CA1120175A - Low-shrink in-mold coating - Google Patents
Low-shrink in-mold coatingInfo
- Publication number
- CA1120175A CA1120175A CA000327842A CA327842A CA1120175A CA 1120175 A CA1120175 A CA 1120175A CA 000327842 A CA000327842 A CA 000327842A CA 327842 A CA327842 A CA 327842A CA 1120175 A CA1120175 A CA 1120175A
- Authority
- CA
- Canada
- Prior art keywords
- diisocyanate
- weight
- coating composition
- composition
- amount
- 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.)
- Expired
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31794—Of cross-linked polyester
Abstract
ABSTRACT OF THE DISCLOSURE
A laminate comprises an adherent in-mold thermo-set coating composition on a thermoset polyester glass fiber substrate, the coating composition comprising essentially the reaction product of an unsaturated aliphatic fumarate polyester diol, a saturated polyester diol flexibilizer, a cross-linking aliphatic polyol having from 3 to 6 OH groups, a diisocyanate in an amount by weight sufficient to provide from about 50% to 120%, preferably from about 80 to 99%, of the stoichiometric amount of -NCO
groups required to react with all of the active hydrogen atoms in the coating composition and an ethylenically unsaturated monomer sufficient to polymerize with and crosslink the unsaturated polyester in admixture with a minor amount by weight of polyvinyl acetate which serves to reduce or eliminate shrinkage of the coating composition.
A laminate comprises an adherent in-mold thermo-set coating composition on a thermoset polyester glass fiber substrate, the coating composition comprising essentially the reaction product of an unsaturated aliphatic fumarate polyester diol, a saturated polyester diol flexibilizer, a cross-linking aliphatic polyol having from 3 to 6 OH groups, a diisocyanate in an amount by weight sufficient to provide from about 50% to 120%, preferably from about 80 to 99%, of the stoichiometric amount of -NCO
groups required to react with all of the active hydrogen atoms in the coating composition and an ethylenically unsaturated monomer sufficient to polymerize with and crosslink the unsaturated polyester in admixture with a minor amount by weight of polyvinyl acetate which serves to reduce or eliminate shrinkage of the coating composition.
Description
~ r~ o ~OW-SI~ NK IN-MOI~ CO~TIN~
This invention relates to a low-shrink thermoset in-mold coating composition containing a minor amount by weight of polyvinyl acetate.
EACKGROUND
A major deficiency of compression molded thermoset (cured) glass fiber reinforced polyester (FRP) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks requiring substantial post-curing handling such as sanding, filling and so forth requiring considerable expense in additional materials and labor.
The in-mold coating process of U.S. Patent No. 4,081,578 masks these imperfections by molding a low viscosity thermosetting composition onto the surface of the thermoset FRP part in a second molding operation. The resulting skin or thin adherent thermoset coating, however, experiences about an 8~ volume shrinkage on curing although pits, pores, cracks, waviness and sink marks are generally elimin-ated. In the case of pits slight dimples in the coating at those locations sometimes remain. The shrinkage is due to polymerization andjor crosslinking and also due to thermal effects caused by cooling.
It is an object of the present invention to avoid the difficulties alluded to hereinabove and to provide an in-mold coating thermosetting composition which exhibits a reduced amount of or no shrinkage on molding and curing.
AnGther object of the present invention is to 11;~017S
provide a thermoset polyester glass fiber reinforced part with an in-mold molded adherent thermoset coating which exhibits a reduced amount of or no shrinkage.
These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description and working examples.
DISCUSSION OF THE PRIOR ART
-In copending Canadian Patent Application Serial No. 301,797, filed April 24, 1978, assigned to The General Tire & Rubber Company there is disclosed an in-mold coating composition comprising a vinyl ester of the reaction product of acrylic acid and the diglycidyl ether of bisphenol A in styrene, CaCO3, peroxide catalyst, inhibitor, mold release agent and polyvinyl acetate (40~ PVA in STY monomer) as the low shrink additive. Additional styrene and other fillers can be used. While polyvinyl acetate is preferred, it is stated that copolymers of vinyl acetate such as the acidic copolymers and rubber or thermoplastic homopolymers and copoly-mers of butadiene such as copolymers of butadiene and styrene or acrylonitrile as well as polymethyl methacrylate, poly-ethylene and polystyrene, also, may be used as low shrink additives. Moreover, the ester resin may be replaced in part by other unsaturated polyester resins made from glycols and unsaturated dicarboxylic acids as well as those made from propylene oxide and maleic anhydride. Copending
This invention relates to a low-shrink thermoset in-mold coating composition containing a minor amount by weight of polyvinyl acetate.
EACKGROUND
A major deficiency of compression molded thermoset (cured) glass fiber reinforced polyester (FRP) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks requiring substantial post-curing handling such as sanding, filling and so forth requiring considerable expense in additional materials and labor.
The in-mold coating process of U.S. Patent No. 4,081,578 masks these imperfections by molding a low viscosity thermosetting composition onto the surface of the thermoset FRP part in a second molding operation. The resulting skin or thin adherent thermoset coating, however, experiences about an 8~ volume shrinkage on curing although pits, pores, cracks, waviness and sink marks are generally elimin-ated. In the case of pits slight dimples in the coating at those locations sometimes remain. The shrinkage is due to polymerization andjor crosslinking and also due to thermal effects caused by cooling.
It is an object of the present invention to avoid the difficulties alluded to hereinabove and to provide an in-mold coating thermosetting composition which exhibits a reduced amount of or no shrinkage on molding and curing.
AnGther object of the present invention is to 11;~017S
provide a thermoset polyester glass fiber reinforced part with an in-mold molded adherent thermoset coating which exhibits a reduced amount of or no shrinkage.
These and other objects and advantages of the present invention will become more apparent to those skilled in the art from the following detailed description and working examples.
DISCUSSION OF THE PRIOR ART
-In copending Canadian Patent Application Serial No. 301,797, filed April 24, 1978, assigned to The General Tire & Rubber Company there is disclosed an in-mold coating composition comprising a vinyl ester of the reaction product of acrylic acid and the diglycidyl ether of bisphenol A in styrene, CaCO3, peroxide catalyst, inhibitor, mold release agent and polyvinyl acetate (40~ PVA in STY monomer) as the low shrink additive. Additional styrene and other fillers can be used. While polyvinyl acetate is preferred, it is stated that copolymers of vinyl acetate such as the acidic copolymers and rubber or thermoplastic homopolymers and copoly-mers of butadiene such as copolymers of butadiene and styrene or acrylonitrile as well as polymethyl methacrylate, poly-ethylene and polystyrene, also, may be used as low shrink additives. Moreover, the ester resin may be replaced in part by other unsaturated polyester resins made from glycols and unsaturated dicarboxylic acids as well as those made from propylene oxide and maleic anhydride. Copending
(2) 11;~017S
Canadian Patent Application , Serial No. 325,902, filed April 19,1979, assigned to The General Tire & Rubber Company has a similar disclosure and additionally discloses the use of a silicate filler having a sheet-like structure such as talc and mica and states that viscosity can be increased by using clay.
Neither one of these applications discloses any data on shrinkage nor the use of any isocyanates or polyisocyanates.
U.S. Patent No. 3,741,799 in column 3, lines 56-62, discloses that the polyester resin used in FRP molding composi-tions can be rendered low-shrink or low-profile by adding finely divided particles of thermoplastic resins like polymethyl methacrylate, polypropylene, polyethylene, high-impact poly-styrene, etc., in solution with a cross-linkable monomer like styrene. It does not disclose polyvinyl acetate. It has nothing to do with in-mold coating but is concerned with paint adhesion to an FRP part.
U.S. Patent No. 3,772,241 discloses in column 4, lines 31-45, that in the FRP composition the thermosetting polymer can be, for example, homopolymers of methyl methacryl-ate, ethyl methacrylate, butyl methacrylate, methyl acrylate,ethyl acrylate, styrene, copolymers of methyl methacrylate and lower alkyl esters of acrylic and methacrylate acids, and copolymers of methyl methacrylate with minor amounts of one or more of the following: lauroyl methacrylate, isobornyl methacrylate, acrylamide, hydroxyethyl methacrylate,styrene, 2-ethylhexyl acrylate, acrylonitrile, methacrylic acid, methacrylamide, methylol acrylamide, and cetyl stearyl
Canadian Patent Application , Serial No. 325,902, filed April 19,1979, assigned to The General Tire & Rubber Company has a similar disclosure and additionally discloses the use of a silicate filler having a sheet-like structure such as talc and mica and states that viscosity can be increased by using clay.
Neither one of these applications discloses any data on shrinkage nor the use of any isocyanates or polyisocyanates.
U.S. Patent No. 3,741,799 in column 3, lines 56-62, discloses that the polyester resin used in FRP molding composi-tions can be rendered low-shrink or low-profile by adding finely divided particles of thermoplastic resins like polymethyl methacrylate, polypropylene, polyethylene, high-impact poly-styrene, etc., in solution with a cross-linkable monomer like styrene. It does not disclose polyvinyl acetate. It has nothing to do with in-mold coating but is concerned with paint adhesion to an FRP part.
U.S. Patent No. 3,772,241 discloses in column 4, lines 31-45, that in the FRP composition the thermosetting polymer can be, for example, homopolymers of methyl methacryl-ate, ethyl methacrylate, butyl methacrylate, methyl acrylate,ethyl acrylate, styrene, copolymers of methyl methacrylate and lower alkyl esters of acrylic and methacrylate acids, and copolymers of methyl methacrylate with minor amounts of one or more of the following: lauroyl methacrylate, isobornyl methacrylate, acrylamide, hydroxyethyl methacrylate,styrene, 2-ethylhexyl acrylate, acrylonitrile, methacrylic acid, methacrylamide, methylol acrylamide, and cetyl stearyl
(3) lC
11;~0175 methacrylate. Other use~ul examples of the thermoplastlc polymer are styrene/acrylonitrile copolymers, vinyl chloride/
vinyl acetate copolymers, cellulose acetate butyrate, and cellulose acetate propionate. The reference has nothing to do with in-mold coating and does not disclose polyvinyl acetate per se.
