CA1186429A - In-mold coating - Google Patents
In-mold coatingInfo
- Publication number
- CA1186429A CA1186429A CA000408586A CA408586A CA1186429A CA 1186429 A CA1186429 A CA 1186429A CA 000408586 A CA000408586 A CA 000408586A CA 408586 A CA408586 A CA 408586A CA 1186429 A CA1186429 A CA 1186429A
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- weight
- parts
- composition
- ethylenically unsaturated
- group
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
- C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Epoxy Resins (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Abstract Of The Disclosure An FRP molding can be in-mold coated using a one-component free radical peroxide initiated composition of (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) a copolymerizable ethylenically unsaturated monomer, (c) a zinc salt of a fatty acid having at least 10 carbon atoms, (d) an accelerator for the peroxide initiator and (e) polyvinyl acetate. Optionally and desirably the composition additionally contains (f) a mono-unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) a liquid copolymerizable compound having from 2-4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1500, (h) a calcium salt of a fatty acid having at least 10 carbon atoms and (i) a filler.
Description
2~
In-Mold Coatin~
This invention relates to a thermosetting in-mold coating composition useful for in-mold coating a molded fiberglass reinforced thermoset plastic such as a polyester resin or a vinyl ester resin (FRP) molding or part that does not require the combining of two or more components immediately prior to use.
Background Of The Invention A major deficiency of compression molded thermoset glass fiber reinforced polyester (FRP) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks. The in-mold coating process of U.S. Patent 4,081,578 generally overcomes these imperfections by molding a low viscosity thermoset on top of the FRP in a second molding operation. m e composition described in U.S. Patent 4,081,578 contains free hydroxyl as well as isocyanate groups that co-react at room temperature, resulting in a limited (about one-hal~ hour) pot life. In practice, the reactive ingredients are kept apart, and combined only immediately prior to application. This necessitates dual pumping e~uipment and an accurate metering device, which increase the cost and complexity of the system.
single component coating would thus offer a significant advantage.
m erefore, it is an object of this invention to avoid the difficulties alluded to and to provide a process for in-mold coating an FRP molding with a one component coating composition.
Another object of this invention is to provide a one component composition suitable for in-mold coating an FRP molding.
A further object of this invention is ~o provide a cured molded FRP molding or part with an adherent coating in-mold coated with a one component in-mold coating composition~
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 e~amples.
, ~
$ummary of the Invention An FRP molding ean be in-mold eoated usi.ng a eomposition useful as a thermosetting molding eomposition eomprising (a) a polymerizable oligomer selected from the group eonsi.sting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligorner having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenieally unsaturated groups and mixtures of the same, tb) a eopolymerizable ethylenieally unsaturated monomer, (e) a zine salt of a fatty aeid having at least 10 carbon atoms, (d) an accelerator for a peroxide initiator and (e) polyvinyl acetate in a minor amount by weight as compared to the polymerizable materials and sufficient for paint adhesion, (f) op-tionally additionally contain-ing a eopolymerizable monoethylenieally unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH group, (.g) optionally additionally containing for partial replaeement of (a) a copoly-merizable liquid eompound having from 2 to 4 vinyl yroups, being free of urethane, cycloaliphatic and aromatie groups and having a moleeular weight of up to about 1500, (h) optionally additionally eontaining a calcium salt of a fatty acid having at least 10 carbon atoms and (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition.
The composition of the present invention may also be defined as a composition useful as a therrnosetting coating composition eomprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups, (b) from about ~0 to 150 parts by weight of at leas-t one ~ a/~
copolymerizable ethylenically unsaturated monomer, (c) up to about 120 par-ts by weight of at least one copolymerizable monoethylenical-ly unsaturated compound having a -CO- grou~ and a -NH2, NH- and/or -OH group, (d) from about 4Q to ~0 parts by weight of polyvinyl acetate, (e) from about 0.2 to ~5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.05 to 2.0 part by weight of at leas-t one accelerator for a peroxide initiator, (g) from about 5 -to 15 parts by weight of conductive carbon black, (h) from about 50 to 150 parts by weight of a filler, and (i) up to about 120 parts by weight of a copoly-merizable or cocurable diac.rylate compound having a weight average molecular weight of up to about 1500 and being selected from -the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane based oligomer having two acryla-te groups and mix-tures of (I) and (II).
In another aspect, the invention provides -the me-thod which comprises in-mold coating a molded -thermoset polyester resin or thermoset vinyl ester resin glass fiber composi-tion containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least ~wo acrylate groups and (3) a olyester based oligomer having a ~p - 2a -plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) a copolymerizable ethylenically unsaturated monomer, (c) a zinc salt of a fatty acid having at least 1~ carbon atoms, ~d) an accelerator for a peroxide initiator and (e) polyvinylacetate in a minor amount by weight as compared to the olymerizable materials and sufficient for paint adhesion, (f) optionally additionally containing a copolymerizable monoethylenically unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) optionally additionally containing for partial replacement of (a) a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1~00, (h) optionally additionally containing a calcium salt of a fatty acid having at least 10 carbon atoms, (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition, and (j) containing an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylencially unsa-turated materials.
The composition flows well and is stable even for about a week even when containing the peroxide. I-t can be molded in a short period of -time. The resulting thermoset coating exhibits good adhesion to different F~P substrates and will accept many paint finishes obviating the need for a primer.
' - 2b -p~
Discussion of Details and Preferred Embodimen-ts The polymerizable or crosslinkable diacrylate terminated polyurethane oligmer may be a polyesterurethane diacrylate, a polyetherurethane diacrylate or a polyesteretherurethane diacrylate or other polyurethane oligomer having more than two acrylate groups. These materials may be made by reacting a polyetherdiol (e.g., a polypropylene ether diol), polyesterdiol ~e.g., a polyethylene adipate diol) and/or a polyetherester diol (e.g., a polypropylene ether adipate diol), or triol etc., and so forth with a diisocyanate like tolylene diisocyanate, ~
diphenylmethane diisocyanate, hexamethylene diisocyanate and the like in an amount sufficient to form an isocyanate terminated poly~rethane prepol~ner which is then reacted with hydxoxy propyl acrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate and so forth to form the diacrylate terminated polyurethane oligomer or polymer. Mixtures of these acrylate terminated polyurethane oligomers may be used~ The term "acrylate" as used here is intended to cover methacrylate and ethacrylates as well as acrylates. Of these materials i~ is preferred to use a diacrylate polyesterurethane oligomer. Acrylate terminated polyurethane oligomers, e.g., curable by light, ultraviolet, electric beam and~or infrared and so forthr are well known, and sometimes are referred to as irradiation or radiation curable materials.
~ le epoxy based oligomer having at least two acrylate (or methacrylate or ethacrylate) groups is prepared by reacting acrylic acid, methacrylic acid or ethacrylic acid and so forth with an ep~xy based oligomer or resin such as a Bisphenol A
epoxy, a tetrabromo Bisphenol A epoxy, phenolic novolak epoxy, tetraphenylolethane epoxy, dicycloaliphatic epoxy and so forth.
Mixtures of these epoxy based oligomers may be used. Of these materials it is preferred to use a diacrylate terminated Bisphenol A epoxy oligomer. These materials are well kno~~ r more information on these materials see "Heat Resistant Vinyl Ester Resin," ~. ~. Launikitis, Technical Bulletin, SC':116-76, Shell Chemical Cbmpany, June,-1976 and Shell Chemical Cbmpany Technical Bulletins SC:16-76 and SC:60-78.
The polyester based oligorner having a plurality of internal ethylenically unsaturated groups used may be made by copolyrnerizing nnaleic anhydride and an alkylene oxide of 2 to carbon atoms such as propylene oxide, ethylene oxide, butylene oxide, isobutylene oxide and so forth and mixture thereof.
Propylene oxide and mixtures of propylene oxide and ethylene oxide are preferred. The alkylene oxide nlay be used in a molar ratio greater than the maleic anhydride to provide a polyester which is essentially or all OH terminated, e.gO, a polyester diol. Up to about 50 mol % of the maleic anhydride may be replaced with a saturated anhydride such as phthalic anhydride or other anhydride and mixture thereof. A telogen like ~umaric acid also may be used. It is preferred to use maleic anhydride.
These unsaturated polyesters may be made in benzene, styrene or other solvent using a double metal cyanide catalyst as shown in U.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 sh~wn by V.S. Patent No. 3,576,909. m ese polyesters may have molecular weights of from about 800 to 2500, preferably from about ]000 to 1500. Polyesters made by reacting maleic anhydride or maleic acid, fumaric acid, itaconic acid, or citraconic acid with a glycol like propylene glycol, dipropylene glycol, l,~-butane diol, bisphenol A and so forth including minor amounts of phthalic acid or phthalic anhydride and other diols and dicarboxylic acids may be used. m e substantially aliphatic polyesters like the fumarate polyesters made using the double metal cyanide catalysts as described above are pre~erable to use. Fbr more in~ormation on making unsaturated polyesters see "Encyclopedia of Polymer Science And Technology," Interscience Publishers, a division of John Wiley & Sons, Inc., New York, Vol.
11, 1969, pages 129 to 168.
An organic ~ree~radical or free radical generating initiator (catalyst) such as a peroxide is used to catalyze the copolymerization or crosslinking o~ the ethylenically unsaturated oligomer and the other ethylerlically unsaturated materials.
Examples of free-radical initiators 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,~-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-clihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethyl hexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di-(benzoyl peroxy) hexane, l-hydroxy cyclohexyl hydroperoxide-l, t-butyl peroxy (2-ethyl butyra-te), 2,5-climethyl-2,5-bis~t-butyl peroxy) hexane, cumyl hydro-peroxide, diacetyl peroxide, t-butyl hydroperoxide, di~ertiary butyl peroxide,
In-Mold Coatin~
This invention relates to a thermosetting in-mold coating composition useful for in-mold coating a molded fiberglass reinforced thermoset plastic such as a polyester resin or a vinyl ester resin (FRP) molding or part that does not require the combining of two or more components immediately prior to use.
