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WO2000071343A1 - Procede de formation de stratifies - Google Patents

Procede de formation de stratifies Download PDF

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Publication number
WO2000071343A1
WO2000071343A1 PCT/US2000/013492 US0013492W WO0071343A1 WO 2000071343 A1 WO2000071343 A1 WO 2000071343A1 US 0013492 W US0013492 W US 0013492W WO 0071343 A1 WO0071343 A1 WO 0071343A1
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WO
WIPO (PCT)
Prior art keywords
component
layer
composition
reactive
reactive adhesive
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
PCT/US2000/013492
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English (en)
Other versions
WO2000071343A8 (fr
Inventor
John Robert Ilkka
Haibin Yu
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Reichhold Inc
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Reichhold Inc
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Filing date
Publication date
Application filed by Reichhold Inc filed Critical Reichhold Inc
Priority to AU50220/00A priority Critical patent/AU5022000A/en
Publication of WO2000071343A1 publication Critical patent/WO2000071343A1/fr
Publication of WO2000071343A8 publication Critical patent/WO2000071343A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207—Heat-activated adhesive
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
    • B29L2031/3005—Body finishings
    • B29L2031/3011—Roof linings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric in the substrate
    • 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
    • C09J2463/00—Presence of epoxy resin
    • C09J2463/006—Presence of epoxy resin in the substrate
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a method of forming laminates, and more particularly, to laminates used in the automotive industry.
  • exemplary laminates include headliners, hoodliners, trunkliners, sound attenuating laminates and the like. These all can be classified as "automotive laminates". Of particular interest are headliners. Automotive headliners and the above mentioned other automotive laminates, must be able to withstand extreme temperature variations, must provide sound attenuation and must be somewhat aesthetically appealing. Exemplary headliners are disclosed, for example, in U.S. Patent Nos. 4,840,832, 4,077,821 , 4,851 ,253 and 5,565,259.
  • a typical automotive laminate involves the bonding of a foam layer, typically polyurethane foam, to one or more glass fiber mats.
  • a foam layer typically polyurethane foam
  • the typical construction is rigid core foam adhesively bonded between two fiberglass mats.
  • a non-woven scrim is bonded to the backside of the headliner, and a decorative fabric is bonded to the front side (i.e., the outer face layer).
  • a popular type of adhesive is polyurethane adhesive.
  • Such adhesives are often referred to as having an A-side and a B-side.
  • the A-side is a free isocyanate group containing oligomer and the B- side contains an active hydrogen curative with or without a catalyst.
  • the liquid A-side is normally roll coated onto the polyurethane foam; the liquid B-side is subsequently sprayed onto the A-side coating.
  • An example of such a polyurethane adhesive system is detailed in U.S. Patent 5,670,21 1 .
  • the existing system also incurs processing difficulties. The most frequent one is open time.
  • the crosslinking reaction occurs once the B-side is applied to the A-side coating. Degree of crosslink increases with time. After a specific time, T, the degree of crosslink can be so high that the adhesive is no longer processable. Additionally the reaction between isocyanate and active hydrogen compounds is greatly affected by environmental conditions, especially temperature and humidity. During summer months, when temperature and humidity are generally highest, parts coated with the two component polyurethane reactive adhesive show a short open time and subsequently, higher than normal scrap rates. Thus there is a need for an adhesive system that provides improvements over these systems.
  • the method of the present invention relates to forming laminates using a two-component reactive adhesive.
  • the two-component reactive adhesive includes a first reactive component and a second reactive component that when contacted together, a crosslinking reaction is initiated such that a thermoset bond between like or different surfaces can be formed.
  • the method comprises applying a first component of the two-component reactive adhesive to a first substrate to form at least one layer, wherein the first component has both binding and curative properties; applying a second component of the two- component reactive adhesive to a second layer, and molding the first layer and second layer under conditions sufficient to utilize the curing properties of the first component to initiate a crosslinking reaction between the first component and second component to bind the first layer and the second layer together.
  • this is under conditions sufficient to provide the automotive laminate in a predetermined shape.
  • conventional spray equipment can be eliminated and open time is controlled in that the reactive components do not begin crosslinking until the molding step.
  • the reaction stoichiometry/mix ratios are more reproducible because the process for pre- coating the reactant/catalyst through either roll coating or the glass mat conversion process is more repeatable and reproducible than the current spray process.
