USRE23753E - Coated plastic products - Google Patents

Coated plastic products Download PDF

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USRE23753E
USRE23753E US23753DE USRE23753E US RE23753 E USRE23753 E US RE23753E US 23753D E US23753D E US 23753DE US RE23753 E USRE23753 E US RE23753E
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polystyrene
coating
solvent
acrylate
cellulose
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of 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 aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • C08L1/10Esters of organic acids, i.e. acylates
    • C08L1/14Mixed esters, e.g. cellulose acetate-butyrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31884Regenerated or modified cellulose
    • Y10T428/31888Addition polymer of hydrocarbon[s] only
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31928Ester, halide or nitrile of addition polymer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31935Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to articles made of polystyrene and more specifically to such articles, covered with a surface coating which imparts to them a greatly enhanced resistance to abrasives,
  • the present invention has for an object to surface coating materials for polystyrene. overcome the disadvantages just mentioned, An-
  • Polystyrene is a widely employed construction other object is to provide a novel coating for material. For example, it is being used in repolystyrenes which forms an integral bond therefr geration equipment and also in automotive and m with, and which imparts to polystyrene enhanced aircraft industries for structural as Well as decresistance to scratching, reduced electrostatic orative purposes.
  • a further object is a polystyrene able properties, namely: 1. Very high electroarticle protected by such coating.
  • a still further static charges which cause excessive attraction object is a process of applying to the polystyrene for dust. 2.
  • Coatdepositing acrylate coatings on polystyrene withings of shellac, while soluble in solvents which do out etching the polystyrene surface: not attack the polystyrene, are not sufiiciently (b) that the etching effect of active solvents tenacious to give the protection desired. Further can be largely checked by the inclusion of cellumore, they are soluble in alcoholic cleaning fluids.
  • esters Ethyl Cellulose coatings f th po y yrenes and (c) that by careful balancing of solvent comof their derivatives have also been tried, and while positions, it is possible to provide a combination these possess a considerable resistance to many 40 solvent which dissolves and deposits acrylates, yet solvents and to electrostatic influences, they are is non-etching to styrene: not very scratch resisting, and, above all, they (d) that cellulose esters, which otherwise do fail to bond to the polystyrene.
  • Ethyl methacrylate polymer made by the Guth Products Company.
  • Example 1 30% ethyl acrylate was polymerized by refluxing with of benzoyl peroxide in 69 ethyleneglycolmonomethylether, until a sample on drying formed a film having 9. mar resistance at least 10% higher than that of polystyrene by the A. S. T. M. Procedure D 673-421 (falling carborundum grit). of the product thus obtained was dissolved in 80% of a solvent consisting of methyl ethyl ketone, 25% ethanol, and diethylene glycol mono ethyl ether.
  • the resultant product was brushed on to a polystyrene object, and dried in a forced draft cabinet at 63 C.
  • the resultant coating had a substantially enhanced mar and solvent resistance.
  • Example 2 25% ethyl methacrylate monomer was polymerized by refluxing in the solvent consisting of equal parts of ethyleneglycolmonomethylether, methyl ethyl ketone, and ethanol. A pressure was maintained so as to permit maintenance of a reaction temperature of 180 C. The reaction was continued until a sample removed and allowed to dry to a. film, gave 9, mar resistance at least 10% higher than that of polystyrene by the A. S. T. M. Procedure D 673-42T.
  • the resultant product was then sprayed on to a polystyrene object and dried at 70 C. It was found to have a substantially enhanced mar and solvent resistance.
  • Example 3 Percent by weight Methyl methacrylate polymer 10
  • the acrylate powder was dissolved in the acetone and esters. When uniform, the remaining solvents were blended into the mixture with agitation.
  • a polystyrene panel was dipped into the lacquer and dried at 55 C.
  • a clear, tenacious coating was deposited on the plastic. This coating had '9. mar resistance substantially higher than polystyrene and was firmly bonded thereto.
  • the present invention provides an article of manufacture comprising a polystyrene surface having integrally bonded thereto an acrylate coating.
  • a polystyrene surface having integrally bonded thereto a coating comprising an acrylate and a cellulose ester.
  • a coating comprising to 1% of an acrylate and from 0 to 99% of a cellulose ester may be used.
