Method of preparing an organic-modified, heat-curable silicone resin and the resin produced thereby

Abstract: A method for preparing an organic-modified, heat-curable silicone resin and the novel resin produced thereby are disclosed. In the method of the invention, a trialkoxysilane, a difunctional diorganosilicon compound, a polyol and a catalytic amount of an acidic cationic siloxane polymerization catalyst are reacted to substantial equilibrium to form an alkoxy-functional product. Substantially all the hydrolyzable alkoxy groups of the alkoxy-functional product are then hydrolyzed and the catalyst inactivated. The product is stripped of water and alcohol and may be diluted with a polar solvent such as xylene to the desired viscosity. The heat-cured resin product obtained in accordance with the invention has superior hardness, flexibility and solvent and impact resistance.

Description: The present invention relates generally to the field of heat-curable silicone resins and, more particularly, to a method for preparing organic-modified silicone resins, which method yields a cured product that has superior physical properties. Heat-curable silicone resins are often incorporated into coating systems, such as high temperature and maintenance paints or release coatings for culinary utensils. They are used to impart the coating systems with numerous properties including heat stability, weatherability and maintenance of gloss or adhesion. Of particular importance are the properties of hardness, impact resistance, flexibility and solvent resistance. One such heat-curable silicone resin and a process for preparing the same are disclosed in U.S. Patent 4,749,764. We have investigated the physical properties of prior art cured resins which, upon information and belief, were prepared in accordance with the teachings of this patent. It was found that the cured resins exhibited some physical properties to a reasonably useful level. However, it has also been found that heat-cured compositions prepared in accordance with our invention exhibit far superior physical properties. A particular drawback associated with prior art resins is the inability of such coatings to provide a combination of high hardness, flexibility and impact resistance. It is well-known in the field of material science that the properties of flexibility and impact resistance are generally sacrificed at the expense of hardness. In other words, hard materials often behave in a brittle manner. Resins made in accordance with the present invention, however, achieve the surprising result of exhibiting both high hardness in combination with flexibility and impact resistance. US-A-4 501 872 discloses a liquid composition comprising a reaction product prepared by reacting: (A) at least one hydrophobic polyol; and (B) an organosilicon-containing material comprising i. at least one organosilicon-containing substance free of functional groups attached to carbon and essentially free of alkali metal ions as defined in claim 1 of said document, wherein at least part of the organo-silicon-containing substance is hydrolyzed to a compound or mixture of compounds containing a residual amount of the moieties directly bonded to silicon which are displaceable by reaction with water and/or alcohol; ii. optionally a nonfunctional organosilane, a hydrolyzed nonfunctional organosilane, or a mixture thereof; and iii.optionally a functional organosilane, a hydrolyzed functional organosilane, or a mixture thereof. Without limiting our invention, it is theorized that this invention results in a cured product having a novel chemical structure. It is believed that the claimed invention results in silicone/organic block copolymers that have a lower polydispersity and a more random structure than resins produced in accordance with the prior art. It is further theorized that lower polydispersity and more random structure give rise to the enhanced physical properties associated with the cured resins of our invention. The present invention provides a method for preparing an organic-modified, heat-curable silicone resin, which imparts the cured resin with superior physical properties. The method of the invention comprises the steps of: (1) reacting to equilibrium, relative to the combined weights of the following components (a), (b) and (c): (a) 35 to 75 parts by weight of a trialkoxysilane of the general formula: R 2 (OR 1 ) 3 Si wherein each OR 1 is independently selected from alkoxy groups having 1 to 4 carbon atoms, and each R 2 is independently selected from aryl or alkyl groups; (b) 3 to 35 parts by weight of a difunctional diorganosilicon compound; and (c) 0.5 to 50 parts by weight of at least one polyol; in the presence of (d) a catalytic amount of an acidic cationic siloxane polymerization