STABILIZER COMPOSITIONS FOR ANTIFOULING PAINTS

Abstract: The undesirable premature viscosity increase in polymer-based antifouling paints is retarded by incorporating into the formulation at least one hydroxylamine or alkanolamine in combination with a triorganotin compound. Alternatively, the reaction product of any of these materials may be utilized either singly or in combination with these components.

Description: STABILIZER COMPOSITIONS FOR ANTIFOU ING PAINTS BACKGROUND OF THE INVENTION FIELD OF THE INVENTION This invention relates to antifouling coating compositions. More particularly, this invention relates t stabilizer compositions that inhibit the increase in viscosity and eventual gelation which often occur during long term storage of • antifouling coating compositions containing cuprous oxide and polymers wherein at least a portion of the repeating units are derived from triorganot salts of ethylenically unsaturated acids. • DESCRIPTION OF THE PRIOR ART The attachment and growth of organisms such as barnacles and algae to submerged portions of a ship's hull substantially increases the resistance of the hull to passage through water. The resultant decrease in fuel efficiency and maximum speed of the vessel is sufficient t justify periodic removal of the accumulated fouling ^ . This costly operation and usually requires that the ship be out of service in a drydoc for a substantial period of time. One method commonly employed to inhibit the attachment and growth of fouling organisms to a hull, and thereby extend the period between successive cleanings and repaintings, i to apply a top coat containing an antifouling agent to all submerged portions of the hull. It has long been recogniz that triorganotin compounds such as (tri-n-butyltin)fluori are particularly effective antifouling agents. United States Patent No. 3,167,473 to John R. Leebrick teaches tha deficiencies associated with many triorganotin compounds, such as high mammalian toxicity and an excessively high rat of extractability of the triorganotin compound from a paint film by sea water, can be avoided by chemically incorpo¬ rating the triorganotin compound into a film-forming polymer. In accordance with the teaching of this patent a triorganotin derivative of an ethylenically unsaturated aci such as acrylic or methacrylic acid is polymerized either alone or in the presence of other ethylenically unsaturated compounds, preferably lower alkyl esters of acrylic or methacrylic acid, that will copolymerize with the triorganotin derivative. United States Patent No. 4,191,579 to G. H. Hails and J. D. Symonds discloses that when an insoluble, seawater- • reactive pigment and an insoluble non-reactive, pigment are present in an anti ouling topcoat applied to a hull, this combination imparts a self-leveling property to the coating as the ship moves through the water. The rate of dissolu- tion is sufficient to release an effective concentration of toxicant while avoiding premature dissolution of the topcoa and the triorganotin-containing polymer employed as both th binder and the antifouling agents. This patent teaches tha cuprous oxide and zinc oxide are two of the preferred seawater-reactive pigments. Coatings containing cuprous oxide and a polymer derived at least in part from a . triorganotin salt of an ethylenically unsaturated acid are preferred due to the antifouling activity of cuprous oxide, however these coatings .cannot be stored for more than six months due to premature gelation of the polymer. The paten discloses that if longer storage periods are required, the organotin-containing polymer and the cuprous oxide must be packaged as separate components. Such a two-package system is undesirable for commercial applications, since it can be difficult to achieve adequate uniform mixing of large amounts of two components. If the final composition is not homogeneous a coating applied using the composition may not contain the same toxicant level over its entire surface. Premature fouling is most likely to occur in those areas of relatively low toxicant concentration. In accordance with the teaching of United States Paten No. 4,187,211 to A. V. Robinson and J. Chapman, the