CA1102781A

CA1102781A - Protective compositions for recording

Info

Publication number: CA1102781A
Application number: CA309,289A
Authority: CA
Inventors: Robert P. Pardee
Original assignee: Ball Corp
Current assignee: Ball Corp
Priority date: 1977-08-15
Filing date: 1978-08-14
Publication date: 1981-06-09
Also published as: IT7850723A0; NL7808456A; CH636901A5; IT1157156B; JPS5464265A; SE7808513L; DE2835663C2; DE2835663A1; SE443369B; BE869731A; GB2002813B; GB2002813A; FR2400746A1; FR2400746B1

Abstract

ABSTRACT OF THE DISCLOSURE
An article of manufacture and a method are disclosed herein for improving lubricity and wear resistance of a given substrate by applying thereto a composition comprising essentially about 0.001 to about 3,000 weight percent of a composition containing 10 to 100 weight percent of a carboxylate ester, 0 to about 90 weight percent of an antistatic agent selected from the group consisting of amines, fatty quaternary ammonium compounds, fatty acid esters, phosphate esters and ethoxylated compounds, and about 97.00 to about 99.999 weight percent of a solvent therefor, and removing the volatile solvent to produce a thin, dry coating upon said substrate. The compositions herein disclosed have been found to be most effective as preservatives for coating gramophone or phonograph records which provide marked reduction of record groove wear while substantially minimizing noise and harmonic distortion.

Description

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PROTECTIVE CO~OS ITIONS FOR RECORDING

T~e present invention relatea.generally to lubrication of substrates and, more particularly, to an impro~ed lubrication composition and method of its.
application. The improved, wear-resistant, low friction 5 s.ubstrates have a coating provided by such composition, :
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~aid su~strates: including sound and video recordings such : as. gramophone or phonographic records, video discs and the like.
Lubrication of various substrates, and lQ particularly of substrates upon which recorded signals have ~een stored and from w.hich said signals can be recalled by dynamic means, has not been generally re-co~ni7ed and where attempts have been made to :
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- , ' lubricate such.substrates they have not proven fully satis.factory. In particular, substrates possessing this special pro~Iem include synthétic, natural and combinations of the thermoplastic materials and include resins ,- shellac;
polyvinly aceta:te, polyvinyl chloride, cellulose .acetate, poly (methyl methacrylatej, cellulose nitrate:and their deriyatives as. weLl as numerous other compositions that are generally formed through various press moulding means into phonographic records or discs as weIl as similar thermoplastic s:tructures. having trackable groove contours and reproaucing recorded monaural and stereophonic and video signals therefrom.
As is generally known, a phonograph cartridge serves to convert th~ variations on the ~alls and/or bo.ttom of.~he grooves of a phonograph:xecord into.
electrical signali whereby ~ -.
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the variations or wavy pattern on the grooves determine the frequency and the amplitude of the sound vibrations. The cartridge includes a stylus or picku~ needle usually in the form of a diamond or sapphire which generally as a hemi-spherical or ellipsoidal tip which rides or dips into the record groove and moves in response to variations of the pattern of said groove. The stylus, in turn, is generally attached to an armature which moves with the stylus to induce variations in an electrical or magnetic field in response to - 10 the stylus movement. This generates an electrical signal representative of the groove configuration which may then be amplified and used to drive speakers. Again, the stylus is caused to mechanically vibrate in response to the variations in amplitude and frequency of the undulations of the record groove wall which comprise the recorded signal.
A stylus has to track a plurality of evenly spaced groove contours with recorded signals on the order of between 15-20 and 20,000 Hz. Moreover, with the introduction of discrete four-channel record system or quadrasonic systems, a stylus must faithfully track grooves with recorded signals to cause vibrations of up to 50,000 Hz. As the stylus rides in the record groove, the relatively hard stylus wears away the relatively soft thermoplastic material of the record forming the groove. There has been heretofore no easy solution to alleviate the problem of record wear caused by the stylus .
' riding in the groove contour of such recordings.
The deterioration of the sound quality of records with increase in the number of plays through wear of their tracks by repeated uses re~ults in records becoming unusable and often being discarded within a short period of time. A
number of factors is responsible for wear including the general wear through abrasive and adhesive wear mechanisms to an extent proportional to stylus loading. This loading is not only the deadweight stylus load on the record which may range from about 1 gram to 4 grams but also includes dynamic inertial forces caused by stylus mass and the frequency of stylus directional changes as it tracks the groove undulations. As .:
known, reduction of deadweight load and stylus mass lowers the rate of groove wear but wear and the conse~uent loss of lS playback fidelity cannot be entirely eliminated. At any rate, most attempts of the prior art via record cleaners or alleged lubricates have simply resulted in cleaning only or depositing chemical ilms onto records without being successful in that such materials generally reduce the record

2~ fidelity due to rapid groove wear if cleaned or to hydro-dynamic damping of the stylus tracking if oily substances are ` deposited. Further, it is often observed in the use of these materials that the noise level is increased due mainly to dust captured along with the formation of a tacky deposit upon the stylus. Moreover, it has been observed that attempts ' .

