MXPA99007559A - Compositions of non-saturated polyester resin that includes monomeros metali - Google Patents

Abstract

A composition useful as a gelling layer, binder, laminating resin or molding resin comprising (A) an unsaturated polyester resin which is the reaction product of one or more polyols and one or more ethylenically unsaturated polycarboxylic acids, anhydrides or amides and optionally one or more polyethylenically unsaturated monomers or a vinyl ester resin, (B) one or more of the first monomers that are selected from the group consisting of styrene, vinyl toluene, methyl methacrylate, N-pyrrolidoan vinyl, ethylene glycol dimethacrylate and Bisphenol A dimethacrylate Alkoxylated, and (C) a second monomer selected from the group consisting of metal salts of alpha, beta-ethylenically unsaturated carboxylic acids without a loss in thermal distortion temperature properties.

Description

"COMPOSITIONS OF NON-SATURATED POLYESTER RESIN COMPRISING METALLIC MONOMERS" This invention relates to the field of ethylenically unsaturated vinyl ester or polyester ester systems comprising the unsaturated vinyl ester or polyester resin and an unsaturated organic monomer such as styrene which serves as a solvent for the ester ester of unsaturated vinyl or polyester. These resin systems are used for laminating, coating and gelling purposes. When used for laminating, resin systems are typically reinforced with fiber, usually with glass fibers. A well-known problem in this technique is that the organic monomer tends to volatilize in significant amounts into the workplace environment. Styrene, the most typical organic monomer, is volatile and is a suspected carcinogen and there are regulations in place to reduce styrene emissions during coating or molding processes in the industry. Others have proposed replacing part of the organic monomer in order to reduce volatile materials. For example, see Smeal, et al., In U.S. Patent No. 5,500,171, assigned to Aristech Chemical Corporation, and other Smeal patents, and others, also assigned to that concessionaire, which disclose replacing some or all of the organic monomer as the styrene with a different organic monomer, for example, a multifunctional (meth) acrylate such as ethylene glycol dimethacrylate or alkoxylated bisphenol-A diacrylate or dimethacrylate. Others have proposed epoxidized soy bean diacrylate and trimethacrylate and trimethylolpropane, to be used together in order to replace part of the styrene. Lee, in U.S. Patent No. 4,465,806, discloses a conventional unsaturated polyester resin wherein the usual styrene is replaced by a reaction product of the polyepoxy compound and the acrylic or methacrylic acid which may be the diacrylate of an ether of bisphenol-A polyglycidyl, wherein a significant portion of the epoxy groups remains unreacted for use in the resin, and subsequently forms the suspended OH groups. Patent Application Number 0234 692 discloses a molding resin having a low residual monomer concentration in the final product, wherein dimethacrylates such as ethoxylated bisphenol-A dimethacrylate can be used to reduce the amount of styrene monomer residual in the processes of molding contents such as cell molding, compression molding and sheet molding. See also Reid and Rex Patent - - North American Number 5,202,366, which includes a low profile additive in a similar composition. These prior compositions reduce the emissions of the volatile compounds but suffer from one or more disadvantages with respect to the crosslinked polyester properties, e.g., the thermal distortion temperature is reduced. It is therefore an object of this invention to provide an unsaturated vinyl ester or polyester composition useful for laminating, coating and gelling applications having lower than normal amounts and volatile unsaturated monomer without reducing thermal distortion properties and other physical properties. This object, and others that will become apparent from the following disclosure, is provided by the present invention which, in one aspect, comprises a composition useful as a gel layer, a binder, or a laminating resin comprising (A) resin unsaturated polyester which is the