U.S. Patent No. 3,883,612 discloses the preparation of a maleic anhydride-propylene glycol polyester partial prepolymer which is then reacted with dicyclopentadiene to make a dicyclopentadiene terminated polyester. Next there is reacted more propylene glycol with the DCPD partial polyester prepolymer. To this composition is added an unsaturated monomer like styrene and a functional thermo-plastic polymer. The functional thermoplastic polymer is the terpolymer resulting from the copolymerization of an unsaturated ester like methyl methacrylate, an unsaturated acid like acrylic acid and vinyl acetate. The terpolymer apparently prevents phase separation between the styrene and polyester resin and also promotes thickening with chemical thickeners(col. 4, lines 63-68, and col. 6, lines 15-21).
The composition is useful for molding with glass fibers and fillers. The reference does not disclose in-mold coating of an FRP part nor polyvinyl acetate.
German Offen. 2,448,929, laid-open April 29, 1976, and English translation thereof (corresponds to U.S.
11;~0175 methacrylate. Other use~ul examples of the thermoplastlc polymer are styrene/acrylonitrile copolymers, vinyl chloride/
vinyl acetate copolymers, cellulose acetate butyrate, and cellulose acetate propionate. The reference has nothing to do with in-mold coating and does not disclose polyvinyl acetate per se.
U.S. Patent No. 3,883,612 discloses the preparation of a maleic anhydride-propylene glycol polyester partial prepolymer which is then reacted with dicyclopentadiene to make a dicyclopentadiene terminated polyester. Next there is reacted more propylene glycol with the DCPD partial polyester prepolymer. To this composition is added an unsaturated monomer like styrene and a functional thermo-plastic polymer. The functional thermoplastic polymer is the terpolymer resulting from the copolymerization of an unsaturated ester like methyl methacrylate, an unsaturated acid like acrylic acid and vinyl acetate. The terpolymer apparently prevents phase separation between the styrene and polyester resin and also promotes thickening with chemical thickeners(col. 4, lines 63-68, and col. 6, lines 15-21).
The composition is useful for molding with glass fibers and fillers. The reference does not disclose in-mold coating of an FRP part nor polyvinyl acetate.
German Offen. 2,448,929, laid-open April 29, 1976, and English translation thereof (corresponds to U.S.
4,051,085), discloses a thermosetting composition useful for impregnating glass fibers and comprising a copolymerizable vinyl compound like styrene, a thermoplastic polymer~ and an unsaturated polyester polyurethane. Fillers etc. can be added. Among the large number of thermoplastic polymers (m.w. 500-10,000,000, preferred m.w. 10,000-50,000;
preferred m.w. 500-5,000 for polycondensates and addition compounds) disclosed, there is suggested homopolymers, copolymers and graft polymer of vinyl acetate. However, the preferred thermoplastic polymers are those containing acid groups and the cellulose esters such as cellulose acetoproprionate or butyrate. The only polyester shown in the examples is one made from maleic anhydride and propylene glycol having a molecular weight of 498, but it is stated that m.w. can be less than 1,240, preferably 370-930. The only polyester polyurethanes actually shown are in Tables II
and III where tolylene diisocyanate and the polyester or polyester plus isopropyl alcohol arereacted in an equivalent ratio (NCO/OH+COOH) of 1:2 or 1:2.17 which represents 50% or less than 50~ of the stoichiometric amount of NGO
required to react with all of the active hydrogen atoms of the unsaturated polyester although it is stated that the equivalent ratio of NCO to OH is 1:1 to 1:3, preferably 1:1.5`to 1:2.5 (a NCO stoichiometry of 100 to 33~, preferably 67~ to 40~). The presence of COOH will produce C02 and foaming. A flexibilizing low m.w. diol and an aliphatic low m.w. cross-linking polyol having from 3-6 OH groups are not shown. Depending on the pressures used Table VII, Runs 1-4, show~ relative shrinkages of 2C-38~ and 49-79~.
preferred m.w. 500-5,000 for polycondensates and addition compounds) disclosed, there is suggested homopolymers, copolymers and graft polymer of vinyl acetate. However, the preferred thermoplastic polymers are those containing acid groups and the cellulose esters such as cellulose acetoproprionate or butyrate. The only polyester shown in the examples is one made from maleic anhydride and propylene glycol having a molecular weight of 498, but it is stated that m.w. can be less than 1,240, preferably 370-930. The only polyester polyurethanes actually shown are in Tables II
and III where tolylene diisocyanate and the polyester or polyester plus isopropyl alcohol arereacted in an equivalent ratio (NCO/OH+COOH) of 1:2 or 1:2.17 which represents 50% or less than 50~ of the stoichiometric amount of NGO
required to react with all of the active hydrogen atoms of the unsaturated polyester although it is stated that the equivalent ratio of NCO to OH is 1:1 to 1:3, preferably 1:1.5`to 1:2.5 (a NCO stoichiometry of 100 to 33~, preferably 67~ to 40~). The presence of COOH will produce C02 and foaming. A flexibilizing low m.w. diol and an aliphatic low m.w. cross-linking polyol having from 3-6 OH groups are not shown. Depending on the pressures used Table VII, Runs 1-4, show~ relative shrinkages of 2C-38~ and 49-79~.
(5) 11;~017S
French Patent No. 2,364,119 (published April, 1978), and English translation thereof, discloses a sheet of polymethylmethacrylate containing an adherent layer of a composition of a polyester resin, styrene, polyvinyl acetate (up to 10%) to improve adhesion, peroxide catalyst, amine accelerator, up to 30% glass fibers, and as a filler preferably CaSO~ (19-25 wt. %). It does not disclose diisocyanates nor in-mold coating.
Union Carbide Corporation, "Bakelite" Low Profile Additives, Bulletin No. F46567, 16 pages, no date, shows on page 3 the use of LP-100 (40% polyvinyl acetate in styrene) in a polyester-styrene-glass fiber composition (BMC formula) to get low (0.3 mils/in.) shrinkage (about 4 parts by weight of PVA on 100 of total components). On page 14, it discloses the use of LP-90 (40% PVA in styrene) in a polyester-styrene-glass fiber premix formulation (BMC formula) composition but does not give any shrinkage data (about 3.9 parts PVA on 100 of total composition). This reference does not disclose in-mold coating nor diisocyanates.
S~M~RY OF THE INVENTION
According to the present invention there is provided a laminate comprising an adherent, thermoset, in-mold coating composition in-mold coated onto a thermoset glass fiber polyester resin substrate, said coating composition comprising essentially the reaction product of:
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexibilizer having an average molecular weight of from about 1,500 to 3,000, (b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene 11;~0175 diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenyl methane diisocyanate, 4,4-dicyclohexyl methane diisocyanate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,4-diphenyl methane diisocyanate and of hydrogenated 4,4-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, . said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said coating composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsaturated polyester, in admixture with ~f) from about 2 to 20 parts by weight of polyvinyl acetate per 100 parts by weight of said total coating composition.
Thus, the invention affords basically comprising an adherent in-mold thermoset coating composition in-mold coated on a thermoset polyester glass fiber substrate, the coating composition comprising essentially the reaction product of an unsaturated aliphatic fumarate polyester diol, a saturated polyester diol flexibili~er, a crosslinking aliphatic polyol having 3 to 6 OH
- 6a -()175 groups, a diisocyanate in an amount by weight suf~icient to provide ~rom about 50 to 120~, preferably from about 80 to 99~, o~ the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in the coating composition and an ethylenically unsaturated monomer sufficient to polymerize with and crosslink the unsaturated polyester in admixture with a minor amount by weight of polyvinyl acetate which serves to reduce or eliminate shrinkage of the coating composition.
The in-mold coating composition reduces the sur-face imperfections as discussed above and additionally provides for reduced or no shrinkage. The adhesion of the coating to the substrate can be very high and the surface is smoother. It is not precisely known what occurs, but it may be that during the thermosetting or curing of the in-mold coating composition the polyvinyl acetate exists as a separate phase and relieves the internal polymerization shrinkage forces by creating minute internal voids in the coating structure so that the bulk shrinkage of the coating remains at a minimum.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
Polyvinyl acetate is a well known polymer and can be prepared by bulk, solution, emulsion or dispersion polymerization processes using free-radical catalysts. See Schildknecht, "Vinyl and Related Polymers," John Wiley &
Sons, Inc., New York, 1952, page 323 to 341; Schildknecht, "Polymer Processes," High Polymers, Vol. X, Interscience Publishers, Inc., New York, 1956; Matthews, "Vinyl and Allied (7) . ~"
11;~0~75 Polymers," Vol. 2, Iliffe Books, London, 1972; and "Encyclopedia of Polymer Science and Technology," Vol. 15, 1971, Interscience Publishers a division of John Wiley &
Sons, Inc., New York, pages 577 to 677. The polyvinyl acetate is used in an amount of from about 2 to 20, pre-ferably in an amount of from about 3 to 13, parts by weight per 100 parts by weight total of the (in-mold) coating composition. If too little polyvinyl acetate is used, the resulting coating evidences little improvement in reduction in shrinkage. If too much polyvinyl acetate is employed, the coating tends to be soft, cheesy and easily attacked by paint solvents.
The unsaturated aliphatic polyester is made by copolymerizing maleic anhydride and an alkylene oxide of 3 to 4 carbon atoms such as propylene oxide, butylene oxide, isobutylene oxide and so forth and mixture thereof.
propylene oxide is preferred. The alkylene oxide should be used in a molar ratio greater than the maleic anhydride to provide a polyester which is essentially or all OH
terminated, e.g., a polyester diol. The polyester should have an average molecular weight of from about 1500 to 4500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds. Up to about 10 mol ~ of the maleic anhydride may be replaced with a saturated anhydride such as phthalic anhydride or other anhydride and mixture thereof as shown in U.S. Patent No. 3~538,o43. Also, up to 10 mol (8) :;"
)175 o~ the a~kylen~ ox-id~ molety may t)e el~lylene oxide;
` greater amounts are undesirable since it may lead to water sensitivity in the final product. These unsaturated ; polyesters are made in benzene, styrene or other solvent - using a double metal cyanide catalyst as shown in ~T .S. Patent No. 3,538,043. As shown in said patent an isomerization catalyst such as piperidine is used to isomerize the maleate double bonds of the polyester to fumarate double bonds. Morpholine, also, may be used as an isomerization catalyst as shown by U.S. Patent No. 3,576,909.
