CA2190683A1 - Interior trim panels and method for manufacturing such panels using silaceous materials - Google Patents
Interior trim panels and method for manufacturing such panels using silaceous materialsInfo
- Publication number
- CA2190683A1 CA2190683A1 CA002190683A CA2190683A CA2190683A1 CA 2190683 A1 CA2190683 A1 CA 2190683A1 CA 002190683 A CA002190683 A CA 002190683A CA 2190683 A CA2190683 A CA 2190683A CA 2190683 A1 CA2190683 A1 CA 2190683A1
- Authority
- CA
- Canada
- Prior art keywords
- panel
- foam
- silaceous
- polymer
- organofunctional
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- 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
- C09J175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
- Finishing Walls (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Described is an interior trim panel (20) and method of manufacturing same comprising the steps of:
providing a foam trim panel (22), treating the foam panel with a coating composition containing a polymerizable polymer, and an organofunctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and cures to assist in the foam panel retaining its desired configuration.
providing a foam trim panel (22), treating the foam panel with a coating composition containing a polymerizable polymer, and an organofunctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and cures to assist in the foam panel retaining its desired configuration.
Description
2 ~ 9~3 TNq'T~'RTnR 'I'RTM pl~NT~T.!2 ~ M~T~In FQR eM~r~rTT~AçTnRTN~
5~JCH p~NT.!T.FI nflTN,~ f:TT.l~T.'~nf~ M~q'l;~RT~T.
CROSS REFERENCE TO RELATED ÇASES
Applicant hereby incorporates by reference Provisional Application Serial No.
60/002,812, filed August 25, 1995, entitled "Method of Preparin~ Metallized Island Coating Product 10 Without Etclling" (Attorney Docket No. PR-301 Davidson) .
FIELD OF THE INVENTION
The invention pertains to interior f oam trim panels utilizing isocyanate reactants to rigidify the f oam panel .
BACRG~OUND OF THE Il~VENTION
~oam panels that are used for interior trim are well know. See for example, U.S. Patent No. 5,393,474, hereby inuuLl~uL~Led by reference.
Foam layers containing an isocyanate group for impregnating a foam and causing it to harden durin~ the curing process are described in a number of patents, see U.S. Patent No. 5,089,328 which is incorporated by reference. In a similar ~ashion, see U.S. Patent ~os. 5,308,678 and 5,068,001 which are incorporated by reference.
The difficulty with the foams that contain an isocyanate material that are used for impregnating and curing of the foam is that the isocyanate is fairly reactive during processing ~ 2~ 9û6~3 conditions such as occurs in high humidity areas.
In addition, utilizatlon of a catalyst that may have undesirable aroma in the working place may be of a concern to certain susceptible individuals.
It is an object of the present invention to describe a foam based interior trim panel where the free-~CO groups have been reacted with an organofunctional ci l ~r~ollc material so that no 10 free-~CO is available for a reaction prior to final curing and rigidifying the foam panel.
S~ RY OF THE INVENTION
Described is a method of forming a trim panel comprising the steps of:
providing a foam trim panel, treating the foam panel with a coating composition containing a polymerizable polymer, 20 e.g. a urethane, and an organo~unctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and 25 cures to assist in the foam panel r~t;~n;ng its desired conf iguration .
Preferably when the urethane coating is used, the polymer has been reacted with an 30 organofunctional silaceous material resulting in a polymeric material having substantially no free -NCO groups, as applied ~o the panel.
BRIEF DESCRIPTION OF TRE DRAWINGS
FIGURE 1 ls an exploded view of the components of the composite article which i8 an 5 interior trim panel described in the present case;
and FIGURE 2 is a schematic representation of the process of making the composite article of the 10 trim panel of the present invention.
DESCRIPTION OF ~KP~KK~;L) RMRr~DIM~NT
The present invention is concerned with 15 interior trim panels. Trim panels are made from a f oam material which can be any open cell construction Generally the foam is a urethane foam. Alternatively, however, the foam based material can be a wide variety of other materials 2 0 such as a non-woven f abric of a synthetic f iber such as polypropylene fiber, polyester fiber, polyamide fiber, acrylic fiber or acetate fiber, a fibrous trim material such as piled fabric, and the like .
In the manufacturing process, the foam material is impregnated with a composition containing a polymerizable polymer, e.g. a urethane containing material. By "polymerizable polymer" is 30 meant that the polymer can react further during processing of the panel.
2 l ~0683 It has been found highly desirable that the urethane containing material contain an organofunctiollal silaceous material to react with the free-~lC0 groups 50 that during the processing 5 steps, there is no f ree-NC0 groups present . The organofunctiol1al silaceous material may be inserted as an additive to the urethane composition.
Alternatively, the silaceous material may be reacted with the urethane polymer system present in 10 the coating composition prior to application to the f oamed structure . The silaceous material also reacts s~ith the moisture in both of these cases to polymerize.
By "organofunctional silaceous material"
it is meant an organofunctional silicon containing material. Such silicon containing materials are characterized as silanes or siloxanes or silsesquioxane and the like. See U.S. Patent Nos.
5,182,174; 5,286,569; 5,225,248; 5,230,962 and 5, 354, 808 which are hereby incorporated by ref erence .
The silaceous containing material is a known material. The amount of organofunctional silaceous material that is utilized ranges from 0.1 to 10% by wt. of total coating composition, preferably, 0 . 5 to 5% .
While Applicant does not wish to be bound to any particular theory, it is believed that the processes outlined herein is a techni~[ue f or the organofunctional silaceous matçrial being operative ~ 2 1 ~0683 in the present case. The organofunctional silaceous material has a function or group that reacts with the isocyanate composition pref erably during preparation o~ the composition. Another 5 portion of the silaceous material is hydrolyzable and therefore, it is believed that it reacts during the curing process.
While the preferred material is a 10 urethane composition, other polymer systems may be utilized providing they preferably do not have free reactive functional groups during the application to the foam.
~he silaceous materials may be silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur containing silanes, amino functional silanes, ureido functional silanes, isocyanato functional silanes and the like. The preferred silane material is bis- (gamma-trimethoxy silylpropyl~ amine.
Other silane materials that may be used are as follows:
Allyltrimethoxysilane Allyltrimethylsilane N- ( 2-Aminoethyl ~ -3-Aminopropyl -Methyldimethoxysilane 3 0 N-2-Aminoethyl-3 -Pminopropyltrimethoxysilane 3 -Pminopropylmethyldiethoxysilane 3-Pminopropyltriethoxysilane 3-Pminopropyltrimethoxysilane Bis (Dimethylamino) dimethylsilane Bis- (N-Methyl h~n7~m; ~ ) ethoxymethylsilane ~ ; 2 1 ~Q683 Bis (Trimethylsily1) Acetamide n-Butyldimethylchloros ilane t-Butyldimethylchlorosilane Chloromethyltrimethylsilane 3 - Chlul u~. u~y ltriethoxys i lane 3 -Chlurv~-L uuy ltrimethoxysilane Di-t-butoxydiacetoxysilane N N-Diethylaminotrimethylsilane D_methylchlorosilane D_methyldichlorosilane D_methyldiethoxysilane D methylethoxysilane d methyloctadecylchlorosilane diphenyldimethoxysilane 1, 3-Divinyltetramethyl(l;c;1~7~nQ or Disiloxane Ethyltriacetoxysilane (3-Glyciduxy,uLu~yl)Methyl~ thn~ysilane ( 3 -Glycidu~y~, u~y 1 ) trimethoxysilane 1, 1., 3, 3, 5, 5-Hexamethylcyclotrisilazane Hexamethyldisilane Hexamethyldisilazane Iso:butyltrimethoxysilane 3-Mercaptopropylmethyldimethoxysilane 3-Mercaptopropyltrimethoxysilane 3-~lercaptu~l.",y~, iethoxysilane 3-Methacryluxy~u~yltrimethoxysilane 3-Methacryloxypropyltris (Methylsiloxy) -5ilane 3 0 N-Methylaminopropyltrimethoxysilane Methylcyclohexydichlorosilane Methyllcyclohexyldimethoxysilane Methyltriacetoxysilane Methyltrichlorosilane Methylltriethoxysilane Methyltrimethoxysilane N-Methyl -N
-Trimethylsilyltrif luoroacetamide Octadecyltrichlorosilane Octamethylcyclotetrasiloxane Octyldimethylchlorosilane Octyltrichlorosil~ne n-Octyltriethoxysilane 1,1,1, 3, 3-Pentamethyl-3-AcetoxydisiloXane Penyltriethoxysilane Phenyltrimethoxysilane n-Propyltrimethoxysilane Ethylpolysilicate Tetra-n-~utoxysilane Tetrachlorosilane Tetraethoxysilane Tetrakis (2-Ethoxyethoxy) Silane Tetrakis (2-Methoxyethoxy-) Silane Tetramethoxysilane 1,1, 3, 3 T~ LL hyldisiloxane Tetramethylsilane Tetrapropoxysilane Trichlorosilane N- [ 3- (Triethoxysilyl) Propyl ] -4, -5 -Dihydroimidazole N- (Triethoxysilylpropyl) Urea Triethylchlorosilane Triethylsilane Trimethoxysilylpropyldiethyleneetriamine N-Tr imethoxys i lylpropyl -N, N, N- -Tr imethyl ; 17m Chloride Tr methylbromosilane Tr- methylchlorosilane Tr- methylsilylacetamide Tr_methylsilyliodide Tr- methylsily1n ' t Tr_methylsilyltrifluorome~7;lnrc7l1 t'onate V nyldimethylchlorosilane V_nylmethyldichlorosilane . V nyltr' chlorosilane V- nyltr ethoxysilane V nyltr methoxysilane V-' nyltr s (2-Methoxyethoxy) Silane Amino Functional Silane 3 o Glycol Functional Silane Di Amino Functional Silane Vinyl-Amino Functional Silane Octyltriethoxysilane Methyltriethoxysilane Methyltrimethoxysilane tris- [3- (Trimethoxysilyl) propyl]
isocyanurate gamma-Methacrylc7~y~Lv~!yltrimethoxysilane 4 a i~eta- ( 3, 4 - Epoxycycl ohexy 1 ) ethyltrimethoxysilane gamma-Glycidoxypropyltrimethoxys i lane gamma-Mercaptopropyltrimethoxysilane Polysulf idesilane gamma-Aminopropyltriethoxysilane Aminoorganosilane gamma-Aminopropyltrimethooxysilane N-~7eta- (Aminoethyl) -gamma -aminopropyltrimethoxysilane Triaminofunction Silane Bis- (gamma-trimethoxysilylpropyl) amine Pol~dimethylsiloxane Pol~azamide Silane gamma-Ureidopropyltrialkoxys i lane gamma-Ureidopropyltrimethoxysilane gamma-Isocyanatopropyltriethoxysilane The compositions may be cured at a temperature range of approximately 150-375F for a period of time of 60 seconds to 300 seconds.