storage stability of those antifouling compositions disclosed in th aforementioned U.S. Patent 4,191,579 containing cuprous oxide as the seawater-reactive pigment can be substantially increased by including in the composition a relatively iner and water insoluble dehydrating agent such as the anhydrous .and hemihydrate forms of calcium sulfate or various water- reactive organic compounds such as the aliphatic iso- cyanates. Experimental data have demonstrated that in an accelerated aging study conducted at a temperature of 50°C the viscosity of a coating composition containing anhydrous calcium sulfate, a polymeric triorganotin toxicant and cuprous oxide increased at a faster rate than a control sample in which the calcium sulfate was omitted. OMPI SUMMARY OF THE INVENTION It has now been found that through the use of specifi triorganotin compounds and nitrogen compounds and/or reaction products of these compounds, the gelation of the coating compositions of the type disclosed in U.S. Patent 4,191,579, can be prevented even after being stored for up to three months or longer at a temperature of 50°C. In addition, the viscosity of the compositions remain within acceptable limits for application to ship hulls by any of the conventional means. This invention provides stabilizer compositions which effectively retard the gradual increase in viscosity and ultimate gelation characteristic of antifouling paints containing a polymeric triorganotin carboxylate and cuprou oxide. The stabilizer compositions comprise one or both o (1) a mixture containing (a) a monomeric triorganotin compound and (b) a secondary or tertiary hydroxylamine or alkanolamine, and (2) a reaction product of (a) and (b). OMH DETAILED DESCRIPTION OF THE INVENTION This invention provides stabilizer compositions for antifouling coating formulations containing a solubilized polymeric, triorganotin carboxylate, cuprous oxide, and/or zinc oxide where the stabilizer comprises one or both of 1 a mixture containing (a) a triorganotin compound and (b) a nitrogen compound of the general formula or 2 ) a reaction product of the triorganotin compound and nitrogen compound, where and R 2 are individually selected from the group consisting of hydrocarbyl,substituted hydrocarbyl, (CH2) n ° H » hydrogen 0 II and -CR 3 where R 3 is hydrocarbyl, with the proviso that R! and R 2 cannot both be hydrogen and n is 0 or an integer from 1 to 4, inclusive. In a narrower embodiment of this invention the triorganotin compound exhibits the formula R^SnX or (R< Sn)2Y where R 4 is hydrocarbyl, X is halogen, pseudohalogen or the residue remaining following removal o the labile hydrogen atom from an alcohol, phenol, mercaptan carboxylic acid or mineral acid, -OR^ or -SR 5 , where 5 is alkyl containing from 1 to 20 carbon atoms, phenyl or benzyl, Y is oxygen or sulfur, R 1 and R 2 of the . foregoing formula or the nitrogen compound are hydrogen , alkyl, CH2)nOH, cycloalkyl or aryl or acyl and n is 0, 2, 3 or 4, or one or both of R 1 and R 2 are (CH2) n OH and any remaining R 1 and R 2 is hydrogen, n is 2 or 3 and the weight ratio of the triorganotin compound to the nitrogen compound is from 1:1 to 10:1, respectively. Preferably the triorganotin compound is an effective antifouling agent, in which instance R^ is lower alkyl LE containing from 1 to 4 carbon atoms, a substituted lower alkyl, phenyl or substituted phenyl group. The nitrogen compound is an N,N-dialkyl, a mixed aryl alkyl, aryl acyl, or alkyl acyl hydroxylamine or a di- or trialkanolamine of the general formula [HO(CH2) n ] n H3_ n where is 2 or 3, n is 2 or 3 and the weight ratio of the triorganotin compound to the nitrogen compound is from 3:1 to 6:1, respectively. Most preferably the triorganotin compound is bis(tri-n-butyltin)oxide, the nitrogen compound is either N,N-di(lower alkyl) hydroxylamine, such as N,N-diethyl- hydroxylamine, or an alkanolamine such as diethanolamine triethanolamine. The weight ratio of the triorganotin com pound to the nitrogen compound is about 5:1, respectively, hen the nitrogen compound is a hydroxylamine and 4:1 to 6: when the nitrogen compound is an alkanolamine. Another aspect of this invention provides