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to use powdered solid lubricants such as graphitel molybdenum disulfide and the like have several disadvantages for they do not only reduce fidelty but also increase noise due to - particulate interference in record grooves.
In general, various silicones and hydrocarbon waxes and certain fluorinated telomeric compositions have been used as lubricants in sundry applications. One example of prior disclosure is a ethylene telomerized with trichlorotrifluoro- -ethane whereby moderately high molecular weight products are provided. In order to obtain a wax-like product~ a second active telogen must be included in the telomerization process.
In general, such active telogens are hydrogen-containing compounds including tertiary hydrocarbons~ aliphatic alcohols, divalent sulfur compounds, aliphatic tertiary amines, aliphatic ethers, carbonyl compounds and dialkyl phosphites. Since these active telogens contain hydrogen, the telomer products contain significant amounts of hydrogen, e.g. from 0.05 to 2% by weight.
Another example of prior disclosure would be compositions~which have ~o hydrogen and are of a lower melting point. In effect, such compositions are derived from the product~ obtained by telomerization of tetrafluoroethylene with cert~in haloalkanes. In fact, the compositions are made by chlorination or fluorination of certain fractions of telomer iodide mixtures whereby the iodine is replaced by chlorine or .

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fluorine. The utility of these composition is found in their application as a general dry lubricant, protective surface treatment, oil and water repellants, and a mold release and anti-stick composition.
The prior art discloses a method for renewing, resurfacing and preserving a phonograph record by the steps of coating the record with a composition consisting e~sentially of acrylic polymer, polyethylene emulsion, a detergent, an ether and water, brushing the composition into ~he grooves, removing any excess, drying and playing the phonograph record.
Also, the prior art discloses a method, composition and article are disclosed for improving lubricity, abra~ion re~istance, and lowering the coefficient friction of substrates such as photographic films, magnetic sur~acas and other recording elements by applying to such substrates a sol~tion comprising tetrafluoroethylene telomer and a copolymer of vinyl chloride and trifluorochloroethylene in a volatile ~olventS drying and removing the exce~s, and substrates so lubricated. In effect it was shown that ~he combination of a lubricant, viz., tetrafluoroethylene telomer and nonlubricant, viz~, poly ttrifluorochloroethylene-co-vinyl chloride) provides a coefficient of friction ~elow that of the lubricant per ~e.
The present invention, which provide~ a wear-- , : .
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resistant lubricous coating for photgraph records and the like is a solution comprising essentially an ester lubricant, and optionally a tetrafluoroethylene telomer or an an antistatic agent, and a volatile solvent therefor. The composition can be easily applied to any nu~ber of thermoplastic substrates generally used in the record or gramophone trade, upon which are recorded signals in the form of undulations or grooves, to provide a glossy coating that promotes a marked increase in lubrication properties thereof.
According to the present invention, a composition is formed for imparting lubricity and wear resistance to a surface having dynamic presentations thereon comprising about l.~Ol to about