reaction product of one or more polyols and one or more non-ethylenically unsaturated polycarboxylic acids, or amides and optionally one or more polyethylenically unsaturated monomers or a vinyl ester resin (B) a monomer which dissolves the vinyl ester or polyester resin that is selected from the group - consisting of styrene, vinyl toluene, vinyl methacrylate, N-vinyl pyrrolidone, ethylene glycol dimethacrylate and Bisphenol A dimethacrylate, and (C) a second monomer selected from the group consisting of metal salts of alpha, beta-ethylenically unsaturated carboxylic acids. In another aspect, the invention comprises a method for preparing a layer of polyester or vinyl ester gel, or rolling resin of a composition comprising an unsaturated polyester resin which is the reaction product of one or more polyols and one or more ethylenically unsaturated polycarboxylic acids, anhydrides or amides and a first monomer selected from the group consisting of styrene, vinyl toluene, methyl methacrylate, N-vinyl pyrrolidone, ethylene glycol dimethacrylate and the alkoxylated Bisphenol A dimethacrylate or vinyl ester resin, the improvement comprises replacing in the composition a portion of the first monomer, with a second monomer selected from the group consisting of metal salts of an alpha, beta-ethylenically unsaturated carboxylic acid resulting in a property of Higher thermal distortion temperature. Another aspect of the invention is the molded laminates, the binder, and gelefication coatings - prepared by the method of the invention from the composition of the invention. Although many others have been sought to provide unsaturated vinyl ester or polyester resins having a reduced volatile monomer content, a satisfactory improvement must be taken in consideration of the widely used equipment and techniques of rolling, gelling and coating applications. Among the restrictions imposed by the market is that of an improved system that must provide a minimum increase in cost when it is marketed, the compatibility between the components of the resin system, the reactivity that is similar to that of the other commercial polyester resins, the viscosity which is similar to that of the other commercial polyester resins, ie, from about 100 to 400 centipoise, and in the case of lamination resin, the ability to wet the glass and bond to the other components of a set. Unlike many previous proposed improvements, the present invention fills all these criteria. One of the specific advantages of resolving a portion of the first monomer by a metal salt salt monomer is that it allows obtaining unsaturated vinyl ester or polyester resin compositions that the same overall ratio of monomers have significantly lower viscosity than the compositions of the prior art. This effect of decrease in viscosity can be further evaluated to obtain compositions which, even when they have the same viscosity, also have: a lower VOC content or a higher resin content (polyester or vinyl ester) and / or a solids content higher for compositions that also contain current solid additives such as fillers or fillers and / or pigments. Another specific advantage of the metal salt monomers is the improvement in thermal stability of the performances of resistance to bending at higher temperature (93 ° C) with respect to the acrylic monomers of reference. The unsaturated polyesters suitable for use in the invention are the conventional unsaturated polyesters which are typically used for lamination and gel coating and which are prepared by polycondensation of the polycarboxylic acid derivatives, one of which must be an alpha polycarboxylic acid, beta-ethylenically unsaturated and polyols. Suitable polycarboxylic acid derivatives include polycarboxylic acids, their lower esters or alcohols, their amides, their acid chlorides and their anhydrides. The ratio of the polycarboxylic acid to the polyol is usually 1: 1 molar ratio. However, in most esterification processes, a slight excess of polyol is used to compensate for polyol losses during esterification. Also, even though dicarboxylic acids and diols are frequently used and a molar ratio of 1: 1 prevails, the use of triols and the like