antifouling coating compositions containing one of the aforementioned stabilizer compositions, cuprous oxide and at least one polymeric triorganotin carboxylate. In a narrower embodiment the triorganotin carboxylate is a homopolymer of a tri(lower alkyl)tin- or triphenyltin salt of an ethylenically unsaturated acid or a copolymer o this salt and at least one additional copolymerizable ethylenically unsaturated compound. In preferred embodiments the ethylenically unsaturate acid is acrylic or methacrylic acid and any comonomers employed to prepare the polymer are esters of acrylic or methacrylic acid and an alcohol containing from 1 to 8 carbon atoms. The repeating units containing the triorganotin (R^Sn-) residue constitute from 20 to about 80 mole % of the repeating units present in the polymeric triorganotin carboxylate. The weight ratio of polymeric triorganotin carboxylate to cuprous oxide and/or zinc oxid is from about 3:1 to 1:7 and R 4 is butyl or phenyl. OMPI THE NITROGEN COMPOUND One of the components of the present stabilizer compo sitions is a hydroxylamine or a di- or trialkanolamine. These compounds exhibit the general formula When the nitrogen compound is hydroxylamine, n is 0 a R 1 and R 2 can be identical or different hydrocarbyl, substituted hydrocarbyl, (CH 2 n 0H» hydrogen or acyl O H (-CR 3 ) groups, where R 3 is hydrocarbyl with the proviso that R 1 and R 2 cannot both be hydrogen. Preferably R 1 and R 2 are identical and represent linear or branched chain alkyl groups containing from 1 to 20 carbon atoms, benzyl, phenyl or benzoyl. Most preferably when R 1 and R 2 are alkyl they contain from 1 to 4 carbon atoms. As used in this specification the term "hydrocarbyl" includes linear and branched chain alkyl containing. rom 1 to 20 carbon atoms, cycloalkyl containing from 5 to 8 carbon atoms, aryl, alkyl substituted aryl groups (referred to as alkaryl) such as tolyl and xylyl and aryl substituted alkyl groups (referred to as aralkyl) such as benzyl and -phenylethyl. The hydrocarbyl groups represented by R 1 and R 2 in the foregoing formula can be unsubstituted or may contain 1 or more substituents. When substituents are present they can be relatively unreactive groups such as hydrocarbyloxy, cyano, carboxyl (RCOO- where R is hydrocarbyl) and nitro, or reactive groups such as halogen, hydroxyl, mercapto (-SH) , carboxy (-COOH) and isocyanato (-N=C=O). Preferably any substituents present should also not react with any components of the final coating formulation containing the stabilizer compositions of this invention, since such reactions could adversely affect the stability o the formulation. The hydroxyla ines and salts thereof that are commer¬ cially available include N,N-diethyIhydroxylamine and N,N-dimeth lhyάroxylammonium hydrochloride. Representative hydroxylamines that can be employed according to the presen invention include N-phenyl, N-benzoyl hydroxylamine N-benzoylhydroxylamine N,N-dibenzoylhydroxylamine N-methyIhydroxylamine N-butylhydroxylamine N,N-dibutyIhydroxylamine N,N-trifluoromethyIhydroxylamine N-benzyl-N-o-tolyihydroxylamine N-furoyl-N-phenyIhydroxylamine ,N-dimethylh άrox 1amine N-ethyIhydroxylamine When the nitrogen compounds is a di- or tri- alkanolamine, n of the foregoing formula is an integer from 1 to 4, R 1 is -(CH 2)nOH and R 2 is -(CH 2_.)nOH, a . hydrocarbyl group or hydrogen. Preferably n is 2, R is -CH 2 CH 2 OH and R 2 is -CH 2 CH 2 0H or hydrogen, this preference being based on the efficacy of stabilization. Alkanolamines that can be employed according to this invention include dimethylethanolamine diethylethanolamine ethylethanola ine diisopropylethanola ine butyldiethanola ine methylethanolamine ethyldiethanolamine ethyldiethanolamine isopropylethanolamine n-butylethanolamine dimethylisopropanolamine cyclohexyldiethanolamine phenylethanola ine N-cyanoethyl-N-hydroxyethyl aniline m-tolyldiethanolamine £-methoxyphenyldiethanolaιnine. ( _ OM THE TRIORGANOTIN COMPOUND The triorganotin compound present in the stabilizer compositions of this invention contains three hydrocarbyl groups bonded to the tin atom. The fourth valence of the tin atom is satisfied by oxygen, sulfur, a halogen