Background Of The Invention A major deficiency of compression molded thermoset glass fiber reinforced polyester (FRP) moldings is surface imperfections such as pits, pores, surface cracks, waviness and sink marks. The in-mold coating process of U.S. Patent 4,081,578 generally overcomes these imperfections by molding a low viscosity thermoset on top of the FRP in a second molding operation. m e composition described in U.S. Patent 4,081,578 contains free hydroxyl as well as isocyanate groups that co-react at room temperature, resulting in a limited (about one-hal~ hour) pot life. In practice, the reactive ingredients are kept apart, and combined only immediately prior to application. This necessitates dual pumping e~uipment and an accurate metering device, which increase the cost and complexity of the system.
single component coating would thus offer a significant advantage.
m erefore, it is an object of this invention to avoid the difficulties alluded to and to provide a process for in-mold coating an FRP molding with a one component coating composition.
Another object of this invention is to provide a one component composition suitable for in-mold coating an FRP molding.
A further object of this invention is ~o provide a cured molded FRP molding or part with an adherent coating in-mold coated with a one component in-mold coating composition~
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 e~amples.
, ~
$ummary of the Invention An FRP molding ean be in-mold eoated usi.ng a eomposition useful as a thermosetting molding eomposition eomprising (a) a polymerizable oligomer selected from the group eonsi.sting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligorner having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenieally unsaturated groups and mixtures of the same, tb) a eopolymerizable ethylenieally unsaturated monomer, (e) a zine salt of a fatty aeid having at least 10 carbon atoms, (d) an accelerator for a peroxide initiator and (e) polyvinyl acetate in a minor amount by weight as compared to the polymerizable materials and sufficient for paint adhesion, (f) op-tionally additionally contain-ing a eopolymerizable monoethylenieally unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH group, (.g) optionally additionally containing for partial replaeement of (a) a copoly-merizable liquid eompound having from 2 to 4 vinyl yroups, being free of urethane, cycloaliphatic and aromatie groups and having a moleeular weight of up to about 1500, (h) optionally additionally eontaining a calcium salt of a fatty acid having at least 10 carbon atoms and (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition.
The composition of the present invention may also be defined as a composition useful as a therrnosetting coating composition eomprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups, (b) from about ~0 to 150 parts by weight of at leas-t one ~ a/~
copolymerizable ethylenically unsaturated monomer, (c) up to about 120 par-ts by weight of at least one copolymerizable monoethylenical-ly unsaturated compound having a -CO- grou~ and a -NH2, NH- and/or -OH group, (d) from about 4Q to ~0 parts by weight of polyvinyl acetate, (e) from about 0.2 to ~5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.05 to 2.0 part by weight of at leas-t one accelerator for a peroxide initiator, (g) from about 5 -to 15 parts by weight of conductive carbon black, (h) from about 50 to 150 parts by weight of a filler, and (i) up to about 120 parts by weight of a copoly-merizable or cocurable diac.rylate compound having a weight average molecular weight of up to about 1500 and being selected from -the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane based oligomer having two acryla-te groups and mix-tures of (I) and (II).
In another aspect, the invention provides -the me-thod which comprises in-mold coating a molded -thermoset polyester resin or thermoset vinyl ester resin glass fiber composi-tion containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least ~wo acrylate groups and (3) a olyester based oligomer having a ~p - 2a -plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) a copolymerizable ethylenically unsaturated monomer, (c) a zinc salt of a fatty acid having at least 1~ carbon atoms, ~d) an accelerator for a peroxide initiator and (e) polyvinylacetate in a minor amount by weight as compared to the olymerizable materials and sufficient for paint adhesion, (f) optionally additionally containing a copolymerizable monoethylenically unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) optionally additionally containing for partial replacement of (a) a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1~00, (h) optionally additionally containing a calcium salt of a fatty acid having at least 10 carbon atoms, (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition, and (j) containing an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylencially unsa-turated materials.
The composition flows well and is stable even for about a week even when containing the peroxide. I-t can be molded in a short period of -time. The resulting thermoset coating exhibits good adhesion to different F~P substrates and will accept many paint finishes obviating the need for a primer.
' - 2b -p~
Discussion of Details and Preferred Embodimen-ts The polymerizable or crosslinkable diacrylate terminated polyurethane oligmer may be a polyesterurethane diacrylate, a polyetherurethane diacrylate or a polyesteretherurethane diacrylate or other polyurethane oligomer having more than two acrylate groups. These materials may be made by reacting a polyetherdiol (e.g., a polypropylene ether diol), polyesterdiol ~e.g., a polyethylene adipate diol) and/or a polyetherester diol (e.g., a polypropylene ether adipate diol), or triol etc., and so forth with a diisocyanate like tolylene diisocyanate, ~
diphenylmethane diisocyanate, hexamethylene diisocyanate and the like in an amount sufficient to form an isocyanate terminated poly~rethane prepol~ner which is then reacted with hydxoxy propyl acrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate and so forth to form the diacrylate terminated polyurethane oligomer or polymer. Mixtures of these acrylate terminated polyurethane oligomers may be used~ The term "acrylate" as used here is intended to cover methacrylate and ethacrylates as well as acrylates. Of these materials i~ is preferred to use a diacrylate polyesterurethane oligomer. Acrylate terminated polyurethane oligomers, e.g., curable by light, ultraviolet, electric beam and~or infrared and so forthr are well known, and sometimes are referred to as irradiation or radiation curable materials.
~ le epoxy based oligomer having at least two acrylate (or methacrylate or ethacrylate) groups is prepared by reacting acrylic acid, methacrylic acid or ethacrylic acid and so forth with an ep~xy based oligomer or resin such as a Bisphenol A
epoxy, a tetrabromo Bisphenol A epoxy, phenolic novolak epoxy, tetraphenylolethane epoxy, dicycloaliphatic epoxy and so forth.
Mixtures of these epoxy based oligomers may be used. Of these materials it is preferred to use a diacrylate terminated Bisphenol A epoxy oligomer. These materials are well kno~~ r more information on these materials see "Heat Resistant Vinyl Ester Resin," ~. ~. Launikitis, Technical Bulletin, SC':116-76, Shell Chemical Cbmpany, June,-1976 and Shell Chemical Cbmpany Technical Bulletins SC:16-76 and SC:60-78.
The polyester based oligorner having a plurality of internal ethylenically unsaturated groups used may be made by copolyrnerizing nnaleic anhydride and an alkylene oxide of 2 to carbon atoms such as propylene oxide, ethylene oxide, butylene oxide, isobutylene oxide and so forth and mixture thereof.
Propylene oxide and mixtures of propylene oxide and ethylene oxide are preferred. The alkylene oxide nlay be used in a molar ratio greater than the maleic anhydride to provide a polyester which is essentially or all OH terminated, e.gO, a polyester diol. Up to about 50 mol % of the maleic anhydride may be replaced with a saturated anhydride such as phthalic anhydride or other anhydride and mixture thereof. A telogen like ~umaric acid also may be used. It is preferred to use maleic anhydride.
These unsaturated polyesters may be made in benzene, styrene or other solvent using a double metal cyanide catalyst as shown in U.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 sh~wn by V.S. Patent No. 3,576,909. m ese polyesters may have molecular weights of from about 800 to 2500, preferably from about ]000 to 1500. Polyesters made by reacting maleic anhydride or maleic acid, fumaric acid, itaconic acid, or citraconic acid with a glycol like propylene glycol, dipropylene glycol, l,~-butane diol, bisphenol A and so forth including minor amounts of phthalic acid or phthalic anhydride and other diols and dicarboxylic acids may be used. m e substantially aliphatic polyesters like the fumarate polyesters made using the double metal cyanide catalysts as described above are pre~erable to use. Fbr more in~ormation on making unsaturated polyesters see "Encyclopedia of Polymer Science And Technology," Interscience Publishers, a division of John Wiley & Sons, Inc., New York, Vol.
11, 1969, pages 129 to 168.
An organic ~ree~radical or free radical generating initiator (catalyst) such as a peroxide is used to catalyze the copolymerization or crosslinking o~ the ethylenically unsaturated oligomer and the other ethylerlically unsaturated materials.
Examples of free-radical initiators 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,~-dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-clihydroxy-3,4-dimethyl-1,2-dioxacyclopentane, t-butylperoxy(2-ethyl hexanoate), caprylyl peroxide, 2,5-dimethyl-2,5-di-(benzoyl peroxy) hexane, l-hydroxy cyclohexyl hydroperoxide-l, t-butyl peroxy (2-ethyl butyra-te), 2,5-climethyl-2,5-bis~t-butyl peroxy) hexane, cumyl hydro-peroxide, diacetyl peroxide, t-butyl hydroperoxide, di~ertiary butyl peroxide,
3,5-dihydroxy-3,5-dimethyl-1,2-oxacyclopentane, and l,l-bis(t-butyl peroxy~-3,3,5-trimethyl cyclohexane and the like and mixtures thereof. It is desirable sometimes to use mixtures of initiators to take advantage of their different decomposition rates and times at different temperatures and so forth. A prefer-red initiator to use is tertiary butyl perbenzoate. The peroxide initiatorshould be used in an amount sufficient to overcome the effect of the inhibitor and to cause crosslinking or curing of the ethylenically unsaturated materials.
In general the peroxide initiator may be used in an amount of up to about 5%, preferably up to about 2~, by weight based on the weight of the ethylenically unsaturated materials employed in the in-mold coating composition.
An accelerator is used for the peroxide initiator and is a material such as a drier, e.g., cobalt octoate. Other materials which may be used are zinc naphthenate, lead naphthenate, cobalt naphthenate and manganese naphthenate.
Soluble Co, Mn and Pb salts of linoleic acid, also, may be used. Only small amounts by weight of the accelerator need be used. In general the accelerator is used in an amount of from about 0.05 to 2 parts by weight per 100 parts by weight of the polymerizable oligomer.