  • FIG. 1 is a schematic view of an embodiment of the invention.
  • Fig. 2 is a cross-sectional view of a mold utilized in the method of the invention prior to the molding step.
  • Fig. 3 is a cross-sectional view of a mold utilized in the method of the invention after the molding step.
  • Fig. 4 is an enlarged cross-sectional view of a laminate provided according to the method of the invention.
  • Fig. 1 there is illustrated the method of the present invention.
  • a first component 15 of a two-component reactive adhesive is applied to a first substrate 20 to form at least one first layer 25.
  • heat 27 can be used to dry or partially cure the first component.
  • the first layer can be wound 28 onto one or more rolls.
  • a second component 30 is applied to a second layer 35.
  • the first layer 25 and second layer 35 are then contacted together to provide a laminate 40 particularly suitable for automotive applications.
  • the laminate 40 can be molded utilizing a conventional mold 41, preferably at a temperature of about 80°C to 200°C to provide a predetermined charge or profile to the article.
  • the laminate 40 can comprise two first layers 25a, 25b and a second layer 35 between the two first layers.
  • a decorative fabric 45 can then be bonded to one or both of the first layers.
  • the first layer 25a can be formed from fiber bundles to which the first component is applied.
  • the fiber bundles used in carrying out the process of the present invention are those composed of a large number of single filaments, and preferably they are yarns or tows composed of bundles of continuous long filaments.
  • they include organic fibers such as fibers such as fibers of polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, etc.; organic heat- resistant fibers such as fibers of aromatic polyamide (for example, Kevler ®
  • fiber bundles composed of a combination of two or more of the above-mentioned fibers.
  • Suitable two-component reactive adhesives comprise a first component having both binding and curative properties and a second component, namely the two-component (second component/first component) system can include free isocyanate containing compound(s)/reactive hydrogen containing compound(s), such as polyamine and polyol, epoxy/amine, epoxy/carboxyl acid, epoxy/anhydride, epoxy/mercaptan, unsaturated ester/free radical initiating composition, vinyl ester/free radical initiating composition, unsaturated composition/ionic initiation composition, unsaturated ester/ami ne composition, vinyl ester/amine composition; urea-formaldehyde composition, melamine- formaldehyde composition, phenolic formaldehyde composition, and aziridine/polyol composition.
  • free isocyanate containing compound(s)/reactive hydrogen containing compound(s) such as polyamine and polyol, epoxy/amine, epoxy/carboxyl acid, epoxy/anhydride, epoxy/mercaptan, unsatur
  • catalysts can be the only active ingredients to promote the reaction.
  • inert compounds are used when necessary as catalyst carriers to help coat the catalysts onto headliner components.
  • the two-component reactive adhesive is a two-component polyurethane adhesive wherein the reactive components are often referred to as the "A-side" and the "B-side".
  • the A-side (second component) contains isocyanate-terminated compounds, preferably polymeric isocyanate.
  • the B-side contains reactive ingredients that can either react/crosslink with A-side's isocyanate-terminated compounds or promote the above crosslink reaction or isocyanate self-crosslink reaction or both, and also provide bonding properties.
  • Polymeric isocyanates are produced through isomerization/ polymerization isocyanate monomers, such as MDI, TDI and
  • HDI through the polymerization carbon-carbon unsaturating monomers, such as TMI, which contains free isocyanate group.
  • TMI carbon-carbon unsaturating monomers
  • the most common pathway for isocyanate-terminated compounds is referred to in the art as a pre- polymer process.
  • polyols are reacted with di- or trifunctional isocyanates under conditions wherein the number of isocyanate groups supplied exceeds the number of labile hydrogen atoms in the polyoi so that the resulting composition is free of labile hydrogen atoms and has instead a substantial number of free isocyanate groups for later reaction.
  • Polyoi usable herein can be di-, tri- and/or multi-functional hydroxyl groups containing compound, most commonly polyether polyoi and polyester polyoi.
  • a proper amount of lower molecular weigh polyhydroxy compounds are also used, such as ethylene glycol, propylene glycol, diethylene glycol, glycerol, sorbitol, pentaerythritol, dipropylene glycol and the likes. Mixture of polyhydroxy compounds can be used. Some of these compounds are described in U.S. Pat. No. 3,644,569 the disclosure of which is incorporated herein in its entirety.