Polyesters made by reacting maleic anhydride or maleic acid with a glycol like propylene glycol, dipropyl-ene glycol, 1,4-butane diol and so forth may likewise be used, but such esterification processes are time consuming and require high temperatures which are expensive. Esters made by processes using catalysts like titanium compounds are undesirable since it is difficult to remove the titanium catalyst residues which can adversely accelerate the isocyanate -OH condensation polymerization causing undesir-able reactions. Preferred are the polyesters made usingthe double metal cyanide catalysts as described above.
A saturated aliphatic dihydroxy terminated polyester, also, is employed in the in-mold coating composition to give some degree of flexibility to the coating.
It is used in a minor molar amount as compared to the unsat-urated polyester diol. The averaee molecular wei~ht o~ the , (9) ,:
~ V~S
,.
, saturated polyester is :Erom about 1,500 to 3,000. It can be made by methods well known to the art and should be free of catalyst residues which would adversely affect the urethane forming reaction. Examples of such poly-esters are polyethylene butylene adipate (preferred), polyethylene butylene sebacate, polypropylene adipate, polybutylene suberate, polypropylene sebacate and the like and mixture thereof.
The aliphatic polyol crosslinker used in the urethane reaction can be glycerol, trimethylol propane, 1,2,6-hexane triol, pentaerythritol, pentols, sorbitol and other aliphatic polyols having from 3 to 6 hydroxyl groups and their propylene oxide, butylene oxide and/or isobutylene oxide adducts (which may contain up to 10 mol ethylene oxide or be endcapped with ethylene oxide) having an average molecular weight of from about 92 to 1,000. Methods of making the alkylene oxide adducts of the polyols (except glycerine) using a double metal cyanide catalyst are shown by U.S. Patent No. 3,829,505. Grafted polyols may, also, be used such as those shown by U.S.
Patents Nos. 3,304,273, 3,383,351 and 3,294,711. If the adducts or telomers are made using KOH or NaOH, the resulting polyetherpolyol should be washed and/or neutraliz-ed to reduce or remove the alkaline material which may adversely catalyze the urethane reaction. The aliphatic polyol crosslinker is used in an amount sufficient with (10) 11~01~5 the unsaturated polyester diol and any other 0~l compound to provide adequate crosslinking with the diisocyanate .~ ~e f~or~r to provide a urethane ~ewto ~ of sufficient crosslink density to provide the desired hardness and toughness. The propylene oxide adducts of pentaerythritol having an average molecular weight of from about 400 to 600 are preferred.
The diisocyanate employed may be used as such or reacted with part of the polyol to form a prepolymer, especially when hexamethylene diisocyanate is employed since this isocyanate is believed to be carcinogenic.
The diisocyanate should be used in an amount by weight sufficient to provide from about 50 to 120%, preferably from about 80 to 99%, of the stoichiometric amo~mt of -NCO groups required to react with all of the active hydrogen atoms (as detèrmined by the Zerewitinoff method, J.A.C.S., Vol. 49, p. 3181 (1927) e.g., hydroxyl groups, of the polyester(s) and polyol(s) and any other OH
containing organic compound in the in-mold coating compound taking into consideration the possibility of forming also some biuret or allophanate linkages. Examples of useful diisocyanates or mixtures thereof to employ are 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), 4,4~diphenyl methane diisocyanate (MDI), hydrogenated 4,4-diphenyl methane diisocyanate (or 4,4-dicyclohexyl methane diisocyanate), polymeric forms of TDI, MDI and hydrogenated MDI, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Of these diisocyanates it is preferred to use 4,4-diphenyl methane diisocyanate.
(11) llZV17S
The ethylenically unsaturated monomer used to crosslink l.he unsatur3te(l ~)olye-;~cr d.iol arl~l E)rovide, together wlth the urethane linkages, a ther~noset coating is selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acryl-amide,acrylonitrile, methyl acrylate and mixtures of these.
Of these monomers styrene is preferred. The ethylenically unsaturated monomer is used in an amount sufficient to copolymerize with and/or crosslink the unsaturated poly-ester diol on being catalyzed by means of a free-radical catalyst to form a crosslinked thermoset polyester resin coating.
A free-radical or free-radical generating catalyst such as a peroxide is used to catalyze the copolymerization or crosslinking between the ethylenically unsaturated low molecular weight monomer and the unsaturated polyester. Examples of free-radical catalysts include tertiary butyl perbenzoate, tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide in dimethyl phthalate, dibenzoyl peroxide, di(p-chlorobenzoyl) peroxide in dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,5-dimethyl-1,2-dioxacyclopentane, t-butyl peroxy (2-ethyl hexanoate), 2,5-dimethyl-2,5-di(benzoyl : peroxy) hexane, t-butyl peroxy (2-ethyl butyrate),2,5-dimethyl-2,5-bis(t-butyl peroxy) hexane, cumyl hydroperoxide, (12) 11'~01~5 dlacetyl peroxide, 3~5-dihydroxy-3,5-dimethyl-1,2-oxacyclo-pentane, and l,l-bis(t-butyl peroxy)-3,3,5-trimethyl cyclo-hexane and the like and mixtures thereof. It is desirable sometimes to use mixtures of peroxides to take advanta~e of their different decomposition rates and times at different temperatures and so forth. Preferred catalysts are tertiary butyl perbenzoate and tertiary butyl peroctoate in diallyl phthalate and mixtures thereof.
For more information on peroxide catalysts please see "Encyclopedia of Polymer Science and Technology," Vol. 9, Interscience Publishers a division of John Wiley & Sons, Inc., New York, 1968, pages 814 to 841.
The polyurethane catalyst, if employed since it is not always needed, should be one which does not accelerate the decomposition of the peroxide catalyst.
The urethane catalyst when used should facilitate readily the curing of the coating composition; that is, the formation of the urethane network between the isocyanate and active hydrogen containing compounds should proceed simultaneously and smoothly along with the crosslinking operation caused by the free-radical catalyst between the unsaturated monomer and the unsaturated polyester. Examples of such catalysts are dibutyl tin dilaurate (preferred), dibutyl tin diacetate, tributyl tin acetate, dilauryl tin diacetate, dibutyl tin di-2-ethyl hexoate, di-2-ethyl hexyl tin bis(2-ethyl hexoate), dibutyl tin distearate, tetramethyl tin and tetra-n-butyl tin and the like and mixtures thereof.
(13) 11;~()1~5 The free-raclical ca-talysts and the pol~urethane formlng ca~alyst;s are use(l in a rninor amoun~ sufficient to chain extend and cross-link the functional eomponents of the coating composition to ob~ain a thermoset mæterial.
The eomposition additionally can be filled or eompounded to give the desired viscosity and flow to the composition for molding and to afford the desired physical properties to the resulting thermoset eoating. Examples of sueh fillers or compounding ingredients are fillers like elay, tale, MgO, Mg(OH)2, CaC03 and siliea, mold release agents, red iron oxide, TiO2, carbon black, organie color pigments like phthalocyanine blue or green, antidegradants, U-V absorbers, calcium silicate, hollow glass or resin micro-spheres, thiekening agents, inhibitors and the like.
Preferred fillers are clay~ talc, MgO, Mg(OH)2, CaC03 and silica and mixtures thereof. These fillers and compounding ingredients should be used in amounts sufficient to provide satisfactory results. However, care should be exercised in the use of high filler contents as this may give high viscosities and result in flow and handling difficulties.
All of the ingredients of the in-mold coating composition should be kept dry or have a minimal amount of moisture or the water content should be controlled to obtain reproducible results, to avoid using unnecessary amounts of isocyanates and to prevent foaming or pore formation.
A11 of the ingredients of the in-mold coating composition can be mixed together and then poured or injected onto the substrate and molded and cured.
(1~) )175 ',ever;Ll rtr~alrls or Lin(~s cnr~ sed ~o (~cliver ~he components of the in-mold coating composition to a mixing head or machine. However, since the mixed in-mold coating composition has a limited shelf-life or storageability due to the reactivity of the diisocyanate with the polyols, it is preferred to react the diisocyanate with a portion of the polyol(s) to form an isocyanate terminated pre-polymer having excess free isocyanate. Moreover, since the diisocyanate may be rather fluid, it is preferred for handling purposes to increase its viscosity by forming the isocyanate prepolymer. Mixing of the ingredients should be thorough. A stream of the prepolymer and a stream containing the unsaturated polyester composition of the desired viscosity are then fed to the mixing head of a mixing machine which then delivers the reactable in-mold coating to the surface of the substrate where it is molded and cured to the substrate. Injection or compression, transfer molding, or other molding apparatus or machines can be used for the in-mold coating, and temperatures and times can be those generally disclosed in U.S. Patent No.
4,081,578, above. Molding apparatus and methods for molding substrates and in-mold coating, also, may be found in U.S. Patents Nos. 4,o76,780, 4,o76,788 and 4,o82,486.
The processes and products of the present invention can be used in the manufacture of automobile parts such as grille and headlamp assemblies, deck hoods, fenders, door panels and roofs as well as in the manufacture of food trays, applicance and electrical components, furniture, machine covers and guards, bathroom components, electronic (15~
` `` llZ()l~S
part encapsulatlon, structural panels and so forth. The flberglass relnrorcecl polyester (FRP) substrate can be a sheet molding compound (SMC) or a bulk molding compound (BMC), wet lay-up or other thermosetting FRP material as shown by "Modern Plastics Encyclopedia," October, 1975, Vol. 52, No. lOA, McGraw-Hill, Inc., New York, pages 105 to 107.
The following examples will serve to illustrate the present invention with more particularity to those skilled in the art.