  • Suitable cellulose esters are cellulose aceto butyrate and cellulose aceto propionate.
  • the percentage of solids is not critical, as a variation in this factor will only affect the thickness of the resultant coating, and not its qualities.
  • methyl ethyl ketone instead of methyl ethyl ketone, we may employ any other ketone, ester, toluene or nitro aliphatic substance excepting nitro methane, which has-a boiling range below about C., or combinations thereof.
  • ethyl alcohol we canuse nitro methane, or any other aliphatic alcohol, or lactate, having less than 6 carbon atoms.
  • Butyl Cellosolve and any other glycol ether having a comparable or higher degree of volatility, diacetone alcohol and the like.
  • the polystyrene surface is etched by the coating composition, then the percentage of these solvents just mentioned should be reduced, in favor of nitro methane, lower aliphaic alcohols, lactates and ethyleneglycolmonomethyl ester, or hydrocarbon nonsolvents such as aliphatic petroleum fractions e. g., kerosene,
  • polystyrene While reference has been made throughout this application to polystyrene, it is fully understood that this term includes such co-polymers or modified products as are commercially known under the generic term, styrene type resins. This includes copolymers between styrenes and acrylates, polymers with acrylonitrile and like materials known as being suitably co-polymerizable with styrene. The di-vinyl benzenes and their polymers and co-polymers are also included in the generic terms polystyrenes.
  • An article of manufacture comprising a polystyrene surface, having integrally bonded thereto a coating comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerized butyl methacryldte, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate, said coating being deposited from a composition containing from 1 to 35% of a solvent selected from the group consisting of aliphatic ketones and esters, toluene and nitro aliphatic substances other than nitro methane, having a boiling range below 120 C.; from 2 to 45% of a solvent selected from the group consisting of nitromethane, aliphatic althan nitromethane having a boiling range below 120 C.; 5 to 35% of a solvent selected from the class consisting of nitromethane, aliphatic alcohols, and lactates having 1 to 5 carbon atoms; and to 40% of a substance
  • a coating composition comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerz'zed butyl methacrylate, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate and a cellulose ester, dissolved in a solvent composition comprising from 3 to of a solvent selected from the group consisting of aliphatic ketones and esters,toluene, and nitroaliphatic substances other than nitromethane having a boiling range below 120 C.; 5 to of a solvent selected from the class consisting of nitromethane aliphatic alcohols, and lactates having 1 to 5 carbon atoms; and 20 to 01' a substance selected from the group consisting of diacetone alcohol, glycol ethers and esters.
  • the cellulose ester being cellulose aceto butyrate.
  • the cellulose ester being cellulose aceto propionate.
  • a coating composition comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerz'zed butyl methacrylate, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate, and a film forming cellulose ester, dissolved in a solvent comprising from 1 to 35% of a solvent selected from the group consisting of aliphatic ketones and esters, toluene and nitro aliphatic substances other than nitro methane, having a boiling range below 120 C.; from 2 to of a solvent selected from the group consisting of nitromethane, aliphatic alcohols and lactates having 1 to 5 carbon atoms; and from 14 to of a solvent selected from the group consisting of diacetone alcohol, glycol ethers and esters.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Description

Reissuecl Dec. 15, 1953 Re,
UNITED STATES PATENT OFFICE COATED PLASTIC PRODUCTS Johan Bjorksten, Madison, Wis., Stuart 0. Fledler, Cleveland, Ohio, and Luther L. Yaeger, Madison, Wis., assignors to Nash-Kelvinator Corporation, Kenosha, Wis., a corporation of Maryland No Drawing. Original No. 2,578,665, dated December 18, 1951, Serial No. 730,192, February 21, 1947. Application for reissue December 17,
1952, Serial No. 326,615
12 Claims. (01. 260-17) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This invention relates to articles made of polystyrene and more specifically to such articles, covered with a surface coating which imparts to them a greatly enhanced resistance to abrasives,
solvents and to other destructive influences; and parency. also to modes of preparing and applying such The present invention has for an object to surface coating materials for polystyrene. overcome the disadvantages just mentioned, An-