  • polyether or polyester polyols can be used in making these adhesives such as diol, triol, tetrol and the likes.
  • Polyether polyols are generally made through polymerization of an alkylene oxide such ethylene oxide and propylene oxide under strong base catalysts, such as potassium hydroxide, preferably in the presence of water, glycols and so forth.
  • alkylene oxides such as ethylene oxide and propylene oxide under strong base catalysts, such as potassium hydroxide, preferably in the presence of water, glycols and so forth.
  • Polyethers having highly branched chains are readily prepared from alkylene oxides and initiators having active hydrogen functionality greater than two.
  • the higher functional initiators that are useful with the alkylene oxides described above include polyols, polyamines and amino alcohol having a total of three or more reactive hydrogen atoms on hydroxyl and primary or secondary amino groups.
  • Suitable polyols include triols, such a glycerol, trimethylolpropane, butanetriols, hexanetriols, trialkanolamines; various diethylenetriamine, such as erythritol and pentaerythritol; pentols; hexols, such as dipentaerythritol and sorbitol, as well as alkyl glucosides, carbohydrates, polyhydroxy fatty acid esters such as caster oil, and polyoxy alkylated derivatives or polyfunctional compounds having three or more reactive hydrogen atoms, such as, for example, the reaction product of trimethylolpropane, glycerol and other polyols with ethylene oxide, propylene oxide or other epoxides or copolymers thereof, e.g., copolymers of ethylene and propylene oxides, and ethylene oxide being used in a molar amount of not over 20 mol % as compared to other
  • Higher functional amino alcohols and polyamines include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2-(2-amino-ethylamino)ethanol, 2- amino-2-(hydroxymethyl)-1 ,3-propanediol, ethylenediamine, diethylenetriamine, triethylenetetramine, and urea as well as various aryl polyamines such as 4,4', 4"- methylidynetrianiline.
  • Polyester polyols are formed through condensation reaction of one or more polyhydric alcohols with one or more polycarboxylic acids.
  • suitable polyhydric alcohols include the following: glycerol; pentaerythritol; trimethylolpropane; 1 ,4,6-octanetriol; butanediol; pentanediol; hexanediol; dodecanediol; octanediol; chloropentanediol; glycerol monoallyl ether; glycerol monoethyl ether; diethylene glycol; 2-ethylhexanediol-1 ,4; cyclohexanediol-1 ,4;
  • polycarboxylic acids include the following: phthalic acid; isophthalic acid; terephthalic acid; tetrachlorophthalic acid; maleic acid; dodecylmaleic acid; octadecenylmaleic acid; fumaric acid; aconitic acid; trimellitic acid; tricarballylic acid; 3,3'-thiodipropionic acid; succinic acid; adipic acid; cyclohexane-1 ,2-dicarboxylic acid; 1 ,4-cyclohexadiene-1 ,2-dicarboxylic acid and the corresponding acid anhydrides, acid chlorides and acid esters such as phthalic anhydride, phthaloyl chloride and the dimethyl ester or phthalic acid.
  • Preferred polycarboxylic acids are the aliphatic and cycloaliphatic dicarboxylic acids containing no more than fourteen carbon atoms and the aromatic dicarboxylic acids containing no more than fourteen atoms with the proviso that any polyhydric alcohol having more than 2 hydroxyl groups or any polycarboxylic acid having more than 2 carboxylic groups should be used in only very minor amounts to prevent crosslinking and gelling.
  • Castor oil, lesqurella oil, cellulose derivatives and other natural hydroxyl compounds are also widely used to synthesize isocyanate pre-polymers.
  • the polyhydroxyl compounds suitable for employment can be conveniently characterized as normally liquid (although meltable solids are not excluded), pourable polyethers, polyesters, etc. having viscosity in the range of from 50 centipoises to about 500,000 centipoises at room temperature (i.e., 25°C.) and preferably having molecular weights in the range of from about 60 to 10,000.