catalyst to form an alkoxy-functional product therefrom; (2) hydrolyzing substantially all the hydrolyzable alkoxy groups in the alkoxy-functional product obtained in step (1) by adding a predetermined amount of water thereto; (3) inactivating the acidic cationic siloxane polymerization catalyst in the hydrolyzed product; and (4) thereafter stripping water and alcohol R 1 OH therefrom. The method of this invention results in a unique organic-modified, heat-curable silicone resin composition and heat-cured resin composition. In particular, our heat-cured resin composition exhibits far superior hardness, flexibility and solvent resistance than similar such resins prepared by prior art methods. The method of our invention may optionally include the addition of (e) a source of triorganosilyl endblocker radicals of the general formula R 3 3 Si- wherein each R 3 is a hydrocarbon radical having 1 to 6 carbon atoms, to components (a) through (d) in the reacting step (1). The triorganosilyl endblocker may be used to control the degree of crosslinking in and therefore the molecular weight of the final heat-curable resin product. It is, therefore, an object of the present invention to provide a method of preparing an organic-modified, heat-curable resin which, upon curing exhibits superior hardness, flexibility and solvent resistance. Another object is that the heat-curable resin of this invention may be combined with various pigments to produce high temperature paints. The invention provides a method of producing an organic-modified, heat-curable silicone resin composition. The method of our invention produces a novel resin composition which, upon curing, exhibits superior hardness, flexibility and solvent resistance. Our method comprises the steps of: (1) reacting, essentially to equilibrium, (a) a trialkoxysilane, (b) a difunctional diorganosilicon compound and (c) at least one polyol in the presence of (d) a catalytic amount of an acidic cationic siloxane polymerization catalyst to form an alkoxy-functional product therefrom; (2) hydrolyzing substantially all the hydrolyzable alkoxy groups of the alkoxy-functional product obtained in step (1); (3) inactivating (d) the acidic cationic siloxane polymerization catalyst; and (4) thereafter stripping water and R 1 OH alcohol therefrom. It will be understood by those skilled in the art that the terms "equilibrium" and "equilibrating," as applied to chemical reactions, denote a theoretical dynamic state that is never completely reached in actual practice. As used herein, then, these terms mean that a reaction is carried out to substantial equilibrium. In the prior art method of U.S. Patent 4,749,764, a polyol is reacted with an alkoxysiloxane. The relative amounts of polyol and alkoxysiloxane are selected such that the number of carbinol groups (COH) on the polyol and the number of OR 1 alkoxy groups on the alkoxysiloxane are approximately in a one-to-one correspondence. The reaction is terminated at a 25% to 80% degree of conversion. In our invention, components (a) through (d) are all reacted essentially to equilibrium, before carrying out an hydrolysis step to form a siloxane. The relative amounts of polyol and trialkoxysilane are selected such that the correspondence between the number of carbinol (COH) groups on the polyol and the number of OR 1 alkoxy groups on the trialkoxysilane are substantially less than one-to-one. Only after the equilibration step (1) are the remaining alkoxy groups hydrolyzed so that a three dimensional siloxane resin structure arises. The trialkoxysilane (a) has a general formula R 2 (OR 1 ) 3 Si wherein each OR 1 is independently selected from alkoxy groups having 1 to 4 carbon atoms and each R 2 is independently selected from aryl or alkyl groups. Preferred trialkoxysilanes are phenyltrialkoxysilanes and more particularly preferred is phenyltrimethoxysilane. The presence of the phenyl groups in the silane contributes to the thermal stability and oxidation resistance of our cured resin. The use of methoxysilanes is preferred because they are easily hydrolyzed and because the methanol generated during hydrolysis is easily stripped. The difunctional diorganosilicon compound (b) utilized in our invention forms linear polymer links in the final resin structure. The term "difunctional diorganosilicon compound" means a compound having a chemical formula that includes at least one silicon atom, two organic radicals bonded to each silicon atom and two reactive or functional groups which render the compound capable of polymerizing to form a linear siloxane in the presence of an acidic cationic siloxane polymerization catalyst. This catalyst is described in further detail below. Accordingly, the term "difunctional diorganosilicon compound" includes diorganodialkoxysilanes