MXPA97010292A - Coating compositions in adecuadastal mold as they are for an application of fi use - Google Patents

Abstract

A mold-coating composition for a fiber-reinforced plastic comprises an aliphatic resin such as a saturated aliphatic ester intermediate polyurethane compound having terminal acrylate end groups, a saturated (cyclo) aliphatic (meth) acrylate such as isobornyl acrylate, a Alkyl hydroxyl (meth) acrylate, polyacrylate polyester of an alkylene polyol, and a substituted vinyl aromatic. The mold coating compositions have good end-use weathering properties, so that there is no need for a subsequent paint coat therein, which at other times had been required. The paint-free coating compositions may already be transparent or pigmented and may contain various additives such as lubricants, adhesion aids, hardeners, and the like.

Description

SUITABLE MOLDING COATING COMPOSITIONS SUCH AS EST N FOR A FINAL USE APPLICATION FIELD OF THE INVENTION The present invention relates to a fiber reinforced plastic (FPR) having a mold composition therein, which is suitable as it is for a final use application. More specifically, the invention relates to the use of generally saturated aliphatic resins, which may be transparent or pigmented, and which have similar properties to the paint such as high gloss, hardness, good adhesion, and good weather resistance. , such that they can be used as they are and do not require a coating of paint or other protective coating on them. BACKGROUND OF THE INVENTION Up to now, in-mold coatings have been applied to fiber-reinforced plastics such as sheet-molded coatings to generally provide a smooth surface and reduce or eliminate the porosity of the substrate. However, such coatings have required paint to produce the desirable end-use properties. Typical for mold coatings as set forth in U.S. Patent No. 4,189,517 and U.S. Patent No. 4,222,929, for Shanos i and Cois., Has been the reaction product of an unsaturated fumarate polyester diol, a diol flexibilizer of saturated polyester, an aliphatic degradation polyol having from 3 to 6 hydroxyl groups, a diisocyanide, and an ethylenically unsaturated degradation compound such as styrene. In-mold coating compositions, as set forth in U.S. Patent No. 4,331,735, relate to (a) a liquid degradable composition having an average molecular weight above about 5,000, having a plurality of polymerizable double ethylenic bonds, which are essentially free of active hydrogen atoms or which are essentially free of isocinato groups, (b) a material selected from the group consisting of (I) a polyisocyanate and (II) the reaction product of an excess of equivalents of a polyisocyanate and an ethylenically unsaturated compound having groups of -NH2, -NH- and / or -OH, said reaction product being free of active hydrogen atoms and (c) an organic free radical peroxide initiator in an amount sufficient to execute the solidification of said mold coating composition, said (b) being used in an amount sufficient to ensure adhesion of said mold. coating composition to said molded thermosetting resin glass fiber composition. A large number of mold coatings refers to coating compositions comprising at least one oligomer based on polymerizable epoxy having at least two acrylate groups thereon, at least one copolymerizable ethylenically unsaturated monomer such as styrene, and minus a copolymerizable monoethylenically unsaturated compound having a group of -CO- and a group of -NH2, -NH- and / or -OH, as well as a polyvinyl acetate as set forth in U.S. Patent Nos. 4,414,173 and 4,515,710 for Cobbledick and Cois. Yet another in-mold coating refers to an epoxy-based oligomer having two acrylate end groups, and the like, as set forth in US Patent No. 5,084,353 to Cobbledick. BRIEF DESCRIPTION OF THE DRAWINGS The drawings refer to a graph comparing gloss retention of the present invention with a composition of the commercial white gel layer. SUMMARY OF THE INVENTION Solidified mold coating compositions are made from compounds, which include a saturated polyester urethane acrylate containing a saturated aliphatic polyester intermediate compound and a saturated aliphatic urethane group; and a saturated hydroxyl alkyl (meth) acrylate. further, it has been found that the use of a diacrylate ester of an alkylene diol, a saturated (cyclo) aliphatic (meth) acrylate, and a vinyl substituted aromatic imparts the properties of the paint coating type to the coating composition in mold such as hardness, water resistance, low shrinkage, and high gloss. Optionally, in addition to the above compounds, occasionally, degrading agents such as triallylcyanurate, ethoxylated trimethylpropane triacrylate, pentaerythritol triacrylate, and the like may be used. The above components react in the presence of a peroxide initiator to chain and form a thermosetting resin. The solidified resin is a clear mold coating composition unless it is pigmented. The present invention thus eliminates the additional step, time and cost of applying a paint coating to the surface of a conventional mold coating and forms a final paint FRP free paint laminate. If a transparent coating is not desired, various pigments, colorants, etc. are added to the components to produce a desired final color and opacity.