  • polyisocyanate compounds can be used for prepolymer preparation. Examples include the isomers and isomeric mixtures of toluene diisocyanate, 1 ,5-napthalenediisocyanate, cumeme-2,4-diisocyanate, 4-methoxy- 1 ,3-phenylenediisocyanate, 4-chloro-1 ,3-phenylene-diisocyante, 4-bromo-1 ,3- phenylenediisocyanate, 4-ethoxy-1 ,3-phenylenediisocyanate, 2,4'- diisocyanatatodiphenylether, 5,6-dimethyl-1 ,3-phenylenediisocyanate, 2,4- dimethyl-1 ,3-phenylenedi isocyanate, 4,4'-diisocyanatodiphenylether, 4,4'- diphenyldi isocyanate, 4,6-dimethyl-1 ,3-phenylened
  • A-side can also be added other ingredients nonreactive with isocyanates such as stabilizers including hydrolytic stabilizers, thickeners, antioxidants, dyestuffs, fillers and the like in amounts considered useful by those skilled in the art.
  • stabilizers including hydrolytic stabilizers, thickeners, antioxidants, dyestuffs, fillers and the like in amounts considered useful by those skilled in the art.
  • the preparing of polyurethane prepolymers having free or reactive — NCO groups is well known.
  • A-side can be in the state of liquid or dry (solid).
  • a liquid A-side can be
  • the B-side (first component) is the curative or crosslinking component/catalyst. It can comprise principally compounds containing reactive hydrogen, normally as hydroxyl or amino hydrogen atoms, as exemplified by the polyhydroxyl compounds discussed supra such as polyether polyols, polyester polyols, etc. of the types described above with multiple active hydrogen functionality.
  • the B-side polyoi can also be the (co-)polymerization product of hydroxyl group containing acrylate, such as hydroxyl ethyl acrylate, hydroxyl ethyl methacrylate, hydroxyl propyl acrylates and hydroxyl propyl methacrylats, etc.
  • B-side composition may also be polymeric amine that is documented arts.
  • the B-side can and generally does contain urethane curing catalysts to promote the isocyanate curing reactions and, optionally, other ingredients such as hydrolytic and UV stabilizers, antioxidants, thickeners, fillers, dyestuffs, etc.
  • urethane curing catalysts to promote the isocyanate curing reactions and, optionally, other ingredients such as hydrolytic and UV stabilizers, antioxidants, thickeners, fillers, dyestuffs, etc.
  • Aliphatic or aromatic polyamines as described in U.S. Pat. No. 3,714,127, the disclosure of which is incorporated herein in its entirety, can be substituted for part/all of the polyhydroxy compound in the second component.
  • amines examples include primary amines or primary polyamines which may contain some secondary amino groups as well as primary amines having hydroxyl groups like ethylene diamine, diethylene-triamine, tetrametbylenediamine, pentamethyl- enediamine, hexamethylenediamine, 2,5-diamino-n-hexane, xylene diamine, l,3-diaminopropanol-2, and the like and mixture of the same.
  • the catalysts used to promote the urethane chain extension and crosslinking reaction can be amine catalyst and metal catalyst.
  • the metal catalyst commonly used are tin compounds such as, for example, stannous carboxylates like stannous acetate, stannous octoate, stannous laurate, stannous oleate and the likes; or dialkyl tin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin di-2- ethylhexoate, dilauryltin diacetate, dioctyltin diacetate and the like.
  • Trialkyltin hydroxide, dialkyltin oxide or dialkylatin chloride can also be used.
  • various tertiary amines can be used such as triethylamine, benzyldimethylamine, triethylenediamine and tetramethylbutanediamine.
  • a number of special aromatic substituted diamines with decreased isocyanate reactivity are sometimes used to chain extend and to crosslink between the free isocyanate groups of the isocyanate-terminated prepolymer and to cure the compound into a rigid, tough cured adhesive.
  • arylene diazanines useful herein include 4,4'-methylene-bis(2- bromoaniline); bis(4-aminophenyl)sulfone; cumene-2,4-diamine; 4-chloro-l,3- phenylenediarnine; 9,10-anthracenediamine; 4,4'-diaminodibenzyl; 2,4. diaminostilbene; 1 ,4-anthradiamine; 2,5-fluorenediamine; 1,8- naphathalenediamine; 2,2'-dimethylbenzidine; and 2,2'-dichloro-5,5 '- diethoxybenzidine and the like and mixtures of the same.
  • the B-side of an adhesive can be in the state of liquid or dry (solid).
  • a liquid B-side can be 100% solids or a solution, emulsion or a dispersion of the functional adhesive ingredients in organic solvent, water solution or in both.