EXAMPLE I
Fiberglass polyester resin compositions were compression molded and cured as plates according to the process of U.S. Patent No. 4,081,578 to make a thermoset substrate. The composition used for the substrate contained the following ingredients:
IngredientParts by Weight "Paraplex" P340 * 4,000 "Paraplex" P681 * 2,240 "Paraplex" P543 772 "Camel-Wite" 10~520 TBP
Zinc stearate 350 Mg(OH)2 316 Glass fibers 7,830 After cure, the thermoset substrate plates were furrowed or drilled (as described below) and in-mold coated with several compositions according to the process of U.S. 4,081,578 by mixing the resin composition and the low shrink additive to~ether and then mixing therewith * Trade Mark (lo) ` ll'Z0l~S
the isocyanate hardener composition. The resultlng mixture was then deposited on the outer surrace of the compression molded substrate and cured under heat and pressure. The ingredients of the in-mold compositions were as follows:
Isocyanate (hardener) Composition IngredientParts by Weight "Isonate" 143L 16.7 "Pluracol" PeP 450 2.4 TBP
PD0 solution .1 Resin Composition A
IngredientParts by Weight Polyester 1050.6 - Georgia Talc 450 748 "Formrez" L4-71 298 "Pluracol" PeP 450 163 "Zelec" UN 1. 7 Benzoquinone solution 13.1 "Stan-Tone" 143 Resin Composition B
Ingredient Parts by Weight Polyester 15 "Formrez" L4-71 4.35 "Pluracol" PeP 450 3.15 "Zelec" UN .025 Benzoquinone solution . 35 T-12 solution .10 * Trade Mark (17) Resin Composition C
InF~re~dient;Pa:rt,s l)y Wei~,ht "Paraplex" P340 50 "Paraplex" P70137.7 CaC03 12.1 Zinc stearate 4.4 PDO solution .5 TBP .5 "Marinco" H 3.9 Low Shrink Additive Composition Ingredient Parts by Weight LP-90, 40~ polyvinyl acetate ïn styrene variable Other Additive Ingredient Parts by Weight Talc and/or CaC03 variable The amounts of materials used and the results obtained are shown in Table I below:
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H p l ~1 ~ ~t ~ cr~ (~ ~ L~\ L~ Ll~ ~1 1-1~ CU CU C~l r~ 1 N C\~l ~3 0 m o ~
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llZ0175 The aclhesion tc~t was done by cross hatching the coating with a knife and attempting to peel-off the coating. Thc deg,ree to which the coaling resisted peelLne-off was a measure of its adhesion to the thermoset poly-ester fiber glass substrate.
Two methods of coating shrinkage evaluation were used. In the first method, see M above, after molding the l5" x l5" FRP plate, a .o8~ x~ 4" furrow was cut into the plate, and the in-mold coating composition was hand-poured. After curing and cooling the coated plate part, , the shrinkage of the coating was visually judged on the .r,'s ' a basc~ of how well it bridged the furrow; for example, how much of a visible depression remained at the furrow due to ~ shrinkage of the coating (excellent = ~1.5%, good = 1.5-3%, !~ fair = 3-4% and poor => 4% shrinkage). In the second , method, see N above, after curing the 15" x 15" FRP
plate, the plate was removed from the mold and a one-inch diameter hole was drilled through it. The plate was ~ then reseated in the mold and the in-mold coating composi-i 20 tion was hand-poured. After curing and cooling, the thickness of the molded-in plug versus the adjacent FRP
thickness was a measure of the coating's shrinkage.
It is noted that while Runs l to 3 (without isocyanate, without polyvinyl acetate) had poor-fair, 0.22~ or excellent shrinkage, the adhesion was unsatisfac-tory. Runs 4 to 6 (with isocyanate, without polyvinyl acetate) had poor to excellent adhesion but the shrinkage was unsatisfactory. Runs 7 to 23 showed good to excellent (21~
11;~017S
shrlnka~e rcsul~l wlth only o~lc rUll ~howitl~ a stlrinkag~
greater than 4~. Also, except in two instances the adhesion was good or excellent.
EXAMPLE II
The method of this example was the same as that of Example I, above. The same isocyanate (hardener) composition was used. The resin composition was as follows:
Resin Composition D
Ingredient Parts by Weight Polyester 1500 "Formrez" L4-71 435 "Pluracol" PeP 450 315 "Zelec" UN 2.5 Benzoquinone solution 35 T-12 solution 10 Georgia Talc 650 1093 The steps of mixing of the components of the in-mold composition, coating the substrate FRP plate, compression molding and curing were the same as thoseof Example I, above. The relative proportions of the components of the in-mold coating composition were as follows:
Component Parts by Weight Isocyanate (hardener) 40.8 composition Resin Composition D 10 Low-shrink additive 20 composition The results obtained on testing are shown in Table II, below:
(2~) )175 TABLE II
Low-Shrink PI.SII/~I
~un ~dd.l.t;:t.ve IMC(:
No . ( mI)0s.Ll.. i orl .:llr.i llkag,~ x x x x 31 "Para~lex" Poor (M) 9.9 32 "Paraplex" Poor (M) 9.9 33 "Formrez" L4-71 Poor (M) 9.9 35~ by weight in styrene 34 "Microthene" Poor (M) 28 (PE) 7609 (SBR) Poor (M) 10.5 36 LP-40 Poor (M) ll 37 LP-60 Poor (M) ll 38 LP-90 Good (M) ll 39 LP-lO0 Fair to . 11 Good (M) *** Parts by weight of low shrink additive per se per 100 parts by weight of entire in-mold coating compositlon.
The results of the runs of this example show that polyvinyl acetate gives fair to good results as to shrinkage as`compared to the poor results exhibited by polymethyl methacrylate, acid modified polymethyl methacrylate, poly-ethylene butylene . adipate, polyethylene, high styrene-butadiene copolymer, acid modified polyvinyl acetate and acid modified polycaprolactone.
* Trade Mark (23) 1.~
11'~01'~5 NOTES:
Polyester - Polypropylene fumarate polyester, 0~
terminated, acid No.of less than 1, average mole-cular weight of about 2,400, about 15 double bonds, in styrene monomer (70~ by weight PE, 30~ STY).
Prepared according to the teachings of U.S. Patent No. 3,538,o43 by reacting propylene oxide and maleic anhydride initiated by fumaric acid using a double metal cyanide catalyst and isomerized with piperidine.
Georgia Talc 450 and 650, magnesium silicate (Soapstone).
"Formrez" L4-71 - Ethylene butylene adipate poly-ester, about 2,000 m.w.,saturated, OH terminated.
Witco Chemical Company.
"Pluracol" PeP 450 - Propylene oxide adduct of pentaerythritol, average molecular weight about 450, equivalent hydroxyl weight of 101. BASF Wyandotte.
"Zelec" UN - Fatty alcohol phosphate, unneutralized.
du Pont.
Benzoquinone - 2~o by weight benzoquinone in styrene.
T-12 - 1~ by weight dibutyl tin dilaurate in styrene.
"Stan-Tone'l - HLC No. 6543 pigment. Mixture o~ TiO2 and carbon black in "Pluracol" PeP 4~0, 60~ solids.
Harwick Chemical Corp.
(24) l~Z0175 "Isonate" 143 L- Essentially diphenylmethane-4, 4-diisocyanate, a liquid. The Up~ohn Compan~.
TBP - ~ertiary butyl perbenzoate.
PDO - Tertiary butyl peroctoate, 50~ by weight in diallyl phthalate.
"Paraplex" P 340 - A 65~ by weight solution of polyester in styrene, the polyester being essentially a polypropylene ~umarate, OH No. of 35, COOH No.
of 35, average molecular weight of about 1,600.
Rohm & Haas Company.
"Marinco" H -Magnesium hydroxide, Merck & Co., Inc.
- "Paraplex" P 681 - 35~ by weight solution of poly-methylmethacrylate containing some carboxyl groups in styrene. Rohm & Haas Company.
"Paraplex" P 543 - 35~ by weight solution of polymethyl methacrylate in styrene. Rohm & Haas Company.
"Paraplex" P 701 - 35~ by weight solution of acid modified polymethyl methacrylate in styrene. Rohm & Haas Company.
"Microthene" - Polyethylene, powdered. U.S.
Industrial Chemical Co.
7609 - XD-7609. Copolymer of about 63~ styrene and 37~ butadiene-1,3, may contain some homopolystyrene.
54.1~ trans-1,4, 13.1~ vinyl,Mn about 115,000.
(25~
11;~0175 About 37~ solids in styrene. Dow Chemical Co.
"~akelite" LP-40 - 40~ by weight solution of acid modirled polyvir~yl acetate in styrene. Union Carbide Corp.
"Bakelite" LP-60 - 40~ by weight solution of acid modified polycaprolactone in styrene. Union Carbide Corp.
"Bakelite" LP-90 - 40% by weight solution of poly-vinyl acetate in styrene, viscosity of 1,800 centi-poises at 25C. (Model LVT Brookfield viscometer #
4 spindle at 60 rpm), specific gravity 20/20C.(H20=1) of l.OOo and solidification temperature of 5C.
Union Carbide Corp.
"Bakelite" LP-100 - 40% by weight solution of polyvinyl acetate in styrene. Viscosity of 5,000 centipoises~ water con~ent of 0.20 weight percent, and acid number of 3Ø Union Carbide Corp.
~'Camel-Wite" - Calcium carbonate (limestone), average particle size of 3.3 microns. Campbell Grove Division of H.M. Royal.
* Trade Mark (2~) C
French Patent No. 2,364,119 (published April, 1978), and English translation thereof, discloses a sheet of polymethylmethacrylate containing an adherent layer of a composition of a polyester resin, styrene, polyvinyl acetate (up to 10%) to improve adhesion, peroxide catalyst, amine accelerator, up to 30% glass fibers, and as a filler preferably CaSO~ (19-25 wt. %). It does not disclose diisocyanates nor in-mold coating.
Union Carbide Corporation, "Bakelite" Low Profile Additives, Bulletin No. F46567, 16 pages, no date, shows on page 3 the use of LP-100 (40% polyvinyl acetate in styrene) in a polyester-styrene-glass fiber composition (BMC formula) to get low (0.3 mils/in.) shrinkage (about 4 parts by weight of PVA on 100 of total components). On page 14, it discloses the use of LP-90 (40% PVA in styrene) in a polyester-styrene-glass fiber premix formulation (BMC formula) composition but does not give any shrinkage data (about 3.9 parts PVA on 100 of total composition). This reference does not disclose in-mold coating nor diisocyanates.