A zinc salt of a fatty acid having at least 10 carbon atoms, also, is employed in the in-mold coa~ing composition and appears to function as a mold release agent and as a secondary accelerator for the cure. Fatty acids are well known. See "Organic Chemistry," Fieser and Fieser, D.C. Ileath and Company, Boston, 1944, pages 88, 381-390, 398 and 401 and "Hackh's Chemical Dictionary,"
Grant, McGraw ~-lill Book Company, New York, 1969, page 261. Mixtures of zinc salts of the fatty acids can be used. Examples of some zinc salts are zinc palmitate) zinc stearate, zinc ricinoleate and the like. It is preferred to use the zinc salt of a saturated fatty acid such as zinc stearatc. See, also, "Whittington's Dictionary Of Plastics," Whittington, Technomic Publishing Co., Inc., Stamford~ Conn., 196~, pages 35, 102 and 261. The zinc salt generally is used in an amount such as from about 0.2 to 5 parts by weight per 100 parts by weight of the polymerizable oligomer.
Optionally and desirably small amounts by weight of a calcium salt of a fatty aci~ having at least 10 carbon atoms, e.g., from about 0.2 to 5 parts by weight of calcium salt per 100 parts by weight of the polymerizable oligomer, are used in the in-mold coating composition as a mold re:lease agent and to con-trol the rate of the cure. Fatty acids are well known, see above. Mixtures of calcium salts of the fatty acids can be used. Examples of some calcium salts are calcium stearate, calcium palmitate, calcium oleate and the like. It is pre-ferred to use the calcium salt of a saturated fatty acid like calcium stearate.
Polyvinyl acetate is employed as to improve paint adhesion to the in-mold coating. The polyvinyl acetate is employed in a minor amount by weigllt as compared to the total weight oE the ethylenically unsaturated materials in the ln-mold coating compositioll and sufficient for paint adhesion. In general the polyvinyl acctate is employed in an amount of from about 40 to 80 parts by weight per 100 parts by weight of the polymerizable oligomer.
A copolymerizable ethylenically unsaturated monomer is used in an amount at least sufficient to copolymerize with and to crosslin]c the polymeriz-able oligomer and includes styrene (preferred), alpha methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, metl-yl methacrylate, diallyl phthalate (with styrene or methyl methacrylate and the like), triallyl cyanurate, triallyl isocyanurate, divinyl benzene, methyl acrylate and so forth and mixtures thereof. The unsaturated monomer is used generally in an amount of from about 80 to 150 parts by weight per 100 parts by weight of the polymerizable oligomer.
Optionally and desirably there may be used in the coating composition for further copolyrilerization and crosslinking and to improve hardness of the resulting coating a mono ethylenically unsaturated compound having a -C O- group and having a -NE~, -NH- and/or -OH group. Examples of such monomeric compounds are hydroxyl propyl methacrylate (preferred), hydroxyethyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl crotonate, hydroxypropyl acrylate, hydroxy polyoxypropylene acrylate, hydroxy polyoxypropylene methacrylate, hydroxy polyoxyethylene methacrylate, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide and so forth and mixtures of the same. These compounds generally may be used in an arrount of from about 0 to 120 parts by weight per 100 parts by weight of the polymerizable oligomer.
Also, optionally and preferably, there may be used in partial replacement of the polymerizable oligomer a liquid copolymerizable or crosslinkable acrylate compolmd having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having an a~erage molecular weight of up to about 1500. Examples of such compounds incl~de trimethylol propane trimethacrylate, trimethylol propane triacrylate, pentaerythritol tetracrylate, triethylene glycol diacrylate tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3 butylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate or polyoxyethylene glycol dimethacrylate (preferred), pentaerythritol triacrylate, 1,6-hexanediol diacrylate, polypropylene glycol dimethacrylate, polyethylene propylene glycol diacrylate, and so forth and mixtures thereof.
Since some of these reactive polyfunctional monomers may be made by reacting unsaturated acids and alcohols~ they may contain some 0~ andVor COOH groups. m e reactive polyfunctional monomers may be used generally in an amount of from about 0 to 120 parts by weight per 100 parts by weight of the polymerizable oligomer.
The unsaturated materials mentioned above, thus, are used in an amount sufficient to provide on cure (e.g., polymerization, copolymeriæation and/or crosslinking) a thermoset composition.
m e monoethylenically unsaturated compound having a -C O-group and having a -N ~ , -NH- and/or -OH group (like hydroxy propyl methacrylate) or the liquid copolymerizable acrylate compound having from 2 to ~ vinyl groups and being free of urethane, cycloaliphatic and aromatic groups (like Folyethylene glycol dimethacr~late), or both of these compounds, should be used in the in-mold coating composition where after curing it is to be painted with a water based system.
To prevent premature gelation of the ethylenically unsaturated materials and to provide for improved shelf-life or storayeability inhibitors are added in the desired arnount to the composition or are provided in the raw materials before use.
Examples of inhibitors are hydroquinone, benzo~uinone, p-t-butyl catechol and the lilce and mixture thereof.
The in mold composition additionally op~ionally can be filled or comFounded to give the desired viscosity and flow to the composition for molding and to afford the desired physical properties to the resulting thermoset coating. Fillers, also, may improve adhesion. Examples of such fillers or comFounding ingredients are fillers like clay, talc, MgO, Mg(OH)2, CaC03 and silica, other mold release agents, red iron oxide, TiO2, carbon black including conductive carbon black~ color piyments~
antidegradants, U-V absorbers, calcium silicate, paraffin wax~
hollow glass or resin micro-spheres, thickening a~ents, other low shrink additives and the like. One preferred filler is talc which may be used in an amount of from about 50 to 150 parts by weight per 100 parts by weiyht of the pol~nerizable oligomer.
The use of an electroconductive filler like conductive carbon ~, _ 9 _ black enables the coating to be painted by standard electrostatic painting techniquesO Such conductive carbon black may be used in an amount of from about 5 to 15 parts by weight per 100 parts by weight of the polymerizable oligomer. l'hese 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. It is not desirable to use in the in-mold composition of this invention materials like carbo~lated butadiene-styrene block copolymers or fatty alcohol phosphates.
For ease in handling, materials like polyvinylacetate may be dissolved in a reactive monomer like styrene. The viscosity of the oligomers may be reduced by dilution with styrene and the like. The ingredients of the in-mold composition should be readily mixed and handled at ambient or room temperature or temperatures below the polymerizatio~ temperature so that they may be readily pumped to the mold and injected into the same.
The ingredients may be warmed or heated before Gr during mixing and mixed in steps to facilitate thorough mixing, dispersion and solution of the same.
With the peroxide initiator or catalyst the in-mold composition exhibits a shelf-life at room temperature (about 25C) of about a week, and without the initiator it exhibits a shelf life of severa] months at room temperature. The initiator is preferably added to the composition and thoroughly mixed therewith just before molding.
A11 of the ingredients of the in-mold coating comp~sition should be kept dry or have a minimal amount of moisture or the water content should be controlled to obtain reproducible results and to prevent pore formation.
Mixing o~ the ingredients of the in mold composition should be thorough. Injection or compression, transfer molding, or other molding apparatus or machines can be used ~or the in-mold coating. Molding apparatus and methods may be found in U.SO
Patents Nos. 4,076,780; 4,076,788; 4,081,578; 4,082,486,
In general the peroxide initiator may be used in an amount of up to about 5%, preferably up to about 2~, by weight based on the weight of the ethylenically unsaturated materials employed in the in-mold coating composition.
An accelerator is used for the peroxide initiator and is a material such as a drier, e.g., cobalt octoate. Other materials which may be used are zinc naphthenate, lead naphthenate, cobalt naphthenate and manganese naphthenate.
Soluble Co, Mn and Pb salts of linoleic acid, also, may be used. Only small amounts by weight of the accelerator need be used. In general the accelerator is used in an amount of from about 0.05 to 2 parts by weight per 100 parts by weight of the polymerizable oligomer.
A zinc salt of a fatty acid having at least 10 carbon atoms, also, is employed in the in-mold coa~ing composition and appears to function as a mold release agent and as a secondary accelerator for the cure. Fatty acids are well known. See "Organic Chemistry," Fieser and Fieser, D.C. Ileath and Company, Boston, 1944, pages 88, 381-390, 398 and 401 and "Hackh's Chemical Dictionary,"
Grant, McGraw ~-lill Book Company, New York, 1969, page 261. Mixtures of zinc salts of the fatty acids can be used. Examples of some zinc salts are zinc palmitate) zinc stearate, zinc ricinoleate and the like. It is preferred to use the zinc salt of a saturated fatty acid such as zinc stearatc. See, also, "Whittington's Dictionary Of Plastics," Whittington, Technomic Publishing Co., Inc., Stamford~ Conn., 196~, pages 35, 102 and 261. The zinc salt generally is used in an amount such as from about 0.2 to 5 parts by weight per 100 parts by weight of the polymerizable oligomer.
Optionally and desirably small amounts by weight of a calcium salt of a fatty aci~ having at least 10 carbon atoms, e.g., from about 0.2 to 5 parts by weight of calcium salt per 100 parts by weight of the polymerizable oligomer, are used in the in-mold coating composition as a mold re:lease agent and to con-trol the rate of the cure. Fatty acids are well known, see above. Mixtures of calcium salts of the fatty acids can be used. Examples of some calcium salts are calcium stearate, calcium palmitate, calcium oleate and the like. It is pre-ferred to use the calcium salt of a saturated fatty acid like calcium stearate.
Polyvinyl acetate is employed as to improve paint adhesion to the in-mold coating. The polyvinyl acetate is employed in a minor amount by weigllt as compared to the total weight oE the ethylenically unsaturated materials in the ln-mold coating compositioll and sufficient for paint adhesion. In general the polyvinyl acctate is employed in an amount of from about 40 to 80 parts by weight per 100 parts by weight of the polymerizable oligomer.
A copolymerizable ethylenically unsaturated monomer is used in an amount at least sufficient to copolymerize with and to crosslin]c the polymeriz-able oligomer and includes styrene (preferred), alpha methyl styrene, vinyl toluene, t-butyl styrene, chlorostyrene, metl-yl methacrylate, diallyl phthalate (with styrene or methyl methacrylate and the like), triallyl cyanurate, triallyl isocyanurate, divinyl benzene, methyl acrylate and so forth and mixtures thereof. The unsaturated monomer is used generally in an amount of from about 80 to 150 parts by weight per 100 parts by weight of the polymerizable oligomer.