In order to achieve the mold coating compositions of the present invention, which have paint-like properties, various compounds and resins are avoided, especially aromatic compounds such as polyether urethane intermediates and / or polyesters. aromatics, resins based on aromatic epoxy, and the like. DETAILED DESCRIPTION OF THE INVENTION An important aspect of the present invention, in order to achieve good properties, similar to paint and a transparent color of the mold coating composition, is the use of an intermediate saturated aliphatic polyester urethane, the which contains acrylate groups, generally in the terminal portions of the polymer. The urethane polyester intermediate can be made from aliphatic dicarboxylic acids or aliphatic anhydrides and glycols and are well known in the art and literature as well as the preparation thereof, and are commercially available. The aliphatic dicarboxylic acids and anhydrides have from 1 to 15 carbon atoms and are desirably saturated (ie, they have no unsaturated carbon for carbon double bonds, with specific examples including carbonic acid, malonic acid, succinic acid, glutaric acid, adipic, pimelic acid, suberic acid, azelaic acid, sebacic acid, the anhydride counterparts thereof, and the like, with adipic acid generally being preferred Mixtures of all of the above acids may also be used.Glycols or diols generally have from 2 to 15 carbon atoms and are saturated, with specific examples including ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, pentanediol, hexanediol, cyclohexanedi ethanol of dipropylene glycol, 2,2-dimethyl -l, 3-propanediol, diethylene glycol, pinacol, and the like The preferred glycols include ethylene glycol and neopentyl glycol. The saturated aliphatic polyester intermediate compound generally has a number average molecular weight of from about 1,000 to about 5,000, and desirably from about 1,500 to about 2,500. An aliphatic polyisocyanide reacts with the saturated polyester intermediate to form a resin type polyurethane. The aliphatic portion is saturated and has from about 5 to 18 carbon atoms such as isophorone diisocyanide (IPDI), hexamethylene diisocyanide, cyclohexyl diisocyanide, and the like, with isophorone diisocyanide being preferred. The average equivalent ratio of the NCO groups to the OH end groups of the intermediate compound is from about 1.5 to about 2.5, desirably from about 1.9 to about 2.1, and preferably about 2.0. Such amounts are generally sufficient to form an isocyanate-terminated polyurethane prepolymer which is then reacted with a hydroxyl alkyl acrylate to form the saturated polyester urethane which generally contains an acrylate or a methacrylate at the terminal portions of the hydroxyl chain. polymer. The acrylates may generally have an ester moiety containing from 2 to 10 carbon atoms, such as ethyl, propyl, n-butyl, ethyl exyl, and the like, with ethyl and propyl being preferred. An example of a preferred polyester urethane acrylate is Craynor CN 963, manufactured by Sartomer Corporation, which is a polyester urethane acrylate. Polyester urethane acrylates, which contain aromatic and / or unsaturated polyester intermediates, such as unsaturated and / or aromatic diisocyanates, are avoided, since they can produce a transparent coating or a non-transparent coating with a tendency to become bitter and degrade with maturation. Thus, polyester urethane acrylates are substantially free of such compounds, meaning that they generally contain aromatic and / or unsaturated polyester intermediates in an amount of less than 50 or 25 percent by weight, desirably less than 10 percent by weight and preferably less than 5 percent by weight, or none at all, of such units or groups based on the total weight of such polymer (s). Similarly, generally less than 50 or 25 percent and preferably less than 10 or 5 mole percent, or none at all, of all the diisocyanate groups within the coating composition are aromatic and / or unsaturated groups based on the total moles of the isocyanide required. Other compounds or monomers, which are avoided in the formation of polyester urethane acrylates, are polyethers and epoxy intermediates in view of the fact that they have been found not to produce a mold coating composition, which provides good weather resistance properties. In this manner, the polyurethane intermediate generally contains less than 50 weight percent and generally less than 25 weight percent, and preferably less than 10 percent or 5 weight percent, or none of all of the groups of epoxy and / or polyether based on the total weight of the polyester urethane acrylates. Various compounds or components are used to react with the polyester urethane acrylate and form a thermosetting resin. One such component is a cycloaliphatic or aliphatic (meth) acrylate wherein the cycloaliphatic and / or aliphatic portion is saturated and contains from about 1 to about 50 carbon atoms and desirably from about 2 to about 20 carbon atoms. Representative examples include methyl (meth) acrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, 2- (2-ethoxy) ethoxy ethacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl methacrylate, stearyl methacrylate, lauryl acrylate, methacrylate and glycidyl, isodecyl acrylate, isobornyl methacrylate, isooctyl acrylate, tridecyl acrylate, tridecyl methacrylate, and caprolactone acrylate, with isobornyl acrylate being preferred. The amount of saturated (cyclo) aliphatic (meth) acrylate is generally from about 20 to about 100 parts by weight, desirably from about 35 to about 90 parts by weight, and preferably from about 50 to about 80 parts by weight per 100 parts. total weight of polyester urethane acrylate. Another compound used in the present invention is one or more alkyl hydroxyl (meth) acrylates, wherein the alkyl group may contain from 1 to 5 or 10 carbon atoms, such as, methyl, ethyl, butyl, etc. with propyl being preferred. The amount of such alkyl hydroxyl (meth) acrylates is generally from about 2 to about 20 parts by weight, desirably from about 6 to about 16 parts by weight and preferably from about 8 to about 12 parts by weight per 100 parts by weight of the polyester urethane acrylate. These compounds are used in addition with the alkyl hydroxyl methacrylates used to form the polyester urethane acrylate resins. Yet another component used in the mold coating compositions of the present invention are one or more vinyl substituted aromatics containing a total from 8 to 12 carbon atoms such as styrene, α-methyl styrene, vinyl toluene, t-butyl styrene, and the like, with styrene being preferred. The amount of this component is generally from about 10 to about 70 parts by weight, desirably from about 20 to about 60 parts by weight, and preferably from about 30 to about 50 parts by weight per 100 parts by weight of the polyester urethane acrylate.

Still another component is a polyacrylate such as a triacrylate or preferably a diacrylate ester of an alkylene polyol wherein the polyol has from about 2 to about 30 carbon atoms and preferably from about 2 to about 10 carbon atoms such as diol of ethylene, butane diol, and the like. An acrylate which is contained at both ends of the alkylene polyol is generally derived from acrylic acid or methacrylic acid. Examples of the preferred diacrylate ester of an alkylene diol include triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-dimethacrylate. -butanediol, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,6 hexanediol diacrylate, 1,6 hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate (600), polyethylene glycol diacrylate (200), tetraethylene glycol diacrylate , triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate (400), polyethylene glycol dimethacrylate (400), polyethylene glycol diacrylate (600), propoxylated neopentyl glycol diacrylate, and alkoxylated aliphatic diacrylate. Examples of trifunctional acrylate esters of an alkylene polyol which may optionally be used include tris (3-hydroxyethyl) isocyanate trimethacrylate, trimethylpropane trimethacrylate, trimethylpropane triacrylate, tris (2-ethyl hydroxyl) isocyanurate triacrylate, tris (2-ethyl hydroxyl) isocyanurate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, and propoxylated glyceryl triacrylate. The amount of polyacrylate ester of the alkylene polyol is generally from about 10 to about 40 parts by weight, desirably from about 15 to about 35 parts by weight, and preferably from about 20 to about 30 parts by weight for each 100 parts by weight of polyester urethane acrylate. The optional amount of the triacrylate ester of the alkylene polyol is low and is generally less than 10 parts by weight and preferably less than 5 parts by weight for every 100 parts by weight of the polyester urethane acrylate. The above five components generally form the resin of the mold coating composition of the present invention. The coating composition is transparent. Alternatively, the transparent coating can be colored by using a pigment, a dye, etc., in an effective or desired amount to produce a desired opacity, hue, tint or color. Pigments and pigment dispersions are well known in the art and include, for example, titanium dioxide, natural gas carbon black, blue fatalocyanine, red fatalocyanine, ferric oxides and chromium, and the like. The mold coating compositions of the present invention may also contain conventional additives and fillers, etc., in conventional amounts. In this way, various solidification inhibitors such as benzoquinone, hydroquinone, methoxyhydroquinone, p-t-butylpyrocatechin, and the like can be used.