S~M~RY OF THE INVENTION
According to the present invention there is provided a laminate comprising an adherent, thermoset, in-mold coating composition in-mold coated onto a thermoset glass fiber polyester resin substrate, said coating composition comprising essentially the reaction product of:
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexibilizer having an average molecular weight of from about 1,500 to 3,000, (b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene 11;~0175 diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenyl methane diisocyanate, 4,4-dicyclohexyl methane diisocyanate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,4-diphenyl methane diisocyanate and of hydrogenated 4,4-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, . said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said coating composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsaturated polyester, in admixture with ~f) from about 2 to 20 parts by weight of polyvinyl acetate per 100 parts by weight of said total coating composition.
Thus, the invention affords basically comprising an adherent in-mold thermoset coating composition in-mold coated on a thermoset polyester glass fiber substrate, the coating composition comprising essentially the reaction product of an unsaturated aliphatic fumarate polyester diol, a saturated polyester diol flexibili~er, a crosslinking aliphatic polyol having 3 to 6 OH
- 6a -()175 groups, a diisocyanate in an amount by weight suf~icient to provide ~rom about 50 to 120~, preferably from about 80 to 99~, o~ the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in the coating composition and an ethylenically unsaturated monomer sufficient to polymerize with and crosslink the unsaturated polyester in admixture with a minor amount by weight of polyvinyl acetate which serves to reduce or eliminate shrinkage of the coating composition.
The in-mold coating composition reduces the sur-face imperfections as discussed above and additionally provides for reduced or no shrinkage. The adhesion of the coating to the substrate can be very high and the surface is smoother. It is not precisely known what occurs, but it may be that during the thermosetting or curing of the in-mold coating composition the polyvinyl acetate exists as a separate phase and relieves the internal polymerization shrinkage forces by creating minute internal voids in the coating structure so that the bulk shrinkage of the coating remains at a minimum.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
Polyvinyl acetate is a well known polymer and can be prepared by bulk, solution, emulsion or dispersion polymerization processes using free-radical catalysts. See Schildknecht, "Vinyl and Related Polymers," John Wiley &
Sons, Inc., New York, 1952, page 323 to 341; Schildknecht, "Polymer Processes," High Polymers, Vol. X, Interscience Publishers, Inc., New York, 1956; Matthews, "Vinyl and Allied (7) . ~"
11;~0~75 Polymers," Vol. 2, Iliffe Books, London, 1972; and "Encyclopedia of Polymer Science and Technology," Vol. 15, 1971, Interscience Publishers a division of John Wiley &
Sons, Inc., New York, pages 577 to 677. The polyvinyl acetate is used in an amount of from about 2 to 20, pre-ferably in an amount of from about 3 to 13, parts by weight per 100 parts by weight total of the (in-mold) coating composition. If too little polyvinyl acetate is used, the resulting coating evidences little improvement in reduction in shrinkage. If too much polyvinyl acetate is employed, the coating tends to be soft, cheesy and easily attacked by paint solvents.
The unsaturated aliphatic polyester is made by copolymerizing maleic anhydride and an alkylene oxide of 3 to 4 carbon atoms such as propylene oxide, butylene oxide, isobutylene oxide and so forth and mixture thereof.
propylene oxide is preferred. The alkylene oxide should be used in a molar ratio greater than the maleic anhydride to provide a polyester which is essentially or all OH
terminated, e.g., a polyester diol. The polyester should have an average molecular weight of from about 1500 to 4500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds. Up to about 10 mol ~ of the maleic anhydride may be replaced with a saturated anhydride such as phthalic anhydride or other anhydride and mixture thereof as shown in U.S. Patent No. 3~538,o43. Also, up to 10 mol (8) :;"
)175 o~ the a~kylen~ ox-id~ molety may t)e el~lylene oxide;
` greater amounts are undesirable since it may lead to water sensitivity in the final product. These unsaturated ; polyesters are made in benzene, styrene or other solvent - using a double metal cyanide catalyst as shown in ~T .S. Patent No. 3,538,043. As shown in said patent an isomerization catalyst such as piperidine is used to isomerize the maleate double bonds of the polyester to fumarate double bonds. Morpholine, also, may be used as an isomerization catalyst as shown by U.S. Patent No. 3,576,909.
Polyesters made by reacting maleic anhydride or maleic acid with a glycol like propylene glycol, dipropyl-ene glycol, 1,4-butane diol and so forth may likewise be used, but such esterification processes are time consuming and require high temperatures which are expensive. Esters made by processes using catalysts like titanium compounds are undesirable since it is difficult to remove the titanium catalyst residues which can adversely accelerate the isocyanate -OH condensation polymerization causing undesir-able reactions. Preferred are the polyesters made usingthe double metal cyanide catalysts as described above.
A saturated aliphatic dihydroxy terminated polyester, also, is employed in the in-mold coating composition to give some degree of flexibility to the coating.
It is used in a minor molar amount as compared to the unsat-urated polyester diol. The averaee molecular wei~ht o~ the , (9) ,:
~ V~S
,.
, saturated polyester is :Erom about 1,500 to 3,000. It can be made by methods well known to the art and should be free of catalyst residues which would adversely affect the urethane forming reaction. Examples of such poly-esters are polyethylene butylene adipate (preferred), polyethylene butylene sebacate, polypropylene adipate, polybutylene suberate, polypropylene sebacate and the like and mixture thereof.
The aliphatic polyol crosslinker used in the urethane reaction can be glycerol, trimethylol propane, 1,2,6-hexane triol, pentaerythritol, pentols, sorbitol and other aliphatic polyols having from 3 to 6 hydroxyl groups and their propylene oxide, butylene oxide and/or isobutylene oxide adducts (which may contain up to 10 mol ethylene oxide or be endcapped with ethylene oxide) having an average molecular weight of from about 92 to 1,000. Methods of making the alkylene oxide adducts of the polyols (except glycerine) using a double metal cyanide catalyst are shown by U.S. Patent No. 3,829,505. Grafted polyols may, also, be used such as those shown by U.S.
Patents Nos. 3,304,273, 3,383,351 and 3,294,711. If the adducts or telomers are made using KOH or NaOH, the resulting polyetherpolyol should be washed and/or neutraliz-ed to reduce or remove the alkaline material which may adversely catalyze the urethane reaction. The aliphatic polyol crosslinker is used in an amount sufficient with (10) 11~01~5 the unsaturated polyester diol and any other 0~l compound to provide adequate crosslinking with the diisocyanate .~ ~e f~or~r to provide a urethane ~ewto ~ of sufficient crosslink density to provide the desired hardness and toughness. The propylene oxide adducts of pentaerythritol having an average molecular weight of from about 400 to 600 are preferred.
The diisocyanate employed may be used as such or reacted with part of the polyol to form a prepolymer, especially when hexamethylene diisocyanate is employed since this isocyanate is believed to be carcinogenic.
The diisocyanate should be used in an amount by weight sufficient to provide from about 50 to 120%, preferably from about 80 to 99%, of the stoichiometric amo~mt of -NCO groups required to react with all of the active hydrogen atoms (as detèrmined by the Zerewitinoff method, J.A.C.S., Vol. 49, p. 3181 (1927) e.g., hydroxyl groups, of the polyester(s) and polyol(s) and any other OH
containing organic compound in the in-mold coating compound taking into consideration the possibility of forming also some biuret or allophanate linkages. Examples of useful diisocyanates or mixtures thereof to employ are 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), 4,4~diphenyl methane diisocyanate (MDI), hydrogenated 4,4-diphenyl methane diisocyanate (or 4,4-dicyclohexyl methane diisocyanate), polymeric forms of TDI, MDI and hydrogenated MDI, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. Of these diisocyanates it is preferred to use 4,4-diphenyl methane diisocyanate.
(11) llZV17S
The ethylenically unsaturated monomer used to crosslink l.he unsatur3te(l ~)olye-;~cr d.iol arl~l E)rovide, together wlth the urethane linkages, a ther~noset coating is selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acryl-amide,acrylonitrile, methyl acrylate and mixtures of these.
Of these monomers styrene is preferred. The ethylenically unsaturated monomer is used in an amount sufficient to copolymerize with and/or crosslink the unsaturated poly-ester diol on being catalyzed by means of a free-radical catalyst to form a crosslinked thermoset polyester resin coating.
A free-radical or free-radical generating catalyst such as a peroxide is used to catalyze the copolymerization or crosslinking between the ethylenically unsaturated low molecular weight monomer and the unsaturated polyester. Examples of free-radical catalysts include tertiary butyl perbenzoate, tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide in dimethyl phthalate, dibenzoyl peroxide, di(p-chlorobenzoyl) peroxide in dibutyl phthalate, di(2,4-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,5-dimethyl-1,2-dioxacyclopentane, t-butyl peroxy (2-ethyl hexanoate), 2,5-dimethyl-2,5-di(benzoyl : peroxy) hexane, t-butyl peroxy (2-ethyl butyrate),2,5-dimethyl-2,5-bis(t-butyl peroxy) hexane, cumyl hydroperoxide, (12) 11'~01~5 dlacetyl peroxide, 3~5-dihydroxy-3,5-dimethyl-1,2-oxacyclo-pentane, and l,l-bis(t-butyl peroxy)-3,3,5-trimethyl cyclo-hexane and the like and mixtures thereof. It is desirable sometimes to use mixtures of peroxides to take advanta~e of their different decomposition rates and times at different temperatures and so forth. Preferred catalysts are tertiary butyl perbenzoate and tertiary butyl peroctoate in diallyl phthalate and mixtures thereof.
For more information on peroxide catalysts please see "Encyclopedia of Polymer Science and Technology," Vol. 9, Interscience Publishers a division of John Wiley & Sons, Inc., New York, 1968, pages 814 to 841.
The polyurethane catalyst, if employed since it is not always needed, should be one which does not accelerate the decomposition of the peroxide catalyst.