Optionally and desirably there may be used in the coating composition for further copolyrilerization and crosslinking and to improve hardness of the resulting coating a mono ethylenically unsaturated compound having a -C O- group and having a -NE~, -NH- and/or -OH group. Examples of such monomeric compounds are hydroxyl propyl methacrylate (preferred), hydroxyethyl methacrylate, hydroxy ethyl acrylate, hydroxy ethyl crotonate, hydroxypropyl acrylate, hydroxy polyoxypropylene acrylate, hydroxy polyoxypropylene methacrylate, hydroxy polyoxyethylene methacrylate, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide and so forth and mixtures of the same. These compounds generally may be used in an arrount of from about 0 to 120 parts by weight per 100 parts by weight of the polymerizable oligomer.
Also, optionally and preferably, there may be used in partial replacement of the polymerizable oligomer a liquid copolymerizable or crosslinkable acrylate compolmd having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having an a~erage molecular weight of up to about 1500. Examples of such compounds incl~de trimethylol propane trimethacrylate, trimethylol propane triacrylate, pentaerythritol tetracrylate, triethylene glycol diacrylate tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3 butylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate or polyoxyethylene glycol dimethacrylate (preferred), pentaerythritol triacrylate, 1,6-hexanediol diacrylate, polypropylene glycol dimethacrylate, polyethylene propylene glycol diacrylate, and so forth and mixtures thereof.
Since some of these reactive polyfunctional monomers may be made by reacting unsaturated acids and alcohols~ they may contain some 0~ andVor COOH groups. m e reactive polyfunctional monomers may be used generally in an amount of from about 0 to 120 parts by weight per 100 parts by weight of the polymerizable oligomer.
The unsaturated materials mentioned above, thus, are used in an amount sufficient to provide on cure (e.g., polymerization, copolymeriæation and/or crosslinking) a thermoset composition.
m e monoethylenically unsaturated compound having a -C O-group and having a -N ~ , -NH- and/or -OH group (like hydroxy propyl methacrylate) or the liquid copolymerizable acrylate compound having from 2 to ~ vinyl groups and being free of urethane, cycloaliphatic and aromatic groups (like Folyethylene glycol dimethacr~late), or both of these compounds, should be used in the in-mold coating composition where after curing it is to be painted with a water based system.
To prevent premature gelation of the ethylenically unsaturated materials and to provide for improved shelf-life or storayeability inhibitors are added in the desired arnount to the composition or are provided in the raw materials before use.
Examples of inhibitors are hydroquinone, benzo~uinone, p-t-butyl catechol and the lilce and mixture thereof.
The in mold composition additionally op~ionally can be filled or comFounded to give the desired viscosity and flow to the composition for molding and to afford the desired physical properties to the resulting thermoset coating. Fillers, also, may improve adhesion. Examples of such fillers or comFounding ingredients are fillers like clay, talc, MgO, Mg(OH)2, CaC03 and silica, other mold release agents, red iron oxide, TiO2, carbon black including conductive carbon black~ color piyments~
antidegradants, U-V absorbers, calcium silicate, paraffin wax~
hollow glass or resin micro-spheres, thickening a~ents, other low shrink additives and the like. One preferred filler is talc which may be used in an amount of from about 50 to 150 parts by weight per 100 parts by weiyht of the pol~nerizable oligomer.
The use of an electroconductive filler like conductive carbon ~, _ 9 _ black enables the coating to be painted by standard electrostatic painting techniquesO Such conductive carbon black may be used in an amount of from about 5 to 15 parts by weight per 100 parts by weight of the polymerizable oligomer. l'hese 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. It is not desirable to use in the in-mold composition of this invention materials like carbo~lated butadiene-styrene block copolymers or fatty alcohol phosphates.
For ease in handling, materials like polyvinylacetate may be dissolved in a reactive monomer like styrene. The viscosity of the oligomers may be reduced by dilution with styrene and the like. The ingredients of the in-mold composition should be readily mixed and handled at ambient or room temperature or temperatures below the polymerizatio~ temperature so that they may be readily pumped to the mold and injected into the same.
The ingredients may be warmed or heated before Gr during mixing and mixed in steps to facilitate thorough mixing, dispersion and solution of the same.
With the peroxide initiator or catalyst the in-mold composition exhibits a shelf-life at room temperature (about 25C) of about a week, and without the initiator it exhibits a shelf life of severa] months at room temperature. The initiator is preferably added to the composition and thoroughly mixed therewith just before molding.
A11 of the ingredients of the in-mold coating comp~sition should be kept dry or have a minimal amount of moisture or the water content should be controlled to obtain reproducible results and to prevent pore formation.
Mixing o~ the ingredients of the in mold composition should be thorough. Injection or compression, transfer molding, or other molding apparatus or machines can be used ~or the in-mold coating. Molding apparatus and methods may be found in U.SO
Patents Nos. 4,076,780; 4,076,788; 4,081,578; 4,082,486,
4,189,517; 4,222,929; 4,245,006, 4,239,796 and 4,239,808. Please see, also, "Proceedings of the Thirty-Second Annual Conference Reinforced Plastics/Composites Institute," SPI, Washington,
5 February, 1977, Griffith et al, Section 2-C, pages 1-3 and "33rd Annual Technical Conference, 1978 Reinforced Plastics/Composites Institute The Society of the Plastics Industry, Inc.," SPI, Ongena, Section 14-B, pages 1-7. The in-mold coating composition can be applied to the substrate and cured at a temperature of from about 290 to 310F. and at a pressure of about 1000 p.s~i.
for from about 0.5 to 3 minutesO
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, appliance and electrical components, furniture, machine covers and guards, bathroom components, structural panels and so forth. The glass fiber reinforced thermoset plastic (FRP~ such as the polyester resin or vinyl ester resin and glass fiber composition substrate to which the in-mold composition is applied can be a sheet molding compound (SMC) or a bulk molding compound (B-~), or other thermosetting FRP material as well as a high strength molcJing compound (HMC) or a thick molding col~pound. The E~P substrate can have from abou~ 10 to 75% by weight of glass fiber~. Ihe SMC
compound usually contains from about 25 to 30% by weight of glass fibers while the HMC compound may contain from about 55 to 60~ by weight of glass fibers. The glass fiber reinforced thermoset plastic (FRP) substrate can be rigid or semirigid (may contain a flexibilizing moiety such as an adipate group in the polyester).
The substrate, also~ may contain other flexibilizing polymers, the elastomers and plastomers, such as the styrene-butadiene block copolymers. Unsaturated polyester glass fiber therm~sets are known as sho~n by "Modern Plastics Encyclopedia~" 1975-1976, October, 1975, Vol. 52, Nb. 10A, McGraw-Hill, Inc.~ New York pages 61, 62 and 105 to 107; "~odern Plastics Encyclopedia,'1 ., 1979-1980, October, 1979, Volume 56, Number 10A, pages 55, 56, 58, 147 and 14~ and "Modern Plastics Encyclopedia," 1980-81, October, 1980, Volume 57, Number 10A, pages 59, 60, and 151 to 153, McGraw-Hill, Inc., New York, N~Yo For information on vinyl ester resins see the Shell Chemical Company Technical sulletins mentioned above.
The compositions of the present invention can exhibit good pumpability and flow in the mold. They can give rapid cures as low as 75 to 90 seconds at 300F. They, also, show good adhesion to paints and can be used not only as an in-mold coating to cover blemishes but as a good conductive coating for electrostatic painting and as a primer for most paint finish systems such as soluble acrylic lacquers, acrylic dispersion lacquers, water borne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersion and urethanes.
The following examples will serve to illustrate the present invention with more particularity to those skilled in the art.
In these examples, the parts are parts by weight unless otherwise indicated.
Example 1 The following ingredients were mixed together:
Parts By We ~
Ingredient - A B C D E
uvl~r~ * 783 150 180 180 225 150 CI~MLINK*600 180 90 - - 90 Hydroxypropyl - 9p - 90 180 methacrylate Styrene 90 135 51 90 45 2% Benzoquinone 13.5 15 9 12 15 in styrene * Trade Mark Then the following ingredients were mixed in:
Zinc stearate 1.62 1.8 1.08 1.53 1.89 Cobalt octoate .54 .6 .36 .51 ,63 (12% as Co in mineral oil) The following ingredients were then mixed in:
W LC~N Carbon Black 27 30 18 25.5 31.5 Talc (630) 159 180 108 156 192 To each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold composition.
The in-mold composition exhibited the following properties:
G~l Time at 230F 7.3/330 9.1/336 4.5/316 7.7/318 14.4/320 minutes/peak temp. F
Brookfield viscosity 8800 6200 160008400 7600 at 86F, #7 spindle at 100 rpm The above compositions were then in-mold coated onto substrates of molded therrrloset conventional polyester-s~trene-glass fibers compositions (about 25~ glass fibers~
containing in some instances additionally a carboxylated butadiene-styrene block copolymer at 1,000 psi and 300F for about 2 minutes. Ihe overall results obtained for the cured in-rnold coating compositions are shown below:
* Trade Mark a~
~ 13 ~
Hot strength Marginal Marginal Marginal Marginal Marginal (Delamination on opening ~old) A~hesion to Pass Pass Marginal Marginal Pass substrate at best to pass Phase separation Yes Yes Yes None Yes (Surface (minor) (minor?) continuity or appearance of coating) Conductivity 160-165 165+ 15Q-160 155 165+
(Ransberg meter reading) Hardness, pencil Fails Pass Pass Pass Pass Finish Properties Good Good Poor* Good Gbod (Paint Acceptahility) *rDb water based acrylics. Good for acrylic lacquers.
