AU609710B2 - Thermoset acrylic coatings having improved gloss retention - Google Patents
Thermoset acrylic coatings having improved gloss retention Download PDFInfo
- Publication number
- AU609710B2 AU609710B2 AU68916/87A AU6891687A AU609710B2 AU 609710 B2 AU609710 B2 AU 609710B2 AU 68916/87 A AU68916/87 A AU 68916/87A AU 6891687 A AU6891687 A AU 6891687A AU 609710 B2 AU609710 B2 AU 609710B2
- Authority
- AU
- Australia
- Prior art keywords
- component
- weight
- percent
- amount
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Agent: Spru 3on and Ferguson No legal~~o or other -wjitness required \L VVr' General Patent Counsel AU-AI-68916/8 7 Pcr WORLD INTELLECTUAL P PERTy ORGANIZATION INTRN TIOA APo at0 urea INTRNTINA APLIATION6BQHUN ERTEPO NTCOOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) Yntemational Publication Number: WO 88,/ 05441 C08F 2/06, 20/26, 20/28 C08F 20/44, 20/50, 22/14 Al C08L 33/14, 33/20, 33/22 (41) International Publication Date: 28 July 1988 (28.07.88) C08L 61/28 (21) Intarnational Application Number: PCT/US87/00092 (22) International Filing Date: 14 January 1987 (14.01.87) (71A) Applicant: THE DOW CHEMICAL COMPANY [US/ US]; 2030 Dow Center, Abbott Road, Midland, MI 48640 This document cratjfs the (72) Inventor: McFADDEN, Russell, T. 424 Bluebonnet Famendments made under Road, Freeport, TX 77541 S ection 49 and is correct for (74) Agent: KARADZIC, Dragan, The Dow Chemical printing Company, P.O. Box 1967, Midland, MI 48641-1967 P- 15 SEP 1988 (81) Designated States: AU, JP.-
AUSTRALIAN
Published 10 AUG 1988 With international search report.
PATENT OFFICE (54) Title: THTERMOSET ACRYLIC COATINGS HAVING IMPROVED GLOSS RETENTION (57) Abstract The weatherabilky of acrylic coatings is enhanced by incorpor@,ting into the acrylic polymer 2-hydroxybutyl acrylate or 2-hydroxybutyl mqthacrylate.
P Ti NT0 'T S WO 88/05441 PCT/US87/00092 -1- THERMOSET ACRYLIC COATINGS HAVING IMPROVED GLOSS RETENTION The present invention pertains to acrylic polymers containing hydroxybutyl acrylate and to coatings prepared therefrom.
Thermoset acrylic coatings have been employed in the automobile industry for top 'coatings on automobiles. While these coatings are very durable and withstand extreme variations in temperature and moisture environments, there is a need to improve their weatherability in terms of gloss retention.
The present invention provides a method for improving the gloss retention of thermoset acrylic coatings by replacing at least a portion of the hydroxy functional component with hydroxybutyl acrylate or hydroxybutyl methacrylate or a combination thereof.
One aspect of the present invention concerns an acrylic polymeric composition comprising a curable polymer resulting from polyermizing a monomer composition consisting of at least one polymerizbe at least one polymerizable WO 88/05441 PCT/US87/00092 -2monoethylenically unsaturated ester of a saturated aliphatic or aromatic monocarboxylic acid in an amount of from 0 to 40, preferably 0 to 14, percent by weight of the total weight of the monomer composition; at least one polymerizable alkyl or aryl ester of a monoethylenically unsaturated monocarboxylic acid in an amount of from 30 to 60, preferably to 54, percent by weight of the total weight of the monomer composition; at least one polymerizable hydroxyalkyl ester of a monoethylenically unsaturated monocarboxylic acid in an amount of from 10 to 40, preferably 25 to 39, percent by weight of the total weight of the monomer composition, at least one polymerizable monoethylenically unsaturated monocarboxylic acid free of ester groups in an amount of from 0 to preferably 1 to 2, percent' by weight of the total weight of the monomer composition; acrylonitrile, methyacrylonitrile or mixture thereof in an amount of from 0 to 15, preferably 0 to 14, percent by weight of the total weight of the monomer composition; at least one polymerizable alkyl or aryl ester of a monoethylenically f WO 88/05441 PCT/US87/00092 unsaturated dicarboxylic acid in an amount of from 0 to 20, preferably 0 to 14, percent by weight of the total weight of the monomer composition; and at least one polymerizable monoethylenically unsaturated aromatic monomer free of acid and ester groups in an amount of from 0 to 50, preferably 20 to 34, percent by weight of the total weight of the monomer composition; and (II) a suitable solvent or mixture of solvents wherein component(I) is present in an amount of from 40 to 80, preferably 65 to percent by weight of the total weight of the polymeric composition and.component (II) is present in an amount of from 20 to 60, preferably 25 to 35, percent by weight of the total weight of the polymeric composition characterized by employing 2hydroxybutyl acrylate or 2-hydroxybutyl methacrylate or a combination thereof as at least a portion of component in an amount such that at least 75 equivalent percent of the hydroxyl groups contained in component is derived from 2hydroxybutyl acrylate, 2-hydroxybutyl methacrylate or a combination thereof.