Polystyrene is a widely employed construction other object is to provide a novel coating for material. For example, it is being used in repolystyrenes which forms an integral bond therefr geration equipment and also in automotive and m with, and which imparts to polystyrene enhanced aircraft industries for structural as Well as decresistance to scratching, reduced electrostatic orative purposes. However, the utility of polysensitivity, and greatly enhanced resistance to styrene is greatly restricted by certain undesircleaning fluids. A further object is a polystyrene able properties, namely: 1. Very high electroarticle protected by such coating. A still further static charges which cause excessive attraction object is a process of applying to the polystyrene for dust. 2. High susceptibility to scratching. articles a protective coating integrally bonded (This does not bear a direct relation to the hardthereto. Further objects will become apparent as ness of the article, inasmuch as the optical effects the following detailed description proceeds. of scratching are more pronounced with poly- By integral bond We mean that the coating styrene than with certain other materials which applied to all practical purposes forms a unity actually have a lower hardness, such as, for exwith the material beneath it, so that it cannot ample, acrylates.) 3. Clouding or dissolving of I be peeled off or loosened as a layer, for example, the styrene surface by commonly used cleaning by scratching with a sharp instrument. fluids. F We have now succeeded in providing acrylate Any one of the reasons is sufficient to greatly coatings which adhere firmly to polystyrene, reduce the applicability of polystyrene as a mawithout disturbing its clarity or appearance. terial for many articles where it would. otherwise Our products and procedures are based on the be desirable by virtue of its excellent physical and discoveries: mechanical properties and its relatively low price. (a) that if the active solvent in which acrylate In the past, it has been attempted to apply to 30 resins are prepared, and furnished commercially, polystyrene various kinds of coating for added is distilled off to a large degree, it is then possible surface protection and to improve its properties. to formulate suitable coating compositions for These attempts have all been unsuccessful. Coatdepositing acrylate coatings on polystyrene withings of shellac, while soluble in solvents which do out etching the polystyrene surface: not attack the polystyrene, are not sufiiciently (b) that the etching effect of active solvents tenacious to give the protection desired. Further can be largely checked by the inclusion of cellumore, they are soluble in alcoholic cleaning fluids. lose esters: Ethyl Cellulose coatings f th po y yrenes and (c) that by careful balancing of solvent comof their derivatives have also been tried, and while positions, it is possible to provide a combination these possess a considerable resistance to many 40 solvent which dissolves and deposits acrylates, yet solvents and to electrostatic influences, they are is non-etching to styrene: not very scratch resisting, and, above all, they (d) that cellulose esters, which otherwise do fail to bond to the polystyrene. It can be said not adhere to polystyrene, can be brought to adgenerally that those coatings ofprior art which here firmly by the addition of even a minor perbond to the polystyrene so as not to become decentage of acrylates, such as from 1% to 40%. tached therefrom are soluble only in solvents In accordance with this invention, we employ which are also solvents for polystyrene, and which as the principal protective ingredient, an acrylate therefore etch and cloud it, and that coatings of or a methacrylate polymer. prior art reasonably suitable in other regards fail For t e ke of brevity, We shall hereafter in,- to adhere to polystyrene. clude the film-forming acrylate and methacry- Attempts made in the past to coat polystyrene with acrylate or methacrylate type polymers failed, because the solvents necessary to dissolve these etched the styrene so as to destroy its trans- Among the numerous types of acrylate employed for the purpose of the invention, the preferred type is:
Ethyl and methyl methacrylate co-polymer made by the E. I. du Pont de Nemours at C0.
Somewhat less favorable film characteristics were obtained with the following type of acrylate:
Ethyl methacrylate polymer made by the Guth Products Company.
The following typesalso gave a coating, but were not preferred because of resistance less favorable than the preferred types of acrylates stated above:
"Butyl methacrylate polymerized to form a solid thermoplastic powder made by the E. I. du Pont de Nemours 8: Co.
Methyl methacrylate polymer.
One acrylate, which gave the best results, was, however, furnished, by the manufacturer, dissolved in ethyleneglycol monoethylether acetate, in which solvent this resin was prepared. This solvent interfered with the proper application of the coating, by etching polystyrene. This neces sitated correction, which could be accomplished:
(a) by removing a large portion of this solvent by distillation;
(b) by carrying out the manufacture of a resin in a different solvent less active on styrene, e. g., ethyleneglycol monomethyl ether;
( c) by compounding with a different film form'- ing body, which has a tendency to repress solvent action on styrene, e. g., a cellulose ester.