Example 2 r~he method of this example was similar to that of Example 1, above, except for the noted changes. I~e results obtained on in-mold coating were satisfactory~
rrhe following ingredients were mixed together:
Parts By Wei~ht Ingredient F G
UVIrHANE 783 100 75 Hydroxypropyl 30 20 Methacrylate Styrene 30 10 2~ Benzoquinone 5 5 in styrene Then the following ingredients were mixed in:
Zinc stearate .675 .675 Cobalt octoate ~225 .225 (12% as Co in 5mineral oil) Calcium stearate .675 .675 The following ingredients were then mixed in:
W LCAN carbon black 11 11 Talc 70 70 Ib each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold composition.
rrhe resulting in-mold compositions, F and G, passed all of the tests shown for Runs A to E of Example 1, abo~e.
This example illustrates a preferred method for preparation of the in-mold coating composition prior to in- ld coating and curing. m e ingredients were mixed in the order as shown below:
LP 90 100.0 pbw CHEMLINK 600 25.0 pbw -Hydroxypropyl Methacrylate 20.0 pbw 2% Benzoquinone in Styrene 5O0 pbw 1. Charge these materials to the reactor and blendO
Styrene 5.0 pbw ) 6.55 pbw Zinc Stearate 00675 pbw Calci~n Stearate 0.675 pbw Cobalt Octoate (12% as 0.~00 pbw Co in mineral oil~
2. Pre-blend the above materials and charge to the reactorO After adding the above charge, heat to 44C ~110F) while mixing.
uvI~rHAN~ 783 ~Preheated to 49C) 75.0 pbw 3O ~dd the UVITHRNE 783 to the reactor and mux until the material is uniform. Cool to 38C (100F).
35 VULC~N carbon black 11.0 pbw
for from about 0.5 to 3 minutesO
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, appliance and electrical components, furniture, machine covers and guards, bathroom components, structural panels and so forth. The glass fiber reinforced thermoset plastic (FRP~ such as the polyester resin or vinyl ester resin and glass fiber composition substrate to which the in-mold composition is applied can be a sheet molding compound (SMC) or a bulk molding compound (B-~), or other thermosetting FRP material as well as a high strength molcJing compound (HMC) or a thick molding col~pound. The E~P substrate can have from abou~ 10 to 75% by weight of glass fiber~. Ihe SMC
compound usually contains from about 25 to 30% by weight of glass fibers while the HMC compound may contain from about 55 to 60~ by weight of glass fibers. The glass fiber reinforced thermoset plastic (FRP) substrate can be rigid or semirigid (may contain a flexibilizing moiety such as an adipate group in the polyester).
The substrate, also~ may contain other flexibilizing polymers, the elastomers and plastomers, such as the styrene-butadiene block copolymers. Unsaturated polyester glass fiber therm~sets are known as sho~n by "Modern Plastics Encyclopedia~" 1975-1976, October, 1975, Vol. 52, Nb. 10A, McGraw-Hill, Inc.~ New York pages 61, 62 and 105 to 107; "~odern Plastics Encyclopedia,'1 ., 1979-1980, October, 1979, Volume 56, Number 10A, pages 55, 56, 58, 147 and 14~ and "Modern Plastics Encyclopedia," 1980-81, October, 1980, Volume 57, Number 10A, pages 59, 60, and 151 to 153, McGraw-Hill, Inc., New York, N~Yo For information on vinyl ester resins see the Shell Chemical Company Technical sulletins mentioned above.
The compositions of the present invention can exhibit good pumpability and flow in the mold. They can give rapid cures as low as 75 to 90 seconds at 300F. They, also, show good adhesion to paints and can be used not only as an in-mold coating to cover blemishes but as a good conductive coating for electrostatic painting and as a primer for most paint finish systems such as soluble acrylic lacquers, acrylic dispersion lacquers, water borne acrylic enamels, high solids solution acrylic enamels, acrylic non-aqueous dispersion and urethanes.
The following examples will serve to illustrate the present invention with more particularity to those skilled in the art.
In these examples, the parts are parts by weight unless otherwise indicated.
Example 1 The following ingredients were mixed together:
Parts By We ~
Ingredient - A B C D E
uvl~r~ * 783 150 180 180 225 150 CI~MLINK*600 180 90 - - 90 Hydroxypropyl - 9p - 90 180 methacrylate Styrene 90 135 51 90 45 2% Benzoquinone 13.5 15 9 12 15 in styrene * Trade Mark Then the following ingredients were mixed in:
Zinc stearate 1.62 1.8 1.08 1.53 1.89 Cobalt octoate .54 .6 .36 .51 ,63 (12% as Co in mineral oil) The following ingredients were then mixed in:
W LC~N Carbon Black 27 30 18 25.5 31.5 Talc (630) 159 180 108 156 192 To each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold composition.
The in-mold composition exhibited the following properties:
G~l Time at 230F 7.3/330 9.1/336 4.5/316 7.7/318 14.4/320 minutes/peak temp. F
Brookfield viscosity 8800 6200 160008400 7600 at 86F, #7 spindle at 100 rpm The above compositions were then in-mold coated onto substrates of molded therrrloset conventional polyester-s~trene-glass fibers compositions (about 25~ glass fibers~
containing in some instances additionally a carboxylated butadiene-styrene block copolymer at 1,000 psi and 300F for about 2 minutes. Ihe overall results obtained for the cured in-rnold coating compositions are shown below:
* Trade Mark a~
~ 13 ~
Hot strength Marginal Marginal Marginal Marginal Marginal (Delamination on opening ~old) A~hesion to Pass Pass Marginal Marginal Pass substrate at best to pass Phase separation Yes Yes Yes None Yes (Surface (minor) (minor?) continuity or appearance of coating) Conductivity 160-165 165+ 15Q-160 155 165+
(Ransberg meter reading) Hardness, pencil Fails Pass Pass Pass Pass Finish Properties Good Good Poor* Good Gbod (Paint Acceptahility) *rDb water based acrylics. Good for acrylic lacquers.
Example 2 r~he method of this example was similar to that of Example 1, above, except for the noted changes. I~e results obtained on in-mold coating were satisfactory~
rrhe following ingredients were mixed together:
Parts By Wei~ht Ingredient F G
UVIrHANE 783 100 75 Hydroxypropyl 30 20 Methacrylate Styrene 30 10 2~ Benzoquinone 5 5 in styrene Then the following ingredients were mixed in:
Zinc stearate .675 .675 Cobalt octoate ~225 .225 (12% as Co in 5mineral oil) Calcium stearate .675 .675 The following ingredients were then mixed in:
W LCAN carbon black 11 11 Talc 70 70 Ib each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold composition.
rrhe resulting in-mold compositions, F and G, passed all of the tests shown for Runs A to E of Example 1, abo~e.
This example illustrates a preferred method for preparation of the in-mold coating composition prior to in- ld coating and curing. m e ingredients were mixed in the order as shown below:
LP 90 100.0 pbw CHEMLINK 600 25.0 pbw -Hydroxypropyl Methacrylate 20.0 pbw 2% Benzoquinone in Styrene 5O0 pbw 1. Charge these materials to the reactor and blendO
Styrene 5.0 pbw ) 6.55 pbw Zinc Stearate 00675 pbw Calci~n Stearate 0.675 pbw Cobalt Octoate (12% as 0.~00 pbw Co in mineral oil~
2. Pre-blend the above materials and charge to the reactorO After adding the above charge, heat to 44C ~110F) while mixing.
uvI~rHAN~ 783 ~Preheated to 49C) 75.0 pbw 3O ~dd the UVITHRNE 783 to the reactor and mux until the material is uniform. Cool to 38C (100F).
35 VULC~N carbon black 11.0 pbw
6~
4. Add the carbon black to the reactor and mix for 30 minutes. Hold the temperature at 38C (100F).
Talc (BEAV~R WHITE 200) 70.0 pbw 5. Add the talc to the reactor and mix for 1 hour while holding the temperature at 38C (100F). Remcve sample.
6. Check the gel time. If below 8 rrlinutes, add 1 pbw of 2~ benzoquinone in styrene and mix for 30 minutesO ~echeck the gel time. Repeat the above procedure until the gel time is between 8 to 10 minutes.
4. Add the carbon black to the reactor and mix for 30 minutes. Hold the temperature at 38C (100F).
Talc (BEAV~R WHITE 200) 70.0 pbw 5. Add the talc to the reactor and mix for 1 hour while holding the temperature at 38C (100F). Remcve sample.
6. Check the gel time. If below 8 rrlinutes, add 1 pbw of 2~ benzoquinone in styrene and mix for 30 minutesO ~echeck the gel time. Repeat the above procedure until the gel time is between 8 to 10 minutes.
7. Subtract the total number of the pbw of 2~ benzoquinone in styrene additions made from the number 5 and add the difference as styrene. Mix Eor 30 minutes, degas for 15 minutes and filter through a 60 mesh screen. Store at 45F.
Brookfield Viscosity 86F, #7 Spindle @ 100 rFm, 13,000 -15,000.
Gel Time, * 230F. 8-10 minutes *1.0 pbw of TBPB/100 pbw total composition. ~nen making up material for checking the gel time, weigh out 100.0 gms total composition and add 1.00 gm of TBPB and mix thoroughly before running gel test~ pbw - parts by weight.
Exam~le 4 The method of this example was sirnilar to the preceding examples:
Pa~
-25 Inqredient H I J K
, _ __ _ E~OCRYL*370 75 CHEMPOL*4825 75 WI~ER*580 75 30 ALTAC*382 E 75 C~EMLINK~60025 25 25 25 Hydroxypropyl 20 20 20 20 methacrylate Styrene 10 10 10 10 * Trade Ma:rk ~ .
Example 4 ~Cont'd) 2% ben~oquinone 5 5 5 5 in styrene Zinc stearate 0.675 0.675 0.675 0.675 Calci~m stearate0.675 0.675 0.675 0.675 Cobalt octoate 0.225 0.225 0.225 00225 (12% as Co in mineral oil) VULC~N 11 11 11 11 carbon black 200, Talc To each composition 1 part by weigh~ of the initiator TBPB
was added per 100 parts by weight of the total in-mold coating composition.