~ wide variety of organic solvents can be utilized for the commercially available coating 15 compositions. It is well known to be able to utilize aromatic hydrocarbons such as toluene and xylene, alkylesters such as ethylacetate, propylacetate, butylacetate and the like; alcohols such as aIkanol materials may likewise be used;
20 ketones as dialkyl ketones may also be utilized;
ethers as dialkylethers may, likewise, be utilized.
Water may also be used when a water based dispersion is the composition applied to the foam panel .
The organo~unctional silaceous material may be reacted with the urethane containing -NC0 groups in a well known manner. The reaction product is the coating applied i~o the foam member.
30 Many patents teach the reaction of silaceous materials with urethane polymers such as U. S.
Patent Nos. 4,645,816; 4,374,237; 5,354,808;
5~JCH p~NT.!T.FI nflTN,~ f:TT.l~T.'~nf~ M~q'l;~RT~T.
CROSS REFERENCE TO RELATED ÇASES
Applicant hereby incorporates by reference Provisional Application Serial No.
60/002,812, filed August 25, 1995, entitled "Method of Preparin~ Metallized Island Coating Product 10 Without Etclling" (Attorney Docket No. PR-301 Davidson) .
FIELD OF THE INVENTION
The invention pertains to interior f oam trim panels utilizing isocyanate reactants to rigidify the f oam panel .
BACRG~OUND OF THE Il~VENTION
~oam panels that are used for interior trim are well know. See for example, U.S. Patent No. 5,393,474, hereby inuuLl~uL~Led by reference.
Foam layers containing an isocyanate group for impregnating a foam and causing it to harden durin~ the curing process are described in a number of patents, see U.S. Patent No. 5,089,328 which is incorporated by reference. In a similar ~ashion, see U.S. Patent ~os. 5,308,678 and 5,068,001 which are incorporated by reference.
The difficulty with the foams that contain an isocyanate material that are used for impregnating and curing of the foam is that the isocyanate is fairly reactive during processing ~ 2~ 9û6~3 conditions such as occurs in high humidity areas.
In addition, utilizatlon of a catalyst that may have undesirable aroma in the working place may be of a concern to certain susceptible individuals.
It is an object of the present invention to describe a foam based interior trim panel where the free-~CO groups have been reacted with an organofunctional ci l ~r~ollc material so that no 10 free-~CO is available for a reaction prior to final curing and rigidifying the foam panel.
S~ RY OF THE INVENTION
Described is a method of forming a trim panel comprising the steps of:
providing a foam trim panel, treating the foam panel with a coating composition containing a polymerizable polymer, 20 e.g. a urethane, and an organo~unctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and 25 cures to assist in the foam panel r~t;~n;ng its desired conf iguration .
Preferably when the urethane coating is used, the polymer has been reacted with an 30 organofunctional silaceous material resulting in a polymeric material having substantially no free -NCO groups, as applied ~o the panel.
BRIEF DESCRIPTION OF TRE DRAWINGS
FIGURE 1 ls an exploded view of the components of the composite article which i8 an 5 interior trim panel described in the present case;
and FIGURE 2 is a schematic representation of the process of making the composite article of the 10 trim panel of the present invention.
DESCRIPTION OF ~KP~KK~;L) RMRr~DIM~NT
The present invention is concerned with 15 interior trim panels. Trim panels are made from a f oam material which can be any open cell construction Generally the foam is a urethane foam. Alternatively, however, the foam based material can be a wide variety of other materials 2 0 such as a non-woven f abric of a synthetic f iber such as polypropylene fiber, polyester fiber, polyamide fiber, acrylic fiber or acetate fiber, a fibrous trim material such as piled fabric, and the like .
In the manufacturing process, the foam material is impregnated with a composition containing a polymerizable polymer, e.g. a urethane containing material. By "polymerizable polymer" is 30 meant that the polymer can react further during processing of the panel.
2 l ~0683 It has been found highly desirable that the urethane containing material contain an organofunctiollal silaceous material to react with the free-~lC0 groups 50 that during the processing 5 steps, there is no f ree-NC0 groups present . The organofunctiol1al silaceous material may be inserted as an additive to the urethane composition.
Alternatively, the silaceous material may be reacted with the urethane polymer system present in 10 the coating composition prior to application to the f oamed structure . The silaceous material also reacts s~ith the moisture in both of these cases to polymerize.
By "organofunctional silaceous material"
it is meant an organofunctional silicon containing material. Such silicon containing materials are characterized as silanes or siloxanes or silsesquioxane and the like. See U.S. Patent Nos.
5,182,174; 5,286,569; 5,225,248; 5,230,962 and 5, 354, 808 which are hereby incorporated by ref erence .
The silaceous containing material is a known material. The amount of organofunctional silaceous material that is utilized ranges from 0.1 to 10% by wt. of total coating composition, preferably, 0 . 5 to 5% .
While Applicant does not wish to be bound to any particular theory, it is believed that the processes outlined herein is a techni~[ue f or the organofunctional silaceous matçrial being operative ~ 2 1 ~0683 in the present case. The organofunctional silaceous material has a function or group that reacts with the isocyanate composition pref erably during preparation o~ the composition. Another 5 portion of the silaceous material is hydrolyzable and therefore, it is believed that it reacts during the curing process.
While the preferred material is a 10 urethane composition, other polymer systems may be utilized providing they preferably do not have free reactive functional groups during the application to the foam.
~he silaceous materials may be silane esters, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfur containing silanes, amino functional silanes, ureido functional silanes, isocyanato functional silanes and the like. The preferred silane material is bis- (gamma-trimethoxy silylpropyl~ amine.