which, in the presence of the aforementioned catalyst, can be hydrolyzed to form linear diorganosiloxanes. The term "difunctional diorganosilicon compound" also includes silanol-terminated diorganosiloxanes and, in particular, silanol-terminated dimethylsiloxanes. It is known in the art that such silanol-terminated diorganosiloxanes are readily obtained by heating diorganocyclosiloxanes in the presence of the aforementioned catalyst. Particularly preferred for this invention are dimethylcyclosiloxanes including three to six silicon atoms in their structure. Component (c) is designated simply as a polyol. Polyol means any organic compound having two or more reactive COH groups in its structure. Polyols that are preferred include ethylene glycol, trimethylolethane, trimethylolpropane, neopentyl glycol, glycerin, pentaerythritol and dimethylolcyclohexane. Component (d) is an acidic cationic siloxane polymerization catalyst. Such catalysts are well-known in the art for making high molecular weight siloxane polymers from cyclosiloxanes and relatively short-chained linear polydimethylsiloxanes. Acidic cationic siloxane polymerization catalysts include strong protonic acids such as H 2 SO 4 or HCLO 4 and a variety of Lewis Acids. Also included are supported catalysts such as H 2 SO 4 -treated montmorillonite clays. Especially preferred in the present invention is the use of strong sulfonic acids such as trifluoromethane sulfonic acid. In the equilibration step (1) there may optionally be added component (e) a source of triorganosilyl endblocker having a radical of the formula R 3 3 Si- wherein each R 3 is a hydrocarbon radical having 1 to 6 carbon atoms. R 3 is a methyl, ethyl, propyl, phenyl or vinyl group. The source of the triorganosilyl endblocker radicals can be any material which, under the reaction conditions of step (1), forms the triorganosilyl radical of the formula R 3 3 Si-. A preferred source is hexamethyldisiloxane, which readily yields up the trimethylsilyl endblocker in the presence of the acidic cationic siloxane polymerization catalyst. The triorganosilyl endblocker is used to control the degree of crosslinking in (and therefore the molecular weight of) the final resin product. Component (d), the acidic cationic siloxane polymerization catalyst, performs several roles in step (1) of the invention, the equilibration reaction. When a cyclosiloxane is used as a source for the difunctional diorganosilicon compound, component (b), the catalyst (d) opens the ring structure of the cyclosiloxane, rendering a silanol-terminated linear siloxane. When a triorganosilyl-terminated linear polydiorganosiloxane is used as a source of component (b), the catalyst cleaves the molecule and forms a linear silanol-terminated diorganosiloxane as well as liberating triorganosilyl endblocker radicals, optional component (e). Likewise, the catalyst (d) causes the generation of triorganosilyl endblocker radicals from specific endblocker sources, such as hexamethyldisiloxane and hexamethyldisilazane. In addition, the catalyst (d) performs another vital function during the equilibration step (1) since it acts as a transesterification catalyst for the reaction of the COH groups on the polyol with the OR 1 alkoxy groups on the trialkoxysilane, (a), thus aiding the formation of the Si-O-C bond therebetween. After the equilibration step (1), the catalyst (d) performs one additional function. In step (2), substantially all the hydrolyzable alkoxy groups in the equilibrated alkoxy-functional product obtained from step (1) are hydrolyzed. The catalyst (d) also works to promote this hydrolysis step. With the addition of water, the catalyst-aided hydrolysis causes polymerization forming an organic-modified, heat-curable siloxane resin network. The hydrolysis step (2) of the alkoxy-functional product obtained from step (1) also yields R 1 OH alcohol. It will be recognized by those skilled in the art that the hydrolysis of alkoxy groups associated with alkoxysilanes and alkoxysiloxanes is rarely, if ever, complete. That is to say, certain of the alkoxy groups are very readily hydrolyzed under the reaction conditions described herein. Other alkoxy groups, depending upon their location in the silane or siloxane structure and the degree of polymerization of the structure, will not hydrolyze under the described reaction conditions. Accordingly, as used herein, the phrase "hydrolyzing substantially all the hydrolyzable groups in the alkoxy-functional product" in connection with step (2) means that sufficient water is added to the system to permit substantially complete hydrolysis of those alkoxy groups that are hydrolyzable under the reaction conditions. It is further understood that the amount of water added to complete the hydrolysis step (2) must, at