atom, a pseudohalogen or the residue remaining following removal of the labile hydrogen atom from an organic or inorganic acid, alcohol, phenol, mercaptan, ercaptoalcohol or ester thereof, mercaptocarboxylic acid or ester thereof, or any other organic or inorganic compound containing a labile hydrogen atom. When an oxygen or sulfur atom is bonded to tin, the compound is a bis(triorganotin)oxide or -sulfide, respectively. Preferably the three hydrocarbyl groups bonded to the tin atom are either lower alkyl containing from 1 to about atoms or phenyl. This preference is based on the relativel high level of activity against fouling organisms exhibited by this class of compounds. This activity complements the antifouling activity of the polymeric triorganotin compound and the cuprous oxide that comprise the toxicant component of antifouling coating compositions containing the stabilizer compositions of this invention. The three hydrocarbyl groups bonded to the tin atom can be identical or different. Triorganotin compounds containing 2 or 3 different hydrocarbyl groups bonded to tin are reported in the. literature. When the fourth group bonded to the tin atom is haloge it can be fluorine, chlorine, bromine or iodine. The term "pseudohalogen" refers to inorganic radicals which, when in the form of anions exhibit chemical properties similar to those of the halide ions, in that they combine with hydroge to form acids and react with silver ion to form water-insoluble salts. The pseudohalide ions include cyanide, thiocyanate (SCN~) , cyanate (OCN~) , isocyanate (NCO~) and isothio- cyanate (NCS~) . Suitable carboxylic acids that can be reacted with a triorganotin halide, hydroxide or bis(triorganotin)oxide to form triorganotin compounds suitable for use in preparing the compositions of this invention include but are not limited to acetic, propionic, butyric, hexanoic, octanoic, dodecanoic, 2-ethylhexoic, eicosanic, benzoic and cyclo- hexanecarboxylic. Suitable inorganic acids can be mono- or polyfunctional and include among others, nitric, phosphoric phosphorous and sulfuric. O PI EXAMPLE I This example demonstrates the reduced rate of viscosi increase exhibited by an antifouling paint formulation containing a stabilizer composition of this invention relative to an unstabilized formulation. A paint formulation was prepared by blending 0.8g of Bentonite Clay (Bentone®27) and 5.2g of Colloidal Silica (Cab-O-Sil-PTG) in a mixture of 0.9g of methanol, 33.7g of methyl isobutyl ketone and 65.2g of xylene, in a quart (1 liter) sized stainless steel container for approximately five (5) minutes. To this container was added 250. g of a organotin acrylate copolymer solution, 229.6g zinc oxide a 164.2g of cuprous oxide (Glidden Co.) along with approxi¬ mately 400ml of steel shot, approximately 1/8" in diameter The paint was shaken on a Red Devil Paint Shaker for approximately one hour. The paint had a fineness of grind of 5 (approximately 30 microns) on a Hegman gauge. The steel shot was removed by passing the paint through a fine mesh tea strainer. A solution of 4.17g of bis(tri-m- butyltin)oxide, 0.83g of N,N-diethyIhydroxylamine and 5.0g of methyl isobutyl .ketone was slowly dispersed into t paint under high speed stirring. Stirring was continued f 5 minutes after complete dispersal. The viscosity was determined at 25°C, using a Brookfield viscometer, Model RVF-100 and a number 4 spindle rotating at a speed of 20rp The organotin acrylate copolymer solution employed in the formulation was prepared as described in United States Patent No. 4,260,535, the relevant portions of which are hereby incorporated by reference. After the viscosity had been measured, a sample of th coating composition was subjected to an accelerated aging test by placing it in a thermostatically controlled oven maintained at a temperature of 50 C C After 12 weeks the viscosity increased from 800 to 1500 centipoises, which is considered acceptable for a commercial antifouling paint. For purposes of comparison, a paint of the same formulatio in which the bis(tri-n-butyl)tin oxide and N, N-diethyl- hydroxylamine were omitted exhibited an initial viscosity 3100 centipoises. After 12 