WO2000071343A1

WO2000071343A1 - Method of forming laminates

Info

Publication number: WO2000071343A1
Application number: PCT/US2000/013492
Authority: WO
Inventors: John Robert Ilkka; Haibin Yu
Original assignee: Reichhold, Inc.
Priority date: 1999-05-20
Filing date: 2000-05-17
Publication date: 2000-11-30
Also published as: WO2000071343A8

Abstract

The method of the present invention relates to forming laminates (40) using a two-component reactive adhesive. The two-component reactive adhesive includes a first reactive component (15) and a second reactive component (30) that when contacted together, a crosslinking reaction is initiated such that a bond between like or different surfaces can be formed. The method includes applying a first component (15) of the two-component reactive adhesive to a first substrate (20) to form at least one layer (25), wherein the first component has both binding and curative properties; applying a second component (30) of the two-component reactive adhesive to a second layer (35), 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. Preferably this is under conditions sufficient to provide the automotive laminate in a predetermined shape.

Description

METHOD OF FORMING LAMINATES

This application claims the benefit of U.S. Provisional Application No. 60/1 35,034, filed May 20, 1 999.

BACKGROUND AND FIELD OF THE INVENTION

The present invention relates to a method of forming laminates, and more particularly, to laminates used in the automotive industry.

There are numerous examples of 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. With respect to headliners, 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).

The same or different adhesives can be used to bond one or more of the various layers together. A popular type of adhesive is polyurethane adhesive. Such adhesives are often referred to as having an A-side and a B-side. For example, 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 .

With the use of such polyurethane adhesive systems, headliner manufacturers are experiencing the problems of inefficient transfer of the sprayed side, and accordingly, improper mix ratios resulting in inaccurate reaction stoichiometry. The off-specification stoichiometry (either high or low) can result in either a low degree of crosslinking (e.g., resulting in soft parts) or pitting (e.g., adhesive penetrating through the cover fabric), respectively.

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.

SUMMARY OF THE INVENTION 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. Preferably this is under conditions sufficient to provide the automotive laminate in a predetermined shape. In this manner conventional spray equipment can be eliminated and open time is controlled in that the reactive components do not begin crosslinking until the molding step. Additionally, 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.

BRIEF DESCRIPTION OF THE DRAWINGS 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.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to 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. Optionally 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. Referring to Figs. 2 and 3, 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. As shown in Fig. 4, 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. For example, 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 ^®

(Dupont, U.S.), polyfluorocarbon, phenol resin (Kynol ^®; Carbonrandam, U.S.), polyamide-imide, polyimide, etc.; rayon and natural fibers; inorganic fibers such as fibers of glass, boron nitride, carbon (including carbonaceous, graphitized, and flame-resisting fibers), silicon nitride, silicon carbide, alumina, zirconia, asbestos, etc.; metal fibers such as fibers of copper, tungsten alloy, iron, aluminum, stainless steel, etc., composite fibers such as fibers of boron with a core of tungsten, boron carbide with a core of tungsten, silicon carbide with a core of tungsten, boron, etc., and all others having a form of fiber. It is also possible to use 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. For those adhesive composition where components are able to proceed via self-crossl inking, such as isocyanate containing compound through dimerization, trimerization/isocyanurate formation, epoxy compound through cationic ring-opening polymerization and reaction carbon-carbon unsaturation containing compound through different types of polymerization, catalysts can be the only active ingredients to promote the reaction. In such cases, inert compounds are used when necessary as catalyst carriers to help coat the catalysts onto headliner components.

In a preferred embodiment, 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. However, the most common pathway for isocyanate-terminated compounds is referred to in the art as a pre- polymer process. During isocyanate pre-polymer synthesis, 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.

A wide range of 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. 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 alkylene oxides like propylene oxide. 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. Examples of 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;

1 ,2,6-hexanetriol; 1 ,3,5-hexanetriol; 1 ,3-bis-(2-hydroxyethoxy)propane and the like. Examples of 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. Generally, 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.