This problem, and the three remedies listed, apply to any acrylate resin prepared and furnished in a solution of an active styrene solvent. When an injection molding type acrylate is employed, this problem does not exist; however, the viscosities of such resins are so high as to preclude spraying as the application method, unless an unusually thin coating (less than about .001") is desired. Such solutions can be applied by dipping the object to be coated, or by brushing.
Specific embodiments of the invention are illustrated by the following examples:
Example 1 30% ethyl acrylate was polymerized by refluxing with of benzoyl peroxide in 69 ethyleneglycolmonomethylether, until a sample on drying formed a film having 9. mar resistance at least 10% higher than that of polystyrene by the A. S. T. M. Procedure D 673-421 (falling carborundum grit). of the product thus obtained was dissolved in 80% of a solvent consisting of methyl ethyl ketone, 25% ethanol, and diethylene glycol mono ethyl ether.
The resultant product was brushed on to a polystyrene object, and dried in a forced draft cabinet at 63 C. The resultant coating had a substantially enhanced mar and solvent resistance.
Example 2 25% ethyl methacrylate monomer was polymerized by refluxing in the solvent consisting of equal parts of ethyleneglycolmonomethylether, methyl ethyl ketone, and ethanol. A pressure was maintained so as to permit maintenance of a reaction temperature of 180 C. The reaction was continued until a sample removed and allowed to dry to a. film, gave 9, mar resistance at least 10% higher than that of polystyrene by the A. S. T. M. Procedure D 673-42T.
The resultant product was then sprayed on to a polystyrene object and dried at 70 C. It was found to have a substantially enhanced mar and solvent resistance.
Example 3 Percent by weight Methyl methacrylate polymer 10 The acrylate powder was dissolved in the acetone and esters. When uniform, the remaining solvents were blended into the mixture with agitation. A polystyrene panel was dipped into the lacquer and dried at 55 C. A clear, tenacious coating was deposited on the plastic. This coating had '9. mar resistance substantially higher than polystyrene and was firmly bonded thereto.
The present invention provides an article of manufacture comprising a polystyrene surface having integrally bonded thereto an acrylate coating. In a more specific aspect it provides the combination of a polystyrene surface having integrally bonded thereto a coating comprising an acrylate and a cellulose ester. A coating comprising to 1% of an acrylate and from 0 to 99% of a cellulose ester may be used. Suitable cellulose esters are cellulose aceto butyrate and cellulose aceto propionate.
In the formulas given, the percentage of solids is not critical, as a variation in this factor will only affect the thickness of the resultant coating, and not its qualities.
We may employ any other cellulose ester which is capable of forming a hard tenacious film, for example, cellulose acetate, cellulose acetate propionate, cellulose propionate, and the like. Therein a. similar connection of cellulose acetate hydrogen phthalate is disclosed and claimed in our co-pending application Serial No. 730,193 filed February 21, 1947.
With reference to the solvent combinations stated, instead of methyl ethyl ketone, we may employ any other ketone, ester, toluene or nitro aliphatic substance excepting nitro methane, which has-a boiling range below about C., or combinations thereof. Instead of ethyl alcohol. we canuse nitro methane, or any other aliphatic alcohol, or lactate, having less than 6 carbon atoms. We can also use Butyl Cellosolve" and any other glycol ether having a comparable or higher degree of volatility, diacetone alcohol and the like.
It is possible to work into the formulations even other solvents, plasticizers, pigments, dyestuffs. perfumes and the like as well as other resins and to co-polymerize these or their components with the acrylates disclosed. The term acrylate we understand to include such products, having the essential characteristics herein described in relation to polystyrenes. When thus modifying the compositions, the balance between polystyrene solvents and polystyrene nons'olvents must be maintained. This is done in the following manner: If the coating composition is turbid, the percentage of ketone type solvent or of glycol ether ester should be increased, and likewise if the bond of the coating to the polystyrene is poor. If, on the other hand, the polystyrene surface is etched by the coating composition, then the percentage of these solvents just mentioned should be reduced, in favor of nitro methane, lower aliphaic alcohols, lactates and ethyleneglycolmonomethyl ester, or hydrocarbon nonsolvents such as aliphatic petroleum fractions e. g., kerosene,
or of combinations of these, or other solvents having similar solvent and volatility characteristics.