Gel Time at 230F5.75/3148~3/32415.9/3228.7/323 Brookfield viscosity 12,800 10,200 at 86F, #7 spindle at 100 rpm In-mold coating properties 011 molded thermoset glass fiber-FlYester-styrene substrates:
Hot Strength Good Marginal Good Adhesion (scapel, a Pass Pass Fail severe test) to substrate Release from moldGood ~ood Good Did not mold well poor flow along with poor release Phase separationNone Nbne None Cond~ctivity 165 160-165 165 (Ransberg meter reading) ~ D~ Z9 Example 5 The method of this example was similar to the preceding examples:
Parts bY Wei~ht 5 Ingredient L M N O
Polyester 75 WIMER*530 75 C~EMLINK*600 25 25 25 25 Hydroxypropyl 20 20 20 20 methacrylate Styrene 10 - 10 2% benzoquinone 5 5 5 5 in styrene Zinc stearate 0.675 0.675 0.675 0.675 Calcium stearate0.675 0.675 0.675 0.675 Cobalt octoate 0.225 0.225 l0.225 0.225 (12% as Co in mineral oil) W LCAN carbon black 11 11 11 11 8EAV~R W~IIT~* 70 70 70 70 200, l'alc lb each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold coating composition.
Gel Time at 230F14.9/3086.1/3227.5/33425.3/248 Brookfield viscosity 17,60014,400 - -at 86F, #7 spindle at 100 rpm * Trade Mark ~,"~. ' .
Example 5 (cont'd) In-mold coating properties on molded thermoset glass fiber-polyester-styrene substrates:
Hot Strength Good Marginal Good Poor 5 Adhesion (scapel, a Pass Pass Fail severe test) to substrate Release ~rom mold Good Good Good Did not mold well - poor cure caused sticking and poor release Phase separation None Yes Excessive Conductivity 165 165 (Ransberg meter reading) O~ Examples 4 and 5 Runs H, I and L were the best.
Notes For Examples: `-LP-90 - BAKEI.ITE LP-90 - 40~ by weight of polyvinyl acetate in styrene, viscosity of 1,800 centipoises at 25C. (Model LVr Broo~field viscometer #4 spindle at 60 rpm), specific gravity 20/20C. (H2O = 1) of 1.008 and solidification temperature of 5C. lh ion Carbide Corp.
UVITHANE*783, a polymerizable urethane based material or oligomer, a diacrylate terminated polyesterurethane peepolymer.
A viscous liquid (Kg/1 1.3 at 25C) having a viscosity at 49C of 600-2000 poise and at 82C of 50-110 poise, having an unsaturation (equiv./100 grams) of 0.17-0.205 and having an isocyanate content (~) of .3 max. Thiokol/Chemical Division, Thiokol Corporation.
CHEMLINK 600 or CL 600 - Polyoxyethylene glycol 600 dimethacrylate. Molecular ~eight of about 770O C36H66017.
The Ware Chemical Corp.
* Trade Mark 6~
VUL Q N - XC-72B. N472. Conductive furnace carbon black.
Cabot Corp.
Talc - hydrous magnesium silicate TBPB - tertiary butyl perbenzoate.
EPCC~YL 370 - Non-volatile diacrylate ester of a liquid Bisphenol A epoxy resin haviny a viscosity, poise, 25C ~100 resin) of 9,000; an acidity eq./100 G of 0~007î an epoxide eq./100 G of 0.02; a Gardner color of 4; a weight/volume, lb/U.S.
Gal, of 9.99; a flash point, C ~ 204 and a viscosity, Gardner, 25C (80% w resin in xylene) of V-Y. Shell Chemical Co.
CHEMPOL 4825 - (19-4325) Solvent free epoxy acrylate resin which contains active acrylic unsaturation on the polymer molecule. It has an acid nur~ber of 3-10; a color of 1-4; a viscosity, centipoise, of 4000-6000 at 140F and 1400-1800 at 160F and a weight per gallon of 9.8-10.0 lbs. It may contain up to 2% by weight of free acrylic acid. Freeman Chemical Corp.
UMIVER 580 - A polyethylenically unsaturated liquid oligomer having a high reactivity in free radical polymerization. An amber colored liquid at room temperature having a mild characteristic odor. It has a viscosity ~Gardner-Holdt) Z6-z7 1200-500 poises), a color (Gardner-Holdt) of 3 max., a weight of 9.6 ~ 0.1 lbs/U.S. gallon and a flash point (closed cup) of 210F (approx.). Polychrome Corporation.
ATLAC 382 E - It is a sisphenol ~ - polyester resin. ICI
Americas Inc.
UVlTHPNE 893 - A polymeri~able urethane oligomer, a viscous liquid. It has a color, APHA, of 110 maxO; a mild odorj a weight of 10 lbs/gal at 77F; viscosity poises of 900-2200 at 1~0F, 80-laO at 160F and 30-80 at 180F; an unsaturation equiv/100 9.
of 0.150-0.175 and an isocyanate content of 0.2~ max. Thiokol Corporation .
Polyester - A polyester made by the copolylneri~ation of propylene oxide, ethylene oxide, rnaleic anhydride~ fumaric acid and phthalic anhydride using a double metal cyanide catalyst. It ~L736~
has been isomerized, and is O~ terminated and has a molecular weight of about 1200.
UVIMER 530 - A polyethylenically unsaturated liquid oligomer with extremely high reactivity in free radical polymerization. It has a viscosity (Gardner-Holdt) Z7-z8 (375-600 poises); a color (Gardner-Holdt) of 5 max.; a weight of 9.8 + 0.05 lbs. per U.S. gallon and a flash point (closed cup) of 210F (approx.). Polychrome Corporation.
NUPOL 46~012 - A mixture of 70% acrylate terminated polymer, 28% styrene and 2~ hydroxyethyl methacrylate.
Brookfield Viscosity 86F, #7 Spindle @ 100 rFm, 13,000 -15,000.
Gel Time, * 230F. 8-10 minutes *1.0 pbw of TBPB/100 pbw total composition. ~nen making up material for checking the gel time, weigh out 100.0 gms total composition and add 1.00 gm of TBPB and mix thoroughly before running gel test~ pbw - parts by weight.
Exam~le 4 The method of this example was sirnilar to the preceding examples:
Pa~
-25 Inqredient H I J K
, _ __ _ E~OCRYL*370 75 CHEMPOL*4825 75 WI~ER*580 75 30 ALTAC*382 E 75 C~EMLINK~60025 25 25 25 Hydroxypropyl 20 20 20 20 methacrylate Styrene 10 10 10 10 * Trade Ma:rk ~ .
Example 4 ~Cont'd) 2% ben~oquinone 5 5 5 5 in styrene Zinc stearate 0.675 0.675 0.675 0.675 Calci~m stearate0.675 0.675 0.675 0.675 Cobalt octoate 0.225 0.225 0.225 00225 (12% as Co in mineral oil) VULC~N 11 11 11 11 carbon black 200, Talc To each composition 1 part by weigh~ of the initiator TBPB
was added per 100 parts by weight of the total in-mold coating composition.
Gel Time at 230F5.75/3148~3/32415.9/3228.7/323 Brookfield viscosity 12,800 10,200 at 86F, #7 spindle at 100 rpm In-mold coating properties 011 molded thermoset glass fiber-FlYester-styrene substrates:
Hot Strength Good Marginal Good Adhesion (scapel, a Pass Pass Fail severe test) to substrate Release from moldGood ~ood Good Did not mold well poor flow along with poor release Phase separationNone Nbne None Cond~ctivity 165 160-165 165 (Ransberg meter reading) ~ D~ Z9 Example 5 The method of this example was similar to the preceding examples:
Parts bY Wei~ht 5 Ingredient L M N O
Polyester 75 WIMER*530 75 C~EMLINK*600 25 25 25 25 Hydroxypropyl 20 20 20 20 methacrylate Styrene 10 - 10 2% benzoquinone 5 5 5 5 in styrene Zinc stearate 0.675 0.675 0.675 0.675 Calcium stearate0.675 0.675 0.675 0.675 Cobalt octoate 0.225 0.225 l0.225 0.225 (12% as Co in mineral oil) W LCAN carbon black 11 11 11 11 8EAV~R W~IIT~* 70 70 70 70 200, l'alc lb each composition 1 part by weight of the initiator TBPB
was added per 100 parts by weight of the total in-mold coating composition.
Gel Time at 230F14.9/3086.1/3227.5/33425.3/248 Brookfield viscosity 17,60014,400 - -at 86F, #7 spindle at 100 rpm * Trade Mark ~,"~. ' .
Example 5 (cont'd) In-mold coating properties on molded thermoset glass fiber-polyester-styrene substrates:
Hot Strength Good Marginal Good Poor 5 Adhesion (scapel, a Pass Pass Fail severe test) to substrate Release ~rom mold Good Good Good Did not mold well - poor cure caused sticking and poor release Phase separation None Yes Excessive Conductivity 165 165 (Ransberg meter reading) O~ Examples 4 and 5 Runs H, I and L were the best.
Notes For Examples: `-LP-90 - BAKEI.ITE LP-90 - 40~ by weight of polyvinyl acetate in styrene, viscosity of 1,800 centipoises at 25C. (Model LVr Broo~field viscometer #4 spindle at 60 rpm), specific gravity 20/20C. (H2O = 1) of 1.008 and solidification temperature of 5C. lh ion Carbide Corp.
UVITHANE*783, a polymerizable urethane based material or oligomer, a diacrylate terminated polyesterurethane peepolymer.
A viscous liquid (Kg/1 1.3 at 25C) having a viscosity at 49C of 600-2000 poise and at 82C of 50-110 poise, having an unsaturation (equiv./100 grams) of 0.17-0.205 and having an isocyanate content (~) of .3 max. Thiokol/Chemical Division, Thiokol Corporation.
CHEMLINK 600 or CL 600 - Polyoxyethylene glycol 600 dimethacrylate. Molecular ~eight of about 770O C36H66017.
The Ware Chemical Corp.
* Trade Mark 6~
VUL Q N - XC-72B. N472. Conductive furnace carbon black.
Cabot Corp.
Talc - hydrous magnesium silicate TBPB - tertiary butyl perbenzoate.