For the purposes of this application, the terms "aromatic" and "aryl" shall refer to "the six-carbon ring characteristic of the molecules of all organic compoun,do of benzene and related series, or the
I
WO 88/05441 PCT/US87/00092 -4condensed six-carbon rings of naphthalene, anthracene, phenanthrene, etc." as defined by the CONDENSED CHEMICAL DICTIONARY, Reinhold Publishing Corp., page 108 for "aromatic nucleus" and page 112 for "aryl".
Another aspect of the present invention pertains to an acrylic coating composition comprising one or more of the aforementioned polymeric compositions and a curing quantity of one or more curing agents 'for component Another aspect of the present invention pertains to an article coated with one or more layers of the aforementioned acrylic coating compositions.
The acrylic polymers of the present invention can be prepared by polymerizing a mixture of the monomers in the presence of a suitable catalyst or mixture of catalysts and in the presence of a suitable solvent or mixture of solvents. The temperature can be from 70°C to 165'C, preferably from 125 0 C to 150 0
C.
Suitable polymerizable monoethylenically unsaturated monocarboxylic acids which can be employed herein include, for example, acrylic acid, methacrylic acid, crotonic acid, vinyl benzoic acid, or mixtures thereof.
Suitable polymerizable alkyl or aryl esters of monounsaturated monocarboxylic acids which can be employed herein include, for example, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, amyl ccA-Y\ Me.A"-crcrYvAe l acrylate, amyl methacrylate, hexyl acrylate/, hexyl Wo 88/05441 PCT'US87/100092 methacrylate, 2-ethyihexyl acrylate, 2-ethyihexyl methacrylate, or mixtures thereof.
Suitable polymerizable monoethylenically unsaturated esters of saturated aliphatic or aromatic monocarboxylic acids which can be employed herein include, for example, vinyl acetate, vinyl propionate, vinyl benzoate, allyl acetate, allyl propionate, allyl benzoate, or mixtures thereof.
Suitable hydroxyalkyl esters of monoethylenically unsaturated monocarboxylic acids which can be employed herein include, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, or mixtures thereof.
Suitable polymerizable alkyl or arylb\ekers of monoethylenically unsaturated dicarboxylic acids which can be employed herein include, for example, diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, di(2-ethylhexyl) maleate, di(2-ethyl- hexyl) fumarate, or mixtures thereof.
Suitable polymerizable monoethylenically unsaturated aromatic monomers which can be employed herein include, for example, styrene, a methyl styrene, t-butyl styrene, chlorostyrene, vinyl toluene, or mixtures thereof.
Suitable solvents which can be employed herein include, for example, aliphatic esters, alcohols, ketones, -aromatic hydrocarbons, C 8 to C 12 aliphatic or cycloalipnatic hydrocarbons. hydroxyethers, glycol ethers, alkoxycarboxylic esters, or mixtures thereof.
(I
1 -z.