a minimum, meet all required stoichiometry and reaction conditions. It will be recognized, however, that water in excess of that required to complete the hydrolysis step (2) will not adversely affect the resin produced thereby except to necessitate its removal during stripping step (4). After the hydrolysis step (2), the acidic cationic siloxane polymerization catalyst (d) is inactivated by known means such as the introduction of an appropriate amount of calcium carbonate. In the preferred embodiment, the amount of components (a), (b) and (c), relative to one another, used in the preparation of the heat-curable resin, are varied such that a desirable balance of physical properties is obtained in the heat-cured product. We have found that a wide range of usable coating compositions are obtained if the following quantities of materials are used in formulating the heat-curable resin: between 35 and 75 parts, by weight, of trialkoxysilane (a); between 3 and 35 parts, by weight, of difunctional diorganosilicon compound (b); and between 0.5 and 50 parts, by weight, of polyol (c), relative to the combined weights of (a), (b) and (c). Even more preferred are the ranges of: between 50 and 70 parts, by weight, of trialkoxysilane (a); between 4 and 20 parts, by weight, of difunctional diorganosilicon compound (b); and between 2 and 15 parts, by weight, of polyol (c). The physical properties of hardness, flexibility, impact resistance and solvent resistance of heat-cured resins produced by the claimed invention and the prior art were measured and compared. In addition, the same properties were measured and compared in paint formulations which independently incorporated the heat-curable resins of our invention and prior art. The tests used to measure each of the properties are explained below. Each of the tests utilized a 3X6 inch (7.52 X 15.24 cm) test panel of 20 mil (0.051 mm) thick cold-rolled steel. The test panel was coated with a heat-curable resin or a paint formulation incorporating the same, using a drawdown bar to insure a coating of uniform thickness. The coating was thereafter cured with the application of heat, in the manner hereinafter noted. Hardness Hardness of the cured resins and paint formulations was measured using ASTM D3363. ASTM D3363 rates coating hardness by attempting to scratch the surface of a coated substrate with drafting pencils of increasing lead hardness. Coating hardness is rated as the highest lead hardness that cannot scratch through the coating. Pencil hardness testing can be carried out at elevated temperatures as well as room temperature. Flexibility and Impact Resistance Flexibility and Impact Resistance were measured using the Gardner Reverse Impact Test in accordance with ASTM D2794. A coated test panel was placed on a flat base (coated side down) over a 1.5 cm diameter hemispherical depression formed in the base. A 1.8 kg shaft, having a 1.3 cm diameter hemispherical tip, was aligned over the hemispherical depression and raised a predetermined distance over the coated panel. The shaft was then dropped onto the test panel, causing deformation. The coated surface was visually inspected for crazing. The greatest height from which the shaft can be dropped without inducing crazing of the coating is a measure of the flexibility and impact resistance of the coating composition. The results are generally reported in the minimum inch-pounds (kg-meters) required to produce cracking in the coating. Solvent Resistance The solvent resistance of the cured coating compositions and paint formulations was measured using a "double rub" test in accordance with ASTM D5402. In the "double rub" test, cold-rolled steel test panels, having a cured resin coating or paint formulation (prepared by the procedure described below) were laid on a flat surface. Eight layers of cheesecloth were secured about the ball end of a 24 oz. (681 g) ball peen hammer. The cheesecloth was then saturated with a solvent, such as methylethylketone, and the ball end of the hammer brought to rest on the coated surface with the handle held horizontally. The handle was moved back and forth, in a direction perpendicular to the direction of drawdown, without the application of downward pressure on the hammer. A single forward and reverse stroke was counted as one "double rub." The double rubbing action was repeated until a breakthrough to metal was noted at the surface, disregarding the positions adjacent the stroke ends. The number of "double rubs" the coating or paint formulation of a given thickness can withstand before the breakthrough of metal is a measure of its solvent resistance. Example 1 An organic-modified, heat-curable resin of this invention was prepared by the procedure described below. No difference was noted in the physical