3.000 weight percent of a composition containing a carboxylate ester, said ester being derived from a perfluoroalkyl alcohol of the formula CnF2n+1(CH2)mH wherein n is from about 3 to about 14 and m is l to 3 and an aliphatic carboxyiic acid having about 3 to 30 carbon atoms, and an antistatic a~ent selected from the group consisting of amines, fatty ammonium compounds, fatty acid esters, phosphate esters and ethoxylated compounds, and about 97.00 to about 99.999 weight percent of a solvent therefor.
The ester lubricants of the preferred embodiment to be hereinafter described are soluble in the solvent and Eor the most part do not exist in the composition herein contemplated as particles or as colloidal suspensions. In effect, the ' #3 composition of the present invention is generally an essentially homogeneous solution that is, it exhibits a uniform composition throughout its entire volume.
The term "substrate" as used herein embraces various surfaces of articles to be treated by the compositions and refex to plastic suhstrates, metal substrates, combination of plastic and metallic substrates, and in particular to playing elements of synthetic, natural and comhinations of thermoplastic materials and include resins, shellac, polyvinyl esters such as polyvinyl acetate, poly-vinyl benzene, polyvinyl chloride, cellulose acetate, po~y (methyl methacrylate), cellulose butyrate, cellulose nitrate, their derivatives as well as copolymers and blends thereof.
In particular, the term "substrates" include those surfaces which are made of numerous compositions that are generally formed through various press molding means into phonographic records or discs as well as similar thermoplastic structures having trackable groove contours thereon which when used in conjunction with certain dynamic means such as styli are capable of following said contours and repxoducing recorded monaural and stereophonic and video signals therefrom~
The compositions herein of the subject invention which impart to a given substrate a low coefficient of friction comprise a solution of a carboxylate ester lubricant including esters derived from alkalene glycol and polyoxyalkylene .
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g alcohols as well as esters in which the alcohol portion thereof is derived from halogenation of an aliphatic alcohol, especially fluoronation thereof. In general, the fluoroalkyl esters may be esters of monocarboxylic acid, viz.~ the fluoroalkyl monoesters; the esters of dicarboxylic acid, viz.
the fluoroalkyl diesters; esters of tricarboxyli~ acid, viz., the fluoroalkyl triesters; and esters of tetracarboxylic acid, viz., the fluoroalkyl tetraesters. Herein the fluoro-alkyl esters are compounds derived from carboxylic acids by replacing the ionizable hydrogen atom by a fluoroalkyl radical.
The fluoroalkyl portion of the molecule is the alcohol moiety thereof and has generally from abo~t two to about twenty carbon atoms. The preferred fluoroalkyl mono-carboxylic acid esters are fluoroalkyl acetate, fluoroalkyl - 15 laurate and fluoroalkyl stearate; the preferred fluoroalkyl dicarboxylic-acid esters are fluoroalkyl malonate and fluoroalkyl azelate, and the preferred fluoroalk~ tri-carboxylic acid ester is fluoroalk~l citrate. These fluoroalkyl esters can be readily prepared by conventional chemical techniques known in the art. In general, the fluoroalkyl monoesters may be produced by condensation of fluoroalcohols with aliphatic monocarboxylic acids. Further, fluoroalkyl polyesters may also be readily produced by the reaction of fluoroalcohols with polycarboxylic acids, either of the aliphatic or aromatic type. Mixed esters are also readily ~-produced by the reaction of fluoroalcohols with polycarboxylic acids, ei~her of the aliphatic or aromatic type. Mixed esters are also readily produced such as those formed from the condensation products of pyromellitic anhydriae with a mixture of fluoroalcohols.
The esters herein contemplated embrace those esters of terminally fluorinated alcohols in which a bridge containing an alkylene group is interposed between the fully fluorinated portion and the ester linkage. It is understood that the fluorinated alcohol may be a branched as well as a straight chain moiety~
In particular, the fluoroalkyl esters used in accordance with this invention may be readily prepared from the perfluoroalkyl aliphatic alcohols (viz., 2-perfluoroalkyl alkanols) of the formula C F2 +1(OEI2) OH where n is from about 3 to 14 and m is 1 to 3 and the corresponding carboxylic acid by art-known procedures. For examples, esterification reaction may be readily carried out by using para-toluene-sulfonic acia or sulfuric acid as a catalyst with the alcohol and carboxylic acid in benzene and heating these ingredients, remo~ing the water of reaction by codistilling with the benzene and thereafter removing any residual by di~tillation to isoLate the given esters. The perfluoroalkylethanols may be prepared by hydrolysis of fluoroalkyl hydrogen sulfate 25 which in turn are produced from the reactions of perfluoro-.. .. . . . . .

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alkylethyl iodides with oleum. Also, the perfluoroalkylethyl iodides may be prepared by known reactions of perfluoroalkyl iodide with ethylene as well as by known telomerization reactions. Conventional separation techni~ues may be employed to isolate selected fractions as, ~or example, the corresponding iodides having the perfluoroalkyl moiety in the range of 6 to 14 car~on atoms may be separated by dic~tillation.
~he fluoroalkyl esters may generally be mixiures which can, if desired, be further refined by fractional distillation or chromatographic techniques. Nonetheless, the esters may cover a somewhat broad ranye; for example, a common fluoroalkyl ester such as fluoroalkyl malonate may generally be a mixture of esters having an average of about 7~/O to 80%
perfluorohexyl to perfluoroheptyl-containing esters, with esters ha~ing a perfluorobutyl moiety and lower, less than about 5% and a per1uorodecyl moiety and higher, making up the balance.
The alkylane glycols used to form the carboxylate est~rs herein include ethylene glycol, propylene glycol, glycerol and trimethylene glycol. Further, the polyoxyalkylene glycols used to form the carboxylate esters herein include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(ethylenepropylene) glycol and the like. The polyoxy-alkylene glycols of the preferred embodiment are those that contain 2 to 4 carbon atoms of the recurring oxyalkylene group and have a molecular weight k,elow ~bout 6000 for the polyoxyalkylene portion of the molecule.
The carboxylic ac:ids herein contemplated that form the acid portion of the ester~ may contain rrom about 3 to 30 carbon atoms. The carboxylic acid moiety of the ester may be aliphatic, alicyclic, aromatic or hete~cyclic and may be saturated or may contain double bond unsaturation, such as ethylenic unsaturation. Representative car~oxylic acids for the esters herein contemplated are the fatty esters, both ~aturated and unsaturated and include acetic, malonic, butyric, isovaleric,azelaic, caproic, caprylic, capric, lauric, myristic, palmitic, palmitolic, stearic, oleic, ricinoleic, vaccenic,linoleic, linolenic, eIeostearic, licanic, parinaric, arachidic, gadoleic, arachidonic, behenic~ cetoleic, erucic, lignoceric, selacholeic and cerotic acids, with lauric, malonic, azelaicg stearic, citric, oleic and palmitic being preferred acids.
The polyoxyalkylene glycol monoesters and polyoxy-alkylene glycol diesters may be represented, respectively, by the general f,ormula:
I R Q o (R-O~- H
1 n ; II R - ~ - O -~R-0~- Q - R
1 n 2 respectively,wherein R and R are alkyl radicals and R is a : .