Another additive is a scrubber such as cobalt octoate. 0, Another class of accelerators includes zinc, or other metal carboxylates. Various light stabilizers can be used such as, for example, the various hindered amines (HALS), substiuid benzophenones, and substituted benztriazoles, and the like. Generally lubricants and mold release agents are used with specific examples that include various metal stearates, such as zinc stearate or stearate of calcium or phosphonic acid esters. Reinforcing fillers such as talc can be used. It was also found that talc helps promote adhesion of the mold coating composition to the fiber reinforced plastic substrate. Another additive is a hardener and thixotrope such as silica. The polyester urethane acrylate and the other solidifying monomers or components of the present invention are chain extended through the use of a free radical initiator such as a peroxide. Examples of suitable free radical initiators include, tertiary butyl perbenzoate, tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide in dimethyl phthalate, dibenzoyl peroxide, di (p-chlorobenzolo) peroxide in dibutyl phthalate, di (2,4-dichlorobenzoyl) peroxide in butylphthalate dilauroyl peroxide, ethyl methyl acetone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,4-dimethyl-l, 2-dioxacyclopentane, t-butylperoxy (2-ethyl-hexanoate), caprylyl peroxide, hexane of 2,5-dimethyl-2,5-di (peroxy benzoyl), 1-hydroxycyclohexyl hexanohydroperoxide-1, t-butyl peroxy (2-ethyl butyrate), hexane of 2, 5-dimethyl-2,5-bis (t-butyl peroxy), cumyl hydroperoxide, diacetyl peroxide, t-butylhydroperoxide, butyl tertiary peroxide, 3,5-dihydroxy-3,5-dimethyl-l, 2-oxacyclopentane, and 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like, and mixtures thereof. Sometimes it is desirable to use mixtures of initiators to take advantage of their different proportions and decay times at different temperatures and so on. A preferred initiator to be used is tertiary butyl perbenzoate. The peroxide initiator should be used in an amount sufficient to overcome the effect of the inhibitor and cause the solidification of the ethylenically unsaturated compounds. In general, the peroxide initiator is used in an amount of above about 5% or from about 0.25 to about 5%, desirably from about 1 to about 4 percent, and preferably from about 1 to about 2% by weight based on to the total weight of all the ethylenically unsaturated components used in the mold coating compositions. The reaction of the polyester urethane acrylate with the solidification components in the presence of the peroxide initiator is generally at a temperature of from about 200 ° F (93 °) to about 330 ° F (165 ° C), and desirably from approximately 270 ° F (132 ° C) to approximately 310 ° F (154 ° C). The mold coating composition of the present invention is prepared as follows. The polyester urethane acrylate is mixed with the substituted vinyl aromatic monomers such as styrene, the cycloaliphatic or saturated aliphatic (meth) acrylates such as isobornyl acrylate, and the hydroxylalkyl methacrylate such as hydroxypropyl methacrylate. After these compounds are mixed, the above-noted fillers and additives such as solidification inhibitors, light stabilizers, lubricants, etc. are added and mixed. The free radical peroxide initiator is added to the latter. The polyacrylate ester of a polyol may be present in the polyester urethane acrylate from the supplier. When it is desired that a mold coating have a specific color, one or more pigments, colorants, etc. can be used in a suitable amount. As is known in the art, various dyes and pigments are often added with a vehicle, for example, a polyester, so that they can be easily mixed. Any conventional or suitable mixing vessel can be used, and the various components and additives are mixed until the compounds are linked. Even if the pigments are not contained in the mixture, the mixture at this point is not transparent. When desired, the mixed ingredients are covered with a fiber reinforced plastic such as a sheet-molded composite as when injection molding with the mold coating composition heated to a solidification temperature. The solidification temperature will vary depending on the particular solidifier or peroxide used. Suitable solidification temperatures generally range from about 200 to about 330 ° F (from about 93 to about 165 ° C). In solidification or chain extension, the mold-coating component becomes transparent. Traditionally, clarity can be measured by a subjective ocular test, that is, the lack of any color imparted to a reinforced substrate. According to the present invention, clarity can also be demonstrated by measuring the color of a substrate with a color spectrometer, but