GB2152846A - Process for marking fluoropolymer articles - Google Patents

Process for marking fluoropolymer articles Download PDF

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Publication number
GB2152846A
GB2152846A GB08500667A GB8500667A GB2152846A GB 2152846 A GB2152846 A GB 2152846A GB 08500667 A GB08500667 A GB 08500667A GB 8500667 A GB8500667 A GB 8500667A GB 2152846 A GB2152846 A GB 2152846A
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GB
United Kingdom
Prior art keywords
dispersion
fluoropolymer
weight percent
marking
process according
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.)
Granted
Application number
GB08500667A
Other versions
GB8500667D0 (en
GB2152846B (en
Inventor
Linda Ann Saunders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of GB8500667D0 publication Critical patent/GB8500667D0/en
Publication of GB2152846A publication Critical patent/GB2152846A/en
Application granted granted Critical
Publication of GB2152846B publication Critical patent/GB2152846B/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised 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 a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised 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 a halogen; Derivatives of such polymers

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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)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Printing Methods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A process for marking fluoropolymer articles, for example to color code them, which employs a composition that is an organic dispersion containing a copolymer of tetrafluoroethylene and hexafluoropropylene, an epoxy compound, and a pigment.

Description

SPECIFICATION Process for marking fluoropolymer articles Thisinvention relates to a process for marking fluoropolyrner objects to color code the objects. The process is especially useful for marking wire coated with a fluoropolymer.
It is difficult to mark fluoropolymer objects because pigments do not adhere well to fluoropolymer surfaces, and ittherefore is desirableto provide new compositionscontaining pigments that adhere well to fluoropolymer surfaces.
The invention provides a process for marking a fluoropolymer article by depositing on a surface of the article a composition which comprises a dispersion of an organic liquid having a surface tension below 40 dynes percm measured at 25"C containing (a) 5 to 95 weight percent of at least one copolymer of 50-90 weight percent tetrafluoroethylene units and 5-50 weightpercent hexafluoropropylene units, of a molecularweight greater than 20,000, (b) 5 to 95 weight percent of at least one epoxy compound, and (c) 1 to 25 weight percent of pigment, and drying the marked surface.
In a preferred aspect, the dispersion composition will be deposited on an elongated fluoropolymer body, such as a fluoropolymerthatforms a coating of insulation on awire, e.g. copper wire, as the body moves past a dispersion applicator.
It has been discovered that an organic dispersion containing components (a) and (b) as defined above provides a system for adhering pigmentto fluoropolymer surfaces. The organic liquid has a surface tension below 40 dynes/cm at 25"C and can be an aromatic hydrocarbon such as benzene ortoluene, a ketone such as methyl isobutyl ketone, a mineral spirit, naphtha or a chlorinated hydrocarbon, and the like.
The copolymer is preferably one in which the tetrafluoroethylene units are present in an amount of 75-95% weight percent, and the hexafluoropropylene units are present in an amount of 5-25 weight percent.
The epoxy compound can be the diglycidyl eitherof bis-phenol A. Common crosslinking agents such as melamineformaldehydeorbenzoquanamineformal- dehyde can be used.
The pigment can be any common pigment dispersable in the dispersion, such as Red 2B, carbon black, phthala cyaninegreen or blue, moly orange, alizarine maroon,TiO2,chromeyellow,andthe like.
The dispersion can be prepared by combining all ingredients butthe pigment as described in U.S.P.
3,661,831 and then stirring in pigment.
In use, the dispersion is simple applied to the surface of afluompolymer article to mark, band, color code, orthe like. The dispersion is particularly useful to bandmarkelongated fluoropolymer bodies such as fluoropolymer coatings on electrical wire. There are several ways of doing this, which include applying by pad brush, wheel, orjetspray.
The fluoropolymer surface can be formed from any fluoropolymer resin. It can betetrafluoroethylene homopolymer or copolymers of tetrafluoroethylene and atleastone copolymerizablefluorinated ethylenically unsaturated comonomer.
Representative copolymerizable fluorinated ethylenically unsaturated comonomers include those ofthe formulas.
wherein R1 is -Rf, -RFX, -O-Rf, or -O-RFX in which Rf is a perfluoroalkyl radical of 1-12 carbon atoms, -RF- is a linear perfluoroalkylene diradical of 1-12 carbon atoms in which the attaching valences are at each end ofthe linear chain, and Xis H or CI; and R2 is Rf -RFX. Representative comonomers include hexafluoropropylene, perfluorohexene-1, perfluorononene-1, perfluoro (methyl vinyl ether), perfluoro (n-propyl vinyl ether), perfluoro (n-heptyl vinyl ether), perfluoromethyl ethylene, perfluorobutyl ethylene, ol-hydroperfluoropentene-1, 3-hyd- roperfluoro (propyl vinyl ether), and the like, or mixtures thereof such as a mixture of hexafluoropropylene, and perfluoro (propyl vinyl ether).
The copolymerizable fluorinated ethylenically unsaturated comonomer is preferably selected from perfluoro (alkyl vinyl ethers) ofthe formula R-O-CF=CF2;whernin Rf is alkyl of 1-5 carbon atoms of perfluoro (terminally unsaturated olefins) of the formula Rf- CF=CF2 wherein Rf is alkyl of 1-5 carbon atoms; or perfluoroalkyl ethylenes of 3-7 carbon atomsofTheformula,R-CH=CH2wherein Rf is alkyl of 1-5 carbon atoms.
Comonomer content in the TFE copolymers can range from 0.005 mole percent upto 20 mole percent, and more than one comonomercan be present. Thus the TFE copolymers comprise both melt-processible TFE copolymers and nonmelt-processibleTFE copolymers.The comonomer content is low enough that the copolymers are plastics ratherthan elastomers, i.e., they are partially crystalline and after extrusion do not exhibit a rapid retraction to original length from a stretched condition of 2X at room temperature. Forexample,whena perfuorinatedolefin isthe comonomer, the content may preferably be 0.02-20 mole percentandwhen a perfluoroalkyl ethylene is thecomonomer,thecomonomercontent preferably can be between 0.02-7 mole percent. When the comonomer is a perfluoro (alkyl vinyl ether) the comonomer content preferably can be between 0.02-2.3 mole percent. Atthe lower levels of these rangesthecopolymernormallytendsto be nonmeltprocessible; while atthe upper ranges the coplymer normally tends to be melt-processible.
Depending on the type fluoropolymer, articles are made by sintering processes, melt extrusion processes, or paste extrusion processes.
EXAMPLE In one application, band marking of wire was accomplished by pumping the dispersion composition through two oscillating opposing nozzles that are not directly aligned. The oscillating motion caused the dispersion to flow in a serpentine pattern. The period of oscillation determines the space between each band. The first nozzle supplied the first half of the band and the second nozzle was synchronized to complete the band.
The band markerwas positioned downstream from but close to the extruderthatwas used to cover the wire with fluoropolymer resin. This allowed the heat from the resin to set the dispersion compositions, providing excellent adhesion without need for the use of in-line post heaters.
In this application the dispersion composition was 1) methyl isobutyl ketone solvent mixture 2) tetrafluoroethylene/hexafluoropropylene copolymer (85/15) of molecular weight over 20,000.
3) The diglycidyl ether of bis-phenol A 4) carbon black, added in a carrier of 5) avinylresin 6) a ketone/alcohol extender 7) benzoquanamineformaldehyde Component 6) comprised about 44% by weight of the dispersion, while components 1) - 5) comprised about 56% . The carbon black and vinyl resin carrier comprised about 1.8 and 4% respectively. Component 1 was present in an amount of about 27%, component 2) in about 12-13%, component 3 in an amountof about8-9%, and component7) in about 2%.
Thefluoropolymercoating was a copolymerof tetrafluoroethylene and hexafluoropropylene (85/15).
It was coated on copperwire.
Gravure wheels or rubbertransfer rolls can be used. Gravurewheels are generally usedforthe identi fication of reguiarsurfaces. The wheel ordinarily has indented symbols around the circumference, and is run through a bath ofthe dispersion. Excessive dispersion is then removed from the wheel by a wiper blade, and the dispersion in the indentations is then transferred to the wire insulated with fluoropolymer resin.
A rubbertransferwheel is used for irregular surfaces. The principle is the same asforthe gravure wheel exceptthatthe rubbertransferwheel accepts the mark fro the gravure wheel and then transfer it to the wire surface.