A wide variety of 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-phenylenediisocyanate, 1 ,10- anthracenedi isocyanate, 4,4'-diisocyanatodibenzyl, pure or polymeric diphenylmethanediisocyanates such as 4,4'-diisocyanatodiphenyl-methane, 3,3- dimethyl-4,4'-diisocyanatodiphenyl methane, 2,6-dimethyl-4,4'- diisocyanatodiphenyl and others and mixtures of the same. While aliphatic polyisocyantes can be used, it is preferred to use the aromatic diisocyanates, particularly the toluene diisocyanates and the commercial polymeric isocyanates based on aniline-formaldehyde condensation products of relatively low molecular weight. To this A-side (second component) 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. 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

100% solids or a solution, emulsion or a dispersion of the functional adhesive ingredients in organic solvent, water solution or in both.

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. 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. Examples of such amines are 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. As an alternative or in addition to the above tin compounds, 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. Examples of 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.

EXAMPLES 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. To demonstrate a laminate manufacture process, an adhesive is used 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. The 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.

Example 2: Existing Headliner Manufacture Process

Ever-o-Lock 2U010, reactive polyurethane manufactured by Reichhold, Inc., is roll coated onto both sides of polyurethane foam. 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., is spray applied onto the Ever-o-Lock coated polyurethane foam. . 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.

Examples 3 to 6: Pre-coat Processes

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/ft² to 6.5 g/ft² 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

to 90% of its original thickness and cured using combinations of the temperatures and cure time cycle used above. Test results are listed in Table 1

Table 1

The results illustrate that as the side B coating weight increases, strength and stiffness values increase.

Example 7: Preparation of Urethane Curatives Powder

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-

30. Barrel temperatures are set at 1 10 °C and 100 °C, respectively. The compounded material is subsequently kneaded into flake, air-cooled and grinder into fine particle of an average particle size of 80μm. DSC analysis reveals the Tg of the powder is 43.6 °C. The powder passes the stability test.

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.

As a comparison, 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.

The present invention has been described in detail above. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein above; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Claims

THAT WHICH IS CLAIMED IS:

1 . A method of forming an automotive laminate using a two- component reactive adhesive, the method comprising:

(a) applying a first component of the two-component reactive adhesive to a first substrate to form at least one first layer, wherein the first component has both binding and curative properties;

(b) applying a second component of the two-component reactive adhesive to a second layer; and

(c) 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, and under conditions sufficient to provide the automotive laminate in a predetermined shape.

2. The method of Claim 1 , wherein the first substrate is fibers, and utilizing the binding properties of the first component, the fibers are bound together to provide a non-woven mat first layer.

3. The method of Claim 2, wherein the first component is a reactive hydrogen-containing compound and the second component is a free-isocyanate- containing compound.

4. The method of Claim 1 , wherein the conditions sufficient to initiate the crosslinking reaction between the first component and second component of the two-component reactive adhesive and conditions sufficient to provide the automotive laminate in a predetermined shape comprises molding at a temperature of 80°C to 200°C.

5. The method of Claim 1 , wherein the second layer is a foam layer.

6. The method of Claim 5, wherein the foam layer is a urethane foam layer.

7. The method of Claim 1 , further comprising the additional step prior to step (c) of bonding a decorative layer to the first layer.

8. The method of Claim 1 , wherein the first component is in solid form and the second component is in liquid form.

9. The method of Claim 1 , wherein the first component is an amine and the second component is an epoxy resin.

10. The method of Claim 1 , wherein the first component is a polyester with free anhydride groups and the second component is an epoxy resin.

1 1 . The method of Claim 1 , wherein the two-component reactive adhesive comprises a second reactive component/first reactive component selected from the group consisting of epoxy/carboxyl acid, epoxy/mercaptan, unsaturated ester/free radical initiating composition, vinyl ester/free radical initiating composition, unsaturated composition/ionic initiation composition, unsaturated ester/amine composition, vinyl ester/amine composition; urea- formaldehyde composition, melamine-formaldehyde composition, phenolic formaldehyde composition, and aziridine/polyol composition.