requires that the ratio of acid to polyol be more accurately expressed as one equivalent of acid per equivalent of polyol. The unsaturated polyesters useful in this invention may be prepared from an acidic mixture when the unsaturated polycarboxylic acid comprises as little as 20 mole percent of the total acids present, even though the unsaturated polycarboxylic acid is generally preferred to comprise about 30 percent or more of the total acid content. Some of the unsaturated polycarboxylic acids useful in preparing the unsaturated polyesters used in this invention include maleic acid, citraconic acid, fumaric acid, glutaconic acid, itaconic acid, chloromaleic acid, mesaconic acid, and the like, wherein the term "acid" it is used to include the corresponding anhydrides where these anhydrides exist. Some of the saturated and aromatically unsaturated polycarboxylic acids optionally useful for preparing the unsaturated polyesters used in this invention include phthalic acidphthalic anhydride, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, glutaric acid, tetrachlorophthalic acid, suberic acid, hexachloroendomethylene phthalic acid, sebacic acid, tetrahydrophthalic anhydride, succinic acid, adipic acid, and the like, wherein The term "acid" includes the corresponding anhydrides in which these anhydrides exist. Polyols useful for preparing polyester for use in this invention are polyfunctional alcohols of the type conventionally used in the preparation of polyester. These polyols include ethylene glycol, 1,5-propanediol, propylene glycol, triethylene glycol, butylene glycol, glycerol, diethylene glycol, 1,4,6-hexanetriol, trimethylolpropane, trimethylolethane, dipropylene glycol, pentaerythritol, neopentyl glycol, 2,2-bis (4-hydroxyphenyl) propane. alkoxylated and the like. Although diols are generally preferred in the preparation of unsaturated polyesters, more highly functional polyols are sometimes used, ie, polyols having a functionality of three to five. In addition, a polyethylenically unsaturated monomer such as dicyclopentadiene and derivatives or such as the dicyclopentadiene of Bisphenol A is preferably included and may be considered as a normal part of the "base" resin as used herein. Vinyl ester resins can replace all or part of the unsaturated polyester resins. The vinyl ester resins suitable for the invention may be any vinyl ester resin known to a person skilled in the art. Examples of these resins are acrylated oligomers based on Bisphenol A and more particularly acrylated oligomers based on alkoxylated Bisphenol A. Suitable unsaturated monomers referred to herein as the first monomer are those conventionally used in the art for laminating resins, gel coatings, molding resins and the like with unsaturated polyesters. The most typical unsaturated monomer is, of course, styrene. Other conventional monomers are vinyl toluene, methyl methacrylate, N-vinyl pyrrolidone, ethylene glycol dimethacrylate, and the alkoxylated Bisphenol A dimethacrylate. The monomer mixtures can be used, for example, a mixture of styrene and the alkoxylated Bisphenol A dimethacrylate. The amount of the first monomer is reduced to less than the conventional amount according to this invention, resulting in volatile materials and reduced emissions. Typical amounts used in the prior art are from about 40 to 50 parts by weight per 60 to 50 parts by weight of the unsaturated polyester or the vinyl ester resin. According to this invention, only about 5 to 47, preferably only about 10 to 30, parts by weight of the first monomer are used, based on 50 to 70 parts by weight of the unsaturated polyester resin or vinyl ester . In accordance with this invention, metal monomers are used as the "second" monomers to replace a portion of the first monomer (s). Suitable metal monomers are prepared by reacting the metal, for example calcium, zinc, magnesium, aluminum and the like. With a saturated organic acid, e.g., acrylic acid and / or methacrylic acid and the like to form the salts. Preferred salts include(meth) multifunctional metal acrylates and more preferably zinc diacrylate, zinc dimethacrylate, calcium diacrylate and calcium dimethacrylate.

