Surface treatment to improve the adhesion of paints to polydicyclopentadiene

Abstract: A method of improving the paint adhesion properties of a cycloolefin polymer article comprising exposing the surface of said article to a solution of sodium hypochlorite or a solution of potassium permanganate. Preferably the solution is of sodium hypochlorite and it further contains a detergent solution.

Description: This invention relates to a method of increasing the adhesion of paint films to the surfaces of molded articles made from cycloolefin polymers such as thermoset poly(dicyclopentadiene). Molded articles made from cycloolefin polymers as exemplified by articles of poly(dicyclopentadiene), the preparation of which is described, for instance, in U.S. Patent 4,400,340, frequently demonstrate poor ability to retain paint coatings. It is highly desirable for products made from this polymer to be painted, both to withstand degradation and for aesthetic reasons. In addition, a painted surface reduces any objectionable odor produced by unreacted dicyclopentadiene (DCPD) monomer remaining in the polymer. Therefore, a topcoat such as a white acrylic-urethane enamel is usually applied, despite the poor retention feature. It is known to treat polymers made from this monomer with a wash to reduce the odor of unreacted monomer. For instance, treatment of such molded products with a water solution of acidic, basic and/or amphoteric compounds, such as a solution of sulfuric acid, is disclosed in Japanese published patent application 62201940, dated September 5, 1987, to remove the residual odor of the dicyclopentadiene monomer. There are also prior disclosures of the treatment of other kinds of polymeric materials to improve printability or bondability to other surfaces or coatings by surface modification with various aqueous solutions. U.S. Patent 3,869,303 discloses a method of surface modification of synthetic rubbers with an aqueous solution of a mineral acid, a mineral oxidant such as potassium permanganate and sodium perchlorate, and a salt of hydrochloric, hydrobromic or hydroiodic acid, U.S. Patent 3,968,316 discloses surface treatment of rubber or synthetic resins containing ethylenic unsaturation with an alkyl hypohalite such as t-butyl hypochlorite and a compound such as hydrochloric acid containing an active hydrogen and a functional group, British Patent 1,396,090 discloses surface treatment of unsaturated rubber articles with an alkyl hypohalite or a halogen-substituted alkyl hypohalite, and Italian Patent 720,390 discloses surface treatment of polyethylene or polypropylene with potassium dichromates or permanganates, potassium or calcium perborates, chlorites or hypochlorites or sodium peroxide to increase adhesion to leather articles. There is a specific need for a surface treatment of articles made of thermoset cycloolefin polymers such as poly(dicyclopentadiene) to increase their paint adhesion properties. According to the invention, a method for improving the paint adhesion properties of a thermoset cycloolefin polymer article is characterized in that it comprises exposing the surface of said article to an aqueous solution of sodium hypochlorite or of potassium permanganate in a concentration of about 0.5% to 5.0%. The preferred treatment solution comprises about 1.0% to 2.5% sodium hypochlorite, and more preferably from about 0.5% to about 2.0% in a solution that also contains a detergent. The surface-wetting properties of the detergent increase the effectiveness of the sodium hypochlorite solution, permitting lower concentrations than would be otherwise necessary. The sodium hypochlorite is available commercially as a 5.25% weight percent aqueous solution, and is normally diluted for use in this invention. In this specification all parts and percentages are by weight unless otherwise noted. The surface treatment according to the invention, which is easily applied, overcomes the poor paint adhesion on articles made from typical thermoset cycloolefin polymers such as poly(dicyclopentadiene) (DCPD) and copolymers of DCPD with other cycloolefins, which otherwise present polymer surfaces from which paint tends to come loose in large pieces. In normal practice, the molded article is washed with a detergent solution prior to it being painted. Therefore it does not add any production steps to the manufacture of such molded articles to add the sodium hypochlorite to the detergent solution. The sodium hypochlorite surface treatment can be applied to the cycloolefin polymer article by any method commonly used in the art including brushing, applying with an absorbent pad, spray-washing or dipping. It is preferred to apply the sodium hypochlorite with an absorbent pad as it provides greater control over the volume of liquid applied to the surface which must be subsequently rinsed and dried prior to the painting step. The following examples are illustrative of