before and after covering with the present invention. The data presented in Table I was obtained with a color spectrometer from Datacolor Spectraflash® SF 600"equipped with a Datamatch 600 software for painting and coating, available from Datacolor International / Americas of Charlotte, North Carolina. The data shown in Table I shows that brightness (L *) and color (a * and b *) are similar for both covered and uncovered substrates, where the same transparent coating (formula A) is used in each case. The molded mold coating compositions of the present invention have very good properties such as, good high clarity (ie, lack of color), good adhesion for an FRP substrate such as a sheet molded composite, good hardness, for example , a pencil hardness of at least H and desirably at least 2H, good tear resistance, good water resistance, as well as good ultraviolet resistance. The solidified thermosetting mold coating compositions of the present invention have smooth surfaces and also have high gloss values of degree 60 of at least 70 and desirably at least 80. The gloss levels can also be affected by the surface and condition of the tool used to mold parts and apply the coating. Such properties result in a mold coating, which has a finished surface since it has good weather resistance and other good properties of the paint so that the paint, which has hitherto been required, is not necessary. That is, when solidified the mold coating composition can be used as it is with respect to a particular end use application and does not need, or is substantially free of any subsequent surface treatment, for example, coating, another layer, etc., such as a painting, and the like. In other words, the surface of the mold coating composition is substantially free of treatment meaning that less than 10 grams and preferably less than 5, 3, or 2 or 1 grams by weight per square inch of any protective coating is generally applied. film, layer, or surface treatment, and preferably is completely free of them. The mold coating compositions of the present invention are generally flexible and can be used on any surface of a fiber reinforced plastic substrate, which may be a thermoplastic or a thermoset, in sheet-molded composites, which are generally thermosetting, in low pressure molding compound (LPCM), and the like. Suitable end uses of the "finished" or "as-is" mold coating compositions of the present invention include various automotive parts such as, brake surfaces, air dampers, truck protective liner, patio furniture, satellite, boat components, and the like. The invention will be better understood with reference to the following examples, which serve to illustrate but not limit the scope of the present invention.

EXAMPLES Formulas A, B, and C, set out below, were mixed and molded as follows: Mixing Procedure Formula A Added to a container in the indicated amount, polyester urethane acrylate, diol hexane diaryl ester, styrene, acrylate of isobornyl and hydroxypropyl methacrylate and were thoroughly mixed using conventional mixing procedures for the organic resin solutions. The hydroquinone, the cobalt octoact, the light hindered amine stabilizer (HALS), the UV absorber, and the calcium and zinc sterates in the above-prepared resin solution were tested, and again mixed thoroughly until the organic and dissolve the stearates. The talc and silica were then tested in the container with the organics and stearates, and thoroughly mixed to disperse the solids. All the mixtures occurred without external heating. The peroxide initiator was added to the mold coating solution prepared above, and mixed thoroughly. The molding of the RPF was prepared in a 16 x 16 chromed steel cutting edge mold from a conventional SMC polyester used commercially to prepare the exterior automotive body panels. The molding conditions for the SMC were 300 ° F, (149 ° C) a solidification time of seventy seconds, and a pressure of 1000 psi. The coating was applied immediately following the solidification of SMC upon opening the mold, emptying into the FRP molding, and reclosing the mold. The solidification conditions for the IMC were 300 ° F, (149 ° C) at a solidification time of sixty seconds, and a pressure of 1000 psi. Formula B It is the same as formula A, with the exception of the addition and mixing of the white pigment dispersion following the dispersion of talc and silica, before the addition of the peroxide initiator. The preparation of the mold-coated RPF panels was the same as that of Formula A. Formula C is the same as formula A, with the exception of the addition and mixing of a dispersion of the blue pigment of eftalocyanine. The preparation of the FRP panels coated in mold was the same as that of Formula A.