Other silane materials that may be used are as follows:
Allyltrimethoxysilane Allyltrimethylsilane N- ( 2-Aminoethyl ~ -3-Aminopropyl -Methyldimethoxysilane 3 0 N-2-Aminoethyl-3 -Pminopropyltrimethoxysilane 3 -Pminopropylmethyldiethoxysilane 3-Pminopropyltriethoxysilane 3-Pminopropyltrimethoxysilane Bis (Dimethylamino) dimethylsilane Bis- (N-Methyl h~n7~m; ~ ) ethoxymethylsilane ~ ; 2 1 ~Q683 Bis (Trimethylsily1) Acetamide n-Butyldimethylchloros ilane t-Butyldimethylchlorosilane Chloromethyltrimethylsilane 3 - Chlul u~. u~y ltriethoxys i lane 3 -Chlurv~-L uuy ltrimethoxysilane Di-t-butoxydiacetoxysilane N N-Diethylaminotrimethylsilane D_methylchlorosilane D_methyldichlorosilane D_methyldiethoxysilane D methylethoxysilane d methyloctadecylchlorosilane diphenyldimethoxysilane 1, 3-Divinyltetramethyl(l;c;1~7~nQ or Disiloxane Ethyltriacetoxysilane (3-Glyciduxy,uLu~yl)Methyl~ thn~ysilane ( 3 -Glycidu~y~, u~y 1 ) trimethoxysilane 1, 1., 3, 3, 5, 5-Hexamethylcyclotrisilazane Hexamethyldisilane Hexamethyldisilazane Iso:butyltrimethoxysilane 3-Mercaptopropylmethyldimethoxysilane 3-Mercaptopropyltrimethoxysilane 3-~lercaptu~l.",y~, iethoxysilane 3-Methacryluxy~u~yltrimethoxysilane 3-Methacryloxypropyltris (Methylsiloxy) -5ilane 3 0 N-Methylaminopropyltrimethoxysilane Methylcyclohexydichlorosilane Methyllcyclohexyldimethoxysilane Methyltriacetoxysilane Methyltrichlorosilane Methylltriethoxysilane Methyltrimethoxysilane N-Methyl -N
-Trimethylsilyltrif luoroacetamide Octadecyltrichlorosilane Octamethylcyclotetrasiloxane Octyldimethylchlorosilane Octyltrichlorosil~ne n-Octyltriethoxysilane 1,1,1, 3, 3-Pentamethyl-3-AcetoxydisiloXane Penyltriethoxysilane Phenyltrimethoxysilane n-Propyltrimethoxysilane Ethylpolysilicate Tetra-n-~utoxysilane Tetrachlorosilane Tetraethoxysilane Tetrakis (2-Ethoxyethoxy) Silane Tetrakis (2-Methoxyethoxy-) Silane Tetramethoxysilane 1,1, 3, 3 T~ LL hyldisiloxane Tetramethylsilane Tetrapropoxysilane Trichlorosilane N- [ 3- (Triethoxysilyl) Propyl ] -4, -5 -Dihydroimidazole N- (Triethoxysilylpropyl) Urea Triethylchlorosilane Triethylsilane Trimethoxysilylpropyldiethyleneetriamine N-Tr imethoxys i lylpropyl -N, N, N- -Tr imethyl ; 17m Chloride Tr methylbromosilane Tr- methylchlorosilane Tr- methylsilylacetamide Tr_methylsilyliodide Tr- methylsily1n ' t Tr_methylsilyltrifluorome~7;lnrc7l1 t'onate V nyldimethylchlorosilane V_nylmethyldichlorosilane . V nyltr' chlorosilane V- nyltr ethoxysilane V nyltr methoxysilane V-' nyltr s (2-Methoxyethoxy) Silane Amino Functional Silane 3 o Glycol Functional Silane Di Amino Functional Silane Vinyl-Amino Functional Silane Octyltriethoxysilane Methyltriethoxysilane Methyltrimethoxysilane tris- [3- (Trimethoxysilyl) propyl]
isocyanurate gamma-Methacrylc7~y~Lv~!yltrimethoxysilane 4 a i~eta- ( 3, 4 - Epoxycycl ohexy 1 ) ethyltrimethoxysilane gamma-Glycidoxypropyltrimethoxys i lane gamma-Mercaptopropyltrimethoxysilane Polysulf idesilane gamma-Aminopropyltriethoxysilane Aminoorganosilane gamma-Aminopropyltrimethooxysilane N-~7eta- (Aminoethyl) -gamma -aminopropyltrimethoxysilane Triaminofunction Silane Bis- (gamma-trimethoxysilylpropyl) amine Pol~dimethylsiloxane Pol~azamide Silane gamma-Ureidopropyltrialkoxys i lane gamma-Ureidopropyltrimethoxysilane gamma-Isocyanatopropyltriethoxysilane The compositions may be cured at a temperature range of approximately 150-375F for a period of time of 60 seconds to 300 seconds.
~ wide variety of organic solvents can be utilized for the commercially available coating 15 compositions. It is well known to be able to utilize aromatic hydrocarbons such as toluene and xylene, alkylesters such as ethylacetate, propylacetate, butylacetate and the like; alcohols such as aIkanol materials may likewise be used;
20 ketones as dialkyl ketones may also be utilized;
ethers as dialkylethers may, likewise, be utilized.
Water may also be used when a water based dispersion is the composition applied to the foam panel .
The organo~unctional silaceous material may be reacted with the urethane containing -NC0 groups in a well known manner. The reaction product is the coating applied i~o the foam member.
30 Many patents teach the reaction of silaceous materials with urethane polymers such as U. S.
Patent Nos. 4,645,816; 4,374,237; 5,354,808;
5,286,569; 5,225,248; 5,632,557; 5,378,735;
5,306.765; 5,182,174; 5,230,962; 5,366,807;
5,368,943; 5,204,404; and 5,270,~)82, all of which are hereby incorporated by ref erence .
2 1 9~683 The overall process of preparing the trim panel can be described as follows. Turning to a review of the drawings, the preferred process involves the f ormation of a laminate o~ the f oam 5 panel together with a layer of reinforcing fibers and an outer layer of a scrim member.
In accordance with the present invention, a rigid multilayer composite article 20 comprises 10 a sheet of an open cell foam material 22, one or more layers of a fibrous reinforcing material 24 disposed on the surfaces of the foam material 22, a polymerized binder containing the silaceous material dispersed throughout the foam material 22, 15 throughout a part or all of the reinforcing material 24, and adhering the foam material 22 and the fibrous reinforcing material 24 together in fixed rigid relationship, and at least one surface layer 2 6 adhesively af f ixed to a surf ace of the 20 fibrous reinforcing material 24.
The present invention pertains to the utilization of foam core materials that are used in trim panels. Such techniques for preparing such 25 foam core materials are well known in the art.
See, for example, U.S. Patent Nos. 5,308,678;
5,068,001; and 5,393,474, hereby incorporated by ref erence .
Referring to Figure l, a composite article 20 according to a preferred embodiment of the present invention is shown. The article 20, a panel, is relatively lightweight and flexible. It ' comprises a foam core 22 having reinforcing layers 24 and 25 located on the surfaces or sides of the f Qam core- 22 .
The reinforcing layers 24 and 25 are preferably made of glass fibers. However, other natural and synthetic f ibers can be used. An adhesive layer or film 28 is applied over the reinforcing layer 24 and is used to bond an outer surface layer 26 to the reinforcing layer 24. The outer surface layer 26 comprises the exterior surface of the composite article 20 of the present invention and is utilized for decorative purposes.
ThQ foam core 22 can be of uniform thickness and can be made from soft, flexible sheets of any suitable expanded, reticulated or open cell ~ plastic material such as a polyether, polyolefin, polyester, polyurethane, or any 2 0 combination thereof .
The foam core 22 is ~mpregnated or saturated with a heat accelerated liquid hardening binder containing the silaceous material which enters and fills the cells of the foam, coating the cell walls.
The f oam panel that is utilized in the present invention has a porosity of 10-50~6. It is characterized as an open cell foam material weighing 1 pound/ft.3 in untreated state. After treatment, it has a specific gravity of about o . 5 to o . 9 g/cc. The urethane m.lterial that is applied 2 1 ~0683 to the foam panel is at a weight ranging from 300 to 1000 grams per sq. meter.
In preparing the preferred embodiment of 5 the invention, as shown in Figure 1, the binder resin, such as a urethane, completely permeates and encapsulates the reinforcing layers 24 and 25 which serves as the outer layers of the composite article .
In preparing a pref erred embodiment of the composite article of the present invention, the foam core 22 is fed from a stock reel (in Figure 2) which ~-nnt;.~nc foam stock which has been previously 15 sized to the desired thickness. In the present invention the th;e.kn~c~ of the foam material is approximately 7mm; however, the foam core 22 can be of any thickness and can be varied to meet manufacturing specifications. The foam which makes 20 up the foam core 22 is unrolled from the stock reel 40 and passes through a binder bath 42 which rnnt~1nc the ~inder. The preferred composition is the urethane system with the organofunctional silaceous material contained therein. There the 25 -NCO component of the urethane polymer is reacted with the organof1lnnt ~ nn;~ silaceous mateiral resulting in no free -NC0 groups. Alternatively, the -NCO groups are available f or reacting during the application of the urethane to the foam panel.
30 In an alternate embodiment, the catalyst activatible liquid binder is preferably polymeric MDI (4-4 '-diphenylmethane di-isocyanate) . EIowever, other isocyallates such as TDI (toluene di-isocyanate) ,IPDI ~isophoronediisocyanate), phenylisocyanate, and Hl2MDI may be used as substitutes f or the MDI .
The MDI binder saturates the f oam and through a process of polymerization of the MDI
rigidizes the cell walls of the foam core 22 by forming isocyanurate linkages, urethane linkages, urea linkages, trimer linkages, biuret linkages, and/or allophante linkages. The binder functions as an adhesive to bind together the layers of the composite article.
The NDI saturated foam 22 exits the binder bath 42 and is compressed between a set o~
calender rolls 44 which are used to control the amount of MDI retained in the foam core 22. The amount of MDI saturation is commonly referred to as the ~ Ur Gll~ level. By controlling the saturant level (amount), it is possible to vary the rigidity of the article 20 produced. Since the degree of rigidity (soft ~ hard) of the composite article 2 0 is a function of both the type and the amount of saturant present, i.e., 96MDI, varying the type or the amount of saturant directly effects the rigidity of the composite article 20. rhat is, by controlling the amount of saturant in the foam 22 by either squeezing the saturant out of the foam 22 using the calender rolls 44 or by diluting or 3 0 ~h i nn; n~ the concentration of saturant in a suitable sol~rent such as 1,1,1-trichloroethane, propylene carbonate, or methylene chloride, a composite article 20 can be produced having any desired degree of resilience or yieldability.