- ~3 -di~alent radical having 2 to 4 carbon atoms and n is an integer from about 2 to 200. Illusl:rative of these mono-and diesters are the following compounds: Polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monoleate, polyethylene glycol dioleate, polyethylene glycol monobehenate, polyethylene glycol dibehenate, and polyethylene glycol coco fatty acid esters.
To the compositions herein disclosed may be readily included certain low-molecular weight telomers of fluorocarbons, and especially telomers of tetrafluoroethylene. As used herein, the term "telomers" includes homotelomers and cotelomers and the term "telomerization" includes homotelo-merization and cotelomerization and the term "low-molecular weight telomers" means telomers having a maximum average molecular weight of about 3700.
One group ofpreferred telomers of this invention may be represented by the general structural formula:
R-(CF CF ) X (I) 2 2 a wherein R is a haloalkyl containing one to four carbon atoms, X is a member oelected from the group consisting of chlorine, iodine, and fluorine and a is an integer from about 6 to about 16. A preferred composition of the present invention is one where X is chlorine or fluorine and the radical R is a group .

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having the structur;ll formula:
R
R - C -F

wherein R and R each independently represent per~luoro-alkyl and monochloroperfluoroalkyl wherei~ each alkyl moiety has one to four carbon atoms. Th-s tetrafluoroethylene telomer has been available commercially under the trade name MP-51. In general, these telomers are completely halogenated telomers, in that they do not contain hydrogen, and have a molecular weight range of about 800 to a~ut 1800.
Other groups of related and preferred telomers are those that ha~e the formula:
Rl(CF -CF ) y (II) 2 2 b -; wherein R' is a hydrogen-containing moiety of a telogen, Yaid telogen being a member selected from the group consisting of tertiary hydrocarbons, aliphatic alcohols, divalent sulfur compounds, aliphatic tertiary amines, aliphatic ethers, .
: aliphatic carbonyl compounds, dialkylamides and dialkyl : phosphites, and Y is chlorine or a chlorofluoroalkyl wherein the alkyl portion has one to two carbon atoms and where b is an integer from about 3 to about 50. In general, these tetrafluoroethylene telomers, as distinguished from the .

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telomers mentioned above, contain hydrc,gen, e.gO, from 0.05 to 2% by weight.
Hydrogen-containing tetrafluoroethylene telomers are available under the trade mark Vydax AR. These telomexs S have a maximum average molecular weight of about 3700, a specific gravity of about 2.16, a melting point of 300C~, and are generally furnished at various concentrations including a 20% solid suspension in trichlorotrifluoroethane.
It has been found possible to separate from Vydax AR a somewhat lower molecular weight fraction by the conventional expedients of extracting, d~canting, filtering, or centrifuging. By such methods, a selected fraction is obtained where, in the above-mentioned structural formula II, b has a value of about 3 to about 84 In general, lack of lS turbidity or presence of clarity of the solution is found to be a good indication of such a selected fraction. The average molecular weight of this lower fraction is between about 400 and 900, the fraction being readily soluble in the herein de~cribed organic solvents~ The melting point of this fraction 2~ is generally~less than 120c.
For the hydrogen-containing telomers, such as Vydax AR, it has been found, for certain preferred embodiments that the use of the lower molecular weight fraction, that is, the fraction having a molecular weight helow about 900, results in favorable properties for certain end uses herein disclosed.