FORMULA TO TRANSPARENT LAYER FORMULA B WHITE COLOR LAYER FORMULA C BLUE COLOR LAYER The formulas A, B and C were tested taking into account various properties such as pencil hardness, tape adhesion, fragmentation and gloss resistance as well as accelerated weathering and adhesion to moisture, and the results of these are set forth in Tables 2 to 6. TABLE 1 Illuminator D65 of Color Space CIÉ L * a * b *, Observer at 10 ° As noted above, a small change in color occurs when using the transparent coating of the present invention. TABLE 2 INITIAL COATING PROPERTIES TABLE 3 COATING PROPERTIES AFTER EXPOSURE TO HUMIDITY BY 96 HR (GM4388M, GM4465P) TABLE 4 COATING PROPERTIES AFTER IMMERSION IN WATER FOR 10 DAYS (FORD ESB-M2P124-A1) TABLE 5 60 ° BRIGHTNESS IN THE COATING AFTER THE ACCELERATED WEATHER RESISTANCE (SAE J1960) TABLE 6 COATING PROPERTIES AFTER EXPOSURE IN SOUTH FLORIDA BY (6) MONTHS (5th SOUTH / EXHIBITION OF THE BLACK BOX) As apparent from the tables, the mold coating compositions of the present invention when solidified had good properties such as pencil hardness, adhesion, weather resistance, and the like. The compositions of the present invention also had good gloss retention generally of at least 50%, 60%, 70%, 75%, or 80% of the initial brightness, generally by at least 1,000 hours, and preferably still in an excess of 2,000 hours. Example B of the present invention was compared with a white gel layer which was a commercialized gel layer sold by a main manufacturer to cover composite vessels. Such gel-coat materials are commercially available from many manufacturers including CCP (Cook Composites and Polymers) Kansas City, Missouri; Neste of Forth Smith, Arkansas; and Lilly Industries of Elkhart Indiana. Gel coatings are typically used in the composite industry as an appearance coat in a fiber reinforced plastic prepared by means of a closed (or open) spray molding. As such, gel coatings are proposed for appearance and do not require painting. As apparent from the drawing, the mold coating composition of the present invention had good gloss retention, even after 2,500 hours, as compared to the rapid decrease in brightness in 500 hours of the white gel layer of control. Although according to the patent statutes, the best mode and preferred embodiment has been established, the scope of the invention is not limited thereto, but rather by the scope of the appended claims

Claims (20)

1. - 2Í NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore the property described in the following claims is claimed as property. 1. A mold coating composition comprising; (a) a saturated aliphatic polyester urethane acrylate, said polyester portion being derived from at least one saturated carboxylic acid or anhydride thereof and a saturated diol, said urethane portion being derived from an aliphatic saturated polysuccianate; (b) a cycloaliphatic or aliphatic (meth) acrylate wherein said aliphatic or said cycloaliphatic group is saturated and has from 1 to 50 carbon atoms; (c) a hydroxyalkyl (meth) acrylate wherein said alkyl group has from 1 to 10 carbon atoms; (d) a substituted vinyl aromatic having from 8 to 12 carbon atoms, and, (e) a polyacrylate ester of an alkylene polyol wherein said alkylene group has from 2 to 30 carbon atoms.
2. 2. A mold coating composition according to claim 1 characterized in that, (a) said saturated or anhydride carboxylic acid has from 1 to 15 carbon atoms, wherein said saturated diol (a) contains from 2 to 15 carbon atoms, wherein said saturated polyisocyanate includes a diisocyanate which - 2! contains from 5 to 18 carbon atoms, wherein said (b) (cycloaliphatic or saturated aliphatic (meth) acrylate has from 2 to 20 carbon atoms, wherein said alkyl group of said (meth) acrylate hydroxylalkyl (c) has from 1 up to 5 carbon atoms, and wherein said alkylene (e) group of said polyol has from 2 to 10 carbon atoms.
3. 3. A mold coating composition according to claim 2 characterized in that, the amount of said saturated cycloaliphatic or aliphatic (meth) acrylate (b) is from about 20 to about 100 parts by weight for each 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a), wherein the amount of said hydroxyalkyl (meth) acrylate is from about 2 parts to about 20 parts by weight for each 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a), and wherein the amount of said vinyl substituted aromatic (d) is from about 10 to about 70 parts by weight for each 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a), and wherein the amount of said diacrylate ester (e) of an alkylene polyol is from about 10 to about 40 parts by weight per 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a).