The urethane catalyst when used should facilitate readily the curing of the coating composition; that is, the formation of the urethane network between the isocyanate and active hydrogen containing compounds should proceed simultaneously and smoothly along with the crosslinking operation caused by the free-radical catalyst between the unsaturated monomer and the unsaturated polyester. Examples of such catalysts are dibutyl tin dilaurate (preferred), dibutyl tin diacetate, tributyl tin acetate, dilauryl tin diacetate, dibutyl tin di-2-ethyl hexoate, di-2-ethyl hexyl tin bis(2-ethyl hexoate), dibutyl tin distearate, tetramethyl tin and tetra-n-butyl tin and the like and mixtures thereof.
(13) 11;~()1~5 The free-raclical ca-talysts and the pol~urethane formlng ca~alyst;s are use(l in a rninor amoun~ sufficient to chain extend and cross-link the functional eomponents of the coating composition to ob~ain a thermoset mæterial.
The eomposition additionally can be filled or eompounded to give the desired viscosity and flow to the composition for molding and to afford the desired physical properties to the resulting thermoset eoating. Examples of sueh fillers or compounding ingredients are fillers like elay, tale, MgO, Mg(OH)2, CaC03 and siliea, mold release agents, red iron oxide, TiO2, carbon black, organie color pigments like phthalocyanine blue or green, antidegradants, U-V absorbers, calcium silicate, hollow glass or resin micro-spheres, thiekening agents, inhibitors and the like.
Preferred fillers are clay~ talc, MgO, Mg(OH)2, CaC03 and silica and mixtures thereof. These fillers and compounding ingredients should be used in amounts sufficient to provide satisfactory results. However, care should be exercised in the use of high filler contents as this may give high viscosities and result in flow and handling difficulties.
All of the ingredients of the in-mold coating composition should be kept dry or have a minimal amount of moisture or the water content should be controlled to obtain reproducible results, to avoid using unnecessary amounts of isocyanates and to prevent foaming or pore formation.
A11 of the ingredients of the in-mold coating composition can be mixed together and then poured or injected onto the substrate and molded and cured.
(1~) )175 ',ever;Ll rtr~alrls or Lin(~s cnr~ sed ~o (~cliver ~he components of the in-mold coating composition to a mixing head or machine. However, since the mixed in-mold coating composition has a limited shelf-life or storageability due to the reactivity of the diisocyanate with the polyols, it is preferred to react the diisocyanate with a portion of the polyol(s) to form an isocyanate terminated pre-polymer having excess free isocyanate. Moreover, since the diisocyanate may be rather fluid, it is preferred for handling purposes to increase its viscosity by forming the isocyanate prepolymer. Mixing of the ingredients should be thorough. A stream of the prepolymer and a stream containing the unsaturated polyester composition of the desired viscosity are then fed to the mixing head of a mixing machine which then delivers the reactable in-mold coating to the surface of the substrate where it is molded and cured to the substrate. Injection or compression, transfer molding, or other molding apparatus or machines can be used for the in-mold coating, and temperatures and times can be those generally disclosed in U.S. Patent No.
4,081,578, above. Molding apparatus and methods for molding substrates and in-mold coating, also, may be found in U.S. Patents Nos. 4,o76,780, 4,o76,788 and 4,o82,486.
The processes and products of the present invention can be used in the manufacture of automobile parts such as grille and headlamp assemblies, deck hoods, fenders, door panels and roofs as well as in the manufacture of food trays, applicance and electrical components, furniture, machine covers and guards, bathroom components, electronic (15~
` `` llZ()l~S
part encapsulatlon, structural panels and so forth. The flberglass relnrorcecl polyester (FRP) substrate can be a sheet molding compound (SMC) or a bulk molding compound (BMC), wet lay-up or other thermosetting FRP material as shown by "Modern Plastics Encyclopedia," October, 1975, Vol. 52, No. lOA, McGraw-Hill, Inc., New York, pages 105 to 107.
The following examples will serve to illustrate the present invention with more particularity to those skilled in the art.
EXAMPLE I
Fiberglass polyester resin compositions were compression molded and cured as plates according to the process of U.S. Patent No. 4,081,578 to make a thermoset substrate. The composition used for the substrate contained the following ingredients:
IngredientParts by Weight "Paraplex" P340 * 4,000 "Paraplex" P681 * 2,240 "Paraplex" P543 772 "Camel-Wite" 10~520 TBP
Zinc stearate 350 Mg(OH)2 316 Glass fibers 7,830 After cure, the thermoset substrate plates were furrowed or drilled (as described below) and in-mold coated with several compositions according to the process of U.S. 4,081,578 by mixing the resin composition and the low shrink additive to~ether and then mixing therewith * Trade Mark (lo) ` ll'Z0l~S
the isocyanate hardener composition. The resultlng mixture was then deposited on the outer surrace of the compression molded substrate and cured under heat and pressure. The ingredients of the in-mold compositions were as follows:
Isocyanate (hardener) Composition IngredientParts by Weight "Isonate" 143L 16.7 "Pluracol" PeP 450 2.4 TBP
PD0 solution .1 Resin Composition A
IngredientParts by Weight Polyester 1050.6 - Georgia Talc 450 748 "Formrez" L4-71 298 "Pluracol" PeP 450 163 "Zelec" UN 1. 7 Benzoquinone solution 13.1 "Stan-Tone" 143 Resin Composition B
Ingredient Parts by Weight Polyester 15 "Formrez" L4-71 4.35 "Pluracol" PeP 450 3.15 "Zelec" UN .025 Benzoquinone solution . 35 T-12 solution .10 * Trade Mark (17) Resin Composition C
InF~re~dient;Pa:rt,s l)y Wei~,ht "Paraplex" P340 50 "Paraplex" P70137.7 CaC03 12.1 Zinc stearate 4.4 PDO solution .5 TBP .5 "Marinco" H 3.9 Low Shrink Additive Composition Ingredient Parts by Weight LP-90, 40~ polyvinyl acetate ïn styrene variable Other Additive Ingredient Parts by Weight Talc and/or CaC03 variable The amounts of materials used and the results obtained are shown in Table I below:
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llZ0175 The aclhesion tc~t was done by cross hatching the coating with a knife and attempting to peel-off the coating. Thc deg,ree to which the coaling resisted peelLne-off was a measure of its adhesion to the thermoset poly-ester fiber glass substrate.
Two methods of coating shrinkage evaluation were used. In the first method, see M above, after molding the l5" x l5" FRP plate, a .o8~ x~ 4" furrow was cut into the plate, and the in-mold coating composition was hand-poured. After curing and cooling the coated plate part, , the shrinkage of the coating was visually judged on the .r,'s ' a basc~ of how well it bridged the furrow; for example, how much of a visible depression remained at the furrow due to ~ shrinkage of the coating (excellent = ~1.5%, good = 1.5-3%, !~ fair = 3-4% and poor => 4% shrinkage). In the second , method, see N above, after curing the 15" x 15" FRP
plate, the plate was removed from the mold and a one-inch diameter hole was drilled through it. The plate was ~ then reseated in the mold and the in-mold coating composi-i 20 tion was hand-poured. After curing and cooling, the thickness of the molded-in plug versus the adjacent FRP
thickness was a measure of the coating's shrinkage.
It is noted that while Runs l to 3 (without isocyanate, without polyvinyl acetate) had poor-fair, 0.22~ or excellent shrinkage, the adhesion was unsatisfac-tory. Runs 4 to 6 (with isocyanate, without polyvinyl acetate) had poor to excellent adhesion but the shrinkage was unsatisfactory. Runs 7 to 23 showed good to excellent (21~
11;~017S
shrlnka~e rcsul~l wlth only o~lc rUll ~howitl~ a stlrinkag~
greater than 4~. Also, except in two instances the adhesion was good or excellent.
EXAMPLE II
The method of this example was the same as that of Example I, above. The same isocyanate (hardener) composition was used. The resin composition was as follows:
Resin Composition D
Ingredient Parts by Weight Polyester 1500 "Formrez" L4-71 435 "Pluracol" PeP 450 315 "Zelec" UN 2.5 Benzoquinone solution 35 T-12 solution 10 Georgia Talc 650 1093 The steps of mixing of the components of the in-mold composition, coating the substrate FRP plate, compression molding and curing were the same as thoseof Example I, above. The relative proportions of the components of the in-mold coating composition were as follows:
Component Parts by Weight Isocyanate (hardener) 40.8 composition Resin Composition D 10 Low-shrink additive 20 composition The results obtained on testing are shown in Table II, below:
(2~) )175 TABLE II
Low-Shrink PI.SII/~I
~un ~dd.l.t;:t.ve IMC(:
No . ( mI)0s.Ll.. i orl .:llr.i llkag,~ x x x x 31 "Para~lex" Poor (M) 9.9 32 "Paraplex" Poor (M) 9.9 33 "Formrez" L4-71 Poor (M) 9.9 35~ by weight in styrene 34 "Microthene" Poor (M) 28 (PE) 7609 (SBR) Poor (M) 10.5 36 LP-40 Poor (M) ll 37 LP-60 Poor (M) ll 38 LP-90 Good (M) ll 39 LP-lO0 Fair to . 11 Good (M) *** Parts by weight of low shrink additive per se per 100 parts by weight of entire in-mold coating compositlon.
The results of the runs of this example show that polyvinyl acetate gives fair to good results as to shrinkage as`compared to the poor results exhibited by polymethyl methacrylate, acid modified polymethyl methacrylate, poly-ethylene butylene . adipate, polyethylene, high styrene-butadiene copolymer, acid modified polyvinyl acetate and acid modified polycaprolactone.
* Trade Mark (23) 1.~
11'~01'~5 NOTES:
Polyester - Polypropylene fumarate polyester, 0~
terminated, acid No.of less than 1, average mole-cular weight of about 2,400, about 15 double bonds, in styrene monomer (70~ by weight PE, 30~ STY).
Prepared according to the teachings of U.S. Patent No. 3,538,o43 by reacting propylene oxide and maleic anhydride initiated by fumaric acid using a double metal cyanide catalyst and isomerized with piperidine.
Georgia Talc 450 and 650, magnesium silicate (Soapstone).
"Formrez" L4-71 - Ethylene butylene adipate poly-ester, about 2,000 m.w.,saturated, OH terminated.
Witco Chemical Company.