EPCC~YL 370 - Non-volatile diacrylate ester of a liquid Bisphenol A epoxy resin haviny a viscosity, poise, 25C ~100 resin) of 9,000; an acidity eq./100 G of 0~007î an epoxide eq./100 G of 0.02; a Gardner color of 4; a weight/volume, lb/U.S.
Gal, of 9.99; a flash point, C ~ 204 and a viscosity, Gardner, 25C (80% w resin in xylene) of V-Y. Shell Chemical Co.
CHEMPOL 4825 - (19-4325) Solvent free epoxy acrylate resin which contains active acrylic unsaturation on the polymer molecule. It has an acid nur~ber of 3-10; a color of 1-4; a viscosity, centipoise, of 4000-6000 at 140F and 1400-1800 at 160F and a weight per gallon of 9.8-10.0 lbs. It may contain up to 2% by weight of free acrylic acid. Freeman Chemical Corp.
UMIVER 580 - A polyethylenically unsaturated liquid oligomer having a high reactivity in free radical polymerization. An amber colored liquid at room temperature having a mild characteristic odor. It has a viscosity ~Gardner-Holdt) Z6-z7 1200-500 poises), a color (Gardner-Holdt) of 3 max., a weight of 9.6 ~ 0.1 lbs/U.S. gallon and a flash point (closed cup) of 210F (approx.). Polychrome Corporation.
ATLAC 382 E - It is a sisphenol ~ - polyester resin. ICI
Americas Inc.
UVlTHPNE 893 - A polymeri~able urethane oligomer, a viscous liquid. It has a color, APHA, of 110 maxO; a mild odorj a weight of 10 lbs/gal at 77F; viscosity poises of 900-2200 at 1~0F, 80-laO at 160F and 30-80 at 180F; an unsaturation equiv/100 9.
of 0.150-0.175 and an isocyanate content of 0.2~ max. Thiokol Corporation .
Polyester - A polyester made by the copolylneri~ation of propylene oxide, ethylene oxide, rnaleic anhydride~ fumaric acid and phthalic anhydride using a double metal cyanide catalyst. It ~L736~
has been isomerized, and is O~ terminated and has a molecular weight of about 1200.
UVIMER 530 - A polyethylenically unsaturated liquid oligomer with extremely high reactivity in free radical polymerization. It has a viscosity (Gardner-Holdt) Z7-z8 (375-600 poises); a color (Gardner-Holdt) of 5 max.; a weight of 9.8 + 0.05 lbs. per U.S. gallon and a flash point (closed cup) of 210F (approx.). Polychrome Corporation.
NUPOL 46~012 - A mixture of 70% acrylate terminated polymer, 28% styrene and 2~ hydroxyethyl methacrylate.
Claims (32)
1. A composition useful as a thermosetting molding composition comprising (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) a copolymerizable ethylenically unsaturated monomer, (c) a zinc salt of a fatty acid having at least 10 carbon atoms, (d) an accelerator for a peroxide initiator and (e) polyvinyl acetate in a minor amount by weight as compared to the polymerizable materials and sufficient for paint adhesion, (f) optionally additionally containing a copolymerizable monoethylenically unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) optionally additionally containing for partial replacement of (a) a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1500, (h) optionally additionally containing a calcium salt of a fatty acid having at least 10 carbon atoms and (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition.
2. A composition useful as a thermosetting molding composition comprising (a) 100 parts by weight of a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) from about 80 to 150 parts by weight of a copolymerizable ethylenically unsaturated monomer, (c) from about 0.2 to 5 parts by weight of a zinc salt of a fatty acid having at least 10 carbon atoms, (d) from about 0.05 to 2 parts by weight of an accelerator for a peroxide initiator and (e) from about 40 to 80 parts by weight of polyvinyl acetate, (f) from about 0 to 120 parts by weight of a copolymerizable mono-ethylenically unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) for partial replacement of (a), from about 0 to 120 parts by weight of a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a mole-cular weight of up to about 1500, and (h) from about 0.2 to 5 parts by weight of a calcium salt of a fatty acid having at least 10 carbon atoms.
3. A composition according to claim 2 where said composition contains addi-tionally an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylenically unsaturated materials.
4. A composition according to claim 2 where (a) is a liquid diacrylate terminated polyesterurethane or a diacrylate ester of a liquid Bisphenol A epoxy resin, (b) is styrene, (c) is zinc stearate, (d) is cobalt octoate, (f) is hydroxy propyl methacrylate, (g) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, (h) is calcium stearate and additionally, (i) a filler comprising talc in an amount of from about 50 to 150 parts by weight and conductive carbon black in an amount of from about 5 to 15 parts by weight.
5. A composition according to claim 4 containing additionally up to about 2% by weight of tertiary butyl perbenzoate based on the weight of said ethylenically unsaturated materials.
6. The method which comprises in-mold coating a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) a polymerizable oligomer selected from the group consisting of (1) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) a copolymerizable ethylenically unsaturated monomer, (c) a zinc salt of a fatty acid having at least 10 carbon atoms, (d) an accelerator for a peroxide initiator and (e) polyvinylacetate in a minor amount by weight as compared to the polymerizable materials and sufficient for paint adhesion, (f) optionally additionally containing a copolymerizable monoethylenically unsaturated compound having a -C O- group and a -NH2, -NH- and/or -OH group, (g) optionally additionally containing for partial replacement of (a) a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1500, (h) optionally additionally containing a calcium salt of a fatty acid having at least 10 carbon atoms, (i) optionally additionally containing a filler, said ethylenically unsaturated materials being present in an amount sufficient on curing to provide a thermoset composition, and (j) containing an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylenically unsaturated materials.
7. The method which comprises in mold coating a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) 100 parts by weight of a polymerizable oligomer selected from the group consisting of (l) a polyurethane based oligomer having at least two acrylate groups, (2) an epoxy based oligomer having at least two acrylate groups and (3) a polyester based oligomer having a plurality of internal ethylenically unsaturated groups and mixtures of the same, (b) from about 80 to 150 parts by weight of a copolymerizable ethylenically unsaturated monomer, (c) from about 0.2 to 5 parts by weight of a zinc salt of a fatty acid having at least 10 carbon atoms, (d) from about 0.05 to 2 parts by weight of an accelerator for a peroxide initiator and (e) from about 40 to 80 parts by weight of polyvinylacetate, (f) optionally additionally containing from about O to 120 parts by weight of a copolymerizable monoethylenically unsaturated compound having a -C 0- group and a -NH2 , -NH- and/or -OH
group, (g) optionally additionally containing for partial replacement of (a) from about O to 120 parts by weight of a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1500, (h) optionally additionally containing from about 002 to 5 parts by weight of a calcium salt of a fatty acid having at least 10 carbon atoms, (i) optionally additionally containing a filler and (j) an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylenically unsaturated materials.
group, (g) optionally additionally containing for partial replacement of (a) from about O to 120 parts by weight of a copolymerizable liquid compound having from 2 to 4 vinyl groups, being free of urethane, cycloaliphatic and aromatic groups and having a molecular weight of up to about 1500, (h) optionally additionally containing from about 002 to 5 parts by weight of a calcium salt of a fatty acid having at least 10 carbon atoms, (i) optionally additionally containing a filler and (j) an organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of said ethylenically unsaturated materials.
8. The method according to claim 7 where (a) is a liquid diacrylate terminated polyesterurethane or a diacrylate ester of a liquid Bisphenol A epoxy resin, (b) is styrene, (c) is zinc stearate (d) is cobalt octoate, (f) is hydroxy propyl methacrylate, (g) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770, (h) is calcium stearate and (i) comprises talc in an amount of from about 50 to 150 parts by weight and conductive carbon black in an amount of from about 5 to 15 parts by weight.
9. The method according to claim 8 in which said initiator is tertiary butyl perbenzoate and is used in an amount of up to about 2% by weight.
10. The product produced by the method of claim 6.
11. The product produced by the method of claim 7.
12. The product produced by the method of claim 8.
13. The product produced by the method of claim 9.
14. A composition useful as a thermosetting coating composition comprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups, (b) from about 80 to 150 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, (c) up to about 120 parts by weight of at least one copoly-merizable monoethylenically unsaturated compound having a -CO-group and a -NH2, -NH- and/or -OH group, (d) from about 40 to 80 parts by weight of polyvinyl acetate, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.05 to 2.0 part by weight of at least one accelerator for a peroxide initiator, (g) from about 5 to 15 parts by weight of conductive carbon black, (h) from about 50 to 150 parts by weight of a filler, and (i) up to about 120 parts by weight of a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of up to about 1500 and being selected from the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane based oligomer having two acrylate groups and mixtures of (I) and (II).
15. A composition according to claim 14 containing additionally at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
16. A composition according to claim 14 where (h) comprises talc.
17. A composition according to claim 16 containing additionally at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
18. A composition according to claim 14 containing additionally (j) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
19. A composition according to claim 18 containing additionally at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
20. A composition according to claim 14 containing additionally (j) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight and where (h) comprises talc.
21. A composition according to claim 20 containing additionally at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
22. A composition according to claim 14 where (a) is a diacrylate ester of a liquid Bisphenol A epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (d) is zinc stearate, (e) if cobalt octoate, (f) is talc and (g) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770.
23. A method which comprises in-mold coating a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers with a thermosetting in-mold coating composition under pressure, at a temperature and for a period of time sufficient to cure said in-mold coating composition to form an adherent thermoset coating on said molded thermoset resin glass fiber composition, said in-mold coating composition comprising (a) 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups, (b) from about 80 to 150 parts by weight of at least one copolymerizable ethylenically unsaturated monomer, (c) up to about 120 parts by weight of at least one copoly-merizable monoethylenically unsaturated compound having a -CO-group and a -NH2, -NH- and/or -OH group, (d) from about 40 to 80 parts by weight of polyvinyl acetate, (e) from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, (f) from about 0.05 to 2.0 part by weight of at least one accelerator for a peroxide initiator.