4. 4. A mold coating composition according to claim 3 characterized in that the number of the average molecular weight of said saturated polyester portion (a) is from about 1,000 to about 5,000, wherein said saturated cycloaliphatic or aliphatic (meth) acrylate ( b) is isobornyl acrylate and wherein the amount thereof is from about 50 to about 80 parts by weight, wherein the amount of said hydroxylalkyl (meth) acrylate (c) is from about 6 to about 16 parts by weight, wherein the amount of said vinyl substituted aromatic (d) is from about 20 to about 60 parts by weight, and wherein the amount of said polyacrylate ester (e) of an alkylene polyol is from about 15 to about 35 parts by weight. weight.
5. A mold coating composition according to claim 4 characterized in that said saturated aliphatic polyester urethane acrylate is prepared from neopentyl glycol, ethylene glycol, adipic acid, isophorone diisocyanate, and hydroxyethyl (meth) acrylate, wherein said hydroxyalkyl (meth) acrylate (c) is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic (d) is styrene, and wherein said polyacrylate ester (e) of an alkyl polyol is a diacrylate ester of hexane diol.
6. 6. A mold coating composition according to claim 1 characterized in that said composition reacts by using a peroxide initiator.
7. 7. A mold coating composition according to claim 4 characterized in that said composition reacts with from about 0.25 to about 5.0 weight percent of a peroxide initiator based on the total weight of all the ethylenically unsaturated components employed in the composition of mold coating.
8. 8. A solidified mold coating composition, comprising; the reaction product of (a) a saturated aliphatic polyester urethane acrylate, said polyester portion being derived from at least one saturated carboxylic acid or anhydride thereof and a saturated diol, (b) a cycloaliphatic or aliphatic (meth) acrylate wherein aliphatic or said cycloaliphatic group is saturated and has from 1 to 50 carbon atoms, (c) a (meth) hydroxylalkyl acrylate, (d) a vinyl substituted aromatic having a total of from 8 to 12 carbon atoms, and (e) a polyacrylate ester of an alkylene polyol wherein said alkylene group has from 2 to 12 atoms of carbon in the presence of a peroxide initiator.
9. 9. A solidified mold coating composition according to claim 8 characterized in that the amount of said saturated cycloaliphatic or aliphatic (meth) acrylate (b) is from about 20 to about 100 parts by weight for each 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a), wherein the amount of said hydroxylalkyl (meth) acrylate (c) is from about 2 parts to about 20 parts by weight for every 100 parts by weight of said aliphatic polyester urethane acrylate saturated (a), and wherein the amount of said vinyl substituted aromatic (d) is from about 10 to about 70 parts by weight for each 100 parts by weight of said saturated aliphatic polyester urethane acrylate (a), wherein the amount of said polyacrylate ester (e) of an alkylene polyol is from 10 to 40 parts by weight per 100 parts by weight of said urethane acrylate. and saturated aliphatic polyester (a).
10. A solidified mold coating composition according to claim 9 characterized in that said saturated carboxylic acid or anhydride (a) has from 1 to 15 carbon atoms, wherein said saturated diol (a) contains from 2 to 15 carbon atoms. carbon, wherein said saturated polyisocyanate (a) includes a diisocyanate containing from 5 to 18 carbon atoms, wherein said saturated cycloaliphatic or aliphatic (meth) acrylate (b) has from 2 to 20 carbon atoms, wherein said group of alkyl of said hydroxylalkyl (meth) acrylate (c) has from 1 to 5 carbon atoms, and wherein said alkylene group (e) of said polyol has from 2 to 10 carbon atoms.
11. A solidified mold coating composition according to claim 10 characterized in that the number of the average molecular weight of said saturated polyester portion (a) is from about 1,000 to about 5,000, and wherein said aliphatic polyester urethane acrylate saturated is prepared from neopentyl glycol, ethylene glycol, adipic acid, isophorone diisocyanate, and hydroxyethyl (meth) acrylate, wherein said saturated cycloaliphatic or aliphatic (meth) acrylate (b) is isobornyl acrylate and wherein the amount thereof is from about 50 to about 80 parts by weight, wherein said (meth) hydroxyalkyl acrylate (c) is hydroxypropyl methacrylate and wherein the amount thereof is from about 6 to about 16 parts by weight, wherein said vinyl substituted aromatic (d) is styrene and wherein the amount thereof is from about 30 to about 50 parts by weight, and wherein said polyacrylate ester (e) of an alkylene polyol is a diacrylate ester of hexane di-ol and wherein the amount thereof is from about 15 to about 35 parts. in weigh.