Therefore, a composite article 20 can be produced wherein the foam core 22 provides structural rigidity ranging from very soft (little or no 5 structural support, very resilient) to very rigid (good struct~lral support, not resilient~. The saturant range can be from 300-1500 g(MDI) for 20mm of foam.
The foam core 22 with the desired amount o~ MDI may be treated in a catalyst spray 4 6 with a polymerization catalyst which catalyzes the polymerization of the isocyanate and water. The catalyst is sprayed directly onto the MDI
impregnated foam core 22 utilizing methods and apparatus kno~n to those skilled in the art.
Catalysts utilized in the isocyanate chemistry are well known in the art. See, for e~ample, U.S. Patent No. 5,354,808 hereby incorporated by reference. catalysts that may be utilized are amine catalysts, the catalysts may also be acids or organic bases. Typical organic bases include triethyl amine, pyridine and the like. While strong acids and Lewig acids may also be utilized. Other catalysts that may be used are organo metallic compounds such as tin derivatives.
Tailoring performance to improve processlng properties of polyurethanes requires the selection of efficient catalysts. Generally, an increase in base strength in tertiary amines increases the catalytic strength, wherein the =
~ 2 1 90683 catalytic activity of tertiary amines i~ the result of the free ,~lectron pair on the nitrogen. The availability of the free electron pair for complexation is more important than its relative 5 base strength. Typical amine catalysts use~ul in the present invention include triethyl-amine, and those known under the trade names "Dabco" (Air Products and Chemicals), "Niax" (Union Carbide Corporation~, "Polycat" (Abbott), and "Thancat"
10 (Jefferson fhPrn;e~l Company).
Organometallic compounds useful in catalyzing the reaction of isocyanates with macroglycols include, di-n-butyltin dilaurate, as 15 well as carboxylic acid salts of calcium, cobalt, lead, manganese, zinc, and zirconium employed as cocatalysts with tertiary amines, tin compounds and tin-amine combinations.
Following exit from the calender roll 44, the multi-layered composite 20 is assembled. The foam core i 22 receives a fibrous reinforcing material in the form of a layer or mat of reinforcing fibers. The foam core 22 can receive one or more layers or mats of fibrous reinforcing material 24. Each surface of the foam core 22 typically receives a layer or mat of ~ibrous reinforcing material 24. The fibrous material which comprises the reinforcing material 24 can be of natural or synthetic material. Natural fibrous materials suitable for use in the reinforcing material 24 include animal or vegetable fibers.
Suitable fibers may include glass fibers, synthetic 2 1 ~0683 fibers such as Kevlar~lg, or other synthetic fibers known to those skilled in the art. The preferred material for use in the reinforcing layer 24 is glass fiber.
The fibrous reinforcing material 24 is necessary in order to provide added strength and St; ffn~ to the composite article 20 .
Additionally, because the reinforcing material 24 10 is typically constructed of chopped or random continuous f iber strand material, voids or interstitial spaces are created within the weave of the reinforcing material 24. These voids or interstitial spaces allow the heat accelerated 15 binder compound, i.e., urethane, to flow through the voids or interstitial spaces and permeate and saturate the fibers of the reinforcing material 24.
Saturation of the fibers of the reinforcing material 24 with the binder compound allows, upon 20 catalyzation, for formation of a mechanical bond between the foam core 22 and the reinforcing material 24. That is, when the binder compound is catalyzed to form a thermosetting material, the same curing reaction that stiffens the foam core 22 25 mechanically bonds the reinforcing material 24 to the foam core forming an essentially integral layer .
After the reinforcing material 24 is 30 applied to the foam core 22, an exterior or outer surface layer 26 may optionally be applied to the reinforcing material 24. ~he outer surface layer 26 can be any suitable material such as scrim, 21 qO683 .
foam, or plastic sheet. The outer surface material 26 is chosen with a particular application in mind.
That is, should a multi-layered composite panel 20 be re~uired to have impact or energy absorbing 5 characteristics, a foam exterior layer can ~e app l ied .
The scrim material can be any suitable material such as a polyester fabric, cellulose, 10 rayon, nylon, propylene, vinyl, olefin, or other suitable thermoplastics known to those skilled in the æt.
The ou~er surf ace layer 2 6 can be 15 adhesively bonded directly to the reinforcing material 24 with the same urethane which bonds the reinforcing material 24 to the foam core.
An additional adhesive layer 28 20 (intermediate layer) may be optionally used to bond the exterior or surface layer 26 to the reinforcing material 24. The adhesive can be a film or sheet of a thermoplastic material such as a polyester, polyamide, or ethylacrylic acids (EAA, Dow 25 Chemical) which melts or forms bonds at die molding and polymerization reaction temperatures. The adhesive layer 28 is applied to the reinforcing material 24 in between the layers of reinforcing material 2~ and the exterior or surface layer 26.
30 IJnder the heat of molding, the adhesive layer 28 melts and fo~-ms a bond between the reinforcing material 24 and the exterior or surface layer 26.
In addition to bonding the exterior or surface layer 26 to the reinforcing material 24, prior to melting, the adhesive layer 28 also serves as an occlusive barrier, preventing migration of 5 the urethane binder to the exterior or surface layers 26. By preventing the migration of the urethane to the exterior or surface layers 26, i.e., a foam exterior layer, the surface characteristics of the foam exterior layer 26 can 10 be maintained without the influence of the urethane hardening solution.
The adhesive layer or film 28 is positioned over the layers of reinforcing material 15 24, and finally the surface layer 26 of foam/scrim is applied to complete the formation of the composite article 20. Each of the constituents which comprise the multi-layered composite article 20, i.e., the reinforcing material 24, the adhesive 20 layer 28, and the surface layers 26 are fed from continuous stock reels (shown in Figure 2). The multi-layered composite 20 is then passed through a second set of calender rolls 48 which impregnate the reinforcing material 24 with the urethane, 25 polymerization catalysts, and any other ingredients .
The continuous length of the multi-layered composite 20 is then conveyed through a 30 shearing apparatus 50 which cuts the multi-layered composite 20 to desired length. The sheared lengths of the multi-layered composite 20 are then placed into a tenter frame (holding frame) (not shown). The tentered composite is then transported to a die press/mold 52.
The die press/mold 52 is maintained at a temperature between 200F and 400F. It is at this temperature that the polymerization reaction occurs, and the foam core 22 becomes a rigid thermosetting plastic. The multi-layered composite 20 is pressed between male and female die halves to reproduce thç configuration of tlle final article to be made such as automotive interior trim components e.g., headliners, dashboards, armrests, etc. The die pressed or molded multi-layered composite article 20 is then allowed to cure for between 15 to 90 seconds and is then removed the press/mold 52 for trimming and other post assembly processing.
The polymerization of diisocyanates with glycols to produce polyurethanes from liquid monomers is well know. Pol~rurethanes contain carbamate groups (-NHC00-), also referred to as urethane groups, in their backbone structure. In the present case, many polyols may be used.
The preferred polyols used to make the polyurethane prepolymers and polymers are polyester polyols. Polyether polyols may also be used and are addition products derived from cyclic ethers such as ethylene oxide, propylene oxide, 3 0 tetrahydrofuran, and the like Polyester polyols are more preferred for use in the present invention than polyether ;
polyols. The polyester polyols of choice are macroglycols (glycols having greater than about 5 repeat units) with a low acid number and low water content, and typically have a molecular weight 5 (number average) of about 2000.
Polyester polyols f or use in the present invention are particularly pre~erably made by the reaction of caprolactone with a suitable glycol 10 such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, and 1, 6-br~Y~nr~r~iol. The reaction of caprolactone with a suitable diol yields a polycaprolactone .
Polycaprolactone diols are available from Union Carbide under the trademark "TONE".
other suitable polyols would include Z0 polytetramethylene ether glycol, polyethylene glycol, polybutylene adipate, hydrogenated bisphenyol A, cyclohexane dimethanol, hydroquinone bis hydroYyethyl ether (HQEE) and the like.
Other active hydrogen containing materials, besides polyols, that can react with the isocyanate are amines.
Pol~amines As previously mentioned, the active hydrogen-containing compounds may be polyamines, particularly nonaromatic rl;i~minr~c. Preferred =
~ 2190683 nonarDmatic diamines f or use in the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, isophoron~ m;n~, cy(~ h~y~n~A;~m;nl~ and bis-5 ( aminopropyl ) methylamine .
Aromatic polyamines may be partially or totally substituted for nonaromatic polyamines as desired .