The amount of the metal monomer (s) used can vary from 0.5 to 35 and preferably from at least about 1 to 30, and more preferably from 1.5 to 15 parts by weight with the proviso that (B) + (C) is from 30 to 50 parts per 100 parts by weight of (A) + (B) + (C). The metal monomer is typically a solid, and therefore, has much lower vapor pressure than the first monomer. However, due to its reactivity, the metal monomer functions to properly crosslink, ie, cure, the unsaturated polyester, together with the first monomer. For the lower contents in the metal monomers, the effect of low VOC is obtained indirectly by allowing the higher contents of polyester resin or vinyl ester (solid content) of about 70 percent or higher for the same viscosity which means lower volatile monomer content (lower VOC). In a preferred embodiment, the composition comprises as a first monomer, styrene and as a second monomer of zinc diacrylate, zinc dimethacrylate and calcium dimethacrylate, with the weight ratio of the first monomer to the second monomer from about 2: 1 to about 20: 1. When preparing the laminating resins, it is very typical to incorporate glass fibers and the like, for - reinforce the molded piece. The typical type of fibers are glass and inorganic (electrical quality) compositions which may, for example, be one or more of silica, calcium oxide, alumina, boron oxide, magnesia, titanium dioxide, ferric oxide, fluorine. It is also necessary, and conventional, to include a free radical initiator, usually a peroxy catalyst to activate or promote cure or crosslinking. Additional fillers or fillers, catalysts, and additives can be used in the composition. More specifically, the compositions of the invention may include from 0.1 to about 2.0 parts of free radical promoters and initiators that are selected from the group consisting of cobalt naphthenate, potassium naphthenate and dimethyl acetoacetamide and methylethyl ketone peroxide. , based on 100 parts of (A), (B) and (C). Transition metals such as cobalt, copper and vanadium can act as catalysts for the decomposition of the peroxide initiator at less than its normal decomposition temperature. Typicalities are added at 0.02 to 0.1 weight percent metal based on the reactive solids. Free radical inhibitors such as the substituted phenol derivatives and the quaternary ammonium salts can be added to prolong shelf life. Many types of filler or filler materials can be used such as ground limestone, kaolin clays, ground silicas, etc. to improve physical properties. Pigments can be used particularly for compositions for coating the gel. Given the significant decrease effect of the metal salt monomer in the viscosity of the composition, highly filled or pigmented compositions can be obtained in significantly higher solids content (higher content of the filling material or filler or pigment), with better dispersion of the solid additives and with improved physical performances of the obtained compounds or coatings. The compositions of the invention can be used in either rolling, coating or molding processes that are very typical in the art. Suitable lamination processes include, for example, sheet molding compound (SMC). Suitable coating processes include gel layers for open mold SMC pieces and mold coatings for example an appropriate molding process would be the bulk molding compound (BMC). The invention helps solve a problem that has been present for a long time in the laminar technique, gelling, coating resins, and BMC, that is, the partial replacement of volatile monomers such as styrene, without a loss in physical properties such as thermal distortion temperature. In accordance with the present invention, the replacement of a portion of these monomers by metal monomers results in an improvement in the temperature of the thermal distortion. The following non-limiting examples illustrate a few embodiments of the invention. Although the invention has been described and exemplified in detail herein, various alternatives, alterations and modifications for those skilled in the art should be apparent without departing from the spirit and scope of the invention. In the following examples, all parts and percentages are by weight, unless otherwise indicated, and the following materials were used in the examples, have the following abbreviations, and were supplied by the following supplier companies: - - Material description Supplier Dicyclopentadiene polyester (DCPD) Aristech Ortho DCPD polyester (Aropol FRP A 220) Ashland ISO polyester (Stypol 40-4339) CCP Vinyl ester resin (Hydrex 100 / Polylite 33350) Reichold Styrene Arc Chemical Vinyl toluene Dow Del Tech 12% cobalt promoter Mooney Chemical 15% potassium octoate promoter Akcros Chemicals Dimethylacetoacetamide (DMAA) Eastman 25% hydroquinone solution Prepared in the laboratory Methyl Ethyl Ketone Peroxide (MEKP) Witco 6 moles of ethoxylated Bisphenol A dimethacrylate (CD-541) as a reference Sart er Ethylene glycol dimethacrylate (SR-206) as a reference Sartomer Trimethylolpropane trimethacrylate (SR-350), as a reference Sartomer Zinc diacrylate (SR-705) Sartomer Zinc dimethacrylate (SR-708) Sartomer Calcium diacrylate (SR-636) Sartomer Epoxidized soybean oil diacrylate (CN 111) Sartomer - Diethylene glycol dimethacrylate (SR 231) as reference Sartomer Example 1 - Preparation of DCPD polyester A basic polyester resin (referred to below as "DCPD polyester") having the following composition was prepared: Component Molar Percentage (for 100 moles of M. anhydride) diclopentadiene 113 Ethylene glycol 60 Maleic anhydride 100 Example 2 - Preparation of the resin formulation A series of rolling resin formulations were prepared based on the DCPD polyester prepared in Example 1, and were tested for healing operation, volatile content and physical properties, including Thermal Distortion Temperature. A basic blend of the net DCPD polyester dissolved in styrene (80/20 by weight) was prepared