  • Another exemplary system is an epoxy/amine system wherein an epoxy polyester or a glycidyl/methacrylate latex is used as the second component and an amine cure agent is used as the first component.
  • Suitable specific epoxies include Pretex 130, Airflint 303-X-90 and Airflint 607, available from Reichhold, Inc.
  • Suitable amine cure agents include Epotuf 680 and Epotuf 681 available from Reichhold, Inc.
  • Another exemplary system is an epoxy/acid anhydride system wherein the second component is an epoxy resin and the first component is a polyester with free anhydride groups.
  • Suitable epoxies are listed above. Suitable polyesters with free anhydride groups include Aroflint 404-XX-60 and Aroflint 251-Z1 -60, available from Reichhold, Inc.
  • Example 1 A formulated adhesive is applied with suitable method and equipment onto laminate component to bond components together for automotive laminates under proper process conditions.
  • an adhesive comprising a reactive polyurethane, such as Ever-o-Lock 2201 3 manufactured and sold by Reichhold, Inc. as the A- side (second component) and a latex polyoi, such as Arolon 1218 manufacture and sold by Reichhold, Inc. with an amine catalyst, such as Dabco TMR manufactured and sold by Air Products and Chemicals, Inc. as the B-side (first component).
  • the B-side of the adhesive is pre-coated and exist as a dry coating film format on the fiber glass mat. Pre-coating can be accomplished either in the glass mat conversion process or in a secondary coating application.
  • A-side of reactive urethane is roll coated on the polyurethane core foam.
  • the coating weights of A-side on the foam and B-side on fiberglass mat per unit area are controlled to be properly/stiochiometrically matched.
  • a final three dimensional headliner laminate is produced by assembling headliner components in the sequence of scrim, glass mat pre-coated with B-side, polyurethane foam with reactive urethane coating on both sides, another pre-coated glass mat and decorative fabric. Such assembly is molded under suitable temperature, pressure, and time cycle the selection of which will be within the skill of one in the art.
  • Ever-o-Lock 2U010 reactive polyurethane manufactured by Reichhold, Inc.
  • the coating weight is controlled at 3 g per square feet per side.
  • Ever-o-Lock 22014 an amine catalyst containing urethane curative also manufactured by Reichhold, Inc.
  • a three dimensional headliner laminate is produced by assembling headliner components in the sequence of scrim, glass mat pre-coated with B-side, polyurethane foam with reactive urethane coating on both sides, another pre-coated glass mat and decorative fabric and subsequently molding the assembly under 285°F for 45 to 60 seconds.
  • the part strength is tested by three-point bending test method, SAE Method J949, with a six-inch sample span and a three-inch wide sample at room temperature.
  • the molded part in Example 2 showed a strength by three point bending of 23.3 N/cm at 3.8 mm deflection.
  • a specific formulation is as follows: A side of Ever-o-Lock 2U010, a reactive polyurethane manufactured by Reichhold, Inc.; B-side of a mixture of 100 g of Arolon 1218, a styrene/acrylic latex polyoi available from Reichhold, Inc. and 5 g of Dabco TMR, an amine catalyst available from Air Products and Chemicals, Inc.
  • the side A material is coated onto both sides of the core foam at a coating weight of 3.0 g/ft2 per side using a two-sided Black Brothers roll coater.
  • the B-side material was applied to the glass mat using it as the binder in the wet process glass mat conversion.
  • the glass mat was comprised of an M- fiber glass strand at a weight of 8.0 g/ft2 glass. Coating weight of B-side material is 2.4 g/ft 2 to 6.5 g/ft 2 as the mat binder. Once A-side material is coated onto both sides of the core foam, the glass mat with the pre-coated with B-side material is placed onto each side of the core foam. The non-woven scrim and decorative fabric are placed on the back and front sides of the composite, respectively. The entire composite is placed in a heated mold and compressed
  • Fine-Clad M-8100 is a polyester resin manufactured by Reichhold, Inc.
  • Potassium HEX-CEM 977 is a potassium octoate solution (1 5% potassium content) supplied by OMG Corporation.
  • Amicure TEDA is supplied by Air Products and Chemicals, Inc.
  • Potassium HEX-CED 977 and Amicure TEDA are the urethane catalyst.