PolYisocYana~es The term "polyisocyanate" includes diisocyanates and compositions including 15 monoisocyanates and diisocyanates, and compositions including mono-, di-, and polyisocyanates. Thus, although diisocycanates are preferred, it is within the scope of the invention to use polyisocyanates in combination with diisocyanates, and even with 2~ small amounts of monoisocyanate, as disclosed in U.S. Patent No. 4,567,228, incorporated herein by reference. The average functionality of the isocyanate reactants is important in controlling the tendency of the polymer to gel. When 25 polyisocyanates are used, some monofunctional isocyanate should be present to reduce the average isocyanate functionality. In some instances it is desirous to use so-called "blocked" isocyanates, in which all isocyanates groups are blocked with a 3C suitable blocking agent Cont~;n;n~ an active hydrogen. Commercial blocking agents include caprolactam, phenol, and acetone oxime. As the "free" or released blocking agent is typically 2~ 90683 generated in a thermal unblocking process, and since the free blocking agents can function as plasticizers, blocked isocyanates may be preferred in certain coating formulations.
iuitable non-aromatic cyclic diisocyanates for use in the present invention included hexamethylene diisocyanate (HDI), methylenebis- (4-cyclohexylisocyanate) (Hl2MDI) and 10 isophorone diisocyanate (IPDI~. Also useful are isophorone-based isomeric trimethyl hexamethylene diisocyanates (TMDI), trimerized IPDI, and 1,3-bis (isocyanatomethy) cycl f)ho~n~ (H6XDI) . A
particularly preferred diisocyanate is Hl2MDI, 15 known under the trade designation "Desmodur W", available from Bayer, Inc.
The coating composition and the various components to the coating composition can be characterized as follows:
Polymerizable Binder 80-98 wt %
e . g ., polyurethane organofunctional silaceous material 1-20 wt g6 catalyst 0. 01-5 wt %
Total 100 wt %.
Having described the invention above, listed below are preferred ornhorli~-nts wherein all parts are parts by weight and all degrees are de~rees centigrade unless otherwise indicated.
2 1 9~683 F~P,MPr,F 1 ~
Following the procedure outlined above and in the drawing for the preparation of the trim 5 panel, Figure 2 tne urethane material is prepared a6 :~ollows from the following composition:
Tone 0305 10.52 DC193 0.30 Rucoflex 105-110 5.14 10Desmodur ~1 16.12 Dibutyl tin dilaurate 0 . 01 BGTSPA 19 . 74 Toluene 48.17 15TOTAL 100. 00 Tone 0305 is a polycaprolactone polyester polyol with an approxi~ate ~unctionality of t_ree, 20 a nydroxyl number of 310, and is sold by Hnion Carbide Corporation, 39 Old Ridgebury Road, Danbury CT 06817-0001.
DC 193 is a reactive silicone sur~'actant 25 tnat is used as a flow control agent with an approximately functionality of tnree, a hydroxyl number of ~75, and is sold by Air Products and ~hf~;r;~ , 72~1 Hamilton Boulevard, Allentown PA
18195-1501 .
Rucoflex 105-110 is a h~ n~;ol adipate based polyester polyol with a functionality of two, a nydroxyl number of 110, and is sold by Ruco Polymer Corporation, New South~ Road, Hicksville, New York 11802.
21906~3 Desmodur W is bis (4-isocyanatocycloheYyl) methane, PICM, llydL~y~lated MDI (HMDI or ~12MDI or dicyclohexylmethane 4.4 '-diisocyanate with an approximately % free NCO of 31.82%, and is sold by 5 Bayer Corporation, 100 Bayer Road, Pittsburgh, Pennsylvania 15205.
B G T S P A i s b i s - ~ g a m m a -trimethoxysilylpropyl) amine with a isocyanate 10 reactive functionality of one. It ls used to react with the isocyanate terminated monomers and oligomers and thus provide an isocyanate free coating. The six methoxy groups on the silane are hydrol~zable using moisture and a catalyst such as 15 dibutyl tin dilaurate. This enables secondary crosslinking reactions to occur with the formation of siloxane linkages.
The silaceous containing composition is 20 prepared from a resin formulation listed ~elow.
This resin formulation is 4096 solids content with a 9.i free =NCO of 2.72~6.
Tone 03 05 13 .11 -DC 193 o . 33 Rucoflex 105-110 6.41 Desmodur W 20. 09 Dibutyl tin dilaurate 0. 01 Toluene 60 . 00 TOTAL 100 . 00 The silaceous containing composition described above is prepared as follows. 100 grams 35 o~ the resin formulation, at room temperature, are weighed into a suitable container. About 1/3 of 2 1 9~683 the amount (8 grams) that represents a 59~ excess of BGTSPA (the total is about 24.1 grams) is added to the container with agitation. There is an exothermic reaction observed. The container is 5 allowed to cool to room temperature (about 15 minutes). Subsequent additions are performed the same way until the total amount is added. The silaceous containing binder composition is now available for use. This 5; 1 ~7Cer-7-C containing 10 binder composition is used to impregnate the foam panel as shown in Figure 2.
R~r~7~7T ~ 2 "
-Another binder may be prepared as follows. The polymer is prepared by reacting the polyol with a slight molar excess (5%) of -NCO, that is, 2 . 05 eguvalent of -NCO to 1 equivalent of polyol. The silaceous material is then added at a 20 slight molar excess (5%) to ensure that all of the -NCO groups are fully reacted.
Another typical formulation that may be used is as follows:
Co~ponents Percent By Weight ~QEE ( l eq . ) 4 3 . 5 9 MDI (2.05 eq.) 5~.41 TOTAL 100. 00 % f ree - NCO = O . 4 8 wt . %
HQEE = }~yaroquinone-bis-hydroxyl ethyl ether M~I = Methylene diphenyl diisocyanate 3~ ~
2 1 ~0683 T~le af orementioned material may be prepared by melting the HQEE in a reactor and adding molten MDI; alternatively, the two materials may be blended together by a twin screw extruder to 5 heat the materials.
The prepolymer is further reacted with gamma-amino isopropyl trimethoxy silane to ensure complete elimination of all free isocyanate groups 10 as follows:
Prepolymer from above formulation:
Components Percent By Wei~ht 15 ~IQ EE 9 6 . 05 Silane (EW 1. 5 3 . 95 EW 1. 05/1 silane/
~QEE) 20 TOTAL 100. 00 wt 96 The silaceous containing coating composition may be used to impregnate the f oam 25 panel as sho~n in Figure 2.
While the forms of the invention herein disclosed constitute presently preferred embodiments, many others are possible. It is not 30 intended here to mention all the p o s s i b l e equivalent fol^ms or ramifications of the invention.
It is understood that the terms used herein are merely descriptive, and ~hat various changes may be made without departing from the spirit or scope of 35 the invention -
5,306.765; 5,182,174; 5,230,962; 5,366,807;
5,368,943; 5,204,404; and 5,270,~)82, all of which are hereby incorporated by ref erence .
2 1 9~683 The overall process of preparing the trim panel can be described as follows. Turning to a review of the drawings, the preferred process involves the f ormation of a laminate o~ the f oam 5 panel together with a layer of reinforcing fibers and an outer layer of a scrim member.
In accordance with the present invention, a rigid multilayer composite article 20 comprises 10 a sheet of an open cell foam material 22, one or more layers of a fibrous reinforcing material 24 disposed on the surfaces of the foam material 22, a polymerized binder containing the silaceous material dispersed throughout the foam material 22, 15 throughout a part or all of the reinforcing material 24, and adhering the foam material 22 and the fibrous reinforcing material 24 together in fixed rigid relationship, and at least one surface layer 2 6 adhesively af f ixed to a surf ace of the 20 fibrous reinforcing material 24.
The present invention pertains to the utilization of foam core materials that are used in trim panels. Such techniques for preparing such 25 foam core materials are well known in the art.
See, for example, U.S. Patent Nos. 5,308,678;
5,068,001; and 5,393,474, hereby incorporated by ref erence .
Referring to Figure l, a composite article 20 according to a preferred embodiment of the present invention is shown. The article 20, a panel, is relatively lightweight and flexible. It ' comprises a foam core 22 having reinforcing layers 24 and 25 located on the surfaces or sides of the f Qam core- 22 .
The reinforcing layers 24 and 25 are preferably made of glass fibers. However, other natural and synthetic f ibers can be used. An adhesive layer or film 28 is applied over the reinforcing layer 24 and is used to bond an outer surface layer 26 to the reinforcing layer 24. The outer surface layer 26 comprises the exterior surface of the composite article 20 of the present invention and is utilized for decorative purposes.
ThQ foam core 22 can be of uniform thickness and can be made from soft, flexible sheets of any suitable expanded, reticulated or open cell ~ plastic material such as a polyether, polyolefin, polyester, polyurethane, or any 2 0 combination thereof .
The foam core 22 is ~mpregnated or saturated with a heat accelerated liquid hardening binder containing the silaceous material which enters and fills the cells of the foam, coating the cell walls.
