Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
  • B05D3/141—Plasma treatment
  • B05D3/142—Pretreatment
  • B05D3/144—Pretreatment of polymeric substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
  • B05D3/065—After-treatment
  • B05D3/067—Curing or cross-linking the coating
• • 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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
  • B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2201/00—Polymeric substrate or laminate
  • B05D2201/02—Polymeric substrate

Definitions

• the invention relates to a method for producing a highly adhesive reactive coating on organic or inorganic substrates.
• Plasma processes have been used for some time to produce reactive coatings on surfaces.
• Plasma polymerization in particular is frequently used in this regard.
• polymerizable precursors are fed to a low-pressure plasma via the gas phase and deposited on the surface in polymerized form.
• Techniques used for this and the resulting surfaces and their use are described, for example, in "Plasma Surface Modification and Plasma Polymerization by N. Inagaki, Technomic Publishing Company Inc., Lancaster 1996”, “Plasma Polymerization by H. Yasuda, Academic Press Inc., New York 1985 "and” Plasma Polymerization Processes by H. Biederman, Y. Osada, Elsevier Science Publishers, Amsterdam 1992 ".
• the above-mentioned plasma techniques require that they be carried out in a vacuum and thus require complex equipment and time-consuming procedures.
• the compounds to be applied or polymerized (precursors) must be evaporated and evaporated condensed again to the substrate, which can lead to high thermal loads and in many cases to decomposition.
• the evaporation and deposition rates are low, making it difficult and lengthy to produce layers with a sufficient thickness.
• Solutions, suspensions or emulsions are applied to the inorganic or organic substrate, the activatable initiator and / or the ethylenically unsaturated compound being incorporated at least one group which interacts with a subsequently applied coating or reacts with groups contained therein, c) the coated substrate heated and / or irradiated with electromagnetic waves and forming an adhesion promoter layer, d) providing the substrate pretreated in this way with the further coating which contains reactive groups which react with those of the adhesion promoter layer and / or which interact with the adhesion promoter layer.
• the activatable initiator is preferably a free radical initiator.
• polymers of mono- and diolefins for example polypropylene, polyisobutylene, poly-butene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and polymers of cycloolefins such as, for example, cyclopentene or norbornene; also polyethylene (which may or may not be crosslinked), e.g.
• HDPE high density polyethylene
• HDPE-HMW high density and high molecular weight polyethylene
• HDPE-UHMW medium density polyethylene
• MDPE polyethylene low density polyethylene
• LDPE linear low density polyethylene
• VLDPE VLDPE
• ULDPE ultra high molecular weight polyethylene
• copolymers of mono- and diolefins with one another or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), and terpolymers of ethylene with propylene and a diene, such as
• Unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications;
• crosslinkable acrylic resins derived from substituted acrylic acid esters, such as epoxy acrylates, urethane acrylates or polyester acrylates;
• Crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of bisphenol A diglycidyl ether, bisphenol F diglycidyl ethers which are crosslinked by means of conventional hard materials such as anhydrides or amines with or without
• He, argon, xenon, N2, 02, H2, water vapor or air can be used as the primary plasma gases.
• the method according to the invention is in itself not sensitive to the coupling of the electrical energy.
• the process can be carried out in batch operation, for example in a rotating drum, or in the case of films, fibers or fabrics in continuous operation. These methods are known and are described in the prior art.
• the method can also be carried out under corona discharge conditions.
• Corona discharges are generated under normal pressure conditions, with air being the most common ionized gas. In principle, however, other gases and mixtures are also possible, such as in COATING Vol. 2001, No. 12, 426, (2001).
• the advantage of air as an ionizing gas in the case of corona discharges lies in the fact that work can be carried out in an apparatus which is open to the outside and, for example, a film can be drawn continuously between the discharge electrodes.
• Such process arrangements are known and z. B. in J. Adhesion Sci. Technol. Vol 7, No. 10, 1105, (1993).
• Three-dimensional workpieces can be treated with a plasma-free jet by tracing the contours with the help of robots.
• the process can be carried out in a wide pressure range, the discharge characteristic shifting from pure low-temperature plasma towards corona discharge with increasing pressure and finally changing to a pure corona discharge at atmospheric pressure of approx. 1000-1100 m
• the process is preferably carried out at a process pressure of 10-6 mbar up to atmospheric pressure (1013 mbar), particularly preferably at atmospheric pressure as a corona process.
• a corona discharge is used, air, CO 2 and / or nitrogen is preferably used as the gas.
• Preferred compounds are: dibenzoyl peroxide, benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, diisopropyl peroxydicarbonate, methyl ethyl ketone, bis (4-t-butylcyclohexyl) peroxydicarbonate, Ammoniumperoxomonosulfat, ammonium peroxodisulfate, Dikaliumpersulfat, Dinatriumpersulfat, N, N-azobisisobutyronitrile, 2,2'-azobis (2,4 - dimethylpentanitrile), 2,2'-azobis (2-methylpropannitrile), 2,2'-azobis (2-methylbutanenitrile), 1, 1 '- azobis (cyanocyclohexane), tert-amylperoxobenzoate, 2,2'-bis (tert -butylperoxy) butane, 1,1 '- bis (tert-butylperoxy) cycl
• Possible coinitiators are, for example, sensitizers which shift or broaden the spectral sensitivity and thereby accelerate the photopolymerization.
• These are, in particular, aromatic carbonyl compounds such as, for example, benzophenone, thioxanthone, in particular also isopropylthioxanthone, anthraquinone and 3-acylcoumarin derivatives, triazines, coumarins, terphenyls, styryl ketones, and 3- (aroylmethylene) thiazolines, camphorquinone, but also eosine, Rhodamine and erythrosine dyes. Certitiators are also tert.
• the ethylenically unsaturated compounds can contain one or more olefinic double bonds. They can be low molecular weight (monomeric) or higher molecular weight (oligomeric, polymeric). Through clever selection, the properties of the reactive layers can be controlled in a wide range.
• acrylonitrile acrylamide, methacrylamide, N-substituted (meth) acrylic amides
• vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl and halogenstyrenes
• maleic acid or maleic anhydride N-vinyl pyrrolidone
• vinyl chloride or vinylidene chloride N-vinyl pyrrolidone
• unsaturated compounds which carry additional groups which react acidic, neutral or basic (e.g. allylamine, 2-aminoethyl methacrylate, 4-vinylpyridine, acrylic acid, 2-propene-1-sulfonic acid).
• Examples of higher molecular weight (oligomeric, polymeric) polyunsaturated compounds are acrylated epoxy resins, acrylated polyesters, polyurethanes and polyethers containing vinyl ether or epoxy groups.
• Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of approximately 500 to 3000.
• vinyl ether monomers and oligomers as well as maleate-terminated oligomers with polyester, polyurethane, polyether, polyvinyl ether and epoxy main chains can also be used.
• Combinations of oligomers and polymers bearing vinyl ether groups, as described in WO 90/01512 are particularly suitable.
• Copolymers of vinyl ether and maleic acid functionalized monomers are also suitable.
• Such unsaturated oligomers can also be referred to as prepolymers.
• unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid.
• Acrylic and methacrylic acid are preferred.
• cationically polymerizable formulations of epoxides and / or vinyl ethers which are started by photochemically and / or thermally activatable acid generators should be mentioned here.
• an improved adhesion of the coating to the surfaces can also be achieved if these have previously been provided with OH groups, which can be achieved by using OH-functionalized initiators and / or unsaturated compounds in step b).
• Anchored epoxy groups can also be reacted with amines and / or alcohols and / or phenols to form stable bonds.