"Pluracol" PeP 450 - Propylene oxide adduct of pentaerythritol, average molecular weight about 450, equivalent hydroxyl weight of 101. BASF Wyandotte.
"Zelec" UN - Fatty alcohol phosphate, unneutralized.
du Pont.
Benzoquinone - 2~o by weight benzoquinone in styrene.
T-12 - 1~ by weight dibutyl tin dilaurate in styrene.
"Stan-Tone'l - HLC No. 6543 pigment. Mixture o~ TiO2 and carbon black in "Pluracol" PeP 4~0, 60~ solids.
Harwick Chemical Corp.
(24) l~Z0175 "Isonate" 143 L- Essentially diphenylmethane-4, 4-diisocyanate, a liquid. The Up~ohn Compan~.
TBP - ~ertiary butyl perbenzoate.
PDO - Tertiary butyl peroctoate, 50~ by weight in diallyl phthalate.
"Paraplex" P 340 - A 65~ by weight solution of polyester in styrene, the polyester being essentially a polypropylene ~umarate, OH No. of 35, COOH No.
of 35, average molecular weight of about 1,600.
Rohm & Haas Company.
"Marinco" H -Magnesium hydroxide, Merck & Co., Inc.
- "Paraplex" P 681 - 35~ by weight solution of poly-methylmethacrylate containing some carboxyl groups in styrene. Rohm & Haas Company.
"Paraplex" P 543 - 35~ by weight solution of polymethyl methacrylate in styrene. Rohm & Haas Company.
"Paraplex" P 701 - 35~ by weight solution of acid modified polymethyl methacrylate in styrene. Rohm & Haas Company.
"Microthene" - Polyethylene, powdered. U.S.
Industrial Chemical Co.
7609 - XD-7609. Copolymer of about 63~ styrene and 37~ butadiene-1,3, may contain some homopolystyrene.
54.1~ trans-1,4, 13.1~ vinyl,Mn about 115,000.
(25~
11;~0175 About 37~ solids in styrene. Dow Chemical Co.
"~akelite" LP-40 - 40~ by weight solution of acid modirled polyvir~yl acetate in styrene. Union Carbide Corp.
"Bakelite" LP-60 - 40~ by weight solution of acid modified polycaprolactone in styrene. Union Carbide Corp.
"Bakelite" LP-90 - 40% by weight solution of poly-vinyl acetate in styrene, viscosity of 1,800 centi-poises at 25C. (Model LVT Brookfield viscometer #
4 spindle at 60 rpm), specific gravity 20/20C.(H20=1) of l.OOo and solidification temperature of 5C.
Union Carbide Corp.
"Bakelite" LP-100 - 40% by weight solution of polyvinyl acetate in styrene. Viscosity of 5,000 centipoises~ water con~ent of 0.20 weight percent, and acid number of 3Ø Union Carbide Corp.
~'Camel-Wite" - Calcium carbonate (limestone), average particle size of 3.3 microns. Campbell Grove Division of H.M. Royal.
* Trade Mark (2~) C
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A laminate comprising an adherent, thermoset, in-mold coating composition in-mold coated onto a thermoset glass fiber polyester resin substrate, said coating composition comprising essentially the reaction product of:
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexi-bilizer having an average molecular weight of from about 1,500 to 3,000,(b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,?-diphenyl methane diisocyanate, 4,?-dicyclohexyl methane diisocya-nate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,?-diphenyl methane diisocyanate and of hydrogenated 4,?-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said coating composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl meth-acrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsat-urated polyester, in admixture with (f) from about 2 to 20 parts by weight of poly-vinyl acetate per 100 parts by weight of said total coating composition.
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexi-bilizer having an average molecular weight of from about 1,500 to 3,000,(b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,?-diphenyl methane diisocyanate, 4,?-dicyclohexyl methane diisocya-nate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,?-diphenyl methane diisocyanate and of hydrogenated 4,?-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said coating composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl meth-acrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsat-urated polyester, in admixture with (f) from about 2 to 20 parts by weight of poly-vinyl acetate per 100 parts by weight of said total coating composition.
2. A laminate according to claim 1 in which in said coating composition said diisocyanate is present in an amount by weight sufficient to provide from about 80 to 99% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said coating composition.
3. A laminate according to claim 1 in which said coating composition contains additionally a filler selected from the group consisting of clay, talc, MgO, Mg(OH)2, CaCO3 and silica and mixtures thereof.
4. A laminate according to claim 1 in which in said coating composition (a) is a copolymer obtained from maleic anhydride and propylene oxide, (b) is polyethylene butylene adipate, (c) is the adduct of propylene oxide and pentaerythritol having an average molecular weight of from about 400 to 600, (d) is 4,?-diphenylmethane diiso-cyanate, (e) is styrene and the polyvinyl acetate of (f) is present in an amount of from about 3 to 13 parts by weight per 100 parts by weight total of said coating composition.
(28)
(28)
5. A laminate according to claim 4 in which said coating composition contains additionally talc and/or CaCO3.
6. A laminate according to claim 4 in which (d) is a diisocyanate terminated polyurethane prepolymer containing excess diisocyanate made by reacting the diisocyanate of (d) with at least a portion of (c).
7. A thermosetting composition comprising essentially:
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexibil-izer having an average molecular weight of from about 1,500 to 3,000, (b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,?-diphenyl methane diisocyanate, 4,?-dicyclohexyl methane diisocyanate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,?-diphenyl methane diisocyanate and of hydrogenated 4,?-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO
groups required to react with all of the active hydrogen atoms in said composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsaturated polyester, in admixture with (f) from about 2 to 20 parts by weight of poly-vinyl acetate per 100 parts by weight of said total composition.
(a) an unsaturated aliphatic polyester fumarate diol having an average molecular weight of from about 1,500 to 4,500 and from about 8 to 30 internal aliphatic carbon-to-carbon double bonds, (b) a saturated aliphatic polyester diol flexibil-izer having an average molecular weight of from about 1,500 to 3,000, (b) being present in a minor molar amount as compared to (a), (c) an aliphatic crosslinking polyol having from 3 to 6 hydroxyl groups and an average molecular weight of from about 92 to 1,000, (d) a diisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,?-diphenyl methane diisocyanate, 4,?-dicyclohexyl methane diisocyanate, polymeric forms of 2,4-tolylene diisocyanate, of 2,6-tolylene diisocyanate, of 4,?-diphenyl methane diisocyanate and of hydrogenated 4,?-diphenyl methane diisocyanate, xylene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate and mixtures thereof, said diisocyanate being present in an amount by weight sufficient to provide from about 50 to 120% of the stoichiometric amount of -NCO
groups required to react with all of the active hydrogen atoms in said composition, and (e) an ethylenically unsaturated monomer selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, methyl methacrylate, acrylamide, acrylonitrile, methyl acrylate and mixtures thereof, said monomer being present in an amount sufficient to copolymerize with and crosslink said unsaturated polyester, in admixture with (f) from about 2 to 20 parts by weight of poly-vinyl acetate per 100 parts by weight of said total composition.
8. A composition according to claim 7 in which said diisocyanate is present in an amount by weight sufficient to provide from about 80 to 99% of the stoichiometric amount of -NCO groups required to react with all of the active hydrogen atoms in said composition.
9. A composition according to claim 7 containing additionally a filler selected from the group consisting of clay, talc, MgO, Mg(OH)2, CaCO3 and silica and mixtures thereof.
10. A composition according to claim 7 in which in said composition (a) is a copolymer obtained from maleic anhydride and propylene oxide, (b) is polyethylene butylene adipate, (c) is the adduct of propylene oxide and pent-aerythritol having an average molecular weight of from about 400 to 600, (d) is 4,4'-diphenylmethane diisocyanate, (e) is styrene and the polyvinyl acetate of (f) is present in an amount of from about 3 to 13 parts by weight per 100 parts by weight total of said coating composition.
11. A composition according to claim 10 in which said composition contains additionally talc and/or CaCO3.
12. A composition according to claim 10 in which (d) is a diisocyanate terminated polyurethane prepolymer containing excess diisocyanate made by reacting the diisocyanate of (d) with at least a portion of (c).