weeks at 50°C, the viscosity increased to 22,000 centipoises. The correlation between the rate of viscosity increas of a paint observed during an accelerated stability test conducted at elevated temperature with the rate that would be observed at ambient temperature is estimated to be twelv weeks at 50°C equals one year at room temperature. Addition examples of this invention appear in Table I. The added stabilizers show significant viscosity stabili- zation over those systems which only contain added solvent. The efficiency of stabilizers of the same composition was found to depend on the method of paint preparation. Th amount of polymer and stabilizer in the grinding or let-dow phases of the paint preparation as well as the grinding tim influenced the viscosity stability of the paint as Table II illustrates. When the paint processing variables are taken into account, the effectiveness of the TBTO/DEHA stabilizer system versus TBTO is clearly demonstrated as Table III illustrates. J 3RE 13a *CU«0 TEST PAINT FORMULATION TEST FORMULA 1 Inσredient Parts by Weight Organotin copolymer solution (50% solids) 276.9 ZnO 254.0 Cu.,0 181.7 Cab-o-Sil a 5.8 Bentone 27 0.84 MeOH 0.98 MIB 21.6 Xylene 72.1 ***Cu,0 TEST PAINT FORMULATION TEST FORMULA 2 Inσredient Parts by Weight Organotin copolymer solution (50% solids) 406.5 Cu 2 0 333.0 Fe 2°3 289.0 Bentone 38 7.5 Methanol 2.5 Xylene 210 .0 . Cabot Corp., Boston, Mass. NL Industries Inc., Hightstown, N.J. OMP TABLE I STABILIZERS FOR ANTIFOULING PAINTS* Viscosity (CPS) Time (Weeks) at 50°C omposition Trial 0 1 10 11 12 %**TBTO/DEUA(5/l) 1 1500 4700 2 1250 3600 3 1600 4600 5200 %R.P. TBT0(1 mole)/ » EHΛ (2 mol) 1 1600 4650 2 1600 3800 5000 % TBTO/DEΔ (5.7/1) 550 5400 10000 %R.P.TB1O/DEΛ (] mol/1 mol) 1100 3700 6000 17200 % TBTO/TFA (5.9/1) 900 5450 10000 % R.P. TIVIO/TI.'Λ (1 nnl/0.67 not) 2600 4950 13000 1 TBTO 1.160 4200 5750 10600 % TBTO 1420 5100 7350 .5% nraiΛ*** 500 Gelled .22% DEIIΛ*** 575 9300 2% DFΛ 1450 13000 2% TFΛ 2600 120000 2% EIOH 3150 25000 2% MIBK 4100 25000 atios are on a weight basis unless otherwise indicated. *Composition of paints attached (Test Formula 1) . **Stabilizers added at 2% by weight of organotin copolymer solution. ***Paint contained only Cu„0 pigment. No ZnO was used (Test Formula 2) R.P. = Reaction Product TBTO bis(tributyltin)oxide DEUA N,N-dieth Ihydroxylamine DFA diethanolamine TEA triethanolaπύne ETOIt ethanol MIBK methyl isobutyl ketone TABLE II Effect of Processing Variables on Stabilizer Efficiency Grind Time 7.5 min. 30 min. 60 min. Stabilizer Processing Variables Vi (cp) Vf(cp) VI (cp) Vf (cp) Vi (cp) Vf (cp) 2% BTO/DEΪIA In grind with 20% polymer 1930 4665 1900 5030 _ it I. n 75% ■■ 1710 3590 1800 1465 _ - 2% TBTO/DEUA In let down with 20% polymar 11.70 2750 1100 1910 1060 2150 II II II II -1CJ 0 1860 3705 1960 3160 1500 3420 TABLE III Effect of Processing Variables on Stabilizer Efficiency With 20% Polymer With 75% Polymer Stabilizer Variables Vi (cp) Vf (cp) %Δ Vi (cp) Vf (cp) %Δ 2% TBT0/DEI1A In grind, 30 minutes 2000 4150 108 2060 2720 32 2% TBTO II II II tl 1240 5115 312 1950 7240 271

Claims: 14 WHAT IS CLAIMED IS: 1. A viscosity stabilizer for compositions comprisin (1) a solubilized polymer derived at least in part from at least one triorganotin derivative of an ethylenically unsaturated carboxylic acid and (2) cuprous oxide, zinc oxide, or a mixture of cuprous and zinc oxides, said viscosity stabilizer comprising at least one of a) a mixture comprising 1) an organotin compound selected from the group consisting of triorganotin halides thioalkoxides, alkoxides, hydroxides, bi (triorganotin) oxides and bis(triorgano- tin) sulfides, 2) a nitrogen compound of the general formu b) the reaction product of said organotin compou and said nitrogen compound, where R and R^ are individually selected from hydrocarbylsu stituted hydrocarbyl groups, (CH 2 ) n ° H » O hydrogen and -CR^, where R^ is hydrocarbyl with the proviso that R and ^ cannot both be hydrogen, and n is 0 or an integer from 1 t 4, inclusive. 2. A viscosity stabilizer according to Claim 1 wherei the weight ratio of the organotin compound to the nitrogen compound is from 1:1 to 10:1. 