Claims (4)

1. Aprocessformarking afluoropolymerarticle which comprises depositing on a surface ofthe article a composition which comprises a dispersion of an organic liquid having a surfacetension below 40 dynes per cm measured at 25"C containing.
(a) 5to 95 weight percent of at least one copolymer of 50-90 weight percent tetrafluoroethylene units and 5-50 weight percent hexafluoropropylene units, of a molecularweight greater than 20,000, (b) 5to 95 weight percent of at least one epoxy compound and a crosslinking agenttherefore and (c) 1 to 25weight percent of pigment, and drying the marked surface.
2. A process according to claim 1 wherein the dispersion is deposited on an elongated fluoropolymer body.
3. A process according to claim 2 wherein the elongated fluoropolymer body is a coating on a wire or cable.
4. A process according to claim 1 substantially as described with reference to the Example.
GB08500667A 1984-01-13 1985-01-11 Process for marking fluoropolymer articles Expired GB2152846B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US57037184A 1984-01-13 1984-01-13

Publications (3)

Publication Number Publication Date
GB8500667D0 GB8500667D0 (en) 1985-02-13
GB2152846A true GB2152846A (en) 1985-08-14
GB2152846B GB2152846B (en) 1987-02-18

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ID=24279393

Family Applications (1)

Application Number Title Priority Date Filing Date
GB08500667A Expired GB2152846B (en) 1984-01-13 1985-01-11 Process for marking fluoropolymer articles

Country Status (5)

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JP (1) JPS60179473A (en)
DE (1) DE3500814A1 (en)
FR (1) FR2558167A1 (en)
GB (1) GB2152846B (en)
IT (1) IT1183116B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8726482D0 (en) * 1987-11-12 1987-12-16 Bicc Plc Marking flourocarbon surfaces
JPH0730711Y2 (en) * 1989-08-29 1995-07-12 日本ウエーブロック株式会社 Colored fluororesin film cross sheet

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1769812B2 (en) * 1964-11-23 1976-06-24 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) PROCESS FOR THE PRODUCTION OF COATINGS ON MOLDED BODIES BY COATING WITH DISPERSIONS BASED ON POLYTETRAFLUORAETHYLENE AND ADDITIONAL FILM FORMERS

Also Published As

Publication number Publication date
GB8500667D0 (en) 1985-02-13
IT8519089A0 (en) 1985-01-11
IT1183116B (en) 1987-10-05
DE3500814A1 (en) 1985-07-25
JPS6139350B2 (en) 1986-09-03
JPS60179473A (en) 1985-09-13
GB2152846B (en) 1987-02-18
FR2558167A1 (en) 1985-07-19

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PCNP Patent ceased through non-payment of renewal fee