properties of the cured resin product when the heat-curable resin was produced in batch sizes ranging from 1 kg and 200 kg. The following materials were used in the corresponding weight percents, which weight percents are based upon the total weight of materials used in the process, regardless whether the material acts in the capacity of a catalyst or is later stripped off. Material Weight Percent (a) phenyltrimethoxysilane 55.1 (b) dimethylcyclosiloxanes 7.7 (c) trimethylolpropane 4.8 (c) ethylene glycol 1.1 (d) trifluoromethane sulfonic acid 0.03 (e) hexamethyldisiloxane 2.5 deionized water 7.5 calcium carbonate 0.04 zinc octoate 0.04 tetrabutyltitanate 0.04 xylene 17.0 isobutyl alcohol 4.2 In accordance with the invention, components (a) through (e) were charged into a glass-lined reaction vessel which had been purged with nitrogen. The components were then heated to 70°C. and held at temperature for four hours, thereby reacting substantially to equilibrium, step (1). The alkoxy-functional product obtained in step (1) was allowed to cool to 50°C. and the deionized water was added thereto, thus initiating hydrolysis, step (2). The addition of water to the alkoxy-functional product obtained in step (1) is highly exothermic. The internal vessel temperature was allowed to reach reflux temperature (68°C.) and held at reflux conditions for one hour. After allowing the hydrolyzed product to cool to 50°C., step (3), inactivation of the acidic cationic siloxane polymerization catalyst, was carried out by adding calcium carbonate in an amount sufficient to neutralize the trifluoromethane sulfonic acid (d). The product was stirred for thirty minutes to insure neutralization of the catalyst (d). Step (4), stripping the composition of water and methanol, was carried out by atmospheric stripping to 110°C. and thereafter vacuum stripping. After stripping, the contents of the vessel were allowed to cool to 50°C. and zinc octoate, tetrabutyltitanate and xylene were added. The zinc octoate and tetrabutyltitanate are optional catalysts known in the art to promote condensation of an hydrolyzed alkoxy-functional product. Xylene was added to obtain a final product that is 70 weight percent solids. Finally, the isobutyl alcohol was added to promote clarity of the final heat-curable resin product. Comparative Example To compare the organic-modified heat-curable siloxane resins of our invention with those of the prior art, a sample of an organic-modified, heat-curable silicone resin, designated as Silikophen™ P80/X, was obtained from Tego Chemie Service USA, a division of Goldschmidt Chemical Corp., P.O. Box 1299, 914 E. Randolph Road, Hopewell, VA 23860. Upon information and belief, the Silikophen™ P80/X was made by the teachings of U.S. Patent 4,749,764. The resin was diluted in solvent and contained 80.2 weight percent solids. Paint Formulations The heat-curable resin of Example 1 and the Comparative Example were used to prepare three different paint formulations: medium gloss white; low gloss black; and aluminum. In each paint formulation, the pigment and resin solids were considered as constituting the total solids for the paint. The resin and pigment mixtures were diluted with xylene until the viscosity permitted the drainage of a #4 Zahn cup in 30 seconds. The paint formulations were then applied to the test panels with a 4 mil (0.1 mm) drawdown and cured for 30 minutes at 450°F. (232°C.) in an oven. The cured paint formulations were then tested for solvent resistance and hot hardness. Medium Gloss White The medium gloss white paint formulation included the following solids: 45 parts resin solids; 45 parts titania (0.35 µm median particle size); and 10 parts mica (1 X 10 -20 µm mean particle size), all by weight. Properties Example 1 Comparative Example Total Solids 80.3% 81.5% Paint thickness, mils (mm) 1.3 (0.033) 1.3 (0.033) Solvent Resistance Double Rubs Methylethylketone 180 5 Hot Hardness at: 200°F. (93.3°C.) 2B >6B 300°F. (149°C.) 3B - 400°F. (204°C.) 5B - 500°F. (260°C.) >6B - Low Gloss Black The low gloss black paint formulation included the following solids: 53.8 parts resin solids; 16.3 (calcined Mn/Cu/Fe coprecipitated compound, 0.40 µ m mean particle size); 22.7 parts mica (1 X 10 -20 µ m mean particle size); and 7.2 parts fumed silica (6.0 µ m mean particle size), all by weight. Properties Example 1 Comparative Example Total Solids 62.9% 61.2% Paint thickness, mils (mm) 1.2 (0.03) 1.2 (0.03) Solvent Resistance Double Rubs Methylethylketone 20 20 Toluene 30 14 Mineral Spirits 200+ 200+ Hardness, ambient temp. B B Aluminum The aluminum paint formulation included the following solids: 50 parts resin solids; and 50 parts aluminum paste (65 weight percent aluminum particles, 99% less than 0.044 mm), all by weight. Properties