  • Amicure TED A/Potassium HEX-CEM 977/Fine-Clad M- 8100/TEDA are weighted and premixed within a Henschel FM-10 min for 30-60 sec. The pre-mixtures are then extruded with a twin screw extruder, W&P ZSK-
  • Example 8 Manufacture of Fiberglass Mat with Urethane Curative Powder
  • the powder prepared in Example 7 is used as binder to manufacture non- woven glass fiber mat.
  • Fiberglass mat is fabricated with Astecnologies's non- woven glass fiber manufacture process. Glass strand is cut onto 1-inch length onto a moving flat TEFLON belt.
  • the powder urethane curative is spread evenly at 5-20 g/m2, preferably 10-15 g/m2 concentration onto the chopped fiberglass.
  • a non-waving glass mat is formed after heat pressing.
  • Thus produced fiberglass mat carries urethane catalysts.
  • Example 9 Headline Manufacture with the Fiber Glass Mat Carrying Urethane Catalysts
  • a non-woven glass fiber mat is manufactured with the following properties, 80g fiber glass per square meter, 10g per square meter urethane catalyst curative powder produced in Example 7 and 5g per square meter Bostik polyester binder.
  • a headliner is manufactured using this non-woven glass fiber mat together with Ever-o-Lock 2201 3 at Heartland Automotive, Inc. The three- point bending strength and flexural modulus for the headline composite are averaged at 250.42 psi and 49.88 Kpsi, respectively.
  • headliner is also manufactured at Heartland Automotive, Inc., using Ever-o-Lock 2201 3 and Ever-o-Lock 22014.
  • the corresponding headliner composite demonstrates a three-point bending strength and flexural modulus 214.69 psi and 35.48 Kpsi, respectively.
  • Example 10 Headliner manufactured with the fiber glass mat carrying urethane catalyst Another non-woven glass fiber mat is manufactured with the following properties, 80g fiberglass per square meter, 20g per square meter urethane catalyst curative powder produced in Example 7. Headliner is manufactured using this non-woven glass fiber mat together with Ever-o-Loc 22013 at Heartland Automotive, Inc. The three-point bending strength and flexural modulus for the headliner composite are averaged at 222.4 psi and 47.01 Kpsi, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

Cette invention se rapporte à un procédé servant à former des stratifiés (40) en utilisant un adhésif réactif à deux composants, lequel contient un premier composant réactif (15) et un second composant réactif (30) qui, lorsqu'ils sont mis en contact, déclenchent une réaction de réticulation telle qu'elle produit une liaison entre des surfaces similaires ou différentes. Ce procédé consiste à appliquer un premier composant (15) de l'adhésif réactif à deux composants sur un premier substrat (20), afin de former au moins une couche (25), le premier composant ayant à la fois des propriétés de liaison et de durcissement; à appliquer un second composant (30) de l'adhésif réactif à deux composants sur une seconde couche (35); et à mouler la première couche et la seconde couche dans des conditions suffisantes pour mettre à profit les propriétés de durcissement du premier composant, afin de déclencher la réaction de réticulation entre le premier composant et le second composant, ce qui entraîne la liaison de la première couche et de la seconde couche. Cette liaison se produit de préférence dans des conditions suffisantes pour créer un stratifié ayant une forme prédéterminée, utilisable dans l'industrie automobile.
PCT/US2000/013492 1999-05-20 2000-05-17 Procede de formation de stratifies Ceased WO2000071343A1 (fr)

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AU50220/00A AU5022000A (en) 1999-05-20 2000-05-17 Method of forming laminates

Applications Claiming Priority (4)

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US13503499P 1999-05-20 1999-05-20
US60/135,034 1999-05-20
US56980300A 2000-05-12 2000-05-12
US09/569,803 2000-05-12

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WO2000071343A8 WO2000071343A8 (fr) 2001-06-21

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WO2003076499A1 (fr) * 2002-03-08 2003-09-18 Owens Corning Systeme de liant de mat de filaments continus
GB2394442A (en) * 2002-10-25 2004-04-28 Lear Corp Making vehicle interior trim parts using a thermosetting adhesive.