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27~1 Thu8, during stylus tracking on a stereo or quadraphonic record coated with a composi*ion of the present invention, there is observed no substartial wear particle build-up on the stylus as compared to an untreated record~ Further, there is no actual clogging or interference of the groove undulations even in a single alternation with a record at fre~uencies up to and ind uding 45,000 ~z., which may occupy no more than about 0.0008 linear inches of space along tha recoxd groove.
In general, the concentration of the above-mentioned telomer additive can vary over a relatively broad range, but a range of about 2.0 weight percent to about 0.00~ weight percent of the total weight of the composition has been found most effectiva. In practice, a concentration of between about 0.15 to about 0.005 weight percent has been found to be satisfactory for treating phonograph records.
An antistatic agent is not always required with the compositions of this invention. It has been noted in the course of worX that some ester lubricants do exhibit the ~0 characteristic of effectively reducing static charge on a substrate without incorporation of a separate antistatic agent as such~
But an antistatic agent may be used, if desired, to render the compositions herein described more e~fective from a practical standpoint in that such compositions having -- ' . . ' `

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incorporated therein said agent elimin~te or sub~tantialLy reduce the electrostatic charge on phonograph record surfaces to which such compositions are applied, thereby reducing the attractice forces which induce the migration o~ dust and other undesirable foreign particles to the record surface. The electrostatic charge can result from several causes, but is especially noticeable upon removing a record from its protective iacket, wiping its sur~ace with cl~th or brush, and otherwise contacting or buffing the record surface. RepresentativP of one group of preferred antistatic agents found highly effective in the compositions herein are the tertiary amines, including the diaIkanolamines.
These amines have been found to be compatible in terms of solubility with the solvents herein disclosed.
The particular dialkanolamines found highly suitable for the herein described composition may be represented by the general structural ~ormula:
HOCH CH N CH CH OH

R"
2Q wherein R" is an alkyl having about four to about twenty ; carbons atoms. These dialkanolamines have a molecular weight o~ about 150 to about 400. IlLustrative of such dialkanola-mines are N,~-bis(2-hydroxyethyl) dodecylamine, N,N-bis(2-hydroxyethyl)tetradecylamine and N,N-bis(2-hydroxyethyl) tetradecylamine. Tha dialkanolamines may be readily made by . .
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conventional chemical techniques known in the art.
Other suitable and preferred antistatic agents may be readily incorporated, if desired, into the compositions herein. Such agents should be soluble in tha solvent employed. Thus other antistatic agent~ include fatty quaternary ammonium compounds, fatty esters, phosphate esters and ethoxylated compounds. The ethoxylated compounds include such compositions as polyethylene glycols as well as ethoxulated triglycerides, ethoxylated sorbitol and the like. The concentration of the antistatic agent can vary over a wide xange so long as it is ef~ective in reducing or removing electrostatic charge. When incorporated, a concentration of about 1.0 to about 0.001 weight percent based on the total composition has been found to be most e~fective.
The solvents utilized with the compositions of the present in~ention include organic compounds as well a~ water.
While certain solvents are useful, provided there is no adverse effect upon the substrate, trichlorotrifluoroethane 2~ is particularly desirable as having suitable oxganic dissolution powers, high volatility, and essentially no physical or chemical effect on the substrate. The trichloro-tri1uoroethane can be either isom~ex, i.e., it may be 1,1,1-trichloro-2,2,2-trifluoroethane or 1,1,2-trichloro-1,2,2-trifluoroethane.

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Other userul solvents of the present invention, either individually or in mi.scible combinations, include the following:
Alcohols Ketones Estç~.rs 5 methanol acetone ethyl acetate ethanol methylethyl ketone propyl acetate n-propanol methylpropyl ketone isopropyl acetate isopropanol methylisopropyl ketone butyl acetate isobutanol methylisobutyl ketone diethyl ketone ethylpropyl ketone ethylisopropyl ketone Haloqenated HydrocarbQns H~drocarbons Etheræ
carbon tetrachloride benzene isopropyl ether chloroform toluene diethyl ether .
methylene chloride xylene dioxane methyl chloroform pentane tetrachloroethylene hexane trichloroethylene heptane dichloroethane octane dichloxoethylene perfluorodimethyl.cyclobutane benzotrifluoride The penetrating ability or penetration coefficient of a given solvent is Important to obtain the proper and effective distribution of lubricant, especially in the fine grooves and tiny crevices of a phonograph record, media, 2d substrate or the like having dynamic presentations thereon.
For example, record grooves are generally closely spaced, IJ-shaped crevices having an opening of about 0.003 inch (7.6 microns) with a bottom radius of often e~ual to or less than 0.002 inch (5.1 microns). In order to get within the grooves of the record track the solvent itself must exhibit ' ' ' , - ' ' ~ :
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a high penetration ability, a propexty ;apparently depending on a number of factors including surface tension ViSCQSity~
volatility, etc. Seemingly, solvents found most effective for their purpose are those that have surface tensions of le-s than about 20 dynes per centimetre (20C.). ~or this reason trichlorotrifluoroethane is one desirable sol~ent.
A preferred composition of the present invention consists of an este~ lu~ricant, an organic solvent and optimally an antistatic agent which is, preferably, a tertiary amine as defined above.
Lubrication of substrates herein contemplated can be accomplished by applying the herein-described composition wherein the ester lubricants are generally present in a solvent in an amount less than three weight percent to a given substrate, i5 evaporating the solvent thererom, and lightly buffing, if desired~ the thus-coated substrate to pxovide a clear coating.
Application of the compo~ition can be accomplished by numerou~
means including spraying, dipping, brushing, swabbing, flowing and doctoring. For mos$ purposes, spraying and swabbing are 2~ preferred because of the complete and uniform coverage these methods afford.