L. WO 98/05441 PCT/LS87fl0092 -6- Particularly suitable solvEnts include, for example, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, octyl acetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, 2-ethoxyethyl acetate, 1-methoxypropyl-2-acetate, n-butanol, l-methoxypropyl-2-propionate, 1-methoxypropyl-2-butyrate, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 2-butyoxyethanol, 2-ethoxyethanol, octane, nonane, decane, undecane, dodecane, or mixtures thereof.
Suitable polymerization catalysts or initiators which can be employed herein include, for example, organic peroxide and organic azo compounds such as, for example, dicumy peroxide, t-butyl peracetate, benzoyl peroxide, di-t-butyl peroxide, tertbutylazo(isovaleronitrile)'ethyl 3,3-di(t-amylpercxy)butyrate, 2,4pentane- dione peroxide, 1,1 -azobis(oyclohexane carbonitrile), or mixtures thereof.
Suitable curing agents which can be employed herein include, for example, melamine-formaldehyde resins, particularly the methylated form, hexamethoxymethyl melamine, or the mixed methylated/butylated forms; urea-formaldehyde resins; or poly(isocyanate)compounds, such as isophorone dilsocyanate as the free isocyanate or in the blocked form, or mixtures thereof., Particularly suitable curing agents include, for example, hexamethoxymethyl melamine.
The coatings can be cured by heating at temperatures of from 70C to 150'C, preferably from. 100C ro 1256C in the presence of a suitabe catalyst.
i WO 1- i.. G~ il- 88/05441 PCT/US87/00092 The coating compositions of the present invention can be applied to any suitable substrate Swhich can withstand the curing conditions. They ire particularly suitable for coating metals, previously coated metals, composite structures such as polyester- -fiber glass, epoxy resin-fiber glass, extruded plastic objects having softening points above the bake temperatures and the like.
The coating compositions of the present invention can also contain, if desired, pigments, fillers, dyes, flow and leveling agents, flatting agens, curing catalysts, and the like in any combination.
The following examples are illustrative of the invention but are not to be construed as to limiting the scope thereof in any manner.' EXAMPLE 1 A. Preparation of Polymer In a conventional glass polymerization vessel was charged 257 g of 2-ethoxyethyl acetate solvent.
After heating to reflux temperature (145°C) with stirring, a mixture consisting of 87.6 g of styrane, 87.6 g of methyl methacrylate, 265 g of butyl acrylate, 142.5 g(1 hydroxy equivalent) of hydroxybutyl acrylate, 29.4 g of acrylic acid and 18 g of tertbutylazo(isovaleronitrile) was added dropwise over a period of 6.75 hours a4 140 0 C to 150 0 C. The mixture was maintained at 150 0 C for 5.25 hours more and then cooled and stored in a suitable container.
i, WCQ 88/05441 PC7kUS87100092, -8- The above procedure was repeated substituting one at a time the following hydroxyalkyl acrylate or methacrylate monomers for the hydroxybutyl acrylate.
116.4 g (1 hydroxyl equiv.) of 2-hydr'oxyethyl acrylate 130.5 g (1 hydroxy equiv.) of 2-hydroxypropyl acrylate 130.5 g (1 hydroxy equiv.) of 2-hydroxyethyl methacrylate 142.5 g (1 hydroxy equiv.) of 2-hydroxypropyl methacrylate The properties of the resulting copolymers are given in the following Table I.
TABLE I liydroxy Alkyl Monomer Appearancet 2-HEA'* 2-IIPA 2-ILIA cl1evr, yellc:q clear, yellow clear, yel low faintly turbid faintly turbid Viscosity cP/Pa-s 508:015.08 356013.56 2860/2.86 5050/5.05 5050/5.05 Non-Vol.
'70.-0 69.2 69._1 70.1i 69.8 9800 6100 5700 5630 3880 21400 2200 Molecular MW6 2200 Wt.
M n
T
2-Il EMA'* 2-IIIMA 2180 15140 *Noft att example of the present invention "2-bydroxyethyl acrylate, -2-hy droxy propyl1 acryla te, ~2-hydroxybutyl acrylate '2-hydrnxyethyl methaerylate ,2-hydroxypropyl methacrylate "14w weight average moleciih2r weight 'Mn =.number average molreular weight WO 88/05441 PTL8/09 B. Preparation of White Pigmented Baking Enamel The copolymer prepared in A above was formulated into a white baking enamel by blending in a one S pint (237 ml) paint Qan by means of a high-shear mechanical disperser, known as a Cowels Dissolver, the fol"owing components.