12. An automotive laminate formed according to the method of Claim 1 .

13. The automotive laminate according to Claim 1 1 , wherein the laminate is a headliner.

14. A method of forming an automotive laminate using a two- component reactive adhesive, the laminate comprising a pair of outer layers and an inner layer between the outer layers, the method comprising:

(a) applying a first component of the two-component reactive adhesive to a first substrate to form the outer layers, wherein the first component has both binding and curative properties;

(b) applying a second component of the two-component reactive adhesive to an inner layer; and

(c) molding the layers 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 layers together, and under conditions sufficient to provide the automotive laminate in a predetermined shape.

15. The method of Claim 14, wherein the substrate is fibers, and utilizing the binding properties of the first component, the fibers are bound together to provide non-woven mat outer layers.

16. The method of Claim 1 5, wherein the first component is a reactive hydrogen-containing compound and the second component is a free-isocyanate- containing compound.

1 7. The method of Claim 14, wherein the conditions sufficient to initiate the crosslinking reaction between the first component and second component of the two-component reactive adhesive and conditions sufficient to provide the automotive laminate in a predetermined shape comprises molding at a temperature of 80°C to 200°C.

18. The method of Claim 14, wherein the inner layer is a foam layer.

19. The method of Claim 18, wherein the foam layer is a urethane foam layer.

20. The method of Claim 14, further comprising the additional step prior to step (c) of bonding a decorative layer to either or both of the outer layers.

21 . The method of Claim 14, wherein the first component is in solid form and the second component is in liquid form.

22. The method of Claim 14, wherein the first component is an amine and the second component is an epoxy resin.

23. The method of Claim 14, wherein the first component is a polyester with free anhydride groups and the second component is an epoxy resin.

24. The method of Claim 14, wherein the two-component reactive adhesive comprises a first reactive component/second reactive component selected from the group consisting of epoxy/carboxyl acid, epoxy/mercaptan, unsaturated ester/free radical initiating composition, vinyl ester/free radical initiating composition, unsaturated composition/ionic initiation composition, unsaturated ester/amine composition, vinyl ester/amine composition; urea- formaldehyde composition, melamine-formaldehyde composition, phenolic formaldehyde composition, and aziridine/polyol composition.

25. An automotive laminate formed according to the method of Claim 14.

26. The automotive laminate according to Claim 24, wherein the laminate is a headliner.

27. A method of forming a laminate using a two-component reactive adhesive, the method comprising:

(c) 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, and under conditions sufficient to provide the laminate in a predetermined shape.

28. The method of Claim 27, wherein the substrate is fibers, and utilizing the binding properties of the first component, the fibers are bound together to provide a non-woven mat first layer.

29. The method of Claim 28, wherein the first component is a reactive hydrogen-containing compound and the second component is a free-isocyanate- containing compound.

30. The method of Claim 27, wherein the conditions sufficient to initiate the crosslinking reaction between the first component and second component of the two-component reactive adhesive and conditions sufficient to provide the automotive laminate in a predetermined shape comprises molding at a temperature of 80°C to 200°C.

31 . The method of Claim 27, wherein the second layer is a foam layer.

32. The method of Claim 31 , wherein the foam layer is a urethane foam layer.

33. The method of Claim 27, further comprising the additional step prior to step (c) of bonding a decorative layer to the first layer.

34. The method of Claim 27, wherein the first component is in solid form and the second component is in liquid form.

35. The method of Claim 27, wherein the first component is an amine and the second component is an epoxy resin.

36. The method of Claim 27, wherein the first component is a polyester with free anhydride groups and the second component is an epoxy resin.

37. The method of Claim 27, wherein the two-component reactive adhesive comprises a first reactive component/second reactive component selected from the group consisting of epoxy/carboxyl acid, epoxy/mercaptan, unsaturated ester/free radical initiating composition, vinyl ester/free radical initiating composition, unsaturated composition/ionic initiation composition, unsaturated ester/amine composition, vinyl ester/amine composition; urea- formaldehyde composition, melamine-formaldehyde composition, phenolic formaldehyde composition, and aziridine/polyol composition.