The f oam panel that is utilized in the present invention has a porosity of 10-50~6. It is characterized as an open cell foam material weighing 1 pound/ft.3 in untreated state. After treatment, it has a specific gravity of about o . 5 to o . 9 g/cc. The urethane m.lterial that is applied 2 1 ~0683 to the foam panel is at a weight ranging from 300 to 1000 grams per sq. meter.
In preparing the preferred embodiment of 5 the invention, as shown in Figure 1, the binder resin, such as a urethane, completely permeates and encapsulates the reinforcing layers 24 and 25 which serves as the outer layers of the composite article .
In preparing a pref erred embodiment of the composite article of the present invention, the foam core 22 is fed from a stock reel (in Figure 2) which ~-nnt;.~nc foam stock which has been previously 15 sized to the desired thickness. In the present invention the th;e.kn~c~ of the foam material is approximately 7mm; however, the foam core 22 can be of any thickness and can be varied to meet manufacturing specifications. The foam which makes 20 up the foam core 22 is unrolled from the stock reel 40 and passes through a binder bath 42 which rnnt~1nc the ~inder. The preferred composition is the urethane system with the organofunctional silaceous material contained therein. There the 25 -NCO component of the urethane polymer is reacted with the organof1lnnt ~ nn;~ silaceous mateiral resulting in no free -NC0 groups. Alternatively, the -NCO groups are available f or reacting during the application of the urethane to the foam panel.
30 In an alternate embodiment, the catalyst activatible liquid binder is preferably polymeric MDI (4-4 '-diphenylmethane di-isocyanate) . EIowever, other isocyallates such as TDI (toluene di-isocyanate) ,IPDI ~isophoronediisocyanate), phenylisocyanate, and Hl2MDI may be used as substitutes f or the MDI .
The MDI binder saturates the f oam and through a process of polymerization of the MDI
rigidizes the cell walls of the foam core 22 by forming isocyanurate linkages, urethane linkages, urea linkages, trimer linkages, biuret linkages, and/or allophante linkages. The binder functions as an adhesive to bind together the layers of the composite article.
The NDI saturated foam 22 exits the binder bath 42 and is compressed between a set o~
calender rolls 44 which are used to control the amount of MDI retained in the foam core 22. The amount of MDI saturation is commonly referred to as the ~ Ur Gll~ level. By controlling the saturant level (amount), it is possible to vary the rigidity of the article 20 produced. Since the degree of rigidity (soft ~ hard) of the composite article 2 0 is a function of both the type and the amount of saturant present, i.e., 96MDI, varying the type or the amount of saturant directly effects the rigidity of the composite article 20. rhat is, by controlling the amount of saturant in the foam 22 by either squeezing the saturant out of the foam 22 using the calender rolls 44 or by diluting or 3 0 ~h i nn; n~ the concentration of saturant in a suitable sol~rent such as 1,1,1-trichloroethane, propylene carbonate, or methylene chloride, a composite article 20 can be produced having any desired degree of resilience or yieldability.
Therefore, a composite article 20 can be produced wherein the foam core 22 provides structural rigidity ranging from very soft (little or no 5 structural support, very resilient) to very rigid (good struct~lral support, not resilient~. The saturant range can be from 300-1500 g(MDI) for 20mm of foam.
The foam core 22 with the desired amount o~ MDI may be treated in a catalyst spray 4 6 with a polymerization catalyst which catalyzes the polymerization of the isocyanate and water. The catalyst is sprayed directly onto the MDI
impregnated foam core 22 utilizing methods and apparatus kno~n to those skilled in the art.
Catalysts utilized in the isocyanate chemistry are well known in the art. See, for e~ample, U.S. Patent No. 5,354,808 hereby incorporated by reference. catalysts that may be utilized are amine catalysts, the catalysts may also be acids or organic bases. Typical organic bases include triethyl amine, pyridine and the like. While strong acids and Lewig acids may also be utilized. Other catalysts that may be used are organo metallic compounds such as tin derivatives.
Tailoring performance to improve processlng properties of polyurethanes requires the selection of efficient catalysts. Generally, an increase in base strength in tertiary amines increases the catalytic strength, wherein the =
~ 2 1 90683 catalytic activity of tertiary amines i~ the result of the free ,~lectron pair on the nitrogen. The availability of the free electron pair for complexation is more important than its relative 5 base strength. Typical amine catalysts use~ul in the present invention include triethyl-amine, and those known under the trade names "Dabco" (Air Products and Chemicals), "Niax" (Union Carbide Corporation~, "Polycat" (Abbott), and "Thancat"
10 (Jefferson fhPrn;e~l Company).
Organometallic compounds useful in catalyzing the reaction of isocyanates with macroglycols include, di-n-butyltin dilaurate, as 15 well as carboxylic acid salts of calcium, cobalt, lead, manganese, zinc, and zirconium employed as cocatalysts with tertiary amines, tin compounds and tin-amine combinations.
Following exit from the calender roll 44, the multi-layered composite 20 is assembled. The foam core i 22 receives a fibrous reinforcing material in the form of a layer or mat of reinforcing fibers. The foam core 22 can receive one or more layers or mats of fibrous reinforcing material 24. Each surface of the foam core 22 typically receives a layer or mat of ~ibrous reinforcing material 24. The fibrous material which comprises the reinforcing material 24 can be of natural or synthetic material. Natural fibrous materials suitable for use in the reinforcing material 24 include animal or vegetable fibers.
Suitable fibers may include glass fibers, synthetic 2 1 ~0683 fibers such as Kevlar~lg, or other synthetic fibers known to those skilled in the art. The preferred material for use in the reinforcing layer 24 is glass fiber.
The fibrous reinforcing material 24 is necessary in order to provide added strength and St; ffn~ to the composite article 20 .
Additionally, because the reinforcing material 24 10 is typically constructed of chopped or random continuous f iber strand material, voids or interstitial spaces are created within the weave of the reinforcing material 24. These voids or interstitial spaces allow the heat accelerated 15 binder compound, i.e., urethane, to flow through the voids or interstitial spaces and permeate and saturate the fibers of the reinforcing material 24.
Saturation of the fibers of the reinforcing material 24 with the binder compound allows, upon 20 catalyzation, for formation of a mechanical bond between the foam core 22 and the reinforcing material 24. That is, when the binder compound is catalyzed to form a thermosetting material, the same curing reaction that stiffens the foam core 22 25 mechanically bonds the reinforcing material 24 to the foam core forming an essentially integral layer .
After the reinforcing material 24 is 30 applied to the foam core 22, an exterior or outer surface layer 26 may optionally be applied to the reinforcing material 24. ~he outer surface layer 26 can be any suitable material such as scrim, 21 qO683 .
foam, or plastic sheet. The outer surface material 26 is chosen with a particular application in mind.
That is, should a multi-layered composite panel 20 be re~uired to have impact or energy absorbing 5 characteristics, a foam exterior layer can ~e app l ied .
The scrim material can be any suitable material such as a polyester fabric, cellulose, 10 rayon, nylon, propylene, vinyl, olefin, or other suitable thermoplastics known to those skilled in the æt.
The ou~er surf ace layer 2 6 can be 15 adhesively bonded directly to the reinforcing material 24 with the same urethane which bonds the reinforcing material 24 to the foam core.
An additional adhesive layer 28 20 (intermediate layer) may be optionally used to bond the exterior or surface layer 26 to the reinforcing material 24. The adhesive can be a film or sheet of a thermoplastic material such as a polyester, polyamide, or ethylacrylic acids (EAA, Dow 25 Chemical) which melts or forms bonds at die molding and polymerization reaction temperatures. The adhesive layer 28 is applied to the reinforcing material 24 in between the layers of reinforcing material 2~ and the exterior or surface layer 26.
30 IJnder the heat of molding, the adhesive layer 28 melts and fo~-ms a bond between the reinforcing material 24 and the exterior or surface layer 26.
In addition to bonding the exterior or surface layer 26 to the reinforcing material 24, prior to melting, the adhesive layer 28 also serves as an occlusive barrier, preventing migration of 5 the urethane binder to the exterior or surface layers 26. By preventing the migration of the urethane to the exterior or surface layers 26, i.e., a foam exterior layer, the surface characteristics of the foam exterior layer 26 can 10 be maintained without the influence of the urethane hardening solution.
The adhesive layer or film 28 is positioned over the layers of reinforcing material 15 24, and finally the surface layer 26 of foam/scrim is applied to complete the formation of the composite article 20. Each of the constituents which comprise the multi-layered composite article 20, i.e., the reinforcing material 24, the adhesive 20 layer 28, and the surface layers 26 are fed from continuous stock reels (shown in Figure 2). The multi-layered composite 20 is then passed through a second set of calender rolls 48 which impregnate the reinforcing material 24 with the urethane, 25 polymerization catalysts, and any other ingredients .
The continuous length of the multi-layered composite 20 is then conveyed through a 30 shearing apparatus 50 which cuts the multi-layered composite 20 to desired length. The sheared lengths of the multi-layered composite 20 are then placed into a tenter frame (holding frame) (not shown). The tentered composite is then transported to a die press/mold 52.