ENAMEL RECIPE Pigment Grind copolymer solution from A above Cymel' 325*, curing agent n-butanol, solvent methyl amyl. ketone, solvent Dow-Corning Paint Additive #57 146 g 42.6 gr 32, 1 g 17.24 g 0. 16 g 0. 11 g 111 g p-toluenesulfonic acid in i-propan].
TIPure W..90? TiD, pigment.
*Cymel" 3P5 is hexarnethoxy methyl melamine commercially available Prom American Cyanamid Co, Di luent methyl amyl. ketone to Provide, the coating with a viscosity of 120 op (0,12 Palls)
A
*1c WO 88/05441 PCT/US87/00092 -11- C. Coating Substrate and Baking Enamel The five enamels prepared as above were airsr-ayed onto primed 24-gauge (0.7 mm) Bonderite panels to give dry-film thicknesses of 1.5-2.0 mils (0.0381-0.0508 mm) after baking 20 minutes at 150 0
C.
These coated panels were then exposed outdoors on a rack facing south and inclined 450 to the vertical, in Freeport, Texas. The panels were tested after twenty months' exposure for gloss retention and after thirty months' exposure for gloss retention and chalking. The results are given in the following Tables XI and III.
The thirty month evaluation was more detailed than the twenty month evaluation. The gloss measurements were 1 taken as is, after rinsing with deionized water, and after washing with-deionized water and a soft cotton cloth. Gloss measurements were made at both 60' and 200C. The coatings were tested for chalking before Q2 rinsing and the forward impact resistance was measured for comparison to the original values.
jIjIiIJ--CkI P.'Ay I I I I CC V J ~LCI 'JI kU IJZ I 1 11 0.I CIIIIUII L JI from 0 to Ipercent by weight of the total weight of the monomer composition; /2
-U.
WO 88/0:5441 PCTi'LS87iOOO92 -12- TABLE II TWENTY MONTH EXPOSURE Hydroxy Alkyl Monomer 2-HEAt* 2 -H P A* 2-HBA' 2 -HEMA 4 2-HPMA"* 600 Gloss Gloss Retention of Original Initial After 20 Mos..
*Not an example of the present invention ~2-hydroxyethyl acrylate 12-hydroxypropyl acrylate '2-hydroxybutyl acrylate '2-hycdroxyethy. zethaorylate 12-hydroxypropyl methaor'ylate TABLE III THIRTY MONTH EXPOSURE P -rE-02 rtY Original 600 Gloss, Gloss Retention,% tnrinsed Rinsed Washed Rinsed Washed Chalking Forward Impact Resistance Original.- in-lb/J Final, in-lb/J 2-KHEA' 2-HPAM*. 2-HBA' 2-HEMA' 2-HPMAi* 94 31 1 3 24 92 92 slight slight slight none very slight 16/1.81 6/0.68 12/1. 36 7/0,79 1 4/1. 5 8 5/0 .56 14/1.58 16/1.81 8/0.90 7/0.79 *Not an example of the present invention 12-hydroxyethyl acrylate *2-hydroxypropyl acryla.'e '2-hydroxylbutyl acrylate 1-2-hydroxyethyl methacrylate 2-hydroxypropyl methaer'ylate
Claims (13)
1. An acrylic polymeric composition comprising: a curable polymer resulting from polymerizing a niunomer composition consisting of: at least one polymerizable monoethylenically unsaturated ester of a saturated aliphatic or aromatic monocarboxylic acid in an amount of from 0 to 40 percent by weight of the total weight of the monomer composition; at least one polymerizable alkyl or aryl ester of a monoethylenically unsaturated monocarboxylic acid in an amount of from 30 to 60 percent by weight of the total weight of the monomer composition; at least one polymerizable hydroxyalkyl ester of a monoethylenically unsaturated monocarboxylic acid in an amount of from 10 to 40 percent by weight of the total weight of the monomer composition; S. at least one polymerizable monoethylenically unsaturated monocarboxylic acid free of ester groups in an amount of from 0 to percent by weight of the total weight of the monomer composition; acrylonitrile, methyacrylonitrile or mixture thereof in an amount of from 0 to 15 percent by weight of the total weight of the monomer