(31)
(31)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/958,771 US4189517A (en) | 1978-11-08 | 1978-11-08 | Low-shrink in-mold coating |
US958,771 | 1978-11-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1120175A true CA1120175A (en) | 1982-03-16 |
Family
ID=25501277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000327842A Expired CA1120175A (en) | 1978-11-08 | 1979-05-17 | Low-shrink in-mold coating |
Country Status (7)
Country | Link |
---|---|
US (1) | US4189517A (en) |
JP (1) | JPS5919583B2 (en) |
CA (1) | CA1120175A (en) |
DE (2) | DE2953345C2 (en) |
FR (1) | FR2440830B1 (en) |
GB (1) | GB2034332B (en) |
IT (1) | IT1121589B (en) |
Families Citing this family (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4327807A (en) * | 1978-09-19 | 1982-05-04 | Maco-Meudon | Percussion tool casing |
US4245006A (en) * | 1979-05-18 | 1981-01-13 | The General Tire & Rubber Company | Low-pressure low-temperature in-mold coating method |
US4280979A (en) * | 1979-09-18 | 1981-07-28 | Union Carbide Corporation | Copolymers, compositions, and articles, and methods for making same |
CA1163410A (en) * | 1980-05-01 | 1984-03-13 | Robert F. Navin | Method for making coated molded articles |
US4366109A (en) * | 1980-05-01 | 1982-12-28 | Freeman Chemical Corporation | Method for making coated molded articles |
US4517323A (en) * | 1981-07-20 | 1985-05-14 | Owens-Corning Fiberglas Corporation | Molded products |
MX173523B (en) * | 1981-11-02 | 1994-03-11 | Gencorp Inc | IMPROVEMENTS IN THERMOSURING COATING COMPOSITION AND METHOD |
US4414173A (en) * | 1981-11-02 | 1983-11-08 | The General Tire & Rubber Company | In-mold coating |
US4409270A (en) * | 1982-04-22 | 1983-10-11 | The General Tire & Rubber Company | Method for repairing glass fiber reinforced plastic parts and product |
NL8403883A (en) * | 1984-12-21 | 1986-07-16 | Dsm Resins Bv | CRYSTALLINE UNSATURATED POLYESTER AND ITS PREPARATION. |
DE3447022A1 (en) * | 1984-12-22 | 1986-06-26 | Hüls AG, 4370 Marl | FUEL CONTAINER MADE OF POLYETHYLENE WITH REDUCED PERMEABILITY |
JPS61190464A (en) * | 1985-02-04 | 1986-08-25 | 松下電器産業株式会社 | Packer |
US4668460A (en) * | 1985-04-02 | 1987-05-26 | The Sherwin-Williams Company | Method of molding and coating a substrate in a mold. |
US4942008A (en) * | 1985-07-10 | 1990-07-17 | Cahill John W | Process for molding a multiple layer structure |
US4916016A (en) * | 1986-01-23 | 1990-04-10 | Ici Americas Inc. | Metal or plastic-clad polyvinyl resin laminates |
US4737403A (en) * | 1987-04-03 | 1988-04-12 | Ppg Industries, Inc. | Method of coating fiber-reinforced plastic substrates |
US5084353A (en) * | 1989-05-12 | 1992-01-28 | Gencorp Inc. | Thermosetting in-mold coating compositions |
US5112462A (en) * | 1990-09-13 | 1992-05-12 | Sheldahl Inc. | Method of making metal-film laminate resistant to delamination |
US6060175A (en) * | 1990-09-13 | 2000-05-09 | Sheldahl, Inc. | Metal-film laminate resistant to delamination |
US5137791A (en) * | 1990-09-13 | 1992-08-11 | Sheldahl Inc. | Metal-film laminate resistant to delamination |
JP2686682B2 (en) * | 1991-10-16 | 1997-12-08 | いすゞ自動車株式会社 | Manufacturing method of molded products |
DE69223806T2 (en) * | 1992-02-21 | 1998-07-23 | Du Pont | RECYCLABLE MOLDED THERMOPLASTIC STRUCTURES REINFORCED WITH HIGH MODULAR FIBER AND METHOD FOR THE PRODUCTION THEREOF |
JP3627222B2 (en) * | 1992-09-30 | 2005-03-09 | 日本ゼオン株式会社 | Form for manufacturing electronic component sealing body, and method for manufacturing electronic component sealing body using the same |
US5906788A (en) * | 1992-10-05 | 1999-05-25 | Cook Composites And Polymers Co. | Dual cure, in-mold process for manufacturing abrasion resistant, coated thermoplastic articles |
DE69408195T2 (en) * | 1993-04-26 | 1998-11-05 | Gencorp Inc | Conductive molded coatings |
US5387750A (en) * | 1993-08-27 | 1995-02-07 | The Sherwin-Williams Company | Two-component urethane in-mold coating composition |
US5447921A (en) * | 1995-03-24 | 1995-09-05 | Aristech Chemical Corporation | Catalyst system for adherent rigid foam |
US5849168A (en) * | 1996-06-14 | 1998-12-15 | Acushnet Company | Method of in-mold coating golf balls |
US5777053A (en) * | 1997-01-17 | 1998-07-07 | Gencorp Inc. | In-mold coating compositions suitable as is for an end use application |
US6165309A (en) * | 1998-02-04 | 2000-12-26 | General Electric Co. | Method for improving the adhesion of metal films to polyphenylene ether resins |
KR20020026948A (en) | 1999-07-27 | 2002-04-12 | 다이니폰 도료 가부시키가이샤 | Method of forming coating on inner surfaces of metal mold |
CA2406453A1 (en) * | 2000-04-20 | 2001-11-01 | Elliott J. Straus | Method of molding a panel |
US6793861B2 (en) | 2000-07-12 | 2004-09-21 | Omnova Solutions Inc. | Optimization of in-mold coating injection molded thermoplastic substrates |
US6617033B1 (en) | 2000-07-12 | 2003-09-09 | Omnova Solutions Inc. | Method for in-mold coating a polyolefin article |
US20040071980A1 (en) * | 2000-07-12 | 2004-04-15 | Mcbain Douglas S. | Method for in-mold coating a polyolefin article |
US6887550B2 (en) * | 2001-10-22 | 2005-05-03 | Omnova Solutions Inc. | Removable defined flange for in-mold coating containment |
US7105231B2 (en) * | 2001-10-22 | 2006-09-12 | Omnova Solutions Inc. | In-mold coating barrier for a substrate injection orifice |
US7045213B2 (en) * | 2001-10-22 | 2006-05-16 | Omnova Solutions Inc. | In-mold coating injection inlet flow control |
US6890469B2 (en) | 2001-10-22 | 2005-05-10 | Omnova Solutions Inc. | Selectively controlling in-mold coating flow |
JP4230692B2 (en) | 2001-11-22 | 2009-02-25 | 大日本塗料株式会社 | Manufacturing method for in-mold coating |
US6676877B2 (en) | 2002-04-03 | 2004-01-13 | Omnova Solutions Inc. | Mold runner for prevention of in-mold coating flow |
US6863981B2 (en) * | 2002-05-31 | 2005-03-08 | Omnova Solutions Inc. | In-mold appearance coatings for nylon and nylon based thermoplastic substrates |
US20040121034A1 (en) * | 2002-12-10 | 2004-06-24 | Mcbain Douglas S. | Integral injection molding and in-mold coating apparatus |
ATE386785T1 (en) * | 2003-07-22 | 2008-03-15 | Omnova Solutions Inc | BASE COAT BACK SPRAY |
GB0408480D0 (en) * | 2004-04-16 | 2004-05-19 | Koninkl Philips Electronics Nv | Variable focus lens having two liquids and electronic device |
EP2139660B1 (en) | 2007-04-27 | 2013-12-25 | Exatec, LLC. | Abrasion resistant plastic glazing with in-mold coating |
WO2008134771A1 (en) | 2007-05-01 | 2008-11-06 | Exatec, Llc | Encapsulated plastic panel and method of making the same |
WO2008141136A1 (en) * | 2007-05-09 | 2008-11-20 | Exatec. Llc | Pre-dry treatment of ink in decorative plastic glazing |
CN113174126A (en) * | 2021-05-13 | 2021-07-27 | 河北英丽达新材料科技有限公司 | High-performance SMC molding compound and preparation method thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA576453A (en) * | 1959-05-26 | Farbenfabriken Bayer Aktiengesellschaft | Hydroxyl polyesters with polyisocyanate and vinyl compound | |
BE625783A (en) * | 1961-12-07 | |||
US3772241A (en) * | 1966-07-20 | 1973-11-13 | Rohm & Haas | Unsaturated polyester resinous compositions |
GB1225803A (en) * | 1967-06-02 | 1971-03-24 | ||
US3576909A (en) * | 1968-01-19 | 1971-04-27 | Gen Tire & Rubber Co | Catalyzed isomerization of alpha-beta unsaturated carboxylic acid esters |
US3763065A (en) * | 1970-09-16 | 1973-10-02 | Hager & Kassner Kg | Thixotropic combination |
US3741799A (en) * | 1971-05-10 | 1973-06-26 | Gen Tire & Rubber Co | Method of improving paint adhesion to low-shrink polyester-based resins |
US3883612A (en) * | 1971-06-07 | 1975-05-13 | Scm Corp | Low-shrink thermosetting polymers |
US3824201A (en) * | 1971-08-30 | 1974-07-16 | Gen Tire & Rubber Co | Maturated polyester polyurethane compositions |
US3862021A (en) * | 1972-02-17 | 1975-01-21 | Asahi Chemical Ind | Polymerizable compositions and laminated articles bonded |
JPS504719B2 (en) * | 1972-03-18 | 1975-02-22 | ||
US3838093A (en) * | 1972-10-25 | 1974-09-24 | Lord Corp | Method and composition for improving adhesion between adhesives and polyester or thermoplastic substrates |
CA1023913A (en) * | 1973-09-04 | 1978-01-10 | General Tire And Rubber Company (The) | In-mold coating composition and method of applying same |
US4081578A (en) * | 1974-06-27 | 1978-03-28 | The General Tire & Rubber Company | In-mold coating composition and method of applying same |
DE2448929C2 (en) * | 1974-10-15 | 1983-06-23 | Bayer Ag, 5090 Leverkusen | Thermosetting molding compounds |
FR2364119A2 (en) | 1975-09-24 | 1978-04-07 | Altulor | Polyester of compensated shrinkage contg. polyvinyl acetate - adheres to poly:methyl methacrylate! to form laminated sheet |
US4032494A (en) * | 1976-03-03 | 1977-06-28 | Union Carbide Corporation | Liquid siloxanes as additives for curable polyester moulding compositions containing vinyl acetate polymer and unsaturated monomer |
DE2848401A1 (en) * | 1978-11-08 | 1980-06-12 | Hoechst Ag | CURABLE DIMENSIONS AND METHOD FOR THEIR PRODUCTION |
-
1978
- 1978-11-08 US US05/958,771 patent/US4189517A/en not_active Expired - Lifetime
-
1979
- 1979-05-17 CA CA000327842A patent/CA1120175A/en not_active Expired
- 1979-06-18 IT IT2369879A patent/IT1121589B/en active
- 1979-06-21 DE DE2953345A patent/DE2953345C2/en not_active Expired
- 1979-06-21 DE DE2925102A patent/DE2925102C2/en not_active Expired
- 1979-06-29 JP JP54081540A patent/JPS5919583B2/en not_active Expired
- 1979-07-06 GB GB7923585A patent/GB2034332B/en not_active Expired
- 1979-07-09 FR FR7917730A patent/FR2440830B1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2440830A1 (en) | 1980-06-06 |
JPS5565511A (en) | 1980-05-17 |
DE2925102A1 (en) | 1980-05-14 |
DE2925102C2 (en) | 1985-01-03 |
IT7923698A0 (en) | 1979-06-18 |
GB2034332B (en) | 1982-10-27 |
GB2034332A (en) | 1980-06-04 |
US4189517A (en) | 1980-02-19 |
FR2440830B1 (en) | 1986-03-28 |
JPS5919583B2 (en) | 1984-05-07 |
DE2953345C2 (en) | 1984-05-10 |
IT1121589B (en) | 1986-04-02 |
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