(g) from about 5 to 15 parts by weight of conductive carbon black, (h) from about 50 to 150 parts by weight of a filler, (i) up to about 120 parts by weight of a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of up to about 1500 and being selected from the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane oligomer having two acrylate groups and mixtures of (I) and (II) and at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
(g) from about 5 to 15 parts by weight of conductive carbon black, (h) from about 50 to 150 parts by weight of a filler, (i) up to about 120 parts by weight of a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of up to about 1500 and being selected from the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane oligomer having two acrylate groups and mixtures of (I) and (II) and at least one organic free radical peroxide initiator in an amount of up to about 5% by weight based on the weight of the polymerizable ethylenically unsaturated materials.
24. A method according to claim 23 where (h) comprises talc.
25. A method according to claim 23 where said in-mold coating composition contains additionally (j) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
26. A method according to claim 23 where said in-mold coating composition contains additionally (j) at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight and where (h) comprises talc.
27. A method according to claim 23 where (a) is a diacrylate ester of a liquid Bisphenol A epoxy resin, (b) is styrene, (c) is hydroxypropyl methacrylate, (d) is zinc stearate, (e) is cobalt octoate, (f) is talc, (g) is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770 and said initiator is tertiary butyl perben-zoate.
28. A laminate comprising an adherent, thermoset in-mold coating composition in-mold coated onto a molded thermoset polyester resin or thermoset vinyl ester resin glass fiber composition containing from about 10 to 75% by weight of glass fibers, said in-mold coating composition comprising the reaction product of 100 parts by weight of at least one polymerizable epoxy based oligomer having at least two acrylate groups from about 80 to 150 parts by weight of at least one copolymerizable ethylenical-ly unsaturated monomer, up to about 120 parts by weight of at least one copolymerizable monoethylenically unsaturated compound having a -CO- group and a -NH2, -NH- and/or -OH group and up to about 120 parts by weight of a copolymerizable or cocurable diacrylate compound having a weight average molecular weight of up to about 1500 and being selected from the group consisting of (I) at least one polyoxyalkylene glycol oligomer having two acrylate groups, and (II) at least one polyurethane oligomer having two acrylate groups and mixtures of (I) and (II) in admixture with from about 40 to 80 parts by weight of polyvinyl acetate, from about 0.2 to 5 parts by weight of at least one zinc salt of a fatty acid having at least 10 carbon atoms, from about 5 to 15 parts by weight of conductive carbon black and from about 50 to 150 parts by weight of a filler.
29. A laminate according to claim 28 in which in said in-mold coating composition said filler comprises talc.
30. A laminate according to claim 28 in which said in-mold coating composition contains additionally at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight.
31. A laminate according to claim 28 in which said in-mold coating composition contains additionally at least one calcium salt of a fatty acid having at least 10 carbon atoms in an amount of from about 0.2 to 5 parts by weight and where in said in-mold composition said filler comprises talc.
32. A laminate according to claim 28 in which in said in-mold coating composition said epoxy based oligomer is a diacrylate ester of a liquid Bisphenol A epoxy resin, said ethylenically unsaturated monomer is styrene, said monoethylenically unsaturated compound is hydroxy propyl methacrylate, said copolymerizable or cocurable compound is polyoxyethylene glycol dimethacrylate having a molecular weight of about 770 and said filler comprises talc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31659281A | 1981-11-02 | 1981-11-02 | |
| US316,592 | 1981-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1186429A true CA1186429A (en) | 1985-04-30 |
Family
ID=23229708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000408586A Expired CA1186429A (en) | 1981-11-02 | 1982-08-03 | In-mold coating |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS6019941B2 (en) |
| AU (1) | AU533510B2 (en) |
| BR (1) | BR8205098A (en) |
| CA (1) | CA1186429A (en) |
| DE (1) | DE3229292C2 (en) |
| ES (1) | ES515071A0 (en) |
| FR (1) | FR2515666B1 (en) |
| GB (1) | GB2108987B (en) |
| IT (1) | IT1195951B (en) |
| MX (1) | MX173523B (en) |
| SE (1) | SE455947B (en) |
| ZA (1) | ZA825562B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1338542C (en) * | 1982-09-13 | 1996-08-20 | Leonard Ornstein | Specimen mounting adhesive composition |
| US4515710A (en) * | 1983-07-18 | 1985-05-07 | Gencorp Inc. | In-mold coating composition |
| JPS6160764A (en) * | 1984-09-03 | 1986-03-28 | Dainichi Seika Kogyo Kk | Coating composition for thin metallic film |
| JPS62143917A (en) * | 1985-12-17 | 1987-06-27 | Nippon Retsuku Kk | Resin composition for use in electronic parts sealing |
| DE3642527A1 (en) * | 1986-12-12 | 1988-06-23 | Hans Ing Grad Germar | Process for producing GRP mouldings with tough and resilient polyurethane surfaces and moulding produced according to this process |
| EP0311288A3 (en) * | 1987-09-30 | 1992-01-08 | Westinghouse Electric Corporation | Improvements in or relating to resin compositions curable with ultraviolet light |
| DE3839940A1 (en) * | 1988-11-26 | 1990-05-31 | Stockhausen Chem Fab Gmbh | Aqueous polyurethane and polyurethane-urea dispersions, and process for the flocking of elastomeric mouldings using these dispersions |
| US5084353A (en) * | 1989-05-12 | 1992-01-28 | Gencorp Inc. | Thermosetting in-mold coating compositions |
| JP2600519B2 (en) * | 1990-08-13 | 1997-04-16 | いすゞ自動車株式会社 | FRP molding plating method |
| JP2686682B2 (en) * | 1991-10-16 | 1997-12-08 | いすゞ自動車株式会社 | Manufacturing method of molded products |
| DE69408195T2 (en) * | 1993-04-26 | 1998-11-05 | Gencorp Inc | Conductive molded coatings |
| JP3404546B2 (en) * | 1995-03-23 | 2003-05-12 | 大日本塗料株式会社 | Mold coating method |
| DE19528929C2 (en) * | 1995-08-07 | 1999-07-01 | Feron Aluminium | Process for the production of plastic films which are used for the production of film capacitors |
| WO2004085549A2 (en) * | 2003-03-19 | 2004-10-07 | Omnova Solutions Inc. | Optical quality coating |
| JP2007313395A (en) * | 2006-05-24 | 2007-12-06 | Rimtec Kk | In-mold coating method and coated molding |
| WO2022018136A1 (en) | 2020-07-21 | 2022-01-27 | Ncapt Ab | METHOD FOR SURFACE TREATMENT PRIOR TO COATING and GLUING |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2104575B2 (en) * | 1970-02-02 | 1980-04-10 | Union Carbide Corp., New York, N.Y. (V.St.A.) | Low shrinkage curable unsaturated polyester compositions |
| GB1468936A (en) * | 1973-08-29 | 1977-03-30 | Mitsubishi Rayon Co | Unsaturated polyester moulding composition and coated moulded article thereof |
| CA1096082A (en) * | 1976-11-01 | 1981-02-17 | Kenneth E. Atkins | Uniformly pigmented, low shrinking polyester molding compositions |
| DE2846573A1 (en) * | 1978-10-26 | 1980-05-08 | Roehm Gmbh | LIQUID TO PASTE-SHAPED, LOCKABLE PLASTIC MATERIAL |
| US4189517A (en) * | 1978-11-08 | 1980-02-19 | The General Tire & Rubber Company | Low-shrink in-mold coating |
| DE2851340A1 (en) * | 1978-11-28 | 1980-06-04 | Bayer Ag | Copolymerisable moulding compsns. based on unsatd. polyurethane(s) - for containers, vehicle parts, etc, with improved impact strength |
| JPS5580423A (en) * | 1978-12-13 | 1980-06-17 | Hitachi Chem Co Ltd | Low shrinkage unsaturated polyester resin composition |
| DE2914984A1 (en) * | 1979-04-12 | 1980-11-13 | Consortium Elektrochem Ind | METHOD FOR PRODUCING POLYMERISATS |
| US4239808A (en) * | 1979-06-13 | 1980-12-16 | The General Tire & Rubber Company | In-mold coating of sheet molding compound moldings |
-
1982
- 1982-01-04 MX MX190806A patent/MX173523B/en unknown
- 1982-08-02 ZA ZA825562A patent/ZA825562B/en unknown
- 1982-08-03 CA CA000408586A patent/CA1186429A/en not_active Expired
- 1982-08-03 AU AU86709/82A patent/AU533510B2/en not_active Ceased
- 1982-08-03 GB GB08222414A patent/GB2108987B/en not_active Expired
- 1982-08-05 DE DE3229292A patent/DE3229292C2/en not_active Expired
- 1982-08-17 SE SE8204737A patent/SE455947B/en not_active IP Right Cessation
- 1982-08-17 ES ES515071A patent/ES515071A0/en active Granted
- 1982-08-18 FR FR8214270A patent/FR2515666B1/en not_active Expired
- 1982-08-31 BR BR8205098A patent/BR8205098A/en not_active IP Right Cessation
- 1982-09-02 IT IT23105/82A patent/IT1195951B/en active
- 1982-10-29 JP JP57189383A patent/JPS6019941B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT8223105A0 (en) | 1982-09-02 |
| SE455947B (en) | 1988-08-22 |
| DE3229292A1 (en) | 1983-05-11 |
| AU533510B2 (en) | 1983-12-01 |
| FR2515666A1 (en) | 1983-05-06 |
| GB2108987B (en) | 1985-08-21 |
| ES8308344A1 (en) | 1983-08-16 |
| JPS58125762A (en) | 1983-07-26 |
| MX173523B (en) | 1994-03-11 |
| ZA825562B (en) | 1985-11-27 |
| IT1195951B (en) | 1988-11-03 |
| SE8204737L (en) | 1983-05-03 |
| SE8204737D0 (en) | 1982-08-17 |
| BR8205098A (en) | 1983-08-09 |
| GB2108987A (en) | 1983-05-25 |
| JPS6019941B2 (en) | 1985-05-18 |
| FR2515666B1 (en) | 1986-12-26 |
| ES515071A0 (en) | 1983-08-16 |
| DE3229292C2 (en) | 1986-01-16 |
| AU8670982A (en) | 1983-05-12 |
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