composition; at least one polymerizable alkyl or aryl biester of a *ses: monoethylenically unsaturated dicarboxylic acid in an amount of from 0 to 20 percent by weight of the total weight of the monomer composition; and at least one polymerizable monoethylenically unsaturated aromatic monomer free of acid and ester groups In an amount of from 0 to 50 percent by weight of the total weight of the monomer composition; and (11) a suitable solvent or mixture of solvents; wherein component is present in an amount of from 40 to percent by weight of the total weight of the polynric composition and component (II) is present in an amount of from to 60 percent by weight of the total weight of the polymeric composition characterized by employing 2-hydroxybutyl acrylate or 2-hydroxybutyl methacrylate /R0148f L 4' SO< *~d -I 15 or combination thereof as at least a portion of component in an amount such that at least 75 equivalent percent of the hydroxyl groups contained in component is derived from 2- hydroxybutyl acrylate, 2-hydroxybutyl methacrylate or a combination thereof.
2. An acrylic polymeric composition of Claim 1 wherein component is present in an amount of from 0 to 14 percent by weight of the total weight of the monomer composition.
3. An acrylic polymeric composition of Claim 1 or Claim 2 wherein component is present in an amount of from 40 to 54 percent by weight of the total weight of the monomer composition.
4. An acrylic polymeric composition of any one of Claims 1 to 3 wherein component is present in an amount of from 25 to 39 percent by weight of the total weight of the monomer composition. An acrylic polymeric composition of any one of Claims 1 to 4 Swherein component is present in an amount of from 1 to 2 percent by weight of the total weight of the monomer composition.
6. An acrylic polymeric composition of any one of Claims 1 to wherein component is present in an amount of from 0 to 14 percent by weight of the total weight of the monomer composition. An acrylic polymeric composition of any one of Claims 1 to 6 wherein component is present in an amount of from 0 to 14 percent by weight of the total weight of the monomer composition.
8. An acrylic polymeric composition of any one of Claims 1 to 7 wherein component is present in an amount of from 20 to 34 percent by weight of the total weight of the monomer composition.
9. An acrylic polymeric composition of any one of Claims 1 to 8 wherein component is present in an amount of from 65 to 75 percent by weight of the total weight of the polymeric composition. An acrylic polymeric composition of any one of Claims 1 to 9 wherein component (II) is present in an amount of from 25 to 35 percent by weight of the total weight of the polymeric composition,
11. The acrylic polymeric composition of any one of Claims 1 to wherein: component is vinyl acetate, vinyl propionate, vinyl benzoate, or mixture thereof; '-AZX KEH/0148f .r 16 (ii) component is ethyl acrylate, n-butyl acrylate, i- butyl acrylate, 2-butyl acrylate, 2-ethylhexyl acrylate, methyl methacylate, n-butyl methacrylate, octyl methacrylate, or mixture thereof; (iii) component is 2-hydroxybutyl acrylate. 2-hydroxybutyl methacrylate or combination thereof; (iv) component is acrylic acid, methacrylic acid, crotonic acid, vinyl benzoic acid, or mixture thereof; component is diethyl maleate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, or mixture thereof; 0(vi) component is styrene, a methyl styrene, or mixture thereof; and (vii) component (II) is selected from ketones, alcohols, glycol NN.. ethers, aromatic hydrocarbons, esters, glycol ether-esters, and mixtures thereof.