The die press/mold 52 is maintained at a temperature between 200F and 400F. It is at this temperature that the polymerization reaction occurs, and the foam core 22 becomes a rigid thermosetting plastic. The multi-layered composite 20 is pressed between male and female die halves to reproduce thç configuration of tlle final article to be made such as automotive interior trim components e.g., headliners, dashboards, armrests, etc. The die pressed or molded multi-layered composite article 20 is then allowed to cure for between 15 to 90 seconds and is then removed the press/mold 52 for trimming and other post assembly processing.
The polymerization of diisocyanates with glycols to produce polyurethanes from liquid monomers is well know. Pol~rurethanes contain carbamate groups (-NHC00-), also referred to as urethane groups, in their backbone structure. In the present case, many polyols may be used.
The preferred polyols used to make the polyurethane prepolymers and polymers are polyester polyols. Polyether polyols may also be used and are addition products derived from cyclic ethers such as ethylene oxide, propylene oxide, 3 0 tetrahydrofuran, and the like Polyester polyols are more preferred for use in the present invention than polyether ;
polyols. The polyester polyols of choice are macroglycols (glycols having greater than about 5 repeat units) with a low acid number and low water content, and typically have a molecular weight 5 (number average) of about 2000.
Polyester polyols f or use in the present invention are particularly pre~erably made by the reaction of caprolactone with a suitable glycol 10 such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, and 1, 6-br~Y~nr~r~iol. The reaction of caprolactone with a suitable diol yields a polycaprolactone .
Polycaprolactone diols are available from Union Carbide under the trademark "TONE".
other suitable polyols would include Z0 polytetramethylene ether glycol, polyethylene glycol, polybutylene adipate, hydrogenated bisphenyol A, cyclohexane dimethanol, hydroquinone bis hydroYyethyl ether (HQEE) and the like.
Other active hydrogen containing materials, besides polyols, that can react with the isocyanate are amines.
Pol~amines As previously mentioned, the active hydrogen-containing compounds may be polyamines, particularly nonaromatic rl;i~minr~c. Preferred =
~ 2190683 nonarDmatic diamines f or use in the present invention include ethylenediamine, propylenediamine, hexamethylenediamine, isophoron~ m;n~, cy(~ h~y~n~A;~m;nl~ and bis-5 ( aminopropyl ) methylamine .
Aromatic polyamines may be partially or totally substituted for nonaromatic polyamines as desired .
PolYisocYana~es The term "polyisocyanate" includes diisocyanates and compositions including 15 monoisocyanates and diisocyanates, and compositions including mono-, di-, and polyisocyanates. Thus, although diisocycanates are preferred, it is within the scope of the invention to use polyisocyanates in combination with diisocyanates, and even with 2~ small amounts of monoisocyanate, as disclosed in U.S. Patent No. 4,567,228, incorporated herein by reference. The average functionality of the isocyanate reactants is important in controlling the tendency of the polymer to gel. When 25 polyisocyanates are used, some monofunctional isocyanate should be present to reduce the average isocyanate functionality. In some instances it is desirous to use so-called "blocked" isocyanates, in which all isocyanates groups are blocked with a 3C suitable blocking agent Cont~;n;n~ an active hydrogen. Commercial blocking agents include caprolactam, phenol, and acetone oxime. As the "free" or released blocking agent is typically 2~ 90683 generated in a thermal unblocking process, and since the free blocking agents can function as plasticizers, blocked isocyanates may be preferred in certain coating formulations.
iuitable non-aromatic cyclic diisocyanates for use in the present invention included hexamethylene diisocyanate (HDI), methylenebis- (4-cyclohexylisocyanate) (Hl2MDI) and 10 isophorone diisocyanate (IPDI~. Also useful are isophorone-based isomeric trimethyl hexamethylene diisocyanates (TMDI), trimerized IPDI, and 1,3-bis (isocyanatomethy) cycl f)ho~n~ (H6XDI) . A
particularly preferred diisocyanate is Hl2MDI, 15 known under the trade designation "Desmodur W", available from Bayer, Inc.
The coating composition and the various components to the coating composition can be characterized as follows:
Polymerizable Binder 80-98 wt %
e . g ., polyurethane organofunctional silaceous material 1-20 wt g6 catalyst 0. 01-5 wt %
Total 100 wt %.
Having described the invention above, listed below are preferred ornhorli~-nts wherein all parts are parts by weight and all degrees are de~rees centigrade unless otherwise indicated.
2 1 9~683 F~P,MPr,F 1 ~
Following the procedure outlined above and in the drawing for the preparation of the trim 5 panel, Figure 2 tne urethane material is prepared a6 :~ollows from the following composition:
Tone 0305 10.52 DC193 0.30 Rucoflex 105-110 5.14 10Desmodur ~1 16.12 Dibutyl tin dilaurate 0 . 01 BGTSPA 19 . 74 Toluene 48.17 15TOTAL 100. 00 Tone 0305 is a polycaprolactone polyester polyol with an approxi~ate ~unctionality of t_ree, 20 a nydroxyl number of 310, and is sold by Hnion Carbide Corporation, 39 Old Ridgebury Road, Danbury CT 06817-0001.
DC 193 is a reactive silicone sur~'actant 25 tnat is used as a flow control agent with an approximately functionality of tnree, a hydroxyl number of ~75, and is sold by Air Products and ~hf~;r;~ , 72~1 Hamilton Boulevard, Allentown PA
18195-1501 .
Rucoflex 105-110 is a h~ n~;ol adipate based polyester polyol with a functionality of two, a nydroxyl number of 110, and is sold by Ruco Polymer Corporation, New South~ Road, Hicksville, New York 11802.
21906~3 Desmodur W is bis (4-isocyanatocycloheYyl) methane, PICM, llydL~y~lated MDI (HMDI or ~12MDI or dicyclohexylmethane 4.4 '-diisocyanate with an approximately % free NCO of 31.82%, and is sold by 5 Bayer Corporation, 100 Bayer Road, Pittsburgh, Pennsylvania 15205.
B G T S P A i s b i s - ~ g a m m a -trimethoxysilylpropyl) amine with a isocyanate 10 reactive functionality of one. It ls used to react with the isocyanate terminated monomers and oligomers and thus provide an isocyanate free coating. The six methoxy groups on the silane are hydrol~zable using moisture and a catalyst such as 15 dibutyl tin dilaurate. This enables secondary crosslinking reactions to occur with the formation of siloxane linkages.
The silaceous containing composition is 20 prepared from a resin formulation listed ~elow.
This resin formulation is 4096 solids content with a 9.i free =NCO of 2.72~6.
Tone 03 05 13 .11 -DC 193 o . 33 Rucoflex 105-110 6.41 Desmodur W 20. 09 Dibutyl tin dilaurate 0. 01 Toluene 60 . 00 TOTAL 100 . 00 The silaceous containing composition described above is prepared as follows. 100 grams 35 o~ the resin formulation, at room temperature, are weighed into a suitable container. About 1/3 of 2 1 9~683 the amount (8 grams) that represents a 59~ excess of BGTSPA (the total is about 24.1 grams) is added to the container with agitation. There is an exothermic reaction observed. The container is 5 allowed to cool to room temperature (about 15 minutes). Subsequent additions are performed the same way until the total amount is added. The silaceous containing binder composition is now available for use. This 5; 1 ~7Cer-7-C containing 10 binder composition is used to impregnate the foam panel as shown in Figure 2.
R~r~7~7T ~ 2 "
-Another binder may be prepared as follows. The polymer is prepared by reacting the polyol with a slight molar excess (5%) of -NCO, that is, 2 . 05 eguvalent of -NCO to 1 equivalent of polyol. The silaceous material is then added at a 20 slight molar excess (5%) to ensure that all of the -NCO groups are fully reacted.
Another typical formulation that may be used is as follows:
Co~ponents Percent By Weight ~QEE ( l eq . ) 4 3 . 5 9 MDI (2.05 eq.) 5~.41 TOTAL 100. 00 % f ree - NCO = O . 4 8 wt . %
HQEE = }~yaroquinone-bis-hydroxyl ethyl ether M~I = Methylene diphenyl diisocyanate 3~ ~
2 1 ~0683 T~le af orementioned material may be prepared by melting the HQEE in a reactor and adding molten MDI; alternatively, the two materials may be blended together by a twin screw extruder to 5 heat the materials.
The prepolymer is further reacted with gamma-amino isopropyl trimethoxy silane to ensure complete elimination of all free isocyanate groups 10 as follows:
Prepolymer from above formulation:
Components Percent By Wei~ht 15 ~IQ EE 9 6 . 05 Silane (EW 1. 5 3 . 95 EW 1. 05/1 silane/
~QEE) 20 TOTAL 100. 00 wt 96 The silaceous containing coating composition may be used to impregnate the f oam 25 panel as sho~n in Figure 2.
While the forms of the invention herein disclosed constitute presently preferred embodiments, many others are possible. It is not 30 intended here to mention all the p o s s i b l e equivalent fol^ms or ramifications of the invention.