WO2005061640A1 (fr) * 2003-11-21 2005-07-07 Arkema Procédé de collage de deux matériaux par un adhésif réticulable
EP1640425A3 (fr) * 2004-09-03 2006-06-07 Hueck Folien Ges.m.b.H Elément de sécurité
US7875355B2 (en) 2005-07-01 2011-01-25 The Sherwin-Williams Company Multi-layer coating system including a hydroxyl modified polyurethane dispersion binder
WO2011117269A1 (fr) * 2010-03-25 2011-09-29 Basf Se Mousses et pièces moulées en matières de base contenant des résines réactives expansibles
WO2011146477A3 (fr) * 2010-05-17 2012-01-12 Anagram International, Inc. Adhésifs autocollants pour aérostats
DE102011118513A1 (de) * 2011-11-14 2013-05-16 Liebherr-Hausgeräte Ochsenhausen GmbH Klebemittel oder Bauteil
EP2746438A1 (fr) 2012-12-20 2014-06-25 Resopal Gmbh Film en résine aminoplaste
DE102015217731A1 (de) * 2015-09-16 2017-03-16 Volkswagen Aktiengesellschaft Fügeverfahren und über das Verfahren erhältliches Verbundwerkstück
CN106903969A (zh) * 2016-05-10 2017-06-30 陶氏环球技术有限责任公司 用于形成包含包括胺引发的多元醇的双组分无溶剂胶粘剂组合物的层压体的方法
CN106926553A (zh) * 2016-05-10 2017-07-07 诺德美克股份公司 用于制备多层膜片的方法
CN109415478A (zh) * 2016-05-10 2019-03-01 陶氏环球技术有限责任公司 包含胺引发的多元醇的双组分无溶剂粘合剂组合物
EP3476911A1 (fr) * 2017-10-31 2019-05-01 Protechnic Composition et structure d'un adhesif multiphasique reticulable
US20190390095A1 (en) * 2016-05-10 2019-12-26 Dow Global Technologies Llc Two-component solventless adhesive compositions comprising an amine-initiated polyol

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GB1262158A (en) * 1968-02-14 1972-02-02 Freudenberg Carl Iron-on interlinings
US4184005A (en) * 1975-11-04 1980-01-15 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process of solvent-free lamination using isocyanate/amine adhesives
US5082716A (en) * 1989-10-16 1992-01-21 Process Bonding, Inc. Headliner
US5439737A (en) * 1992-04-10 1995-08-08 Lainiere De Picardie Two-phase fusible interlining made of a semi-interpenetrating network of thermoplastic resins
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GB2284381A (en) * 1993-11-01 1995-06-07 Seismic & Oilfield Services Lt Method of forming a reactive polymer system
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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076499A1 (fr) * 2002-03-08 2003-09-18 Owens Corning Systeme de liant de mat de filaments continus
US7083855B2 (en) 2002-03-08 2006-08-01 Owens Corning Fiberglass Technology, Inc. Continuous filament mat binder system
GB2394442A (en) * 2002-10-25 2004-04-28 Lear Corp Making vehicle interior trim parts using a thermosetting adhesive.
GB2394442B (en) * 2002-10-25 2005-03-02 Lear Corp Method of making an interior trim part
WO2005061640A1 (fr) * 2003-11-21 2005-07-07 Arkema Procédé de collage de deux matériaux par un adhésif réticulable
EP1640425A3 (fr) * 2004-09-03 2006-06-07 Hueck Folien Ges.m.b.H Elément de sécurité
US7875355B2 (en) 2005-07-01 2011-01-25 The Sherwin-Williams Company Multi-layer coating system including a hydroxyl modified polyurethane dispersion binder
WO2011117269A1 (fr) * 2010-03-25 2011-09-29 Basf Se Mousses et pièces moulées en matières de base contenant des résines réactives expansibles
CN102821941A (zh) * 2010-03-25 2012-12-12 巴斯夫欧洲公司 由包含可发泡的反应性树脂的基材制成的泡沫和模制品
WO2011146477A3 (fr) * 2010-05-17 2012-01-12 Anagram International, Inc. Adhésifs autocollants pour aérostats
DE102011118513A1 (de) * 2011-11-14 2013-05-16 Liebherr-Hausgeräte Ochsenhausen GmbH Klebemittel oder Bauteil