12. The acrylic polymeric composition of Claim 11 wherein: component is vinyl acetate; (11) component is n-butyl acrylate; (iii) component is acrylic acid; (iv) component is acrylonitrile; component is dibutyl maleate; (vi) component is styrene; and S(vii) component is 2-hydroxybutyl acrylate. 13, An acrylic coating composition comprising at least one acrylic polymeric composition of any one of Claims 1 to 11 and a curing quantity of one or more curing agents for component
14. An acrylic coating composition of Claim 13 wherein said curing agent is a melamine-formaldehyde resin. An acrylic coating composition of Claim 14 wherein said curing agent is hexamethoxymethyl melamine,
16. An article coated with one or more layers of an acrylic coating composition of any one of Claims 13 to An acrylic polymeric composition substantially as herein described with reference to Example 1, Part A, excluding the comparative examples.
18. An acrylic coating composition comprising at least one acrylic polymeric composition of Claim 17 and a curing quantity of one or more curing agents for component 17
19. An acrylic coating composition, substantially as herein described with reference to Example 1, Part B and C, excluding the -comparative examples. An article coated with one or more layers of an acrylic coating composition of Claim 18 or Claim 19. DATED this TWENTY-NINTH day of NOVEMBER 1990 The Dow Chemical Company Patent Attorneys for the Applicant SPRUSON FERGUSON foot oe 9.6 o .48 4 5 u* *goo S S M EH/0148f INTERNATIONAL SEARCH REPORT International Application No prT/yTS87 /flofl9 4 1. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all)3 According to International Patent Classiflcation (IPC) or to both National Classification and IPC 33/20,33/22 IPC(4): C08F 2/06,20/26,20/28,20/44,20/50,22/14; C08L 33/14 61,/28 US CL 524/364,512.7Z9.76175l7 ,73 810 'I R ;d.C;9ir/VP '131 1%31QAZ2,.' 11. FIELDS SEARCHED Minimum Documentation Searched 4 Classification System IClassification Sym~ois u~s.524/364:512,759,761,765,773,776,830,853,854S' 52/3 81,3183,38.4 ,32 Documentation searched other than minimum Documentation to the Extent I- such Documents are Included In the Fields Searched 1l1. DOCUMENTS CONSIDERED TO BE RELEVANT t4 Category *I Citation of Document, ta with indication, where appropriate, of the relevart passages t7 Relevant to Claim No. 1 A US,A, 4,532,294 (BOUBC3ILIS) 30 JUrLY 1985. See entire 1-7 docurrent. A US,A, 4,530,957 (TEOORE ET AL) 23 JULY 1985. See 1-7 corm 7, line 63 to coltui 8, line 8. A US,,A, 4,501,868 (BOUOULIS ET AL) 26 FEBRUARY 1985. 1-7 See col~mn 2, line 58 colurmn 3, line A US,A, 4,440,894 (ZYCHCWSKI ET' AL) 03 APRIL 1984. 1-7 See the Abstract. A US,A, 4,435,556 (MASLER) 06 MARCH 1984. See co~lxnn 6, 1-7 lines 23-33. A iUS,A, 3,883,453 (TAKAHASHI El' AL) 13 MAY 1975. See 1-7 olun 2, lines 42-57. A 1US,Aj 2,686,172 (WOLF) 10 AUGUST 1954. See colurm 3j 1-7 2.iYes 24-41. A UP,A, 2,460,329 (BOEMER ET' AL) 01 JULY 1976. See 1-7 Abstract. special categories of cited documental t4 later document published after the International filing date document definng the general state of the art which Is not or priority date and not In conflict with the application~ but cosdrdto be of particular relevance cited to understand the principle or theory underlying the consieredInvention "El earlier document but published on or after the international 11)(1 document opatcular relevencel the claimed Invention filing date cannot be considered novel or cannot be conaidervil to "L document which may throw doubts on priority claim(s) or involve an inventive step, which Is cited to establish the publication date of another 14~ document of particuilar relevance; the claimed Invention citation or other spec~ial reason (as specified) cannot be considered to Involve an inventive step when the I'Q" document referring to an oral