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- 21 _ There can be added to the composition of the present invention minor amounts of various conventional components including antioxidants, pigments, hardeners, illers, binders, odorants, dyes and the li~e if there is S need to do so and to the extent that such ingredierts are soluble or dispersible in the solvent and do not degxade the pexformance characteristic of the present compositions.
The ester lubricants herein contemplated are those that are solubla in the aforementioned solvents and for the most part do not exist in the compositions hereindescribed as particles ox as colloidal suspensions. In effect, the compositions of the present invention are generally essentially clear, homogeneous solutions, that is, each exhibits a uniform composition through its entire volume without any turbidity.
The ester lubricants herein contemplated and disclosed may be employed in amounts ranging from about 3.0 to about 0.001 weight percent based on the total weight of the solution, preferably from about 0.2 to about 0.01 weight percent and especially from about 0.1 to about 0.03 weight percent.
The resulting treated axticle which also forms a part of this invention is made by applying the compositions to the surface and removing the carrier therefrom whereby there is deposited thereon a coating of the ester ranging from about 0.3 to 3 micrograms per square centimeter.

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Treatrnent of the various substrates herein contemplated can be accompli~;hed by applying the above-described compositions in a concentration generally less about three weight percent, evaporating the solvent therefrom to provide a coating or film t:hereon which comprises an ester.
In practice a concentration of between about O.l to 0.03 weiqht pexcent has been found to be satisfactory for treating phonograph records. Further, it has been found advantageous ; to buff or polish after treatment to impart a good luster to the playing surface thereof.
- There will be illustrated herein preferred examples of the lubricating composition of this invention and method of using the same. The specific illustration~, however, are not intended to be a limitation upon the breadth of the invention. Generally, the invention taught herein is one in which a volatile but effective carrier transports therein an ester, the composition forming a ~ilm upon a given substrate after the solvent has volatilized.
EXAMPLE I
A solution was prepared comprising 99.96 percent by C~ frad~?al~K
B weight of trichlorotrifluoroethane (Freon TF~) and 0.04 percent by weight of perfluoroalkyl citrate (this triester is available under the trade mark Zonyl TBC from E.I. du Pont de ~emours & Co., Wilmington, DE), the average perfluoroalkyl moiety thereof ranging from heptyl to octyl. A clear homogeneous Z~

solution resulted and was sprayed onto a clean phonograph test records, National Association of Broadcaster~ (NAB~
test record No. 12-5-98, the trichlorotrifLuoroethane was allowed to evaporate, and t:he playing surface was lightly buf~ed to leave a thin coating of said ester thereon.
A stylus/groove coefficient of friction t08t wa8 conducted~on the phonograph record before and after the treatment descxibed by measuring the change in the deceleration rate of the freely rotating phonograph record on a turntable, the deceleration change being cau~ed by the engagement of the tone arm stylus with the record groo~e.
This chaage in deceleration is converted to stylus/groove coefficient of friction by the following formula:
f a I (A -A ) sin 45 t t ~ _ SR
f = coefficient of friction.
I - moment of inertia of total rotating system.
A = angular decelexation for the total effectQ
t of stylus and turntable bearings.
A c angular deceleration for the effect of the turntable bearings alone.
S a Stylus force on record.
R - mean record radius at groove where stylus is sliding.
Using the above formula l:he coefficient of friction , - . . . . :

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before coating with the aforementioned citrate composition was 0~35 and after application of said composition tha - coefficient of friction was reduced to 0~180 Another composition was prepared a~ above with the exception that 0.04 weight percent fluoroalkyl stearate wa~
used in place of the a~orementioned citrate, thiæ monoester being available from E.I. di Pont de Nemours & Co., Wilmington, Delaware, United States America. The avaxage perfluoroalkyl moiety of said monoester ranged from heptyl to octyl. The coefficient o~ friction of the untreated record was 0~33 where the treated record with the fluoroalkyl stearate gave a coefficient of friction of 0.11.
EXANPLE II
Accelerated phonograph record wear tests were conducted on NAB test records which had been treated with the compositions hereinafter disclosed. The results achieved from cleaned and treated records were compared with the results of the wear test conducted on a cleaned test record which had not been treated in accordance with the present invention. A
graduated scale was established ranging from a rating of zero for a clean, mint condition appearance to a rating of 100 for a surface heavily covered with wear debris. A test utilized ; a;standard type automatic record turntable rotating at 33-1/3 rpm type with the stylus on the tone arm adjusted to 9.5 grams load on the record surface. This high stylus load was used in .