Suggested ranges of percentage for these groups of solvents are as follows:
Aliphatic ketones and esters, toluene and nitro-aliphatic substances other than nitro- ,methane having a boiling range below 120 0.,
preferred 3 to 25%; usable 1 to 35%.
Nitromethane, aliphatic alcohols and lactates having less than 6 carbon atoms, preferred 5 to the skilled chemist to establish the proper balance for the purposes of this invention, for any particular solvents he may desire to employ.
While reference has been made throughout this application to polystyrene, it is fully understood that this term includes such co-polymers or modified products as are commercially known under the generic term, styrene type resins. This includes copolymers between styrenes and acrylates, polymers with acrylonitrile and like materials known as being suitably co-polymerizable with styrene. The di-vinyl benzenes and their polymers and co-polymers are also included in the generic terms polystyrenes.
It is thus seen that this invention is broad in scope. The specific ranges and examples have been given to illustrate only, and not to restrict the invention in any manner; The invention is to be limited only by the claims in which we intend to cover all novelty inherent in the invention as broadly as possible, in view of prior art.
Having thus disclosed our invention, we claim:
1. An article of manufacture comprising a polystyrene surface, having integrally bonded thereto a coating comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerized butyl methacryldte, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate, said coating being deposited from a composition containing from 1 to 35% of a solvent selected from the group consisting of aliphatic ketones and esters, toluene and nitro aliphatic substances other than nitro methane, having a boiling range below 120 C.; from 2 to 45% of a solvent selected from the group consisting of nitromethane, aliphatic althan nitromethane having a boiling range below 120 C.; 5 to 35% of a solvent selected from the class consisting of nitromethane, aliphatic alcohols, and lactates having 1 to 5 carbon atoms; and to 40% of a substance selected from the group consisting of diacetone alcohol, glycol ethers and esters.
3. A coating composition comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerz'zed butyl methacrylate, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate and a cellulose ester, dissolved in a solvent composition comprising from 3 to of a solvent selected from the group consisting of aliphatic ketones and esters,toluene, and nitroaliphatic substances other than nitromethane having a boiling range below 120 C.; 5 to of a solvent selected from the class consisting of nitromethane aliphatic alcohols, and lactates having 1 to 5 carbon atoms; and 20 to 01' a substance selected from the group consisting of diacetone alcohol, glycol ethers and esters.
4. As claim 3, the cellulose ester being cellulose aceto butyrate.
5. As claim 3, the cellulose ester being cellulose aceto propionate.
6. A coating composition comprising a substance selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polymerz'zed butyl methacrylate, ethyl and methyl methacrylate co-polymer and polymethyl methacrylate, and a film forming cellulose ester, dissolved in a solvent comprising from 1 to 35% of a solvent selected from the group consisting of aliphatic ketones and esters, toluene and nitro aliphatic substances other than nitro methane, having a boiling range below 120 C.; from 2 to of a solvent selected from the group consisting of nitromethane, aliphatic alcohols and lactates having 1 to 5 carbon atoms; and from 14 to of a solvent selected from the group consisting of diacetone alcohol, glycol ethers and esters.
7. The article of claim 1, further characterized by said coating additionally comprising a cellulose ester.
8. The article of claim 1, further characterized by said coating additionally comprising cellulose acetobutyrate.
9. The article of claim 1, further characterized by said coating additionally comprising cellulose acetopropionate.
10. In a process for enhancing the surface properties of polystyrene by utilizing the high specific adhesivity therefor of certain, synthetic resins, which depends on applying to a polystyrene surface synthetic resinous material having superior surface properties, dissolved in a solvent which does not dissolve or attack polystyrene, the step of applying to a polystyrene surface the composition of claim 2,
resins, which depends on applying to a polystyrene surface synthetic resinous material hav ing superior surface properties, dissolved in a solvent whichdoes not dissolve or attack poly styrene, the step of applying to a polystyrene surface the composition of claim 6.