Example 1 Comparative Example Total Solids 52.8% 48.8% Paint thickness, mils (mm) 1.1 1.1 Solvent Resistance Double Rubs Methylethylketone 75 20 Toluene 110 50 Mineral Spirits 200+ 200+ Hardness, ambient temp. 2H 2H From the foregoing data, it is readily apparent that paint formulations that utilize the heat-curable resins of our invention, exhibit solvent resistance and hardness that is at least as good as or superior to that exhibited by the same formulation incorporating the heat-curable resin of the prior art. Examples 2 and 3 Examples 2 and 3 of the present invention were prepared in accordance with the procedure described in connection with Example 1, excepting differences as a result of formulation. The materials that were utilized are set forth below. Example 2 Weight Percent Example 3 Weight Percent (a) phenyltrimethoxysilane 62.0 64.7 (a) methyltrimethoxysilane 4.5 3.1 (b) dimethylcyclosiloxanes* 5.5 5.0 (c) trimethylolpropane 8.6 8.4 (c) ethylene glycol 2.0 1.9 (d) trifluoromethane sulfonic acid 0.03 0.03 (e) hexamethyldisiloxane 1.8 0.0 deionized water 8.4 8.8 calcium carbonate 0.03 0.03 zinc octoate 0.0 0.0 tetrabutyltitanate 0.0 0.0 xylene 3.5 3.5 isobutyl alcohol 0.0 0.0 Samples of the heat-curable resins of Examples 2 and 3 and the Comparative Example (at 80 weight percent solids in xylene) were coated over the previously described test panels using a 5 mil (0.127 mm) drawdown. The coated panels were cured at 600°F. (316°C.) for 10 minutes. The cured panels were then tested for hardness, solvent resistance and flexibility and impact resistance, as reported below. Comparative Example Example 2 Example 3 Solvent Resistance Double Rubs Methylethylketone 30 500 160 Hardness ambient temp. 2B 2H 2H Gardner Reverse Impact inch-lbs. (kg-meters) <1 (<0.012) 4 (0.46) 2 (0.23) It should be noted that Example 3 of the invention utilized no source of triorganosilyl endblocker radicals, component (e), in their preparation. Even so, the physical properties of the heat-cured resin of our invention are far superior to those of the prior art. The above data show that our heat-cured silicone resins represent a substantial improvement in providing coating compositions that are hard, flexible and resistant to impact and solvent attack.

Claims: A method of preparing an organic-modified, heat-curable silicone resin comprising the steps of: (1) reacting to equilibrium, relative to the combined weights of the following components (a), (b) and (c): (a) 35 to 75 parts by weight of a trialkoxysilane of the general formula: R 2 (OR 1 ) 3 Si wherein each OR 1 is independently selected from alkoxy groups having 1 to 4 carbon atoms, and each R 2 is independently selected from aryl or alkyl groups; (b) 3 to 35 parts by weight of a difunctional diorganosilicon compound; and (c) 0.5 to 50 parts by weight of at least one polyol; in the presence of (d) a catalytic amount of an acidic cationic siloxane polymerization catalyst to form an alkoxy-functional product therefrom; (2) hydrolyzing substantially all the hydrolysable alkoxy groups in the alkoxy-functional product obtained in step (1) by adding a predetermined amount of water thereto; (3) inactivating the acidic cationic siloxane polymerization catalyst in the hydrolyzed product; (4) and thereafter stripping water and alcohol R 1 OH from the product. The method of claim 1 wherein said polyol is selected from ethylene glycol, trimethylolethane, trimethylolpropane, neopentyl glycol, glycerin, pentaerythritol and dimethylolcyclohexane. The method of claim 1 wherein there is included (e) a source of triorganosilyl endblocker radicals of the general formula R 3 3 Si- wherein each R 3 is a hydrocarbon radical having 1 to 6 carbon atoms in said step (1). The method of claim 1 wherein said predetermined amount of water is in excess of the amount necessary to hydrolyze substantially all the hydrolyzable alkoxy groups in said alkoxy-functional product. The method of claim 1 wherein said difunctional diorganosilicon compound (b) is obtained by said acidic cationic siloxane polymerization catalyst (d) acting on a diorganocyclosiloxane. The method of claim 1 further comprising the step of (5) adding a condensation-promoting catalyst after said stripping step (4). The heat-curable, organic-modified silicone resin produced by the method of claim 1. An article of manufacture comprising a cured organic-modified silicone resin produced by heating the product of claim 1 coated on a substrate. A paint formulation comprising an organic-modified, heat-curable silicone resin produced by the method of claim 1 in combination with a pigment.

Inventors: WITUCKI GERALD LAWRENCE, WITUCKI, GERALD LAWRENCE
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1995
Main classification: C08G77
IPC codes: C09D183, C08G77