this invention. Example 1 An aqueous solution of sodium hypochlorite is prepared. An approximately 5% aqueous solution (sold under the trademark Clorox at an undiluted concentration of 5.25%), is diluted in water to a 2.5% level. (For ease in calculations, the original undiluted concentration has been rounded to 5%, with other calculations rounded to the nearest 0.5%). Throughout the tests of paint adhesion, one-half of a molded poly(DCPD) article was treated with the solution while the other half of the article was wrapped tightly in aluminum foil to prevent experimental results from being influenced by exposure to any volatile elements in the solution. This experimental procedure was necessary since it had been found that even within a group of samples gathered from the same production run there was a wide deviation from sample to sample as to the paint adhesion properties. It was consistently found that the treated half of the poly(DCPD) article demonstrated excellent paint adhesion properties while the half wrapped in aluminum foil of the article demonstrated very poor paint adhesion properties. Paint adhesion was measured by ASTM standard D3359-83. The basis of the method is the adhesion of the coating to the substrate after a lattice pattern is cut through the coating. A pressure-sensitive adhesive tape with adhesion strength of approximately 45 g/mm width is pressed down over the lattice cut and then removed. The approximate amount of coating removed determines the adhesion rating which ranges from 5B for no detachment to OB for greater than 65% detachment. However, since the lowest classification under that standard was for a peeling level of over 65%, an additional classification was created for the experiments performed to indicate where substantially all of a paint film peeled off upon performance of the test or where the samples displayed gross amounts of peeling even in uncut sections. A total of four sets of tests were run. Five poly(DCPD) articles were manually wiped with 5% NaOCl. Five articles were treated in the same manner with a 1:3 dilution of the 5% NaOCl to water (1.67% NaOCl). The NaOCl remained on the surface of the article for 40 minutes before it was removed at the washing station. Five articles were treated with 2.5% NaOCl which had been prepared by diluting the 5% NaOCl 1:1 in a standard detergent solution. Another group of five articles were treated with a 1:3 dilution of the 5% NaOCl in the detergent solution to produce a solution having a NaOCl concentration of 1.67%. Five articles was treated with a 0.5% NaOCl concentration in detergent solution. All of the first group of articles exhibited excellent paint adhesion properties. The articles treated in the 1:3 dilution in water exhibited inconsistent paint adhesion properties ranging from poor to excellent while the group of samples untreated with NaOCl exhibited gross levels of paint peeling. The two sets of articles treated with the 2.5% and 1.67% dilutions of NaOCl in the detergent solution exhibited excellent paint adhesion properties. Even the lowest concentration of NaOCl at the 0.5% level in detergent exhibited excellent paint adhesion. The detergent used was Oakite Liqui-Det (manufactured by Oakite Products, Berkeley Heights, New Jersey). The active ingredients of the detergent include diethylene glycol butyl ether, ethoxylated cocoamine, dodecylbenzene sulfonic acid, ethanolamine and sodium acid pyrophosphate. The detergent is diluted, 170.5 ml (six fluid ounces) of concentrated detergent in 22.7 l (five gallons) of water. The detergent solution is mixed with a 5.25% sodium hypochlorite solution at a 4:1 ratio to produce a solution which is about 1% sodium hypochlorite. Other types of detergents may be used as long as the dilute solution of detergent used is not easily oxidized by NaOCl and does not react with the NaOCl to produce any hazardous gases. Other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures.

Claims: A method for improving the paint adhesion properties of a thermoset cycloolefin polymer article, characterized in that it comprises exposing the surface of the article to an aqueous solution of sodium hypochlorite or of potassium permanganate in a concentration of about 0.5% to 5.0%. A method for improving paint adhesion as claimed in claim 1, further characterized in that an aqueous solution of sodium hypochlorite in a concentration of from 1.0% to about 2.5% is used. A method for improving paint adhesion as claimed in claim 1 or 2, further characterized in that the solution also contains a detergent. A method for improving paint adhesion as claimed in claim 3, further characterized in that a solution of sodium hypochlorite in a concentration of from about 0.5% to 2.0% is used.

Inventors: HAAG HAROLD FRED, HAAG, HAROLD FRED
Applicants: HERCULES INC, HERCULES INCORPORATED
Application year: 1989
Main classification: C08J7
IPC codes: B05D3, C08J7