EP2746438A1 (fr) 2012-12-20 2014-06-25 Resopal Gmbh Film en résine aminoplaste
US9592649B2 (en) 2012-12-20 2017-03-14 Resopal Gmbh Amino resin film and method of producing the same
DE102015217731A1 (de) * 2015-09-16 2017-03-16 Volkswagen Aktiengesellschaft Fügeverfahren und über das Verfahren erhältliches Verbundwerkstück
DE102015217731B4 (de) 2015-09-16 2022-03-10 Volkswagen Aktiengesellschaft Fügeverfahren zur Herstellung eines Verbundwerkstücks
WO2017195012A1 (fr) * 2016-05-10 2017-11-16 Nordmeccanica S.P.A. Procédé de production d'un film multicouche
CN106903969B (zh) * 2016-05-10 2022-01-25 陶氏环球技术有限责任公司 用于形成包含包括胺引发的多元醇的双组分无溶剂胶粘剂组合物的层压体的方法
WO2017196528A1 (fr) * 2016-05-10 2017-11-16 Dow Global Technologies Llc Procédé de formation d'un stratifié comprenant une composition adhésive sans solvant à deux composants comprenant un polyol amorcé par une amine
CN106926553A (zh) * 2016-05-10 2017-07-07 诺德美克股份公司 用于制备多层膜片的方法
CN109415478A (zh) * 2016-05-10 2019-03-01 陶氏环球技术有限责任公司 包含胺引发的多元醇的双组分无溶剂粘合剂组合物
TWI822656B (zh) 2016-05-10 2023-11-21 美商陶氏全球科技有限責任公司 用於形成包括含胺引發多元醇之雙組分無溶劑黏著劑組合物之層製品的方法
EP4095176A1 (fr) * 2016-05-10 2022-11-30 Dow Global Technologies LLC Compositions adhésives sans solvant à deux composants comprenant un polyol amorcé par une amine
US20190177575A1 (en) * 2016-05-10 2019-06-13 Dow Global Technologies Llc Two-component solventless adhesive compositions comprising an amine-initiated polyol
US20190202172A1 (en) * 2016-05-10 2019-07-04 Dow Global Technologies Llc A method for forming a laminate comprising a two-component solventless adhesive composition including as amine-initiated polyol
US20190390095A1 (en) * 2016-05-10 2019-12-26 Dow Global Technologies Llc Two-component solventless adhesive compositions comprising an amine-initiated polyol
RU2728191C2 (ru) * 2016-05-10 2020-07-28 Нордмекканика С.П.А. Способ получения многослойной пленки
RU2742989C2 (ru) * 2016-05-10 2021-02-12 Дау Глоубл Текнолоджиз Ллк Способ получения ламината, содержащего двухкомпонентную клеевую композицию без растворителя, включающую инициируемый амином полиол
US11014334B2 (en) 2016-05-10 2021-05-25 Dow Global Technologies Llc Method for forming a laminate comprising a two-component solventless adhesive composition including an amine-initiated polyl
US11041100B2 (en) * 2016-05-10 2021-06-22 Dow Global Technologies Llc Two-component solventless adhesive compositions comprising an amine-initiated polyol
US11078382B2 (en) * 2016-05-10 2021-08-03 Dow Global Technologies Llc Two-component solventless adhesive compositions comprising an amine-initiated polyol
RU2753834C2 (ru) * 2016-05-10 2021-08-23 Дау Глоубл Текнолоджиз Ллк Двухкомпонентная не содержащая растворителя адгезивная композиция, содержащая инициированный амином полиол
ITUA20163315A1 (it) * 2016-05-10 2017-11-10 Nordmeccanica Spa Metodo per la produzione di un film multistrato
CN106903969A (zh) * 2016-05-10 2017-06-30 陶氏环球技术有限责任公司 用于形成包含包括胺引发的多元醇的双组分无溶剂胶粘剂组合物的层压体的方法
EP3455274B1 (fr) * 2016-05-10 2022-09-07 Dow Global Technologies LLC Compositions adhésives sans solvant à deux composants comprenant un polyol amorcé par une amine
US11498323B2 (en) 2016-05-10 2022-11-15 Nordmeccanica S.P.A. Method for producing a multilayer film
FR3072965A1 (fr) * 2017-10-31 2019-05-03 Protechnic Composition et structure d’un adhesif multiphasique reticulable
EP3476911A1 (fr) * 2017-10-31 2019-05-01 Protechnic Composition et structure d'un adhesif multiphasique reticulable

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