by grinding the polyester to a fine powder with a mortar and grinder and then solubilizing in styrene with stirring. The basic batch of polyester / styrene was diluted with an additional reactive diluent, either styrene or (meth) acrylate monomer, correspondingly. In the examples of the - - In the invention, 10 percent of the total styrene in the formulation was replaced by the metallic monomer that was dispersed in the basic mixture before being diluted. The co-promoters (12 percent cobalt naphthenate, 15 percent potassium naphthenate and dimethyl acetoacetamide) and the additional inhibitor (25 percent HQ solution) were then added. Finally, the MEK peroxide was added just before molding. Example 3 - Preparation of crystalline castings The crystalline castings of various lamination resins were prepared to test the volatile emissions, the mechanical properties and the temperature of thermal distortion. Volatile emissions were tested in accordance with Rule 1162 (melting 100 grams of the formulation at room temperature in a 3,785-gallon paint can with the cap turned up on the top of the rest of the top load with a paper staple in the center bent at an angle of 90 and measuring the loss in weight as the formulation gels or heals). The gelation temperature is the temperature at which the lid of the paint can can be lifted by the paper clip after the material hardens around it. The crystalline castings for mechanical and thermal strength properties were prepared by melting the formulations between two glass plates held together with binder staples and separated by a 3.18 millimeter packing material as a spacer. The formulations were cured at room temperature (25 ° C) for 2 hours and then baked at 100 ° C for 2 hours. The temperature of thermal distortion was tested according to the method D648 of the American Society for the Testing of Materials. Example 4 - Test of crystalline castings The results of the test of the properties of crystalline cast iron are shown in Table 1, and show that when the styrene is partially replaced or the formulation is completely replaced by bisphenol A dimethacrylate ethoxylate and dimethacrylate of Ethylene glycol (SR-206), or diacrylate of epoxidized soybean oil (CN 111) and trimethylpropane trimethacrylate (SR-350), the volatile emissions are reduced while the temperature of thermal distortion is also reduced. In the formulations of the invention, when the metal monomers are added, the thermal distortion temperature is maintained and increased. In formulation number 3, 25 percent replenishment of styrene resulted in a thermal distortion temperature of 121 ° C (-3.89 ° C higher than control formulation number 1 and from 7.22 ° to 18.5 ° C higher than the other formulations modified with the (meth) acrylate monomer). Table 1 - Compendium of experimental results (% by weight) Formulation Number 1 2 3 4 5 6 Invention or Comp. Comp. Comp. Inv. Inv. Inv. Comparison DCPD polyester 60 60 60 60 60 60 Styrene 40 20 30 30 30 Vinyl toluene 10 CD-541 40 SR-206 20 CN 111 SR-350 10 SR-705 10 SR-708 10 SR-636 10 12% cobalt 0.3 0.3 0.3 0.3 0.3 0.3 % potassium 0.2 0.2 0.2 0.2 0.2 0.2 DMAA 0.3 0.3 0.3 0.3 0.3 0.3 % of HQ 0.3 0.3 0.3 0.3 0.3 0.3 MEKP 1.5 1.5 1.5 1.5 1.5 1.5 Temperature of Thermal distortion Method D648 ° C of the American Society for the Testing of Materials 107 83 94 108 121 108 - Table 2, 3, 4 show additional data with the operation of three types of resins: Ortho-polyester resin modified with DCPD (Table 2) Iso-polyester resin (Table 3) - Vinyl ester resin (Table 4) Comparative thermal stability of high temperature (93 ° C) flexural resistance performances expressed in terms of percent loss of flexural strength with respect to the room temperature performances are presented in Figure 1 for the resin ortho polyester modified with DCPD. Figure 2 for the iso-polyester resin and Figure 3 for vinyl ester resin. 100 parts by weight of each resin was used as received (pre-diluted with styrene monomer and pre-promoted with a Cobalt Dryer and other accelerators of unknown quantity and type). 2 and 5 parts by weight, respectively, of the metal monomers of the invention was added to the resins by mixing in a high shear mechanical mixer equipped with a cowles blade. The percentage content of the volatile material was calculated based on the solids content of the formulation. The viscosity of each formulation was measured by a Brookfield RVT Viscometer using a spindle number 2 at 3 revolutions per minute. The gelation times for each formulation initiated with 1.25 parts by weight of methyl ethyl ketone peroxide were measured. Significant reductions in viscosity were observed for each resin when the metal monomer was added as mentioned in the invention. However, in order for there to be a comparison data for the crystalline castings, a small percentage of the fuming silica was added as the thixotropic to bring the viscosity to that of the control. In addition, significant increases in gel times were observed for each resin when the metal monomer was added. Since the application of white requires 45 to 60 minutes, the additional gelling times of Cobalt Octoate and dimethylacetoacetamide (DMAA) were added to reduce the gelling time again for the control in order to carry out the comparison test. . Crystalline castings were prepared and tested in a manner similar to Examples 3 and 4. The preparation of the laminate and the test was as follows: 1) Laminates were prepared by hand-fabrication using 3 layers of fiberglass batt NEWFC 2308 (0/90 tissue) and initiated resin formulations (1.25 parts by weight of MEKP) of the invention. ) the resulting panels were post-cured for 2 hours at 65.5 ° C before being tested. ) the comparison bending properties were tested at 25 ° C and 93 ° C using the D790 method of the American Society for the Testing of Materials on a 0 ° reinforcement axis, which was loaded on the face of the mold of the laminate ( CS).