I JOHAN BJORKSTEN.
STUART O. FIEDLER. LUTHER L. YAEGER.
References Cited in the file of this patent or the original lpaten't UNITED STATES PATENTS Number Name Date 2,071,419 1Moss Feb. 23, 1937 2,034,415 Strain June 22, 1937 2,238,694 Graves Apr. 15, 1941 2,254,904 Moss Sept. 2, 1941 2 ,292,393 Mitchell Aug. 11, 1942 2,332,461 Muskat et a1 M Oct. 19, 1943
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US2860110A (en) * 1954-06-04 1958-11-11 Du Pont Coating composition comprising a methyl methacrylate polymer and a cellulose ester and process for preparing same
US2934510A (en) * 1956-02-02 1960-04-26 Du Pont Coating compositions containing polymer of methyl methacrylate
US3368916A (en) * 1964-05-28 1968-02-13 Richardson Co Light resistant flame retardant polymers

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US2650909A (en) * 1951-12-03 1953-09-01 Carl L Betsch Coating compositions
DE1015359B (en) * 1952-06-04 1957-09-05 Bosch Gmbh Robert Method for preventing surface stress cracks in objects made of thermoplastics, in particular polystyrene housings of vehicle batteries
DE1172164B (en) * 1955-05-24 1964-06-11 Bayer Ag Process for the production of well-adhering protective coatings made of natural or synthetic rubber on molded parts made of polyamides
US2872429A (en) * 1956-08-15 1959-02-03 Minnie G Schwartz Method of preparing elastomeric plastigels
US2955955A (en) * 1957-11-05 1960-10-11 Sheffield Plastics Inc Protecting polystyrene
US2955055A (en) * 1958-04-25 1960-10-04 Rohm & Haas Heat-convertible coating composition, enameled article, and method of finishing surface with said composition
US3060148A (en) * 1958-07-29 1962-10-23 Du Pont Low viscosity methyl methacrylate coating composition containing high viscosity methyl methacrylate polymer
US3058846A (en) * 1960-07-05 1962-10-16 Dow Chemical Co Coating of shaped articles
US3328196A (en) * 1963-11-05 1967-06-27 Monsanto Co Process for coating polystyrene articles with vinylidene chloride copolymers and the resultant article
US3353990A (en) * 1964-01-31 1967-11-21 Interchem Corp Novel coated polystyrene articles and method for producing the same
US3320033A (en) * 1964-03-18 1967-05-16 Kerr Mc Gee Oil Ind Inc Absorbent, its preparation and use to recover metal values
US3582398A (en) * 1965-05-18 1971-06-01 Gen Electric Polycarbonate substrate with an acrylate coating thereon
US3304196A (en) * 1965-09-28 1967-02-14 American Cyanamid Co Mar-resistant products and process for producing same
US4350742A (en) * 1979-12-26 1982-09-21 Standard Oil Company (Indiana) Method to adhere acrylic films to styrenic polymers

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GB414040A (en) * 1933-01-18 1934-07-18 British Celanese Improvements in the treatment of textile materials
US2084415A (en) * 1933-04-26 1937-06-22 Du Pont Resinous composition and process for the manufacture thereof
US2137235A (en) * 1937-02-15 1938-11-22 Du Pont Shaped articles from polymeric materials
US2254904A (en) * 1937-03-04 1941-09-02 Celanese Corp Cellulose derivatives, polyvinyl compounds, or polymerized acrylic esters
US2292393A (en) * 1939-08-01 1942-08-11 Du Pont Moistureproof sheet wrapping material
US2332461A (en) * 1939-11-02 1943-10-19 Pittsburgh Plate Glass Co Artificial glass

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2860110A (en) * 1954-06-04 1958-11-11 Du Pont Coating composition comprising a methyl methacrylate polymer and a cellulose ester and process for preparing same
US2934510A (en) * 1956-02-02 1960-04-26 Du Pont Coating compositions containing polymer of methyl methacrylate
US3368916A (en) * 1964-05-28 1968-02-13 Richardson Co Light resistant flame retardant polymers

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NL73376C (en) 1900-01-01
CH297418A (en) 1954-03-31

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