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• Plasma & Fusion (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Applications Claiming Priority (3)

Publications (1)

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• 2003
  • 2003-12-15 KR KR1020057011651A patent/KR20050084451A/ko not_active Application Discontinuation
  • 2003-12-15 JP JP2004561494A patent/JP2006510774A/ja active Pending
  • 2003-12-15 US US10/538,890 patent/US20060159856A1/en not_active Abandoned
  • 2003-12-15 AU AU2003299237A patent/AU2003299237A1/en not_active Abandoned
  • 2003-12-15 RU RU2005122900/04A patent/RU2338760C2/ru not_active IP Right Cessation
  • 2003-12-15 CA CA002510380A patent/CA2510380A1/en not_active Abandoned
  • 2003-12-15 EP EP03799570A patent/EP1576037A1/de not_active Withdrawn
  • 2003-12-15 BR BR0317581-2A patent/BR0317581A/pt not_active Application Discontinuation
  • 2003-12-15 MX MXPA05006547A patent/MXPA05006547A/es active IP Right Grant
  • 2003-12-15 WO PCT/EP2003/051010 patent/WO2004056910A1/de active Application Filing
  • 2003-12-15 CN CNA200380106811XA patent/CN1729237A/zh active Pending
  • 2003-12-19 TW TW092136198A patent/TW200422108A/zh unknown
• 2005
  • 2005-05-27 ZA ZA200504341A patent/ZA200504341B/en unknown

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