- Table 2 - GP Data Compendium (DCPD / Ortho) Polyester (Aropol Ashland FRP to 220) for 100 parts of polyester + styrene (solids content of 52 percent) Table 2a - Crystalline Castings SR-705 control 0 parts) 2 parts 5 parts VOC content (base: solids content) 48 47 46 Viscosity adjustment w / Thixotrope Initial viscosity Pa.s 2.95 1.84 2.14 Final viscosity Pa.s 2.60 1.92 3.04 Amount of Fumed Silica none 1.0% 1.0% Gel Time Adjustment Initial gel time (minutes) 64 155 165 Final gel time (minutes) 50 69 72 Amount of Co added none 0.20% 0.20 Amount of DMAA added none 0.15% 0.15 - - Table 2 (continued) Tension Properties (Method D638 of the American Society for the Testing of Materials) Resistance to tension MPa 34.67 29.50 32.64 Elongation at break (%) 1.01 0.82 0.95 Voltage module MPa 3357 3612 3275 Flex properties (Method D790 of the American Society for the Testing of Materials) Resistance to Bending MPa 57.31 55.8 < 55.85 Bending module MPa 3667 3846 3777 Hardness Barcol 40 42 42 Linear Shrinkage (%) 1.8? 1.76 1.65 HDT, 1.82 MPa (° C) 67 63 65 (Method 2583 of the American Society for the Testing of Materials) - - Table 2b - Laminate Test SR-705 control (0 parts) 2 parts 5 parts Bending Properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural Resistance MPa 393.6 286.5 282.9 Bending module MPa 11 825 9982 8886 Flexural properties at 93 ° C Flexural strength MPa 87.0 106.5 119.3 Bending module MPa 4058 5253 5625 % loss of flexural strength at 93 ° C compared to 25 ° C 77.9 62.8 59.3 Hardness Barcol 52 46 49 Table 2b (continued) SR-708 SR-231 2 parts 5 parts 2 parts 5 parts Flex properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural Resistance MPa 399.7 417.0 416.4 440.0 Bending module MPa 11 926 11 665 12 512 12 285 Bending properties at 93 ° C Flexural strength MPa 96.3 116.6 125.1 122.9 Bending module MPa 4612 4491 4722 5053 % loss of flexural strength at 93 ° C compared to 25 ° C 75.9 70.7 75.3 73.0 Hardness Barcol 53 51 54 53 - Table 3 - Data Compendium for ISO Polyester (CCP Stypol 40-4339) for 100 parts of polyester + styrene (solids content of 53 percent) Table 3a - Crystalline castings SR-705 control (0 parts) 2 parts 5 parts VOC content (base: solids content) 47 46 45 Viscosity adjustment w / Thixotrope Initial viscosity Pa.s 1.53 0.23 0.24 Final viscosity Pa.s 1.65 0.77 0.99 Amount of Fumed Silica none 2.5% 2.5% Gel Time Adjustment Initial gel time (minutes) 27 170 270 Final gel time (minutes) 25 58 65 Amount of Co added none 0.25% 0.25 Amount of DMAA added none 0.15% 0.15 Table 3 (continued) Tension Properties (Method D638 of the American Society for the Testing of Materials) Resistance to tension MPa 54.60 47.04 44.47 Elongation at break () 2.00 1.52 1.50 Voltage module MPa 2889 3020 3047 Flex properties (Method D790 of the American Society for the Testing of Materials) Flexural strength MPa 114.8 99.92 79.92 Modulus of flexion MPa 3171 3330 3233 Hardness Barcol 40 42 42 Linear Shrinkage (%) 1.88 1.76 1.65 HDT, 1.82 MPa (° C) 67 63 65 (Method 2583 of the American Society for the Testing of Materials) Table 3b - Laminate Test SR-705 control 0 