disciosure, use, exhibition or document is combined with one or more other such docu. other means merits, such combination being obvious to a person skillied "Pl' document published prior to the International flung date but in the art, later than the priority date claimed 1141 document member of the same patent family IV., CERTIFICATION Osloj of the Actual completion of the International Search' D ate ot Mailing of this International Search Report'1 24 FEBRUARY 1987 2 0 MAR 1987___ international Searching Authority tSignat urie of Auh st., -fier Form PCTIISA210 (socond sliest) (October 101) (9 I International Application No. PCTs~/USS0092 PcrTAT87/0092 Ill. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEFT) CategoryI Citation of Docliment, is with indication, where appropriate, of the relevant passages '17 Relevant to Claim No 'a I Ujs,A, 3,542,741 (HA? 1ANN ET AL) 24 NOVEMBER 1970. See oolumn 2, lines 21-35. 1 1-7 US,A, 3,832,217 (SATO ET AL) 27 AUGUST 1974. See column 3, line 72 column 4, line 16. U9,A, 3,844,993 (MILLER) 29 OCIOBER 1974. See colunm lines 1-6. US,A, 3,941,912 (TAJIMA ET AL) 02 MARCH 1976. See Abstract. US,A, 4,237,038 (PAMPOUCHIDIS ET AL) 02 DECEMBER 1980 See column 2, line 60 to column 3, line 12. USIA, 4,259,224 (DALIBOR ET AL) 31 MARCH 1981. See column 3, line 60 to column 4, line 33, JPiA, 54-126054 (TOYO) 29 SEPTEMBER 1979. See Abstract. 1-7 1-7 1-7 1-7 1-7 1-7 Form PCT'ISAi1o (extra sheet) (October 1981)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/779,001 US4654398A (en) | 1985-09-23 | 1985-09-23 | Thermoset acrylic coatings having improved gloss retention |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6891687A AU6891687A (en) | 1988-08-10 |
| AU609710B2 true AU609710B2 (en) | 1991-05-09 |
Family
ID=25115000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68916/87A Ceased AU609710B2 (en) | 1985-09-23 | 1987-01-14 | Thermoset acrylic coatings having improved gloss retention |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU609710B2 (en) |
| WO (1) | WO1988005441A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670512A (en) * | 1986-03-14 | 1987-06-02 | The Dow Chemical Company | Acrylic coating compositions and method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4627485A (en) * | 1984-08-17 | 1986-02-20 | Akzo N.V. | Hydroxyl group-containing polymer as binder |
| AU5439386A (en) * | 1985-03-08 | 1986-09-11 | Mitsubishi Rayon Company Limited | Acrylic coating with hydroxyalkyl groups and method for forming a multi-layered coating |
| AU8322387A (en) * | 1986-11-24 | 1988-06-16 | E.I. Du Pont De Nemours And Company | Aqueous polymer dispersion for use in automotive basecoat under solvent clear coat |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2686172A (en) * | 1951-05-22 | 1954-08-10 | Goodrich Co B F | Tough, strong, and easily processed vinyl chloride interpolymers containing free side-chain hydroxyl groups |
| DE1720265C3 (en) * | 1967-02-23 | 1975-01-30 | Basf Ag, 6700 Ludwigshafen | Process for the production of lightfast coatings |
| US3832217A (en) * | 1970-12-15 | 1974-08-27 | Mitsubishi Rayon Co | Process for forming exterior finish coating films for automobile bodies |
| US3844993A (en) * | 1971-06-28 | 1974-10-29 | Du Pont | Floor mop having pivotable handle for changing directions air-drying coating composition of an acrylic enamel and an isocyanate cross-linking agent |
| JPS515660B2 (en) * | 1972-07-11 | 1976-02-21 | ||
| AU474688B2 (en) * | 1973-08-15 | 1975-02-20 | Sumitomo Naugatuck Co. Ltd. | Copolymer latex and paper coating composition thereof |
| DE2460329A1 (en) * | 1974-12-20 | 1976-07-01 | Bayer Ag | LOW MOLECULAR ACRYLATE RESINS WITH LOW DISPERSALITY AND A METHOD FOR THEIR PRODUCTION |
| DE2644691B2 (en) * | 1976-10-02 | 1981-02-12 | Hoechst Ag, 6000 Frankfurt | Copolymer solution from acrylic resin, process for their production and use of the same in reactive varnishes |