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o order to accelerate the wear process and thereby provide better discrimination among record treatment$. Various compositions of the present invention were applied to the record surfaces in accordance with the proçedure described in Example I. Test results after 125 to 127 playing cycles are presented in the tabulation below:
Phono Record SurPace graph Appearance at Test Test Termin-Record Composition of Record Treating a~ion and Iae~tifi- Solution: Trichlorotrifluoro- Relative cation __ _ ethane Plus the followinq (wt.%
A 0.04 wt.% fluoroalkyl citrate Relatively (average perfluoroalkyl portion clean surface 7 to 8 carbon atoms) --scattered ~ine wear particles:
Rating = 15 B 0.04 wt.% fluoroalkyl stearate Quite clean:
(average perfluoroalkyl portion scattered very 7 to 8 carbon atoms) fine particle$:
Rating = 7 C Control Record Heavily (~ecord cleaned via mild covered with detergent) various sizes particles of wear debris:
Rating = 100 The above examples show that compositions of the subject invention effectively prevent phonograph record groove wear, for the a~ove test results indicate that the compostions herein described significantly reta.rd wear over a laxge number . of actual playings~

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I

A solution was prepared comprising 99.96% by weight of trichlorotrifluoroethane (Freon T~) and 0~04/O by weight of perfluoroalkyl malonate, the perfluoroalkyl moiety average thereof ranging from heptyl to octyl. A clear, homogeneous solution resulted and was sprayed onto a clean p~onograph test record, ~ational Association of Broadcasters (NAB) test re~ord No. 12-5-98, the trichlorotrifluoroethane was allowed to evaporate and the playing surface of the record was lightly bu~fed to leave a thin coating of diester thereon.
The stylus/groove coefficient of friction test.wa~
conducted in accordance with Example I. The stylys/groove coefficient of friction determined on the treated record was 0.18. In comparison, the coefficient of friction as determined.
on untreated ~AB records averaged about 0.32.
The accelerated record wear test was also conducted on the treated record in accordance with Example II and resulted in the record having a very clean surface appearance indicating very little record wear and gave a relative rating ~0 of 1Ø
EXAM_LE_IV
A solution was prepared comprising of 99.97 percent ~y weight of denatured alcohol (90% ethyl alcohol, 5% methyl alcohol and 5% water) and 0.03 percent by weight of polyoxy-othylene glycol monostearate, the molecular weight of the ~ .
', , ~ ',.

polyoxyethylene gly~ol porticn beir~ about 400. A cle~r solution resulted and was sprayed onto a phonograph test record, ~ational Association o~ Broædcasters (NAB), the alcohol was allowed to evaporate, and the playing surface was lightly buffed to leave a thin coating of said monoester thereon. The record was then subjected to playing and compared with an untreated record to determine changes in any surface noise. For this purpose,-the signal from the stylus, tracking at one gram load in the record groove, was fed to an oscilloscope for display. During the first number of playing~, the coated record showed significantly less surface noise than did an uncoated record; and progressively throughout some 120 playings, the level of background or surface noise of the coated record ultimately reached the noise level that the - 15 uncoated record showed on its first playing.

A solution was prepared comprising about 99.02 weight percent of denatured alcohol (90/O ethyl alcohol, 5% methyl alcohol and ~% water)~ about 0.05 weight percent polyoxy-ethylene glycol monostearate, and about 0~03 weight percent alkyldiethanolamine. The molecular weight of the polyoxy-ethylene glycol portion of the stearate ester was about 400, and the alkyl portion of the alkyldiethanolamine was C to C

A clear solution resulted and was sprayad onto a NAB test ~5 record, the alcohol was allowed to evaporate t and the playing : - :
: . - . :

.
. - ,, ': ',, - . . : ,:
'- :~ . ' " ' :' - ~ ' ' ' ' ~ 27i~

surace was lightly buffed. The accelerated record w~ar t~st as descr~bed in Bxample II was cond~cted on the treated record and resulted in the record 'naving a very clean surface indicating very little record wear and gave a relative rating of 2Ø
EXAMPLE VI
~nother series of accelera~ed phonograph record wear tests was conducted on NAR test records which had been treated with the compositions hereinafter disclosed. The results achieved from cleaned and treated records were compared with the results ~f the wear test conducted on a cleaned test record which had not been treated in accordance with the present invention. A graduated scale was established ranging from a rating of zero for a clean, mint condition appearance to a rating of 100 for a surface heavily covered with wear debxis. A test utilized a standard type automatic record turntable rotating at 33-1/3 rpm type with the stylus on the tone ar~ adjusted to 9.5 grams load on the record surface.
This high stylus load was used in order to accelerate the wear process and thereby provide better discrimination among record treatme~ts. Various compositions of the present invention were applied to thq record surfaces in accordance with the procedure described in Example I. Test re~ults after 125 to 127 playing cycles are presented i31 the tabulation bPlow:

:

~z~

Phono Record Surface graph Appearance at ~est Composition of Record Treating Test Termin-Record Solution: Trichlorotrifluoro- ation and Relative Identi~i- et~ane plus the followin~ (wt~%) Rating cation _ _ A 1.0% tetrafluoroethylene Quite cle~n: a telomer concentrate (20% solids) small numher of Vydax AR, (decanted), plus 0.02% fine wear polyethylene glycol monolaurate particles:
(mol. wt. of the polyethylene Rat:ing = 3 glycol portion was about 600) B 0~03% polyethylene glycol mone- Very clean: a laurate (mol. wt. of poly- few fine wear ethylene glycol portion was particles:
about 600) Rating = 2 C 0.06% fluoroalkyl stearate Very clean:
(average perfluoroalkyl portion a few fine w~ar was 7 to 8 carbon atoms) plus particles:
0.04% polyethylene glycol mono- Rating = 3 laurate (mol. wt. of polyethy-lene glycol portion was about 600).

D Control Record Heavily covered (Record cleaned via mild with various detergent). sized particles of wear debris:
Rating = 100 The above examples show that compositions of the subject invention effectively prevent phonograph record groov~
wear, since the compositions have been found to significantly retard wear over a large number of actual playings~
2( There have been disclosed herein a method of and a composition for lubricating surfaces, and in particular those surfaces which are capable of having or have dynamic presentations thereon. In view of this specification, those skilled in the art will have man~ r;lodifications which fall ~, - . - - .
,, . , - ~ ~:
: . . ,' . : : : .' :.
:- . ~

27~

within the true spirit and scope o~ thi~ in~ntion. It is intended that all such modiications be within the scope of the appended claims.

Claims

The embodiments of the invention in which an exclusive property or previledge is claimed are defined as follows:

1. A composition for imparting lubricity and wear resistance to a surface having dynamic presentations thereon comprising about 0.001 to about 3.000 weight percent of a composition containing a carboxylate ester, said ester being derived from a perfluoroalkyl alcohol of the formula CnF2n+1(CH2)mOH wherein n is from about 3 to about 14 and m is 1 to 3 and an aliphatic carboxylic acid having about 3 to 30 carbon atoms, and an antistatic agent selected from the group consisting of amines, fatty ammonium compounds, fatty acid esters, phosphate esters and ethoxylated compounds, and about 97.00 to about 99.999 weight percent of a solvent there-for.

2. A composition of claim 1 wherein the amines are dialkanolamines and the solvent is a halogenated hydrocarbon.

3. A method of treating a surface having dynamic presentations thereon to render said surface lubricous and wear resistant, which comprises the steps of treating the surface with a solution comprising about 0.001 to about 3.000 weight percent of a composition containing a carboxylate ester derived from a perfluoroalkyl aliphatic alcohol of the formula CnF2n+1(CH2)mOH wherein n is from about 3 to about 14 and m is 1 to 3 and an aliphatic acid selected from the group consisting of monocarboxylic and polycarboxylic acids said acids having about 3 to 30 carbon atoms, and an antistatic agent selected from the group consisting of amines, fatty quaternary ammonium compounds, fatty esters, phosphate esters and ethoxylated compounds, and about 97.00 to about 99.999 weight percent of a solvent therefor, and removing the solvent therefrom.

4. A method of claim 3 wherein the removing of solvent is accomplished by frictional contact with a moving member.

5. A method of claim 3 wherein the solvent is a halogenated hydrocarbon.

6. A method of claim 3 wherein the amines are dialkanol-amines and the solvent is a halogenated hydrocarbon.

7. A substrate having dynamic presentations thereon having a composition comprising a carboxylate ester derived from a perfluoroalkyl alcohol of the formula CnF2n+1(CH2)mOH
wherein n is from about 3 to about 14 and m is 1 to 3 and an aliphatic acid selected from the group consisting of mono-carboxylic and polycarboxylic acids and an antistatic agent selected from the group consisting of amines, fatty quaternary ammonium compounds, fatty acid esters, phosphate esters and ethoxylated componds.

8. A substrate of claim7 wherein the ester is a fluoro-alkyl ester selected from the group consisting of fluoroalkyl monoesters, fluoroalkyl diesters, fluoroalkyl triesters and fluoroalkyl tetraesters.

9. A phonograph record having deposited over the playing surface of said phonograph record a composition comprising a carboxylate ester derived from fluoroalkanols having the formula CnF2n+1(CH2)mOH wherein n is from about 3 to about 14 and m is 1 to 3, and an aliphatic acid selected from the group consisting of monocarboxylic acid and polycar-boxylic acids, said acid having about 3 to 30 carbon atoms, and an antistatic agent selected from the group consisting of amines, fatty quaternary ammonium compounds, fatty acid esters, phosphate esters and ethoxylated componds.