parts) 2 parts 5 parts Flexural Properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural Resistance MPa 391.1 342.0 320.3 Modulus of flexion MPa 12071 11 623 10 913 Flexural properties at 93 ° C Flexural strength MPa 202.7 204.0 225.1 Bending module MPa 8245 7431 8500 % loss of flexural strength at 93 ° C compared to 25 ° C 48.2 40.4 29.7 Hardness Barcol 54 49 53 Table 3b (continued) SR-708 SR-231 2 parts 5 parts 2 parts 5 parts Flexural properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural strength MPa 447.6 436.8 418.8 410.3 Flexural modulus MPa 12 740 12 953 12 912 12 885 Flexural properties at 93 ° C Resistance to Bending MPa 274.5 431.6 265.6 245.4 Bending module MPa 9452 9066 9238 9038 % loss of flexural strength at 93 ° C compared to 25 ° C 38.6 32.8 36.6 40.2 Hardness Barcol 47 46 52 51 - - Table 4 - Data Compendium for Vinyl Ester (Reichold Hydrex 100 / Polylite 33350) for 100 parts of polyester + styrene (solids content of 55 percent) Table 4a - Crystal Fade Pieces SR-705 control (0 parts) 2 parts 5 parts VOC content (base: solids content) 45 44 43 Viscosity adjustment w / Thixotrope Initial viscosity Pa.s 2.37 0.37 0.36 Final viscosity Pa.s 3.12 0.94 1.08 Amount of Fumed Silica none 2.5% 2.5% Gel Time Adjustment Initial gel time (minutes) 42 248 252 Final gelling time (minutes) 50 68 61 Amount of Co added none 0.18% 0.18% Amount of DMAA added none 0.13% 0.13% - - Table 4 (continued) Tension Properties (Method D638 of the American Society for the Testing of Materials) Resistance to tension MPa 64.53 68.75 68.56 Elongation at break (%) 2.98 3.08 3.01 Voltage module MPa 2958 3061 3033 Flexural properties (Method D790 of the American Society for the Testing of Materials) Flexural strength MPa 85.37 114.7 91.32 Modulus of flexion MPa 2958 3399 3364 Hardness Barcol 35 39 36 Linear Shrinkage (%) 0.53 0.68 0.90 HDT, 1.82 MPa (° C) 71 69 72 (Method 2583 of the American Society for the Testing of Materials) Table 4b - Laminate Test SR-705 control (0 parts) 2 parts 5 parts Flexural properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural strength MPa 358.4 327.3 332.2 Modulus of flexion MPa 11 458 11 465 12 320 Flexural properties at 93 ° C Flexural strength MPa 275.3 249.7 276.3 Bending module MPa 9555 8969 9286 % loss of flexural strength at 93 ° C compared to 25 ° C 23.2 23.6 16.8 Hardness Barcol 53 53 46 Table 4b (continued) SR-708 SR-231 2 parts 5 parts 2 parts 5 parts Flexural properties at 25 ° C (Method D790 of the American Society for the Testing of Materials) Flexural strength MPa 444.7 414.1 461.3 429.2 Modulus of flexion MPa 12 457 11 823 12 712 11 878 Flexural properties at 93 ° C Resistance to Bending MPa 398.8 386.9 378.1 379.3 Bending module MPa 12 968 13 037 12 699 12 464 % loss of flexural strength at 93 ° C compared to 25 ° C 10.3 6.6 18.0 11.6 Hardness Barcol 54 54 54 54 Although the invention has been described in detail herein, various alternative modifications and improvements should be made evident by those skilled in the art without departing from the spirit and scope of the invention as set forth in the appended claims.