15 3. A viscosity stabilizer according to Claim 2 wherei the weight ratio of the organotin compound to the nitrogen compound is from 3:1 to 6:1. 4. A viscosity stabilizer according to Claim 1 where Rl and R 2 are individually selected from the group consisting of alkyl, cycloalkyl, aryl, (CH2> n OH, hydrogen and acyl. 5. A viscosity stabilizer according to Claim 4 where R and R 2 are alkyl containing from 1 to 20 carbon atoms and n is 0. 6. A viscosity stabilizer according to Claim 5 where Rl and R 2 are lower alkyl containing from 1 to 8 carbon atoms. 7. A viscosity stabilizer according to Claim 6 where Rl and R 2 are ethyl. 8. A viscosity stabilizer according to Claim 1 where R 1 is (CH_2) n OH, R 2 is H or (CH2 n 0 H and n is 2. 9. A viscosity stabilizer according to Claim 1 where said triorganotin derivative is a tri(lower alkyl)tin derivative, where each alkyl group contains from 1 to 4 carbon atoms, or a triphenyltin derivative. 10. A viscosity stabilizer according to Claim 9 where said tri(lower alkyl) in derivative is a tributyltin derivative. 16 11. A viscosity stabilizer according, to Claim 1 wher said ethylenically unsaturated acid is acrylic or methacrylic acid. 12. A viscosity stabilizer according to Claim 1 wher said polymer is derived in part from at least one non-tin-containing ethylenically unsaturated compound. 13. A viscosity stabilizer according to Claim 12 whe the non-tin-containing ethylenically unsaturated compound an ester of acrylic or methacrylic acid and an alcohol containing from 1 to 8 carbon atoms. 14. A viscosity stabilizer according to Claim 1 wher R 1 and R 2 are lower alkyl containing from 1 to 8 carbon atoms and n is 0 or 2. 15. A viscosity stabilizer according to Claim 14 wher and R 2 are methyl, ethyl or n-propyl. 16. A viscosity stabilizer according to Claim 1 where the organotin compound is of the general formula RgSnX or R3Sn)2 where R 4 is hydrocarbyl or substituted hydrocarbyl, X is halogen, -OH, -SR 5 or OR^, where R 5 is alkyl containing from 1 to 20 carbon atoms and Y is oxygen or sulfur. 17. A viscosity stabilizer according to Claim 16 wher R 4 is phenyl, inertly substituted phenyl, cycloalkyl containing from 6 to 8 carbon atoms, lower alkyl containing from 1 to 4 carbon atoms, -or substituted lower alkyl. 17 18. A viscosity stabilizer according to Claim 16 whe the organotin compound is bis(tri-n-butyltin) oxide, triphenyltin hydroxide or bis(triphenyltin)oxide. 19. An antifouling paint composition comprising (1) solubilized polymer derived at least in part from at least one triorganotin derivative of an ethylenically unsaiturat acid, (2) a pigment comprising cuprous oxide, zinc oxide o a mixture of cuprous and zinc oxides and (3) a viscosity stabilizer of any of Claim 1-18. 20. An antifouling paint composition according to Claim 19 where the concentration of the viscosity stabiliz is from 0.1 to 10, based on the weight of the polymer solids. 21. An antifouling paint composition according to Claim 20 where the concentration of the viscosity stabiliz is from about .5 to about 6% , based on the weight of the polymer solids. 22. An antifouling paint composition according to Claim 19 where the composition includes an non-reactive solvent. 23. A method for stabilizing the viscosity of- a pain composition comprising (1) a solubilized polymer derived at least in part from at least one triorganotin derivative of an ethylenically unsaturated carboxylic acid and (2) cupro oxide, zinc oxide, or a mixture of cuprous and zinc oxides, where the method comprises incorporating into said composition a viscosity stabilizer in accordance with any o Claim 1-18. OMPI 18 24. A method according to Claim 23 where the concentration of the viscosity stabilizer is from 0.1 to 10%, based on the weight of the polymer solids. 25. A method according to Claim 24 where the concentration of the viscosity stabilizer is from .5 to 6.0%, based on the weight of the polymer solids.

Inventors: BEDNARSKI JOHN RICHARD, GITLITZ MELVIN H, RUSSO DAVID ALAN, BEDNARSKI, JOHN, RICHARD, GITLITZ, MELVIN,H., RUSSO, DAVID, ALAN
Applicants: M & T CHEMICALS INC, M&T CHEMICALS INC.
Application year: 1983
Main classification: C09D5
IPC codes: C09D5