| AT356226B (en) * | 1977-10-24 | 1980-04-10 | Vianova Kunstharz Ag | METHOD FOR PRODUCING CATHODICALLY DEPOSIBLE BINDERS |
| JPS54126054A (en) * | 1978-03-24 | 1979-09-29 | Toyo Contact Lens Co Ltd | Soft contact lens |
| US4501868A (en) * | 1982-06-28 | 1985-02-26 | Exxon Research & Engineering Co. | Superior solvent blends for synthesis of acrylic resins for high solids coatings |
| US4440894A (en) * | 1982-10-08 | 1984-04-03 | Desoto, Inc. | Thermosetting vinyl acetate tetrapolymer coatings |
| US4530957A (en) * | 1983-01-05 | 1985-07-23 | Ford Motor Company | Non-aqueous dispersions based on capped stabilizers and reactants comprising polyfunctional monomers I |
| US4435556A (en) * | 1983-03-28 | 1984-03-06 | Masler Iii William F | Method of making and using novel scale inhibiting terpolymer |
| US4532294A (en) * | 1983-12-07 | 1985-07-30 | Exxon Research & Engineering Co. | Superior high solids coatings |
-
1987
- 1987-01-14 WO PCT/US1987/000092 patent/WO1988005441A1/en unknown
- 1987-01-14 AU AU68916/87A patent/AU609710B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4627485A (en) * | 1984-08-17 | 1986-02-20 | Akzo N.V. | Hydroxyl group-containing polymer as binder |
| AU5439386A (en) * | 1985-03-08 | 1986-09-11 | Mitsubishi Rayon Company Limited | Acrylic coating with hydroxyalkyl groups and method for forming a multi-layered coating |
| AU8322387A (en) * | 1986-11-24 | 1988-06-16 | E.I. Du Pont De Nemours And Company | Aqueous polymer dispersion for use in automotive basecoat under solvent clear coat |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1988005441A1 (en) | 1988-07-28 |
| AU6891687A (en) | 1988-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69720042T2 (en) | Non-aqueous coating agents based on a polymer dispersion with a high glass transition temperature | |
| US4525521A (en) | Coating composition of an acrylic polymer having amino ester groups and a glycidyl acrylic polymer | |
| US5407707A (en) | Powder coating composition based on epoxy containing polymers and polyacid curing agents | |
| US4338379A (en) | High-solids thermosetting enamel coating composition | |
| US20150017451A1 (en) | Polymer, process and composition | |
| DE69318165T2 (en) | THERMOCURING GLYCIDYL MODIFIED ACRYLIC POWDER COATINGS | |
| DE2540834A1 (en) | COATING DIMENSIONS | |
| CN101090917A (en) | Alcoholic soluble resin and preparation method thereof | |
| US3622651A (en) | Novel polymer having pendent ester groups for low temperature bake coatings | |
| US4877837A (en) | Epoxy functional and silicone thermosetting powder coatings | |
| JPH0216110A (en) | Acrylic polymer | |
| US4654398A (en) | Thermoset acrylic coatings having improved gloss retention | |
| EP1283226A1 (en) | Hydroxyl-functional copolymer and coating compositions formed therewith | |
| JPH08509768A (en) | Thermosetting coating composition | |
| DE69804313T2 (en) | FILM-FORMING COMPOSITION | |
| AU609710B2 (en) | Thermoset acrylic coatings having improved gloss retention | |
| AU604002B2 (en) | Two component coating composition of an anhydride containing polymer and a clycidyl component | |
| DE1595243B2 (en) | PROCESS FOR PRODUCING SOLUTIONS OF NEW MIXED POLYMERIZES | |
| EP0398387B1 (en) | High solids low VOC paint compositions | |
| EP0546640B1 (en) | Interpolymer-based binders | |
| US4515835A (en) | High solids thermosetting coating compositions, cured coatings, coated articles, and processes | |
| JP2857178B2 (en) | Methacrylic lacquer composition | |
| KR101756879B1 (en) | Randomly branched copolymers, preparation thereof and use thereof as levelling agents in coating substances | |
| US3850871A (en) | Acrylic organosol coating composition containing a plasticizer of a dibasic acid/glycol/monobasic acid plasticizer | |
| CA1312164C (en) | Thermoset acrylic coatings having improved gloss retention |