Claims (17)

CLAIMS:

1. A composition useful as a gel layer, binder, or lamination resin comprising (A) an unsaturated polyester resin which is the reaction product of one or more polyols and one or more ethylenically unsaturated polycarboxylic acids, anhydrides or amides, optionally from one or more saturated or aromatically unsaturated polycarboxylic acids and optionally from one or more polyethylenically unsaturated monomers or a vinyl ester resin, (B) one or more of the first monomer selected from the group consisting of styrene , vinyl toluene, methyl methacrylate pyrrolidone N-vinyl, ethylene glycol dimethacrylate and bisphenol A dimethacrylate alkoxylated, and (C) one or more of the second monomers selected from the group consisting of metal salts of carboxylic acids alpha, beta-ethylenically unsaturated.

2. The composition according to claim 1 wherein it comprises from about 5 to 35 parts by weight of (B) and about 0.5 to 35 parts by weight of (C) with (B) + (C) from about 30 to about 50 parts to 100 parts by weight of (A) + (B) + ( C).

3. The composition according to claim 2, wherein it comprises from 10 to 30 parts by weight of (B) and from 1 to 30 parts by weight of (C), with (B) + (C) from about 30 to about 50 parts to 100 parts by weight of (A) + (B) + (C).

4. The composition according to any of claims 1 to 3 further comprising from 0.1 to about 2.0 parts of free radical promoters and initiators that are selected from the group consisting of cobalt naphthenate, potassium naphthenate, and dimethyl acetoacetamide. , and methylethyl ketone peroxide, based on 100 parts of (A) + (B) + (C).

The composition according to any of claims 1 to 4, wherein the second monomer, (C) is selected from the group consisting of multifunctional metal (meth) acrylates.

6. The composition according to any of claims 1 to 5 wherein (C) is selected from the group consisting of zinc diacrylate, zinc dimethacrylate, calcium diacrylate, and calcium dimethacrylate.

The composition according to any of claims 1 to 6, wherein the polyethylenically unsaturated monomer is present and is dicyclopentadiene. -

8. The composition according to any of claims 1 to 7, wherein the polyol is selected from the group consisting of ethylene glycol, 1,5-propanediol, propylene glycol, triethylene glycol, butylene glycol, glycerol, diethylene glycol, 1,4,6-hexanetriol, trimethylolpropane, trimethylolethane, dipropylene glycol, pentaerythritol, neopentyl glycol, and 2,2-bis (4-hydroxyphenyl) propane alkoxylate.

9. The composition according to any of claims 1 to 8, wherein the ethylenically unsaturated polycarboxylic acids, anhydrides or amides are selected from maleic acid, fumaric acid, glutaconic acid, itaconic acid, chloromaleic acid, esaconic acid or its anhydrides. and amide derivatives.

The composition according to any of claims 1 to 8, wherein the saturated or automatically unsaturated polycarboxylic acids are present and are selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, glutaric acid, tetrachlorophthalic acid, suberic acid, phthalic acid - - hexachloroendomethylene, sebacic acid, succinic acid and adipic acid.

The composition according to any of claims 1 to 10, wherein the unsaturated polyester is the reaction product of maleic anhydride, ethylene glycol and dicyclopentadiene of Bisphenol A.

12. The composition according to any one of claims 1 to eleven, wherein the first monomer is styrene and the second monomer is selected from the group consisting of zinc diacrylate, zinc dimethacrylate and calcium diacrylate and the weight ratio of the first monomer to the second monomer is from about 2: 1 to 20: 1.

A method for preparing a polyester gelling layer, a binder, a laminating resin or a casting resin comprising the step of curing a composition as defined in any of claims 1 to 12, in the presence of an initiator of free radical.

A method for preparing a polyester gelling layer, binder, laminating resin or molding resin comprising reacting a composition consisting of an unsaturated polyester resin which is the reaction product of one or more polyols and one or more ethylenically unsaturated polycarboxylic acids, anhydrides or amides or a vinyl ester resin, one or more of the first monomer selected from the group consisting of styrene, vinyl toluene, methyl methacrylate, N-vinyl pyrrolidone, dimethacrylate of ethylene glycol and bisphenol A methacrylate Alkoxylated, and one or more of the second monomers selected from the group consisting of metal salts of the alpha, beta-ethylenically unsaturated carboxylic acids.

15. The article comprising a laminate prepared by molding the composition of any of claims 1 to 12 in the presence of a glass fiber reinforcement and a free radical initiator.

16. The article comprising a coating preparing by curing the composition of any of claims 1 to 12 in the presence of a free radical initiator.

17. The molded article prepared according to the method of claim 13.