It is understood that the terms used herein are merely descriptive, and ~hat various changes may be made without departing from the spirit or scope of 35 the invention -
Claims (13)
1. A method of forming a trim panel comprising the steps of:
providing a foam trim panel, treating the foam panel with a binder composition containing a polymerizable polymer, and an organofunctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and cures to assist in the foam panel retaining its desired configuration.
providing a foam trim panel, treating the foam panel with a binder composition containing a polymerizable polymer, and an organofunctional silaceous material; and shaping and curing the treated panel to a desired configuration so that the organofunctional silaceous material reacts and cures to assist in the foam panel retaining its desired configuration.
2. The method of claim 1 wherein the trim panel has a back and a front face and one face has applied to it, prior to shaping, a fiber strengthening member.
3. The method of claim 2 wherein the fiber member has applied to it a scrim member.
4. The method of claim 1 wherein the binder composition is a urethane containing polymer wherein the organofunctional silaceous material reacts with the urethane polymeric material resulting in no free -NCO groups present in the coating composition as applied to the panel.
5. The method of claim 1 wherein the composition is a urethane containing polymer prepared from - NCO containing reactants and polyol reactants in a ratio of OH/NCO greater than 1Ø
6. The method of claim 4 wherein the polyol group is a polyester polyol group which is a combination of polycaprolactone polyester polyol and a polyester polyol from an alkanediol of from 3 to 12 carbon atoms and an alkanoic acid of from 3 to 12 carbon atoms.
7. The method of claim 1 wherein the amount of polymer applied to the foam panel to impregnate the panel ranges from about 50 to 1000g/
meter2 of panel member.
meter2 of panel member.
8. The method claim 1 wherein the panel has a density of 1 to 20 g/sq ft. prior to application of polymer.
9. The method claim 1 wherein the polymer applied to the panel has the following components:
Components (wt % of total composition) Polymerizable Binder 80-98 wt %
silaceous material 1-20 wt %
catalyst 0.01-5 wt %
Total 100 wt %.
Components (wt % of total composition) Polymerizable Binder 80-98 wt %
silaceous material 1-20 wt %
catalyst 0.01-5 wt %
Total 100 wt %.
10. The method of claim 1 wherein the polymerizable polymer is a urethane containing composition.
11. The method of claim 1 wherein the organofunctional silaceous mateiral is reacted with the polymerizable polymer prior to application to the trim panel.
12. The method of claim 1 wherein the organofunctional silaceous material is a silane.
13. A shaped foam panel of any one of claims 1-12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/577,915 US6562268B1 (en) | 1995-12-21 | 1995-12-21 | Interior trim panels and method for manufacturing such panels using silaceous materials |
| US577,915 | 1995-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2190683A1 true CA2190683A1 (en) | 1997-06-22 |
Family
ID=24310670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002190683A Abandoned CA2190683A1 (en) | 1995-12-21 | 1996-11-19 | Interior trim panels and method for manufacturing such panels using silaceous materials |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6562268B1 (en) |
| EP (1) | EP0783018A3 (en) |
| JP (1) | JPH09174696A (en) |
| KR (1) | KR970042715A (en) |
| CA (1) | CA2190683A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19923382A1 (en) * | 1999-05-21 | 2000-11-23 | Bsh Bosch Siemens Hausgeraete | Heat-insulating wall, like refrigerator housing, refrigerator door or similar has inner and/or outer cladding provided on side facing thermally insulating layer with devices |
| JP2001047544A (en) * | 1999-08-04 | 2001-02-20 | Sumitomo Bayer Urethane Co Ltd | Manufacture of car interior material of sandwich structure |
| US20050042470A1 (en) * | 2003-08-22 | 2005-02-24 | Vogler John William | Cellulose ester based products and methods for making them |
| GB2425282A (en) * | 2005-04-22 | 2006-10-25 | Celotex Ltd | A laminate structure for use in insulation boards |
| US8063113B2 (en) * | 2008-04-23 | 2011-11-22 | Momentive Performance Materials Inc. | Polyurethane foam-forming compositions containing polysilsesquioxane cell opening agents |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3894165A (en) * | 1973-05-23 | 1975-07-08 | G S Staunton & Co Inc | Coated flexible reticulate structures and method for the preparation thereof |
| US3979344A (en) * | 1974-11-19 | 1976-09-07 | Inmont Corporation | Vulcanizable silicon terminated polyurethane polymer composition having improved cure speed |
| JPS5744636A (en) * | 1980-09-01 | 1982-03-13 | Wako Chem Kk | Impregnating agent for preparing mainly semirigid or rigid resin foam |
| US4374237A (en) | 1981-12-21 | 1983-02-15 | Union Carbide Corporation | Silane-containing isocyanate-terminated polyurethane polymers |
| US4567228A (en) | 1984-05-21 | 1986-01-28 | Ppg Industries, Inc. | Aqueous dispersion, internally silylated and dispersed polyurethane resins, and surfaces containing same |
| US4645816A (en) | 1985-06-28 | 1987-02-24 | Union Carbide Corporation | Novel vulcanizable silane-terminated polyurethane polymers |
| US5108691A (en) | 1986-09-03 | 1992-04-28 | Astechnologies, Inc. | Compressing and shaping thermoformable mats using superheated steam |
| US5087311A (en) | 1986-09-09 | 1992-02-11 | Astechnologies, Inc. | Process of laminating fabric to a concave substrate |
| US5068001A (en) | 1987-12-16 | 1991-11-26 | Reinhold Haussling | Method of making a sound absorbing laminate |
| US5089328A (en) | 1988-02-26 | 1992-02-18 | Van Dresser Corporation | Panel and method of making the same |
| US5248334A (en) | 1988-12-12 | 1993-09-28 | Dow Corning Corporation | Primer composition, coating method and coated silicone substrates |
| US5204404A (en) | 1989-03-21 | 1993-04-20 | E. I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
| EP0601219B1 (en) | 1990-08-16 | 1997-09-10 | E.I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
| US4910067A (en) | 1989-07-21 | 1990-03-20 | Neill Michael A O | Thermoplastic/foam core/fiber-reinforced resin structural composite material, a process for making said material and a boat structure made from said material |
| US4983442A (en) | 1990-07-13 | 1991-01-08 | United Technologies Automotive Inc. | Composite article and method of making same |
| US5270082A (en) | 1991-04-15 | 1993-12-14 | Lin Tyau Jeen | Organic vapor deposition process for corrosion protection of metal substrates |
| US5182174A (en) | 1991-05-13 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Flexible etch-resistant finishes with siloxane cross-linking |
| US5225248A (en) | 1991-05-13 | 1993-07-06 | E. I. Du Pont De Nemours And Company | Method of curing a topcoat |
| JPH05104665A (en) | 1991-10-16 | 1993-04-27 | Ikeda Bussan Co Ltd | Base material for interior trim |
| US5368943A (en) | 1991-12-20 | 1994-11-29 | Adco Products, Inc. | Polyurethane block copolymer |
| EP0565044B1 (en) | 1992-04-06 | 1999-03-10 | Mitsubishi Chemical Corporation | Ultraviolet-curing covering composition with hardwearing properties |
| US5306765A (en) | 1992-10-22 | 1994-04-26 | Sanyo Chemical Industries, Ltd. | Reactive polymers, dispersions thereof and articles coated therewith |
| US5354808A (en) | 1992-12-08 | 1994-10-11 | Minnesota Mining And Manufacturing Company | Polyurethanes including pendant hindered amines and compositions incorporating same |
| US5230962A (en) | 1992-12-11 | 1993-07-27 | E. I. Du Pont De Nemours And Company | Etch-resistant finishes with siloxane cross-linking |
| DE4319188A1 (en) * | 1993-06-09 | 1994-12-15 | Bayer Ag | Heat-insulating body |
| US5393474A (en) | 1993-08-19 | 1995-02-28 | Davidson Textron Inc. | Method for molding a shaped plastic trim panel |
| US5426166A (en) * | 1994-01-26 | 1995-06-20 | Caschem, Inc. | Urethane adhesive compositions |
| US5632557A (en) | 1994-12-16 | 1997-05-27 | Weed Instrument Company, Inc. | Modular temperature sensing apparatus |
-
1995
- 1995-12-21 US US08/577,915 patent/US6562268B1/en not_active Expired - Fee Related
-
1996
- 1996-11-19 CA CA002190683A patent/CA2190683A1/en not_active Abandoned
- 1996-11-21 EP EP96118656A patent/EP0783018A3/en not_active Withdrawn
- 1996-12-19 JP JP8353930A patent/JPH09174696A/en active Pending
- 1996-12-20 KR KR1019960069190A patent/KR970042715A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09174696A (en) | 1997-07-08 |
| EP0783018A3 (en) | 1998-05-13 |
| US6562268B1 (en) | 2003-05-13 |
| EP0783018A2 (en) | 1997-07-09 |
| KR970042715A (en) | 1997-07-24 |
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| FZDE | Discontinued |