12. 12. A solidified mold coating composition according to claim 8 adhered to a fiber reinforced plastic substrate.
13. 13. A solidified mold coating composition according to claim 11 adhered to a fiber reinforced plastic substrate.
14. 14. A solidified mold coating composition according to claim 12, characterized in that said mold coating composition is substantially free of any other layer therein.
15. 15. A solidified mold coating composition according to claim 13, characterized in that said mold coating composition has less than 3 grams per square inch of any layer therein.
16. 16. A solidified mold coating composition according to claim 12, characterized in that said coating composition has a grade 60 gloss retention of at least 75% of its original value according to SAE J1960 after 1,000 hours.
17. 17. A process for molding a mold-coating composition on a fiber-reinforced plastic substrate and forming a coating thereon of a predetermined thickness, comprising; molding said substrate between separate dies, which act together in a first fully closed position to define a cavity in the mold that corresponds in size and shape to the substrate; allowing said substrate to harden in said cavity; separating one of said dies from said substrate to provide a first interval therebetween, which is greater than said predetermined thickness of said coating; injecting a measured amount of a mold coating composition in said first range, said amount being sufficient to provide said predetermined but insufficient thickness to fill said first range; applying molding pressure to said die to reduce said first interval to a second interval, which has the same measure of said predetermined thickness and to distribute said injected material substantially and uniformly through said second interval and on said surface; maintaining said pressure while said material is bonded to said surface and solidifies sufficiently to allow complete separation of said dies without fracturing the coating thus formed; and completely separating said dies and removing said coated substrate from said cavity; the improvement comprising a composition in the mold, which includes the reaction product of (a) a urethane acrylate of aliphatic saturated polyester, said portion is derived from at least one carboxylic acid or anhydride thereof saturated and a saturated diol, ( b) a (meth) cycloaliphatic or aliphatic acrylate, (c) a (meth) acrylate hydroxyalkyl, (d) a substituted vinyl aromatic having a total of from 8 to 12 carbon atoms, and (e) a polyacrylate ester of an alkylene polyol wherein said alkylene group has from 2 to 12 carbon atoms, in the presence of a peroxide initiator such that a solidified mold coating composition is produced.
18. 18. A process for molding a mold coating composition according to claim 17 characterized in that said saturated carboxylic acid or anhydride (a) has from 1 to 15 carbon atoms, wherein said saturated diol (a) contains from 2 to 15 carbon atoms, wherein said saturated polyis-ocyanate (a) includes a diisocyanate containing from 5 to 18 carbon atoms, wherein said cycloaliphatic or aliphatic (meth) acrylate (b) is saturated and has from 2 to 20 carbon atoms. carbon, wherein said alkyl group of said hydroxylalkyl (meth) acrylate (c) has from 1 to 5 carbon atoms, and wherein said alkylene (e) group of said polyol has from 2 to 10 carbon atoms.
19. A process for molding a mold coating composition according to claim 18 characterized in that the amount of said saturated cycloaliphatic or aliphatic (meth) acrylate (b) is from about 20 to about 100 parts by weight for every 100 parts by weight said urethane acrylate saturated (a) aliphatic polyester, wherein the amount of said (meth) acrylate hdiroxialquilo (c) is from about 2 parts to about 20 parts by weight for 100 parts by weight of said urethane acrylate polyester saturated aliphatic (a), and wherein the amount of said aromatic substituted vinyl (d) is from about 10 to about 70 parts by weight for 100 parts by weight of said urethane acrylate aliphatic saturated polyester (a) , and wherein the amount of said polyacrylate ester (e) of an alkylene polyol is from about 10 to about 40 parts by weight per 100. parts by weight of said saturated aliphatic polyester urethane acrylate (a).
20. 20. A process for molding a mold coating composition according to claim 19, characterized in that said saturated aliphatic polyester urethane acrylate (a) is prepared from neopropyl glycol, ethylene glycol, adipic acid, isophorone diisocyanate and (meth) acrylate. of hydroxyethyl, where said (meth) hydroxyalkyl acrylate (c) is hydroxypropyl methacrylate, wherein said vinyl substituted aromatic (d) is styrene, and wherein said polyacrylate ester (e) of an alkylene polyol is a diacryl ester of hexane diol.