolymers which optionally give the woven fabric additional flexibility, toughness and strength.
  • hydrophilic polymers for example polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl methyl ether, polyethylene oxide, polyvinyl pyrrolidone, polyethyloxazoline or starch or CeUulose ester, in particular the acetates with a degree of substitution of less than 2.5, which increase the wettability of the adhesives.
  • DPG dipropylene glycol
  • PPG polypropylene glycol
  • NCO isocyanate group content
  • OPA oriented polyamide
  • PE ⁇ 08! 8 LLDPE / LDPE blend, thickness: approx. 70 ⁇ m, M. ildenberger and WiUing
  • the polyol components of the first stage were introduced and mixed homogeneously.
  • the isocyanate was then added and the temperature of the reaction mixture was raised to 50.degree.
  • the temperature then rose sharply due to the exothermic reaction between isocyanate groups and OH groups and was kept at this temperature by cooling after reaching 90 ° C.
  • the components of the second stage were added to the reaction product of the first stage and the mixture was adjusted to a temperature of 85 ° C. The mixture was stirred for a further hour.
  • Example 9 the first and second stages are each produced separately and the products thus obtained are subsequently mixed
  • Examples 10, 11 and 12 were carried out with isophorone diisocyanate (IPDI) as the first isocyanate component.
  • IPDI isophorone diisocyanate
  • the migratory content is determined as follows (see Deutche L. Foods Rundschau, 87 :, (1991), 280-281):
  • a sealed film composite bag produced with the adhesive according to the invention is filled with 3% acetic acid and stored at 70 ° C. for 2 hours.
  • the contents of the bag are then diazotized, subjected to an .azole coupling with N- (l-naphthyl) ethylenediamine and concentrated on a Cig column. Then the concentration of .azo sorbent is determined photometrically.
  • the test results can be found in Table 4 below.

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  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne des liants polyuréthanes à basse viscosité, à faible formation d'éléments migrants et à faible teneur en monomères volatils portant des groupes isocyanate. L'invention concerne en outre un procédé de production de tels liants polyuréthanes ainsi que l'utilisation de ceux-ci pour revêtir, en particulier pour coller, des objets.
EP98963418A 1997-11-11 1998-11-06 Liants polyurethanes a faible teneur en monomeres volatils Ceased EP1030869A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06110268A EP1666513B1 (fr) 1997-11-11 1998-11-06 Procedure de manufacture d'un liant à base de polyuréthane avec un contenu réduit de monomères

Applications Claiming Priority (3)

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DE19749834 1997-11-11
DE19749834 1997-11-11
PCT/EP1998/007094 WO1999024486A1 (fr) 1997-11-11 1998-11-06 Liants polyurethanes a faible teneur en monomeres volatils

Related Child Applications (1)

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CA2378222A1 (fr) * 1999-07-02 2001-01-11 Henkel Kommanditgesellschaft Auf Aktien Composition de polyurethanne auto-adhesive a faible teneur en monomere
PL362645A1 (en) * 2000-10-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Reactive adhesive with a low monomer content and with multistage hardening
DE10157488A1 (de) 2000-12-15 2002-06-20 Henkel Kgaa Polyurethan-Prepolymere mit NCO-Gruppen und niedrigem Gehalt an monomeren Polyisocyanat
DE10150722A1 (de) 2001-10-13 2003-04-30 Henkel Kgaa Reaktive Polyurethan-Zusammensetzungen mit niedrigem Restmonomergehalt
DE10163857A1 (de) 2001-12-22 2003-07-10 Henkel Kgaa Reaktive Polyurethane mit einem geringen Gehalt an monomeren Diisocyanaten
DE10215641C1 (de) * 2002-02-22 2003-11-27 Jowat Ag Verfahren zur Herstellung einer Polyurethan-Zusammensetzung mit einem geringen Anteil an Diisocyanatmonomeren
DE50309990D1 (de) 2002-02-22 2008-07-31 Jowat Ag Polyurethan-Zusammensetzungen mit geringem Anteil an Diisocyanatmonomer(en)
DE10344448A1 (de) 2003-09-25 2005-04-28 Henkel Kgaa Bindemittel mit Barriere-Eigenschaft
US7115697B2 (en) 2004-08-31 2006-10-03 E. I. Du Pont De Nemours And Company Adhesive for high-temperature laminate
WO2008058703A1 (fr) * 2006-11-17 2008-05-22 Bostik S.A. Adhésif de stratification exempt de solvant
DE102006056478A1 (de) 2006-11-28 2008-05-29 Henkel Kgaa Isocyanatprepolymer mit unterschiedlich reaktiven NCO-Gruppen
DE102007062316A1 (de) 2007-12-21 2009-06-25 Evonik Degussa Gmbh Reaktive Isocyanatzusammensetzungen
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ES2331483T3 (es) 2010-01-05
CN1278835A (zh) 2001-01-03
EP1666513A3 (fr) 2006-10-04
WO1999024486A1 (fr) 1999-05-20
DE19851182A1 (de) 1999-05-12
HUP0100117A2 (hu) 2001-06-28
JP4249898B2 (ja) 2009-04-08
EP1666513B1 (fr) 2009-09-30
PL340365A1 (en) 2001-01-29
HUP0100117A3 (en) 2001-09-28
BR9814131A (pt) 2000-10-03
PL200433B1 (pl) 2009-01-30
ATE444317T1 (de) 2009-10-15
KR20010031995A (ko) 2001-04-16
DE59814397D1 (de) 2009-11-12
JP2001522908A (ja) 2001-11-20
EP1666513A2 (fr) 2006-06-07
CA2309593A1 (fr) 1999-05-20

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